Organic compounds -- part of the class 532-570 series – Organic compounds – Azo
Reexamination Certificate
2001-03-21
2002-12-03
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Azo
C534S781000, C534S784000, C534S786000, C534S792000, C534S793000, C534S588000, C106S031450, C106S031500
Reexamination Certificate
active
06489452
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel azo dye, a process for making the dye, an ink-jet printing ink using the dye, and an ink-jet recording method.
2. Description of the Related Art
In recent years, the mainstream of new image-recording materials has been materials for forming color images in particular. More specifically, these materials include recording materials based on ink-jet recording, heat-sensitive recording materials based on image transfer, pressure-sensitive recording materials, recording materials based on electronic photography, silver halide photosensitive materials based on transfer, printing inks, and recording pens. Because of inexpensive material costs, capability of high-speed recording, low noise in recording operations, and ease in color recording, ink-jet recording has rapidly come into wide use and is still making further progress. Ink-jet recording methods include a method in which liquid droplets, applied a pressure by a piezoelectric element, are ejected, a method in which liquid droplets are ejected by bubbles generated in the ink by heat, a method in which ultrasonic waves are used, and a method in which liquid droplets are suction-ejected by electrostatic force. In these methods, aqueous ink, oil-based ink, and solid (fusion-type) ink are used.
The properties required for the dye in the ink-jet printing ink are high solubility in a solvent, capability of high-density recording, excellent hue, excellent durability to light, heat, air, water, and chemicals, excellent fixing and little blur on image-receiving materials, excellent storability as ink, freedom from toxicity, high purity, and low cost of production. However, it is very difficult to obtain a dye that highly satisfies these requirements. In particular, there is a strong demand for a dye that has a good magenta hue and exhibits excellent lightfastness. Heretofore, various dyes have been disclosed as pyrazole azo dyes in Japanese Patent Application Laid-Open (JP-A) Nos. 55-161856, 61-36362, 61-152768, 6-145543, and 7-224230, U.S. Pat. Nos. 4,650,861 and 4,301,070, PCT National Publication No. 11-504958 (WO 9634916), and so on. However, none of these dyes meets the requirements of hue and fastness at the same time.
Meanwhile, pyrazole azo dyes were heretofore synthesized according to methods disclosed in U.S. Pat. Nos. 3,336,285 and 3,639,384, U. K. Patent No. 1,566,985, and so on. According to the methods disclosed in the above-mentioned U.S. Patents, a 1-alkyl-4-cyano-pyrazole-5-yl azo dye is synthesized via a step of diazotization and subsequent coupling of a 1-alkyl-4-cyano-5-aminopyrazole. However, since the diazonium salt to be formed in the step described above is very unstable, it is difficult to obtain the pyrazole azo dye with good yield and high purity (Weaver and Shuttleworth, Dyes and Pigments 3, 81(1982)). Besides, Japanese Patent Application Publication (JP-B) No. 6-19036 discloses a method of synthesizing a pyrazole azo dye. The 1-alkyl-3-(secondary or tertiary alkyl)-4-cyano-pyrazole-5-yl azo dyes obtained by this method have short-wave length hues and a dye satisfactory as a magenta dye has not been obtained.
According to the method disclosed in the above-mentioned U. K. Patent No. 1,566,985, a dye is synthesized by subjecting a 1-alkyl-3-alkyl- or aryl-4-cyano-pyrazole-5-yl azo dye and a 1-alkyl-3-alkyl- or aryl-4-halogeno-5-aminopyrazole to diazotization and coupling together with an aromatic coupling component, followed by substituting halogen in a 4-position with cyanide. Since a step of using a heavy metal cyanide such as CuCN or Zn(CN)
2
is involved, this method presents problems of waste disposal after use, purification of the dye to be formed, and the like.
SUMMARY OF THE INVENTION
It is an object of the present invention to solve the problems described above and to provide a novel azo dye having a good hue and capable of forming images having high lightfastness, an ink-jet printing ink using the dye, and an ink-jet recording method using the ink. Another object of the present invention is to provide a novel manufacturing process enabling production of the azo dye with a high yield. A further object is to provide a novel azo dye which is useful as a water-soluble dye or as a synthesis intermediate for the production of a water-soluble dye and which can become an intermediate of chemicals, drugs, and organic agricultural chemicals.
After close studies of pyrazolyl aniline azo dye derivatives having good hue and high lightfastness, the present inventors found that the above-described problems can be solved by a pyrazole-based azo dye having a specific structure hitherto unknown. Further, after close studies of the manufacturing process of the pyrazole-based azo dye, the present inventors found that the pyrazole-based azo dye can be obtained in a high yield by synthesis via a diazotization step, a coupling step, and an arylation or heterylation step. That is, the above-described objects were achieved by the following means.
A first aspect of the present invention is an azo dye which is represented by general formula (1) or (11) as follows.
In the general formula (1) and (11), X and X
11
represent an electron-withdrawing group having a Hammett's constant &sgr;
p
of at least 0.20; R
1
, R
2
, R
11
and R
12
each independently represents a substituted or unsubstituted one of an alkyl group, an alkenyl group, a cycloalkyl group, and an aralkyl group; R
3
, R
4
, R
5
, R
6
, R
13
, R
14
, R
15
and R
16
each independently represents one of a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, an amido group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclicoxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclicthio group, a sulfinyl group, a phosphoryl group, an acyl group, and an ionic hydrophilic group, each of which groups may have at least one of substituent; and each of pair of R
1
and R
2
, R
3
and R
1
, R
5
and R
2
, R
11
and R
12
, R
13
and R
11
, and R
15
and R
12
may be joined to form a ring; Y represents one of a secondary or tertiary alkyl group and a substituted or unsubstituted aryl group; A represents a group made up of nonmetallic atoms necessary for forming a 5- to 8-membered ring, which ring may have a substituent, may be a saturated ring, and may have an unsaturated bond; Z
11
and Z
12
each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, an amido group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclicoxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclicthio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group; and at least one of R
11
, R
12
, R
13
, R
14
, R
15
, R
16
, X
11
, Y
11
, Z
11
, Z
12
, Z
13
, Z
14
, and Z
15
represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent.
A second aspect of the present invention is a process for making an azo dye. The process comprises the steps of:
(a) forming a diazonium salt by reacting an aminopyrazole represented by the general fo
Fujiwara Toshiki
Tateishi Keiichi
Yamada Makoto
Burns Doane , Swecker, Mathis LLP
Fuji Photo Film Co. , Ltd.
Powers Fiona T.
LandOfFree
Azo dyes, process for making the same, ink-jet printing ink,... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Azo dyes, process for making the same, ink-jet printing ink,..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Azo dyes, process for making the same, ink-jet printing ink,... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2965453