U.S. patent application number 09/883904 was filed with the patent office on 2002-04-25 for black azo dyes.
Invention is credited to Beach, Bradley Leonard, Feeman, James F., Holloway, Ann P..
Application Number | 20020049309 09/883904 |
Document ID | / |
Family ID | 24575349 |
Filed Date | 2002-04-25 |
United States Patent
Application |
20020049309 |
Kind Code |
A1 |
Beach, Bradley Leonard ; et
al. |
April 25, 2002 |
Black azo dyes
Abstract
Provided are novel black 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.
Inventors: |
Beach, Bradley Leonard;
(Lexington, KY) ; Holloway, Ann P.; (Lexington,
KY) ; Feeman, James F.; (Wyomissing, PA) |
Correspondence
Address: |
LEXMARK INTERNATIONAL INC
INTELLECTUAL PROPERTY LAW DEPARTMENT
740 WEST NEW CIRCLE ROAD
LEXINGTON
KY
40550
US
|
Family ID: |
24575349 |
Appl. No.: |
09/883904 |
Filed: |
June 18, 2001 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09883904 |
Jun 18, 2001 |
|
|
|
09642136 |
Aug 18, 2000 |
|
|
|
6288217 |
|
|
|
|
Current U.S.
Class: |
534/827 ;
534/810 |
Current CPC
Class: |
C09B 31/08 20130101;
C09D 11/328 20130101 |
Class at
Publication: |
534/827 ;
534/810 |
International
Class: |
C09B 033/02; C09B
033/18 |
Claims
We claim:
1. A compound of Formula (I): 28wherein: R.sub.1 is
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--CO.sub.2M, or --SO.sub.3M; R.sub.2 is --H, --CO.sub.2M, -lower
alkyl, -lower alkoxy, nitro; --CF.sub.3, halogen, --NHCO-lower
alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M, or
--(CH.sub.2).sub.n--CO.sub.2M; R.sub.3 is -lower-alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl, --NHC(O)O-lower-alkyl, or --NH--CO--CO.sub.2M;
R.sub.4 is -lower-alkyl, -lower alkoxy,
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl, or NHCOCO.sub.2M;
R.sub.5 is --N--(R.sub.6)(R.sub.7), or a group of the formula
29R.sub.6 is --H, -lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2M,
-lower-hydroxyalkyl, or -lower-cyanoalkyl; R.sub.7 is --H,
-lower-alkyl, --(CH.sub.2).sub.n--CO.s- ub.2M, -lower-hydroxyalkyl;
or -lower-cyanoalkyl; R.sub.8 is --H, lower-alkyl,
-lower-hydroxyalkyl, or --(CH.sub.2).sub.nCO.sub.2M; R.sub.9 is
--H, -lower-alkyl, -lower-hydroxyalkyl, or
--(CH.sub.2).sub.nCO.sub.2M- ; R.sub.10 is --H, -lower-alkyl,
-lower alkoxy, -lower-hydroxyalkyl, --(CH.sub.2).sub.n--CO.sub.2M,
-halogen; --NR.sub.8R.sub.9; --(CH.sub.2).sub.nSO.sub.3M; or
--O--(CH.sub.2).sub.mCO.sub.2M; m is 1, 2, or 3; n is 1, 2, or 3; M
is --H, --Li, Na, --K, or --N--(R.sub.11).sub.4; R.sub.11 is --H,
-lower alkyl, or --(CH.sub.2--CH(R.sub.12)--O).sub.p--H; p is 1
to4; x is 1 or 2; R.sub.12 is --H, --CH.sub.3,
--CH.sub.2--CH.sub.3, or --CH.sub.2--OH; and R.sub.13 is --H, lower
alkyl, lower alkoxy, halogen, --CO.sub.2M, or --SO.sub.3M.
2. A compound of Formula (II): 30wherein: R.sub.2 is --H,
-lower-alkyl, -lower-alkoxy, --CO.sub.2M, --CF.sub.3, --NO.sub.2,
-halogen, --NHCO-lower-alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M, or
--(CH.sub.2).sub.n--CO.sub.2M; R.sub.3 is -lower-alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl, or --NHCOCO.sub.2M;
R.sub.4 is -lower-alkyl, -lower alkoxy,
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl, or --NHCOCO.sub.2M; m is
1, 2, or 3; n is 1, 2, or 3; M is --H, --Li, Na, --K, or
--N--(R.sub.11).sub.4; R.sub.11 is --H, -lower alkyl, or
--(CH.sub.2--CH(R.sub.12)--O).sub.p--H; p is 1 to 4; x is 1 or 2;
and R.sub.12 is --H, --CH.sub.3, --CH.sub.2--CH.sub.3, or
--CH.sub.2--OH.
3. The compound of claim 2, which is a compound of Formula (III):
31wherein: R.sub.2, R.sub.4, x, and M are as defined in claim
2.
4. The compound of claim 3, wherein R.sub.2 is --H.
5. The compound of claim 3, wherein R.sub.5 is --NH.sub.2.
6. The compound of claim 4, wherein R.sub.5 is --NH.sub.2.
7. The compound of claim 4 which has the formula: 32
8. The compound of claim 4 which has the formula: 33
9. The compound of claim 4 which has the formula: 34
10. The compound of claim 4 which has the formula: 35wherein M is
--N--(R.sub.11).sub.4 and R.sub.11 is --H, or lower alkyl,
optionally substituted by hydroxy.
11. The compound of claim 10, wherein M is selected from the group
consisting of --NH.sub.4, --N(CH.sub.3).sub.4,
--N(CH.sub.2CH.sub.3).sub.- 4, and
--NH(CH.sub.2CH.sub.2OH).sub.3;
12. The compound of claim 4 having the formula: 36
13. An ink composition comprising: (a) at least 0.1% by weight of a
compound of Formula I: 37 wherein: R.sub.1 is
--O--(CH.sub.2).sub.m--CO.- sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--CO.sub.2M, or --SO.sub.3M; R.sub.2 is --H, --CO.sub.2M, -lower
alkyl, -lower alkoxy, nitro; --CF.sub.3, halogen, --NHCO-lower
alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M- , or
--(CH.sub.2).sub.n--CO.sub.2M; R.sub.3 is -lower-alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl; or --NH--CO--CO.sub.2M;
R.sub.4 is -lower-alkyl, -lower alkoxy,
--O--(CH.sub.2).sub.m--CO.sub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl; or NH.sub.2CO.sub.2M;
R.sub.5 is --N--(R.sub.6)(R.sub.7), or a group of the formula
38R.sub.6 is --H, -lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2- M,
-lower-hydroxyalkyl, or lower-cyanoalkyl; R.sub.7 is --H,
-lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2M, lower-hydroxyalkyl; or
-lower-cyanoalkyl; R.sub.8 is --H, lower-alkyl,
-lower-hydroxyalkyl, --(CH.sub.2).sub.nCO.su- b.2M; R.sub.9 is --H,
-lower-alkyl, -lower-hydroxyalkyl, --(CH.sub.2).sub.nCO.sub.2M;
R.sub.10 is --H, -lower-alkyl, -lower alkoxy, -lower-hydroxyalkyl,
--(CH.sub.2).sub.n--CO.sub.2M, -halogen, --NR.sub.8R.sub.9,
--(CH.sub.2).sub.nSO.sub.3M, or --O--(CH.sub.2).sub.mCO.sub.2M; m
is 1, 2, or 3; n is 1, 2, or 3; M is --H, --Li, Na, --K, or
--N--(R.sub.11).sub.4; R.sub.11 is --H, -lower alkyl, or
--(CH.sub.2--CH(R.sub.12)--O).sub.p--H; p is 1 to 4; x is 1 or 2;
R.sub.12 is --H, --CH.sub.3, --CH.sub.2--CH.sub.3, or
--CH.sub.2--OH; and R.sub.13 is --H, lower alkyl, lower alkoxy,
halogen, --CO.sub.2M, or --SO.sub.3M; (b) water, and (c) at least
one cosolvent.
14. The ink composition of claim 13, wherein the compound of
Formula (I) is a compound of Formula (II): 39wherein: R.sub.2 is
--H, -lower-alkyl, -lower-alkoxy, --CO.sub.2M, --CF.sub.3,
--NO.sub.2, -halogen, --NHCO-lower-alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M, or --(CH.sub.2).sub.n--CO.sub.2M;
R.sub.3 is -lower-alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --NHCO-lower-alkyl,
--NHC(O)O-lower-alkyl, or NHCOCO.sub.2M; R.sub.4 is -lower-alkyl,
-lower alkoxy, --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --NHCO-lower-alkyl,
--NHC(O)O-lower-alkyl, --NHCOCO.sub.2M, or --NHCOCO.sub.2M; m is 1,
2, or 3; n is 1, 2, or 3; M is --H, --Li, Na, --K, or
--N--(R.sub.11).sub.4; R.sub.11 is --H, -lower alkyl, or
--(CH.sub.2--CH(R.sub.12)--O).sub.p--H; p is 1 to 4; x is 1 or 2;
and R.sub.12 is --H, --CH.sub.3, --CH.sub.2--CH.sub.3, or
--CH.sub.2--OH.
15. The ink composition of claim 13, wherein the compound of
Formula (I) is a compound of Formula (III): 40wherein: M, R.sub.2,
R.sub.4 x, and M are as defined in claim 13.
16. The ink composition of claim 15, wherein R.sub.2 is H and
R.sub.4 is methoxy.
17. The ink composition of claim 13, wherein the compound of
Formula (I) is selected from 41wherein: M is as defined in claim
13.
18. A substrate or medium coated with the ink composition of claim
13.
19. The medium of claim 13, 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] U.S. Pat. No. 5,198,022 describes certain alkali-soluble azo
dyes for waterfast ink compositions.
[0004] U.S. Pat. No. 5,667,571 describes certain non-pollutive ink
compositions using alcohol or glycol ether as solvent, which can be
used as writing ink, (industrial) ink jet printing ink, stamp ink,
etc. Certain triazinylamino substituted disazo dyes are
described.
[0005] U.S. Pat. No. 5,795,970 describes certain disazo dyes useful
in ink compositions which claims to provide sharp printing images
having high optical density and no bleeding which also result in
rapid fixing of the ink, water resistance and light resistance,
even when printed on plain paper.
[0006] U.S. Pat. No. 5,753,016 describes certain disazo dyes which
are useful in ink compositions and claim to offer a combination of
a high-quality image with a waterfast printing image.
[0007] U.S. Pat. No. 5,453,495 describes certain piperazinyl
substituted disazo dyes which are useful in ink jet
compositions.
[0008] U.S. Pat. No. 5,891,230 describes certain disazo dyes useful
in ink jet printing. Further examples of disazo dyes can be found
in the following: U.S. Pat. Nos. 5,725,644; 5,480,478; 5,888,286;
5,882,392; 5,843,218; and 5,756,693.
SUMMARY OF THE INVENTION
[0009] Provided are novel black 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, color value, water fastness and light fastness.
Especially preferred dyes have the following structural formula:
1
[0010] wherein:
[0011] R.sub.2, R.sub.4, x and M are as defined herein.
DETAILED DESCRIPTION OF THE INVENTION
[0012] In a first embodiment, the present invention provides a
compound of Formula (I): 2
[0013] wherein:
[0014] R.sub.1 is --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --CO.sub.2M, or --SO.sub.3M;
[0015] R.sub.2 is --H, --CO.sub.2M, -lower alkyl, -lower alkoxy,
nitro; --CF.sub.3, halogen, --NHCO-lower alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M- , or
--(CH.sub.2).sub.n--CO.sub.2M;
[0016] R.sub.3 is -lower-alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --NHCO-lower-alkyl;
--NHC(O)O-lower-alkyl; or --NH--CO--CO.sub.2M;
[0017] R.sub.4 is -lower-alkyl, -lower alkoxy,
--O--(CH.sub.2).sub.m--CO.s- ub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl; or --NHCOCO.sub.2M;
[0018] R.sub.5 is --N--(R.sub.6)(R.sub.7), or a group of the
formula 3
[0019] R.sub.6 is --H, -lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2M,
-lower-hydroxyalkyl, or -lower-cyanoalkyl;
[0020] R.sub.7 is --H, -lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2M,
-lower-hydroxyalkyl; or -lower-cyanoalkyl;
[0021] R.sub.8 is --H, lower-alkyl, -lower-hydroxyalkyl, or
--(CH.sub.2).sub.nCO.sub.2M;
[0022] R.sub.9 is --H, -lower-alkyl, -lower-hydroxyalkyl, or
--(CH.sub.2).sub.nCO.sub.2M;
[0023] R.sub.10 is --H, -lower-alkyl, -lower alkoxy,
-lower-hydroxyalkyl, --(CH.sub.2).sub.n--CO.sub.2M, -halogen;
--NR.sub.8R.sub.9; --(CH.sub.2).sub.nSO.sub.3M; or
--O--(CH.sub.2).sub.mCO.sub.2M;
[0024] m is 1, 2, or 3;
[0025] n is 1, 2, or 3;
[0026] M is --H, --Li, Na, --K, or --N--(R.sub.11).sub.4;
[0027] R.sub.11 is --H, -lower alkyl, or
--(CH.sub.2--CH(R.sub.12)--O).sub- .p--H;
[0028] p is 1 to 4;
[0029] x is 1 or 2;
[0030] R.sub.12 is --H, --CH.sub.3, --CH.sub.2--CH.sub.3, or
--CH.sub.2--OH; and
[0031] R.sub.13 is --H, lower alkyl, lower alkoxy, halogen,
--CO.sub.2M, or --SO.sub.3M.
[0032] In a further preferred embodiment, there is provided a
compound of Formula (II): 4
[0033] wherein:
[0034] R.sub.2 is --H, -lower-alkyl, -lower-alkoxy, --CO.sub.2M,
--CF.sub.3, --NO.sub.2, -halogen, --NHCO-lower-alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M, or
--(CH.sub.2).sub.n--CO.sub.2M;
[0035] R.sub.3 is -lower-alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --NHCO-lower-alkyl,
--NHC(O)O-lower-alkyl, or --NHCOCO.sub.2M;
[0036] R.sub.4 is -lower-alkyl, -lower alkoxy,
--O--(CH.sub.2).sub.m--CO.s- ub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl, --NHC(O)O-lower-alkyl, or --NHCOCO.sub.2M;
[0037] m is 1, 2, or 3;
[0038] n is 1, 2, or 3;
[0039] M is --H, --Li, Na, --K, or --N--(R.sub.11).sub.4;
[0040] R.sub.11 is --H, -lower alkyl, or
--(CH.sub.2--CH(R.sub.12)--O).sub- .p--H;
[0041] p is 1 to 4;
[0042] x is 1 or 2; and
[0043] R.sub.12 is --H, --CH.sub.3, --CH.sub.2--CH.sub.3, or
--CH.sub.2--OH.
[0044] In a further preferred embodiment, there is provided a
compound of Formula (III): 5
[0045] wherein:
[0046] R.sub.2, R.sub.4, x, and M are as defined above. In an
especially preferred embodiment, R.sub.2 is H and R.sub.4 is
methoxy.
[0047] In the above formulae, it is further preferred that R.sub.2
is --H, and that R.sub.5, R.sub.6, and R.sub.7 are each --H.
Further examples of preferred compounds include the following:
6
[0048] wherein M is --N--(R.sub.11).sub.4 and R.sub.11 is --H, or
lower alkyl, optionally substituted by hydroxy. Especially
preferred groups M include --NH.sub.4, --N(CH.sub.3).sub.4,
--N(CH.sub.2CH.sub.3).sub.4, and
--NH(CH.sub.2CH.sub.2OH).sub.3.
[0049] In an especially preferred embodiment, there is provided a
compound having the formula: 7
[0050] The compounds of the present invention are useful as dyes,
especially as dyes in ink jet ink compositions. Thus, as a further
aspect of the invention, there is provided an ink composition
comprising:
[0051] (a) at least 0.1% by weight of a compound of Formula I:
8
[0052] wherein:
[0053] R.sub.1 is --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --CO.sub.2M, or --SO.sub.3M;
[0054] R.sub.2 is --H, --CO.sub.2M, -lower alkyl, -lower alkoxy,
nitro; --CF.sub.3, halogen, --NHCO-lower alkyl,
--O--(CH.sub.2).sub.m--CO.sub.2M- , or
--(CH.sub.2).sub.n--CO.sub.2M;
[0055] R.sub.3 is -lower-alkyl, --O--(CH.sub.2).sub.m--CO.sub.2M,
--(CH.sub.2).sub.n--CO.sub.2M, --NHCO-lower-alkyl;
--NHC(O)O-lower-alkyl; or --NH--CO--CO.sub.2M;
[0056] R.sub.4 is -lower-alkyl, -lower alkoxy,
--O--(CH.sub.2).sub.m--CO.s- ub.2M, --(CH.sub.2).sub.n--CO.sub.2M,
--NHCO-lower-alkyl; --NHC(O)O-lower-alkyl or --NHCO.sub.2M;
[0057] R.sub.5 is --N--(R.sub.6)(R.sub.7), or a group of the
formula 9
[0058] R.sub.6 is --H, -lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2M,
-lower-hydroxyalkyl, or -lower-cyanoalkyl;
[0059] R.sub.7 is --H, -lower-alkyl, --(CH.sub.2).sub.n--CO.sub.2M,
-lower-hydroxyalkyl; or -lower-cyanoalkyl;
[0060] R.sub.8 is --H, lower-alkyl, -lower-hydroxyalkyl,
--(CH.sub.2).sub.nCO.sub.2M;
[0061] R.sub.9 is --H, -lower-alkyl, -lower-hydroxyalkyl,
--(CH.sub.2).sub.nCO.sub.2M;
[0062] R.sub.10 is --H, -lower-alkyl, -lower alkoxy,
-lower-hydroxyalkyl, --(CH.sub.2).sub.n--CO.sub.2M, -halogen;
--NR.sub.8R.sub.9; --(CH.sub.2).sub.nSO.sub.3M; or
--O--(CH.sub.2).sub.mCO.sub.2M;
[0063] m is 1, 2, or 3;
[0064] n is 1, 2, or 3;
[0065] M is --H, --Li, Na, --K, or --N--(R.sub.11).sub.4;
[0066] R.sub.11 is --H, -lower alkyl, or
--(CH.sub.2--CH(R.sub.12)--O).sub- .p--H;
[0067] p is 1 to 4;
[0068] x is 1 or 2;
[0069] R.sub.12 is --H, --CH.sub.3, --CH.sub.2--CH.sub.3, or
--CH.sub.2--OH; and
[0070] R.sub.13 is --H, lower alkyl, lower alkoxy, halogen,
--CO.sub.2M, or --SO.sub.3M;
[0071] (b) water, and
[0072] (c) at least one cosolvent.
[0073] The dyes of the present invention, when formulated into inks
for drop-on-demand jet printing, exhibit all of the necessary
properties for producing waterfast printed characters: (1) they
become water-insoluble at acidic pH; (2) they produce intense black
characters at 2% and above dye concentration in the ink; (3) they
are stable in aqueous ink formulations; and (4) they do not clog
the small printhead orifices during non-use, thus providing good
printhead maintenance when used for drop-on-demand printing.
Preferred inks have at least about 0.5% by weight of the dye and at
least by 3, preferably 5-25% by weight of cosolvent.
[0074] In the above formula, the term "lower alkyl" preferably
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, isobutyl.
[0075] The term "lower alkoxy" preferably refers to a
C.sub.1-C.sub.4 alkoxy group. Examples include methoxy, ethoxy,
propoxy, butoxy and the like.
[0076] 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.
[0077] The term "lower alkylene" preferably refers to a divalent
group of the formula --(CH.sub.2)--.sub.m wherein m is an integer
of from 1 to 4. Examples include methylene, ethylene, propylene,
and butylene.
[0078] Examples of especially preferred compounds of Formula (I)
include the following wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, and M are set forth in the following table:
1 10 R1 R2 R3 R4 R5 M 1 3-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M
5-CH.sub.3 NH.sub.2 --H or --NH.sub.4 2 4-CO.sub.2M --H
2-OCH.sub.2CO.sub.2M 5-CH.sub.3 NH.sub.2 --H or --NH.sub.4 3
3-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or
--NH.sub.4 4 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3
NH.sub.2 --H or --NH.sub.4 5 3-CO.sub.2M 5-CO.sub.2M
2-OCH.sub.2CO.sub.2M 5-CH.sub.3 NH.sub.2 --H or --NH.sub.4 6
3-CO.sub.2M 5-CO.sub.2M 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2
--H or --NH.sub.4 7 3-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 8 4-CO.sub.2M --H
2-CH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 9
3-CO.sub.2M 6-CH.sub.3 2-CH.sub.2CO.sub.2M 5-CH.sub.3 NH.sub.2 --H
or --NH.sub.4 10 3-CO.sub.2M 6-CH.sub.3 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 11 3-CO.sub.2M 2-CH.sub.3
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 12
3-CO.sub.2M 6-Cl 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or
--NH.sub.4 13 4-CO.sub.2M 2-Cl 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3
NH.sub.2 --H or --NH.sub.4 14 3-CO.sub.2M 4-Cl 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 15 4-CO.sub.2M 3-OH
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 16
2-CO.sub.2M 5-CO.sub.2M 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2
--H or --NH.sub.4 17 4-CO.sub.2M 3-OnC.sub.4H.sub.9
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 18
2-CO.sub.2M 4F 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 NH.sub.2 --H or
--NH.sub.4 19 3-CO.sub.2M 4-CO.sub.2M 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 NH.sub.2 --H or --NH.sub.4 20 3-CO.sub.2M 4-OH
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 21
2-CO.sub.2M 4-NO.sub.2 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2
--H or --NH.sub.4 22 2-CO.sub.2M 5-NO.sub.2 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 23 5-CO.sub.2M 2-OCH.sub.3
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 24
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.2CO.sub.2M
--NH.sub.2 --H or --NH.sub.4 25 4-CO.sub.2M --H 2-CH.sub.2CO.sub.2M
5-OCH.sub.2CO.sub.2M --NH.sub.2 --H or --NH.sub.4 26 4-CO.sub.2M
--H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.2CO.sub.2M --NH.sub.2 --H or
--NH.sub.4 27 2-CO.sub.2M 5-Br 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3
--NH.sub.2 --H or --NH.sub.4 28 2-CO.sub.2M 5-OCH.sub.3
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 29
4-CO.sub.2M --H 2-OCH.sub.2CH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2
--H or --NH.sub.4 30 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 --NH.sub.2 --N(CH.sub.3).sub.4 31 4-CO.sub.2M --H
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2
--N(C.sub.2H.sub.5).sub.4 32 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 --NH.sub.2 --NH-- (CH.sub.2CH.sub.2OH).sub.3 33
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 H 34
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 Li 35
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 Na 36
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 K 37
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2
--NH[CH.sub.2CH.sub.2-- OCH.sub.2CH.sub.2OH].sub.3 38 4-CO.sub.2M
--H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 11 --H or --NH.sub.4 39
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 12 --H or
--NH.sub.4 40 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 13
--H or --NH.sub.4 41 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 14 --H or --NH.sub.4 42 4-CO.sub.2M --H
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 15 --H or --NH.sub.4 43
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 16 --H or
--NH.sub.4 44 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 17
--H or --NH.sub.4 45 3-SO.sub.3M --H 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 46 4-CO.sub.2M --H
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NHCH.sub.3 --H or --NH.sub.4 47
3-CO.sub.2M 5-CO.sub.2M 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3
--N--(CH.sub.2CH.sub.2OH).sub.2 --H or --NH.sub.4 48 4-CO.sub.2M
2-Cl 2-OCH.sub.2CO.sub.2M 5-CH.sub.3
--N--(CH.sub.2CH.sub.2OH).sub.2 --H or --NH.sub.4 49 5-CO.sub.2M
2-OCH.sub.3 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NHC.sub.4H.sub.9 --H
or --NH.sub.4 50 4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3
--N--(CH.sub.2CH.sub.2OH).sub.2 --H or --NH.sub.4 51 4-CO.sub.2M
--H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NHCH.sub.2CH.sub.2CO.sub.2M
--H or --NH.sub.4 52 4-SO.sub.3M --H 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 53 5-SO.sub.3M 2-Cl
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 --NH.sub.2 --H or --NH.sub.4 54
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 18 --H or
--NH.sub.4 55 3-SO.sub.3M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 19
--H or --NH.sub.4 56 5-SO.sub.3M 2-OCH.sub.3 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 20 --H or --NH.sub.4 57 3-SO.sub.3M --H
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 21 --H or --NH.sub.4 58
4-CO.sub.2M --H 2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 22 --H or
--NH.sub.4 59 3-CO.sub.2M 6-CH.sub.3 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 23 --H or --NH.sub.4 60 4-SO.sub.3M --H
2-OCH.sub.2CO.sub.2M 5-OCH.sub.3 24 --H or --NH.sub.4 61
3-SO.sub.3M --H 2-OCH.sub.2CO.sub.2M 5-NH--CO--CO.sub.2M NH.sub.2
--H or --NH.sub.4 62 3-CO.sub.2M 5-CO.sub.2M 2-OCH.sub.2CO.sub.2M
5-OCH.sub.3 25 --H or --NH.sub.4
[0079] The compounds of this invention may be prepared by
diazotizing an optionally and appropriately substituted
aminobenzoic acid, an aminobenzenesulfonic acid, or an
aminophthalic acid, coupling with an appropriately substituted
aminophenoxyacetic, propionic or butyric acid or an appropriately
substituted aminophenylacetic, 2-propionic or butyric acid,
rediazotizing the resultant aminoazo intermediate compound, then
coupling with an optionally substituted
6-amino-4-hydroxynaphthalene-2-su- lfonic acid. If
6-amino-4-hydroxynaphthalene-2-sulfonic acid itself is employed,
the disazo intermediate compound may be rediazotized and further
coupled with, for example, an optionally substituted coupleable
aromatic amine such as, for example, phenyldiethanolamine or
dialkylaniline to produce the trisazo dye of Formula I as set forth
above.
[0080] Examples of aminobenzoic or aminophthalic acids from which
ring (A) (as annotated above) may be derived include: 2-, 3-, or
4-aminobenzoic acid, 3-, or 4-aminophthalic acid, 4- or
5-aminoisophthalic acid, 2-aminoterephthalic acid,
2-amino-5-bromobenzoic acid, 2-amino-3-, 4-, or 5-chlorobenzoic
acid, 3-amino-4-chlorobenzoic acid, 4-amino-2-chlorobenzoic acid,
5-amino-2-chlorobenzoic acid, 4-amino-5-chloro-2-methoxybenzoic
acid, 2-amino-4- or 5-fluorobenzoic acid, 2-amino-5-iodobenzoic
acid, 2-amino-3-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid,
4-amino-3-methoxybenzoic acid, 2-amino-3-, 5-, or 6-methylbenzoic
acid, 3-amino-2- or 4-methylbenzoic acid, 4-amino-3-methylbenzoic
acid, 2-amino-4- or 5-nitrobenzoic acid, 4-amino-3-nitrobenzoic
acid, 2-n-butoxy-4-aminobenzoic acid. Also aminobenzenesulfonic
acids from which ring A can be derived include metanilic acid,
sulfanilic acid, 4- or 6-chlorometanilic acid, anthranilic acid,
sulfanilic acid, a toluidinesulfonic acid, or an anisidinesulfonic
acid.
[0081] Suitable precursors to ring (B) include, for example,
2'-amino-4'-methoxy-phenoxyacetic acid,
2'-amino-4'-methylphenoxyacetic acid,
2'-amino-4'-methoxy-phenoxypropionic acid,
2'-amino-4'-methylphenox- ypropionic acid,
2'-amino-4'-acetamidophenoxyacetic acid;
2'-amino-4'-propoxy-phenoxyacetic acid,
2'-amino-4'-butoxy-phenoxyacetic acid.
[0082] Examples of couplers which provide ring (C) include, for
example, gamma acid, N-methyl-gamma acid, N-butyl-gamma acid,
N,N-dimethyl-gamma acid, N-carboxymethyl-gamma acid,
N,N-di(carboxymethyl)-gamma acid, N-(2-carboxyethyl)-gamma acid,
and N,N-diethyl-gamma acid.
[0083] Suitable precursors for ring (D), i.e., 26
[0084] as the R.sub.5 substituent include, for example,
phenyldiethanolamine, m-tolyl-diethanolamine,
2',5'-dimethoxyphenyl-dieth- anolamine, N-phenylglycine,
N-phenyl-3-aminopropionic acid,
N,N-bis-(2-carboxyethyl)-m-toluidine,
2'-chloro-phenyl-diethanolamine, N,N-bis-(carboxymethyl)-aniline,
anthranilic acid, and m-phenylenediamine sulfonic acid.
[0085] The compounds of this invention may be isolated readily from
aqueous solution as the free acid at pH values below 5. They are
quite soluble at alkaline pH in various salt forms including the
alkali metal salts (lithium, sodium, potassium) and, especially, as
the ammonium, alkanolamine and lower alkyl amine salts. The acid
form is readily converted to any of the alkali metal, ammonium, or
aliphatic or alkanolamine salts by simply adjusting the pH of an
aqueous slurry of the free acid with the appropriate amine, alkali
hydroxide or alkali carbonate. Residual undesired salts may be
removed from the alkaline dye solutions by means of reverse
osmosis.
[0086] The compounds of this invention, when applied as the
ammonium or substituted ammonium salts by usual ink-jet printing
methods, produce water-fast prints on paper because of their
decreased water solubility at the lower pH values present on the
surface of the paper, especially after removal of solvents and
volatile amine by drying.
[0087] The dyes of the present invention are thus preferably
present in a concentration of about 0.5 to 5 weight % in the ink
jet composition, more preferably 1-4%. The dyes are dissolved in a
water miscible solvent such as a C.sub.1-C.sub.4 alcohol, such as
methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol,
t-butanol, or isobutanol; an amide such as N,N-dimethylformanide or
dimethylacetamide; a ketone or ketone alcohol such as acetone or
diacetone alcohol; an ether such as tetrohydrofuran or dioxane; an
oligo- or poly alkylene glycol such as diethylene glycol,
triethylene glycol, poly(ethylene glycol), or poly(propylene
glycol) of MW up to about 500; an alkylene glycol or thioglycol
such as ethylene glycol, propylene glycol, butylene glycol,
1,5-pentanediol or hexylene glycol; a thiodiglycol; a polyol such
as gylcerol or 1,2,6-hexanetriol; a C.sub.1-C.sub.4 alkyl ether of
a C.sub.2-C.sub.4 alkylene glycol or oligo-C.sub.2-C.sub.4 alkylene
glycol such as 2-methoxyethanol, 2-(2-methoxy-ethoxy)ethanol,
2-(2-ethoxyethoxy) ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol,
2-[2-(2-ethoxyethoxy)ethox- y]ethanol or
2-[2-butoxy-ethoxy]ethanol; a heterocyclic amide such as
2-pyrrolidone, N-methyl-2-pyrrolidone or a sulfone such as
sulpholane; or a mixture thereof.
[0088] Preferred water-miscible solvents include 2-pyrrolidone,
N-methylpyrrolidone, sulpholane, ethylene glycol, diethylene
glycol, triethylene glycol, and 2-methoxy-2-ethoxy-2-ethoxyethanol,
1,2-hexanediol, thiodiethanol, and poly(ethylene glycol) having
weight average molecular weights of 200-1000.
[0089] The above water-miscible solvents aid in the solubility of
the dye in the aqueous ink composition and tend to promote
penetration of the dye into the substrate during the printing
process. Further examples of such components can be found in U.S.
Pat. Nos. 4,963,189; 4,704,113; 4,626,284; 5,891,230; 5,453,495;
and 5,198,022, incorporated herein by reference.
[0090] The ink compositions may be applied to a substrate in an ink
jet printing process. In this process, the ink is formed into small
droplets by ejection from a reservoir through a small orifice so
that the droplets are directed at a substrate. Such processes are
referred to as piezoelectric ink jet printing or thermal ink jet
printing. In thermal ink jet printing, programmed pulses of heat
are applied to the ink by means of a resistor, adjacent to the
orifice during relative movement between the substrate and the
reservoir.
[0091] Preferred substrates for printing include projector slides;
paper, which may have a neutral, acidic or basic character; and
textile materials such as cotton, viscose, jute, hemp, flax, nylon
and the like.
[0092] This invention is further illustrated by the following
examples in which all parts and percentages are by weight unless
otherwise indicated.
Experimental Section
[0093] 27
[0094] The dye depicted above is referred to in the following
experiment as Dye #542. This dye is straight-forward to make and
results in a dye suitable for ink jet printing. In an ink jet
formulation it exhibits good color, optical density, light fastness
and water fastness properties, good maintenance performance, and
uniform drop formation resulting in good print quality.
[0095] The preferred formulation is show below.
2 % by Weight Ingredient Function 2.5 Dye 542 Colorant 0.1
Chelating Agent Metals control 0.1 Penetrant/Surfactant Dry time
reduction 6.25 Co-solvent Humectant 0.20 Biocide Bacteria control
0.25 Buffer pH control Balance Water Solvent/jetting agent
[0096] Comparisons were made against the above formulation by
substituting alternate colorants for Dye 542. The Pro-Jet.RTM. Fast
Black 2 dye is the only colorant of the ones evaluated that came
close to Dye 542. The dyes evaluated against Dye 542 include:
3 Colorant Supplier Basacid Black X-38 BASF Duasyn Direct Black
HEF-SF Clariant Corporation Liquid Pro-Jet [ .TM. ] Fast Black 2
Zeneca Food Black 2 Tricon Colors Incorporated Bayscript Special
Black SP Liquid Bayer Water Black 187-LM Orient Chemical
Industries
[0097] Inks were made with each of the six colorants and tested on
a Lexmark Execjet IIC. The properties evaluated include idling
maintenance, continuous print performance, and uncapped start up
after 24 and 72 hours. On several different papers the optical
density, color values, water fastness and light fastness properties
were compared.
[0098] Functional Testing Scoring
[0099] Idling Maintenance
[0100] The printhead is idled for 30, 60, 90, 120, and 180 seconds
and after each time period all of the nozzles are fired. The print
sample is then scored by the number of missing or misdirected
nozzles at each time and then totaled. The higher the number the
worse the performance.
[0101] Continuous Print Performance
[0102] The printhead is fired for 1 million, then 2 million, and
then 3 million fires. The print sample is then scored by the number
of missing or misdirected nozzles after each test and then totaled.
The higher the number the worse the performance.
[0103] Start Up
[0104] The printhead remains undisturbed and uncapped for 24 hours
and then again for 72 hours. After each time the head is tested to
see how m any nozzles are firing at the top and bottom of the print
sample. A score of 56-56 is perfect indicating that all 56 nozzles
are firing at the top and bottom of the page.
[0105] Optical Density (OD)
[0106] The optical density is measured on a solid block of print
over six different plain papers and then averaged. The higher the
number the better the OD.
[0107] Waterfastness (WF)
[0108] An image is printed and allowed to dry for three hours. It
is then soaked for 5 minutes in DI water. The delta (i.e., change)
in optical density is reported before and after soaking the image.
This was averaged on two different papers. The smaller the value
the better the WF.
[0109] Light Fastness (LF)
[0110] The .DELTA.E (i.e., change) is reported before and after
exposing an image to a Xenon lamp for 72 hours. This was averaged
over three different papers including photo and coated papers. The
smaller the value the better the LF.
[0111] The table below summarizes the results of the Dye 542
against alternate black dyes which are commercially available and
registered worldwide.
[0112] After the table the remaining discussion is related to dye
synthesis.
4EXAMPLE 1 Continuous Overall Idling Print 24 Hour 72 Hour
Functional Dye Maint. Test Start Up Start Up OD WF LF Ranking Dye
542 37 37 5-56 56-56 1.35 0.12 9 2 Basacid 257 17 3-56 5-55 1.19
0.05 27 5 Black X38 Duasyn 343 37 0-56 0-55 1.28 0.14 5 6 Direct
Blk HEF-SF Liq. Projet Fast 20 17 56-56 56-56 1.33 0.12 11 1 Black
2 Food 92 29 56-56 56-56 1.26 0.10 41 4 Black 2 Bayscript 4 17
56-56 56-56 1.17 0.09 29 3 Special Blk SP Liq. Water 184 104 53-56
0-56 1.25 0.43 19 7 Black 187-LM
EXAMPLE 1
[0113] Preparation of Dye #542
[0114] 4-Amino-benzoic acid (13.7 g., 0.1 mole) was stirred in 50
mL water and 50 g. ice. Then 25 g. of 37% hydrochloric acid was
added and further ice to 0.degree. C. With good stirring a solution
of 7 g. sodium nitrite was slowly added as absorbed while adding
ice as needed to maintain the low temperature. After stirring an
additional 30 minutes with excess nitrous acid present, as shown by
testing with starch-iodide test paper, the slight excess was
removed by addition of a small amount of sulfamic acid.
[0115] 2'-Amino-4'-methoxyphenoxyacetic acid (19.7 g., 0.1 mole)
was dissolved in about 400 mL water as the hydrochloride and ice
added to 0-5.degree. C. With good stirring the 4-aminobenzoic acid
diazo solution was added in a thin stream. Coupling began at once
and after 2 hours appeared to be complete. The monoazo product was
filtered, and washed well on the filter with deionized water. The
paste was redissolved in 250 mL water with 50% NaOH to pH<10.
Sodium nitrite (7 g.) was added and dissolved. To the solution was
then added rapidly with stirring 30 mL 37% hydrochloric acid. The
slurry was allowed to stir at room temperature for 16 hours. The
precipitated diazonium salt was filtered and the cake washed with
200 mL 2.5% HCl. The filter cake was slurried in water and ice at
about 200 mL volume. Gamma acid monohydrate, 95% (270.8/mole) 30g.
was dissolved in 75 mL water and 18 g. ammonia. The solution was
clarified with 2 g. filteraid to remove a small amount of
impurities. To the filtrate was added 150 g. ice. The slurry of
monoazo-diazonium salt was added with good stirring in a thin
stream forming a deep black-colored solution. After stirring for 30
minutes, the coupling solution was treated with 25% (on volume
basis) NaCl to precipitate the dye which was then filtered after
stirring for 1 hour to allow the salt to dissolve completely. The
cake was washed with 100 mL 25% salt solution, redissolved and
again salted out and filtered to further purify the product. The
dye was finally dissolved in deionized water at 400 mL volume,
clarified with 1 g. Darco and 2 g. filteraid by filtration, and
reprecipitated by acidification with acetic acid, dropping it in
slowly with good stirring to pH 4.5, whereupon the product dye
completely precipitated. It was filtered and washed with 100 mL 1%
acetic acid, and dried. The black dye, when formulated into inks
and applied to paper by ink-jet printers, gave water-fast prints
having good light fastness and excellent tinctorial value.
[0116] The 2'-amino-4'-methoxyphenoxyacetic acid used in the above
synthesis was prepared from commercially available
2-nitro-4-methoxyphenol by reaction with ethyl chloroacetate,
hydrolysis of the ester with sodium hydroxide, and catalytic
reduction of the nitro group to the amine, all by usual procedures
known to those skilled in the art.
* * * * *