Black azo dyes

Details Black azo dyes Black azo dyes

2001-06-18

2002-09-17

Powers, Fiona T. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Azo

C534S810000, C534S815000, C534S829000, C534S836000, C106S031520

Reexamination Certificate

active

06451989

ABSTRACT:

FIELD OF THE INVENTION
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
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.
U.S. Pat. No. 5,198,022 describes certain alkali-soluble azo dyes for waterfast ink compositions.
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.
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.
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.
U.S. Pat. No. 5,453,495 describes certain piperazinyl substituted disazo dyes which are useful in ink jet compositions.
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
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:
wherein:
R
2
, R
4
, x and M are as defined herein.
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment, the present invention provides a compound of Formula (I):
wherein:
R
1
is —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —CO
2
M, or —SO
3
M;
R
2
is —H, —CO
2
M, -lower alkyl, -lower alkoxy, nitro; —CF
3
, halogen, —NHCO-lower alkyl, —O—(CH
2
)
m
—CO
2
M, or —(CH
2
)
n
—CO
2
M;
R
3
is -lower-alkyl, —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —NHCO-lower-alkyl;
—NHC(O)O-lower-alkyl; or —NH—CO—CO
2
M;
R
4
is -lower-alkyl, -lower alkoxy, —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —NHCO-lower-alkyl;
—NHC(O)O-lower-alkyl; or —NHCOCO
2
M;
R
5
is —N—(R
6
)(R
7
), or a group of the formula
R
6
is —H, -lower-alkyl, —(CH
2
)
n
—CO
2
M, -lower-hydroxyalkyl, or -lower-cyanoalkyl;
R
7
is —H, -lower-alkyl, —(CH
2
)
n
—CO
2
M, -lower-hydroxyalkyl; or -lower-cyanoalkyl;
R
8
is —H, -lower-alkyl, -lower-hydroxyalkyl, or —(CH
2
)
n
CO
2
M;
R
9
is —H, -lower-alkyl, -lower-hydroxyalkyl, or —(CH
2
)
n
CO
2
M;
R
10
is —H, -lower-alkyl, -lower alkoxy, -lower-hydroxyalkyl, —(CH
2
)
n
—CO
2
M, -halogen;
—NR
8
R
9
; —(CH
2
)
n
SO
3
M; or —O—(CH
2
)
m
CO
2
M;
m is 1,2,or 3;
n is 1,2, or 3;
M is —H, —Li, Na, —K, or —N—(R
11
)
4
;
R
11
is —H, -lower alkyl, or —(CH
2
—CH(R
12
)—O)
p
—H;
p is 1 to 4;
x is 1 or 2;
R
12
is —H, —CH
3
, —CH
2
—CH
3
, or —CH
2
—OH; and
R
13
is —H, lower alkyl, lower alkoxy, halogen, —CO
2
M, or —SO
3
M.
In a further preferred embodiment, there is provided a compound of Formula (II):
wherein:
R
2
is —H, -lower-alkyl, -lower-alkoxy, —CO
2
M, —CF
3
, —NO
2
, -halogen, —NHCO-lower-alkyl, —O—(CH
2
)
m
—CO
2
M, or —(CH
2
)
n
—CO
2
M;
R
3
is -lower-alkyl, —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —NHCO-lower-alkyl,
—NHC(O)O-Iower-alkyl, or —NHCOCO
2
M;
R
4
is -lower-alkyl, -lower alkoxy, —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —NHCO-lower-alkyl, —NHC(O)O-lower-alkyl, or —NHCOCO
2
M;
m is 1,2, or 3;
n is 1,2, or 3;
M is —H, —Li, Na, —K, or —N—(R
11
)
4
;
R
11
is —H, -lower alkyl, or —(CH
2
—CH(R
12
)—O)
p
—H;
p is 1 to 4;
x is 1 or 2; and
R
12
is —H, —CH
3
, —CH
2
—CH
3
, or —CH
2
—OH.
In a further preferred embodiment, there is provided a compound of Formula (II):
wherein:
R
2
, R
4
, x, and M are as defined above. In an especially preferred embodiment, R
2
is H and R
4
is methoxy.
In the above formulae, it is further preferred that R
2
is —H, and that R
5
, R
6
, and R
7
are each —H. Further examples of preferred compounds include the following:
wherein M is —N—(R
11
)
4
and R
11
is —H, or lower alkyl, optionally substituted by hydroxy. Especially preferred groups M include —NH
4
, —N(CH
3
)
4
, —N(CH
2
CH
3
)
4
, and —NH(CH
2
CH
2
OH)
3
In an especially preferred embodiment, there is provided a compound having the formula:
The compounds of the present invention are usefull 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:
(a) at least 0.1% by weight of a compound of Formula I:
 wherein:
R
1
is —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —CO
2
M, or —SO
3
M;
R
2
is —H, —CO
2
M, -lower alkyl, -lower alkoxy, nitro; —CF
3
, halogen, —NHCO-lower alkyl, —O—(CH
2
)
m
—CO
2
M, or —(CH
2
)
n
—CO
2
M;
R
3
is -lower-alkyl, —O—(CH
2
)
m
—CO
2
M, —(CH
2
)
n
—CO
2
M, —NHCO-lower-alkyl;
—NHC(O)O-lower-alkyl; or —NH—CO—CO
2
M;
R
4
is -lower-alkyl, -lower alkoxy, O—(CH
2
)
m
—CO
2
M, —(CH
2
)n—CO
2
M, —NHCO-lower-alkyl;
—NHC(O)O-lower-alkyl or —NHCO
2
M;
R
5
is —N—(R
6
)(R
7
), or a group of the formula
R
6
is —H, -lower-alkyl, —(CH
2
)
n
—CO
2
M, -lower-hydroxyalkyl, or -lower-cyanoalkyl;
R
7
is —H, -lower-alkyl, —(CH
2
)
n
—CO
2
M, -lower-hydroxyalkyl; or -lower-cyanoalkyl;
R
8
is —H, lower-alkyl, -lower-hydroxyalkyl, —(CH
2
)
n
CO
2
M;
R
9
is —H, -lower-alkyl, -lower-hydroxyalkyl, —(CH
2
)
n
CO
2
M;
R
10
is —H, -lower-alkyl, -lower alkoxy, -lower-hydroxyalkyl, —(CH
2
)
n
—CO
2
M, -halogen;
—NR
8
R
9
; —(CH
2
)
n
SO
3
M; or —O—(CH
2
)
m
CO
2
M;
m is 1,2, or 3;
n is 1,2, or 3;
M is —H, —Li, Na, —K, or —N—(R
11
)
4
;
R
11
is —H, -lower alkyl, or —(CH
2
—CH(R
12
)—O)
p
—H;
p is 1 to 4;
x is 1 or 2;
R
12
is —H, —CH
3
, —CH
2
—CH
3
, or —CH
2
—OH; and
R
13
is —H, lower alkyl, lower alkoxy, halogen, —CO
2
M, or —SO
3
M;
(b) water, and
(c) at least one cosolvent.
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.
In the above formula, the term “lower alkyl” preferably refers to a straight or branched-chain C
1
-C
4
alkyl group. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl.
The term “lower alkoxy” preferably refers to a C
1
-C
4
alkoxy group. Examples include methoxy, ethoxy, propoxy, butoxy and the like.
Likewise, the terms “lower hydroxyalkyl” and “lower cyanoalkyl” preferably refer to C
1
-C
4
alkyl groups substituted by at least one hydroxy or cyano group, respectively.
The term “lower alkylene” preferably refers to a divalent group of the formula —(CH
2
)—
m
wherein m is an integer of from 1 to 4. Examples include methylene, ethylene, propylene, and butylene.
Examples of especially preferred compounds of Formula (I) include the following wherein R
1
, R
2
, R
3
, R
4
, R
5
, and M are set forth in the following table:

R1
R2
R3
R4
R5
M
3-CO
2
M
—H
2-OCH
2
CO
2
M
5-CH
3
NH
2
—H or —NH
4
4-CO
2
M
—H
2-OCH
2
CO
2
M
5-CH
3
NH
2
—H or —NH
4
3-CO
2
M
—H
2-OCH
2
CO
2
M
5-OCH
3
NH
2
—H or —NH
4
4-CO
2
M
—H
2-OCH
2
CO
2
M
5-OCH
3
NH
2
—H or —NH
4
3-CO
2
M
5-CO
2
M
2-OCH
2
CO
2
M
5-CH
3
NH
2
—H or —NH
4
3-CO
2
M

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