Organic compounds -- part of the class 532-570 series – Organic compounds – Azo
Reexamination Certificate
2002-10-01
2003-11-25
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Azo
C008S674000, C008S680000
Reexamination Certificate
active
06653454
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a formazan compound, a method for dyeing using the same, and a cellulosic high molecular material dyed therewith.
BACKGROUND ART
The dianisidine type dye such as C.I.Direct Blue 200, 202 and 203 has been known as a dyestuff to dye a cellulosic high molecular material fast in blue and has been used on a large scale in textile dyeing industry and in paper manufacturing industry. However, in production and use of an dianisidine, which is a mother compound for the dye, a particular attention and restriction for use are inevitable because it is a prescribed chemical.
Various substitutes for dianisidine have been developed, but any products have not yet brought a satisfactory effect. For example, JP No.2510876 discloses a formazane type direct dye, which is disadvantageously inferior in fitness for dyeing at a high temperature and in fastness to washing. It is desired that there should be developed a blue dye that is safer for environmental protection and is more excellent in dyeing performance. The dye is also required to retain an affinity for a cellulose fiber even at a high temperature because the product obtained by blending a cellulose fiber with a polyester fiber is dyed at the high temperature.
Therefore, it is an important problem to develop the blue dye to meet the above requirements, in other words, a dye that can be synthesized without dianisidine compound used for the raw material and is suitable for dyeing a cellulosic high molecular material to provide the dyed product that has a high color value, a high build-up and various kinds of good fastness.
DISCLOSURE OF THE INVENTION
The present inventors made a diligent study to solve the above problem and, as a result, have arrived at the present invention.
The present invention relates to the followings:
1. A formazan compound represented by Formula (1) as shown below or the salt thereof,
(In Formula (1), R
1
is hydrogen, sulfo, hydroxy, chloro, methoxy, carboxyl or alkyl; either of R
2
and R
3
is hydrogen and the other is sulfo; X is morpholino, 2-hydroxyethylamino or bis(2-hydroxyethyl)amino; and Y is a phenylene diimino represented by Formula (2) as shown below)
(In Formula (2), R
4
is sulfo or carboxyl)
2. A formazan compound or the salt thereof according to the item 1, wherein R
1
is hydrogen; either of R
2
and R
3
is hydrogen and the other is sulfo; X is morpholino, 2-hydroxyethylamino, or bis(2-hydroxyethyl)amino; and Y is a group represented by Formula (2) wherein the two imino groups bind to the phenylene group at their respective para-positions.
3. A formazan compound or the salt thereof according to the item 1, wherein R
1
is hydrogen; R
2
is hydrogen; R
3
is sulfo; X is morpholino or bis(2-hydroxyethyl)amino; and Y is a group represented by Formula (2) wherein the two imino groups bind to the phenylene group at para-position.
4. A formazan compound or the salt thereof according to the item 1, wherein R
1
is hydrogen; R
2
is hydrogen; R
3
is sulfo; X is morpholino; and Y is a group represented by Formula (2) wherein R
4
is sulfo and the two imino groups bind to the phenylene group at para-position.
5. A method for dyeing a cellulosic high molecular material which is characterized by using the formazan compound or the salt thereof according to any one of the item 1 to 4.
6. A cellulosic high molecular material dyed with the formazan compound or the salt thereof according to any one of the item 1 to 4.
BEST MODE FOR CARRYING OUT THE INVENTION
The novel formazan compound of the present invention is represented by Formula (1) as shown above. In Formula (1), the alkyl group for R
1
includes a C1-C4 alkyl group such as methyl, ethyl, n-propyl and n-butyl. Methyl or ethyl is preferable. R
1
is preferable to substitute at the 2-position or 4-position.
The typical examples of the novel formazan compounds of the present invention represented by Formula (1) as shown above are listed in Table 1. In the column Y, PAS is a group represented by Formula (2) wherein R
4
is sulfo and the two imino groups bind to the phenylene group at para positions; PAK is a group represented by Formula (2) wherein R
4
is carboxyl and the two imino groups bind to the phenylene group at para positions; MAS is a group represented by Formula (2) wherein R
4
is sulfo and the two imino groups bind to the phenylene group at meta positions; and MAK is a group represented by Formula (2) wherein R
4
is carboxyl and the two imino groups bind to the phenylene group at meta positions. When the two imino groups in Formula (2) bind to the phenylene group at para positions and when the two imino groups in Formula (2) bind to the phenylene group at meta positions, the respective chemical formula is shown in following Formula (2-1) and Formula (2-2)) repectively:
TABLE 1
No.
R
1
R
2
R
3
X
Y
1
H
H
SO
3
H
morpholino
PAS
2
H
H
SO
3
H
2-hydroxyethyl amino
PAS
3
H
H
SO
3
H
bis(2-hydroxyethyl) amino
PAS
4
H
H
SO
3
H
morpholino
PAS
5
H
H
SO
3
H
2-hydroxyethyl amino
PAK
6
H
H
SO
3
H
morpholino
MAS
7
H
H
SO
3
H
bis(2-hydroxyethyl) amino
MAK
8
H
SO
3
H
H
morpholino
PAS
9
2-SO
3
H
SO
3
H
H
morpholino
PAS
10
2-OH
H
SO
3
H
morpholino
PAS
11
4-Cl
H
SO
3
H
morpholino
PAS
12
4-OCH3
H
SO
3
H
morpholino
PAS
13
4-COOH
H
SO
3
H
morpholino
PAS
14
4-C
2
H
4
H
SO
3
H
morpholino
PAS
In order to obtain a formazan compound of the present invention represented by Formula (1), the formazan amino compound represented by Formula (3) as shown below is at first synthesized by a process as described below for example:
An amino benzoic acid is diazotized to get the diazo product, from which the hydrazine is derived. 1 mol of the hydrazine is condensed with 1 mol of a benzaldehyde in the aqueous solution at 80-95° C. to get the phenylhydrazone. The phenylhydrazone is coupled with 1 mol of the diazotized product of 6-acetylamino-2-aminophenol-4-sulfonic acid in the aqueous solution under the presence of soda ash at 0-5° C. Then, 1-1.5 mol of copper sulfate or copper chloride is added to introduce copper into the coupling compound. The compound thus obtained is treated with a strong alkali at 60-90° C. for 3-6 hours to hydrolyze the acetylamino group and the formazan amino compound represented by Formula (3) is obtained.
(In Formula (3), R
1
, R
2
, and R
3
show their respective same meanings as described above)
The formazan compound of Formula (1) is then synthesized through a process as described below for example.
1 mol of the formazan amino compound represented by Formula (3) is reacted with 1 mol of 2,4,6-trichloro-1,3,5-triazine at a pH of 6-8 at 0-10° C. for 2-3 hours to get the first condensate. 2 mol of a primary condensate is then reacted with 1 mol of a diamine corresponding to Y at a pH of 6-9 at 50-65° C. for 8-24 hours to get a secondary condensate. 1 mol of a secondary condensate is reacted with 2 mol of an amine corresponding to X at a pH of 6-9 at 80-95° C. for 6-18 hours to get a tertiary condensate, that is, the formazan compound represented by Formula (1).
The formazan compound represented by Formula (1) of the present invention also can be synthesized through the following process.
2 mols of 2,4,6-trichloro-1,3,5-triazine are reacted with 1 mol of diamine corresponding to Y at a pH of 5-8 at 0-10° C. for 2-4 hours to get the first condensate. 1 mol of a primary condensate is reacted with 2 mol of the formazan amino compound represented by Formula (3) at a pH of 6-9 at 50-65° C. for 2-4 hours to get a secondary condensate. 1 mol of a secondary condensate is reacted with 2 mol of an amine corresponding to X at a pH of 6-9 at 80-95° C. for 6-18 hours to get the formazan compound represented by Formula (1).
The formazan compound represented by Formula (1) thus synthesized is generally isolated as the sodium salt thereof by a conventional procedure, for example, by salting out with sodium chloride.
The compound represented by Formula (1) of the present convention may be used in any form of the free acid and the salt. The salt is preferably soluble in water. The salt includes an alkali metal salt, an alkaline
Nomura Hideshiro
Nomura Shigeko
Ogawa Eiichi
Shirasaki Yasuo
Umeda Mariko
Nippon Kayaku Kabushiki Kaisha
Nomura Shigeko
Powers Fiona T.
LandOfFree
Formazane compounds and method of dyeing using the same does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Formazane compounds and method of dyeing using the same, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Formazane compounds and method of dyeing using the same will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3184333