U.S. patent application number 09/919937 was filed with the patent office on 2002-04-25 for azo dye, ink-jet recording ink containing the same, and ink-jet recording method.
Invention is credited to Azuma, Yasushi, Fujiwara, Toshiki, Tateishi, Keiichi.
Application Number | 20020049310 09/919937 |
Document ID | / |
Family ID | 18729692 |
Filed Date | 2002-04-25 |
United States Patent
Application |
20020049310 |
Kind Code |
A1 |
Tateishi, Keiichi ; et
al. |
April 25, 2002 |
Azo dye, ink-jet recording ink containing the same, and ink-jet
recording method
Abstract
The present invention provides a novel heterylaniline azo dye as
well as an ink-jet recording ink and an ink-jet recording method
enabling the formation of an image having a good hue and high
durability to light and ozone gas. The ink-jet recording ink
contains a heterylaniline azo dye derivative having a novel
structure. The ink-jet recording method is characterized in that an
image is formed by using the ink described above on an
image-receiving material comprising a support having thereon an
ink-receiving layer containing white inorganic pigment
particles.
Inventors: |
Tateishi, Keiichi;
(Kanagawa, JP) ; Fujiwara, Toshiki; (Kanagawa,
JP) ; Azuma, Yasushi; (Kanagawa, JP) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Family ID: |
18729692 |
Appl. No.: |
09/919937 |
Filed: |
August 2, 2001 |
Current U.S.
Class: |
534/875 ;
106/31.48; 534/751 |
Current CPC
Class: |
C09B 29/0811 20130101;
C09B 29/0037 20130101; C09D 11/328 20130101 |
Class at
Publication: |
534/875 ;
534/751; 106/31.48 |
International
Class: |
C09D 011/00; C09B
029/08 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 7, 2000 |
JP |
2000-237911 |
Claims
What is claimed is:
1. An ink-jet recording ink comprising the azo dye represented by
the following general formula (I): 24wherein R.sub.1 represents a
substituted or unsubstituted aryl group or a substituted or
unsubstituted heterocyclic group; R.sub.2 represents a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted cycloalkyl
group, a substituted or unsubstituted alkenyl group, a substituted
or unsubstituted aralkyl group, or a substituted or unsubstituted
heterocyclic group; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each
independently represents 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 amide 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 heterocyclooxy group, an azo group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, an
aryloxycarbonyl group, an aryloxycarbonylamino group, an imide
group, a heterocyclothio group, a sulfinyl group, a phosphoryl
group, an acyl group, or an ionic hydrophilic group, which groups
may each have a substituent; any of each R.sub.1 and R.sub.2,
R.sub.3 and R.sub.1, and R.sub.2 and R.sub.5 may be bonded to form
a ring; and W represents a group of atoms necessary for forming a
nitrogen-containing, 5- to 8-membered heterocycle ring which may be
condensed with other ring to form a condensed ring.
2. An ink-jet recording ink according to claim 1, wherein R.sub.2
in the general formula (I) is a substituent selected from the group
consisting of a substituted or unsubstituted alkyl group and a
substituted or unsubstituted aryl group.
3. An ink-jet recording ink according to claim 1, wherein R.sub.3,
R.sub.4, and R.sub.5 in the general formula (I) are each a hydrogen
atom.
4. An ink-jet recording ink according to claim 1, wherein R.sub.6
in the general formula (I) is a substituent selected from the group
consisting of an amide group, a ureido group, and a sulfonamide
group.
5. An ink-jet recording ink according to claim 1, wherein the ionic
hydrophilic group is a carboxyl group or a sulfo group.
6. An ink-jet recording ink according to claim 1, wherein any one
group of R.sub.1 and R.sub.2, R.sub.3 and R.sub.1, and R.sub.2 and
R.sub.5 in the general formula (I) forms a ring indicated by one of
the following formulae: 25
7. An ink-jet recording ink according to claim 1, wherein the
nitrogen-containing heterocycle, which is made up of the group W of
atoms, and the condensed ring of the heterocycle in the general
formula (I) are selected from the group consisting of imidazole,
benzimidazole, pyrazole, triazole, thiazole, benzothiazole,
isothiazole, benzisothiazole, oxazole, benzoxazole, thiadiazole,
3H-pyrrole, 3H-indole, isoxazole, and benzisoxazole.
8. An ink-jet recording ink according to claim 1, wherein the
ink-jet recording ink can be prepared by dissolving and/or
dispersing the azo dye in an aqueous medium.
9. An ink-jet recording ink according to claim 1, wherein the azo
dye represented by the general formula (I) is the azo dye
represented by the general formula (II): 26wherein R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are defined in the
same way as R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 in the general formula (I), respectively; X represents an
electron-withdrawing group having a Hammett's constant
.sigma..sub.p of 0.20 or greater; Y represents a substituted or
unsubstituted secondary or tertiary alkyl group, a substituted or
unsubstituted aryl group, or a substituted or unsubstituted
heterocyclic group; and A represents a group made up of nonmetallic
atoms necessary for forming a 5- to 8-membered ring which may have
a substituent and may be a saturated ring or may have an
unsaturated bond.
10. An ink-jet recording ink according to claim 9, wherein X in the
general formula (II) is a substituent selected from the group
consisting of a cyano group, an alkylsulfonyl group having 1 to 12
carbon atoms, and an arylsulfonyl group having 6 to 18 carbon
atoms.
11. An ink-jet recording ink according to claim 9, wherein Y in the
general formula (II) is a substituent selected from the group
consisting of a secondary or tertiary alkyl group and an aryl
group.
12. An ink-jet recording ink according to claim 9, wherein the
ionic hydrophilic group is a carboxyl group or a sulfo group.
13. An ink-jet recording ink according to claim 9, wherein A in the
general formula (II) is represented by any one of the following
general formulae (III): 27wherein Z.sub.1, Z.sub.2, Z.sub.3,
Z.sub.4, Z.sub.5, Z.sub.7, Z.sub.8, Z.sub.10, Z.sub.11, Z.sub.12,
Z.sub.13, Z.sub.14, Z.sub.15, Z.sub.16, Z.sub.17, Z.sub.18,
Z.sub.19, Z.sub.20, Z.sub.21, Z.sub.22, Z.sub.23, Z.sub.24,
Z.sub.25, and Z.sub.26 each independently represents 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
amide 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
heterocyclooxy group, an azo group, an acyloxy group, a
carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an
aryloxycarbonylamino group, an imide group, a heterocyclothio
group, a sulfinyl group, a phosphoryl group, an acyl group, or an
ionic hydrophilic group; and Z.sub.6 and Z.sub.9 each independently
represents --NR.sub.7--, an oxygen atom, or a sulfur atom, where
R.sub.7 represents a hydrogen atom or a substituent.
14. An ink-jet recording ink according to claim 1, wherein the azo
dye in an amount between 0.2 and 10 parts by weight is incorporated
in 100 parts by weight of the ink-jet recording ink.
15. An ink-jet recording method in which an image is formed on an
image-receiving material comprising a support having thereon an
ink-receiving layer containing white inorganic pigment particles by
using an ink-jet recording ink comprising the azo dye represented
by the following general formula (I): 28wherein R.sub.1 represents
a substituted or unsubstituted aryl group or a substituted or
unsubstituted heterocyclic group; R.sub.2 represents a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted cycloalkyl
group, a substituted or unsubstituted alkenyl group, a substituted
or unsubstituted aralkyl group, or a substituted or unsubstituted
heterocyclic group; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each
independently represents 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 amide 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 heterocyclooxy group, an azo group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, an
aryloxycarbonyl group, an aryloxycarbonylamino group, an imide
group, a heterocyclothio group, a sulfinyl group, a phosphoryl
group, an acyl group, or an ionic hydrophilic group, which groups
may each have a substituent; any of R.sub.1 and R.sub.2, R.sub.3
and R.sub.1, and R.sub.2 and R.sub.5 may be bonded to form a ring;
and W represents a group of atoms necessary for forming a
nitrogen-containing 5- to 8-membered heterocycle ring which may be
condensed with other ring to form a condensed ring.
16. An ink-jet recording method according to claim 15, wherein the
ink-jet recording ink comprising the azo dye represented by the
general formula (I) is an ink-jet recording ink comprising the azo
dye represented by the following general formula (II): 29wherein
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are
defined in the same way as R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, and R.sub.6 in the general formula (I), respectively; X
represents an electron-withdrawing group having a Hammett's
constant .sigma..sub.p of 0.20 or greater; Y represents a
substituted or unsubstituted secondary or tertiary alkyl group, a
substituted or unsubstituted aryl group, or a substituted or
unsubstituted heterocyclic group; and A represents a group made up
of nonmetallic atoms necessary for forming a 5- to 8-membered ring
which may have a substituent and may be a saturated ring or may
have an unsaturated bond.
17. An ink-jet recording method according to claim 16, wherein A in
the general formula (II) is represented by any one of the following
general formulae (III): 30
18. An azo dye represented by the general formula (IV): 31wherein X
represents an electron-withdrawing group having a Hammett's
constant .sigma..sub.p of 0.20 or greater; R.sub.1 represents a
substituted or unsubstituted aryl group or a substituted or
unsubstituted heterocyclic group; R.sub.2 represents a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted cycloalkyl
group, a substituted or unsubstituted alkenyl group, a substituted
or unsubstituted aralkyl group, or a substituted or unsubstituted
heterocyclic group; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each
independently represents 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 amide 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 heterocyclooxy group, an azo group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, an
aryloxycarbonyl group, an aryloxycarbonylamino group, an imide
group, a heterocyclothio group, a sulfinyl group, a phosphoryl
group, an acyl group, or an ionic hydrophilic group, with the
proviso that these groups may each have a substituent and any of
each R.sub.1 and R.sub.2, R.sub.3 and R.sub.1, and R.sub.2 and
R.sub.5 may be bonded to form a ring; Y represents a substituted or
unsubstituted secondary or tertiary alkyl group, a substituted or
unsubstituted aryl group, or a substituted or unsubstituted
heterocyclic group; and A represents a group made up of nonmetallic
atoms necessary for forming a 5- to 8-membered ring which may have
a substituent and may be a saturated ring or may have an
unsaturated bond.
19. An azo dye according to claim 18, wherein A in the general
formula (IV) is represented by any one of the following general
formulae (V): 32in the general formulae (V), Z.sub.1, Z.sub.2,
Z.sub.3, Z.sub.4, Z.sub.5, Z.sub.7, Z.sub.8, Z.sub.10, Z.sub.11,
Z.sub.12, Z.sub.13, Z.sub.14, Z.sub.15, Z.sub.16, Z.sub.17,
Z.sub.18, Z.sub.19, Z.sub.20, Z.sub.21, Z.sub.22, Z.sub.23,
Z.sub.24, Z.sub.25, and Z.sub.26 each independently represents 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
amide 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
heterocyclooxy group, an azo group, an acyloxy group, a
carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an
aryloxycarbonylamino group, an imide group, a heterocyclothio
group, a sulfinyl group, a phosphoryl group, an acyl group, or an
ionic hydrophilic group; and Z.sub.6 and Z.sub.9 each independently
represents --NR.sub.7--, an oxygen atom, or a sulfur atom, where
R.sub.7 represents a hydrogen atom or a substituent.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a novel heterylaniline azo
dye, an ink-jet recording ink containing the dye, and an ink-jet
recording method.
[0003] 2. Description of the Related Art
[0004] Image-recording materials containing specific dyes are
mainly materials for forming images, and in particular color
images. More specifically, these materials include ink-jet
recording materials, heat-sensitive transfer-type image recording
materials, pressure-sensitive recording materials,
electrophotography recording materials, transfer-type silver halide
photosensitive materials, printing inks, and recording pens.
Preferably, these materials are ink-jet recording materials,
heat-sensitive transfer-type image recording materials, and
electrophotography recording materials. Further preferably, these
materials are ink-jet recording materials.
[0005] Because of inexpensive material costs, capability of
high-speed recording, reduced noise in recording operations, and
ease in color recording, ink-jet recording has rapidly come into
wide use and is being further developed.
[0006] The ink-jet recording methods include a method in which
liquid droplets, pressed 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, water-based ink, oil-based
ink, and solid (fusion-type) ink are used.
[0007] The properties required for the jet printing ink are high
solubility in a solvent, capability of high-density recording,
excellent hue, excellent durability with respect to light, heat,
air (in particular NO.sub.x, SO.sub.x, and ozone), water, and
chemicals, excellent fixation and little blur on image-receiving
materials, excellent storability as ink, freedom from toxicity,
high purity, and being inexpensive. 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 and ozone gas
resistance. 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, and so on. However, none of these dyes meets the
requirements of hue and fastness at the same time.
[0008] Further, pyrazole dyes are conventionally synthesized
according to methods described in U.S. Pat. Nos. 3,336,285 and
3,639,384 and U.K. Patent 1,566,985. The above-mentioned U.S.
Patents disclose a method in which a 1-alkyl-4-cyano-pyrazol-5-yl
azo dye is synthesized by diazotization of
1-alkyl-4-cyano-5-aminopyrazole followed by coupling. However,
since the diazonium salt in this method is very unstable, it is
difficult to obtain the dye with high yield and high purity by this
diazotization and coupling (Weaver and Shuttleworth, Dyes and
Pigments 3, 81 (1982)). Japanese Patent Application Publication
(JP-B) No. 6-19036 discloses a synthesis method in which
1-alkyl-3-(secondary or tertiary alkyl)-4-cyano-pyrazol-5-yl-azo
dyes are obtained. These azo dyes are not preferable as magenta
dyes, because their hues are in the short wavelength range.
[0009] In the method disclosed in U.K. Patent No. 1,566,985, a
1-alkyl-3-alkyl or aryl-4-cyano-pyrazol-5-yl-azo dye is synthesized
by dizaotization of 1-alkyl-3-alkyl or
aryl-4-halogeno-5-aminopyrazole with an aromatic coupling
component, followed by coupling, and then substitution of halogen
in the 4-position with cyanide. However, this method uses a harmful
heavy metal cyanide such as CuCN and Zn(CN).sub.2, and so there are
problems with disposal of waste and purification of the resulting
dye.
SUMMARY OF THE INVENTION
[0010] It is accordingly the task of the present invention to
overcome the problems in the prior art and to achieve the following
objective. That is, the objective of the present invention is (1)
to provide a novel heterylaniline azo dye derivative having a
specific structure which is useful as a dye for ink jet printing
ink or as an intermediate for synthesis of the dye and can also be
an intermediate for useful chemical, medical, or agricultural
organic chemical compounds and (2) to provide an ink-jet recording
ink and an ink-jet recording method which, by use of the
heterylaniline azo dye derivative, enable the formation of images
having excellent hue and excellent durability with respect to light
and ozone gas.
[0011] The present inventors have carefully studied the
heterylaniline azo dye derivative having excellent hue and
excellent lightfastness. As a result, they have found that the
above-mentioned problems can be solved by the azo dye which is
represented by the following general formula (I) and has a dye
structure bearing a specific substituent hitherto unknown. Based on
this finding, they have achieved the present invention. The means
for solving the above-mentioned problems are as follows.
[0012] That is, the first aspect of the present invention is an
ink-jet recording ink containing the azo dye represented by the
following general formula (I): 1
[0013] In the general formula (I), R.sub.1 represents a substituted
or unsubstituted aryl group or a substituted or unsubstituted
heterocyclic group; R.sub.2 represents a hydrogen atom, a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted cycloalkyl
group, a substituted or unsubstituted alkenyl group, a substituted
or unsubstituted aralkyl group, or a substituted or unsubstituted
heterocyclic group; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each
independently represents 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 amide 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 heterocyclooxy group, an azo group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, an
aryloxycarbonyl group, an aryloxycarbonylamino group, an imide
group, a heterocyclothio group, a sulfinyl group, a phosphoryl
group, an acyl group, or an ionic hydrophilic group, which groups
may each have a substituent; any of R.sub.1 and R.sub.2, R.sub.3
and R.sub.1, and R.sub.2 and R.sub.5 may be bonded to form a ring;
and W represents a group of atoms necessary for forming a
nitrogen-containing 5- to 6-membered heterocycle which may be
condensed with other ring to form a condensed ring.
[0014] Any one group of R.sub.1 and R.sub.2, R.sub.3 and R.sub.1,
and R.sub.2 and R.sub.5 in the general formula (I) may form a ring
indicated by one of the following formulae: 2
[0015] In the ink-jet recording ink according to the first aspect,
the azo dye represented by the general formula (I) is preferably an
azo dye represented by the general formula (II): 3
[0016] In the general formula (II), R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, and R.sub.6 are defined in the same way as
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 in the
general formula (I), respectively; X represents an
electron-withdrawing group having a Hammett's constant
.sigma..sub.p of 0.20 or greater; Y represents a substituted or
unsubstituted secondary or tertiary alkyl group, a substituted or
unsubstituted aryl group, or a substituted or unsubstituted
heterocyclic group; and A represents a group made up of nonmetallic
atoms necessary for forming a 5- to 8-membered ring which may have
a substituent and may be a saturated ring or may have an
unsaturated bond.
[0017] In an ink-jet recording ink, A in the general formula (II)
is preferably represented by any one of the following general
formulae (III): 4
[0018] In the general formulae (III), Z.sub.1, Z.sub.2, Z.sub.3,
Z.sub.4, Z.sub.5, Z.sub.7, Z.sub.8, Z.sub.10, Z.sub.11, Z.sub.12,
Z.sub.13, Z.sub.14, Z.sub.15, Z.sub.16, Z.sub.17, Z.sub.18,
Z.sub.19, Z.sub.20, Z.sub.21, Z.sub.22, Z.sub.23, Z.sub.24,
Z.sub.25, and Z.sub.26 each independently represents 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
amide 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
heterocyclooxy group, an azo group, an acyloxy group, a
carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an
aryloxycarbonylamino group, an imide group, a heterocyclothio
group, a sulfinyl group, a phosphoryl group, an acyl group, or an
ionic hydrophilic group; and Z.sub.6 and Z.sub.9 each independently
represents --NR.sub.7--, an oxygen atom, or a sulfur atom, where
R.sub.7 represents a hydrogen atom or a substituent.
[0019] Another aspect of the present invention is an ink-jet
recording method in which an image is formed using the ink-jet
recording ink according to the first aspect on an image-receiving
material comprising a support having thereon an ink-receiving layer
containing white inorganic pigment particles.
[0020] Another aspect of the present invention is an azo dye
represented by the general formula (IV): 5
[0021] In the general formula (IV), X represents an
electron-withdrawing group having a Hammett's constant
.sigma..sub.p of 0.20 or greater; R.sub.1 represents a substituted
or unsubstituted aryl group or a substituted or unsubstituted
heterocyclic group; R.sub.2 represents a hydrogen atom, a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted cycloalkyl
group, a substituted or unsubstituted alkenyl group, a substituted
or unsubstituted aralkyl group, or a substituted or unsubstituted
heterocyclic group; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each
independently represents 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 amide 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 heterocyclooxy group, an azo group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, an
aryloxycarbonyl group, an aryloxycarbonylamino group, an imide
group, a heterocyclothio group, a sulfinyl group, a phosphoryl
group, an acyl group, or an ionic hydrophilic group, which groups
may each have a substituent; any of R.sub.1 and R.sub.2, R.sub.3
and R.sub.1, and R.sub.2 and R.sub.5 may be bonded to form a ring;
Y represents a substituted or unsubstituted secondary or tertiary
alkyl group, a substituted or unsubstituted aryl group, or a
substituted or unsubstituted heterocyclic group; and A represents a
group made up of nonmetallic atoms necessary for forming a 5- to
8-membered ring which may have a substituent and may be a saturated
ring or may have an unsaturated bond.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] The details of the present invention are explained
below.
[0023] First, Hammett's constant of substitution .sigma..sub.p used
herein is explained. The Hammett's rule is an empirical rule
proposed by L. P. Hammett in 1935 to quantitatively describe the
effect of a substituent on the reaction or equilibrium of a benzene
derivative. Presently, the appropriateness of this rule is widely
acknoledged. There are .sigma..sub.p and .sigma..sub.m as constants
of substitution obtained by the Hammett's rule. These values are
described in many common books. For example, details of these
values are described in "Lange's Handbook of Chemistry", edited by
J. A. Dean, 12th edition, 1979 (McGraw-Hill), and "Extra issue of
Kagakuno Ryoiki", No. 122, pp.96-103, 1979 (Nankodo Publishing Co.,
Ltd.). In the present invention, substituents are defined and
explained using Hammett's constant of substitution a .sigma..sub.p.
However, it must be noted that substituents are not necessarily
limited to the substituents having Hammett's constants which are
known and described in the literature. Therefore, needless to say,
even if the Hammett's constant of a substituent is not described in
the literature, the substituent whose Hammett's constant falls
within the range when measured based on the Hammett's rule is
included in the scope of the present invention. Although the
compounds represented by the general formula (I) or (II) of the
present invention are not benzene derivatives, the values of
.sigma..sub.p are each used as a measure indicating the electronic
effect of a substituent irrespective of the position of the
substitution.
[0024] In the present invention, the values of .sigma..sub.p are
used as stated above.
[0025] [Azo Dyes]
[0026] First, the azo dyes represented by the general formula (I)
in the present invention are explained in detail. 6
[0027] In the general formula (I), R.sub.1 represents a substituted
or unsubstituted aryl group or a substituted or unsubstituted
heterocyclic group.
[0028] R.sub.1 may further have a substituent, and examples of such
substituent include the following.
[0029] A halogen atom (e.g., a chlorine, or bromine atom), a
straight-chain or branched alkyl group having 1 to 12 carbon atoms,
an aralkyl group having 7 to 18 carbon atoms, an alkenyl group
having 2 to 12 carbon atoms, a straight-chain or branched alkynyl
group having 2 to 12 carbon atoms, a straight-chain or branched
cycloalkyl group having 3 to 12 carbon atoms, a straight-chain or
branched cycloalkenyl group having 3 to 12 carbon atoms (e.g.,
methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl,
3-phenoxypropyl, trifluoromethyl, or cyclopentyl), an aryl group
(e.g., phenyl, 4-t-butylphenyl, or 2,4-di-t-amylphenyl), a
heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl,
2-furyl, 2-thienyl, 2-pyrimidinyl, or 2-benzothiazolyl), a cyano
group, a hydroxyl group, a nitro group, a carboxyl group, an amino
group, an alkyloxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy,
or 2-methanesulfonylethoxy), an aryloxy group (e.g., phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy,
3-t-butyloxycarbamoylphenoxy, or 3-methoxycarbamoyl), an acylamino
group (e.g., acetamide, benzamide, or
4-(3-t-butyl-4-hydroxyphenoxy)butaneamide- ), an alkylamino group
(e.g., methylamino, butylamino, diethylamino, or methylbutylamino),
an anilino group (e.g., phenylanilino or 2-chloroanilino), a ureido
group (e.g., phenylureido, methylureido, or N,N-dibutylureido), a
sulfamoylamino group (e.g., N,N-dipropylsulfamoylam- ino), an
alkylthio group (e.g., methylthio, octylthio, or
2-phenoxyethylthio), an arylthio group (e.g., phenylthio,
2-butoxy-5-t-octylphenylthio, or 2-carboxyphenylthio), an
alkyloxycarbonylamino group (e.g., methoxycarbonylamino), a
sulfonamide group (e.g., methanesulfonamide, benzenesulfoneamide,
p-toluenesulfonamide, or octadecanesulfonamide), a carbamoyl group
(e.g., N-ethylcarbamoyl or N,N-dibutylcarbamoyl), a sulfamoyl group
(e.g., N-ethylsulfamoyl, N,N-dipropylsulfamonyl, or
N,N-diethylsulfamoyl), a sulfonyl group (e.g., methanesulfonyl,
octanesulfonyl, benzenesulfonyl, or toluenesulfonyl), an
alkyloxycarbonyl group (e.g., methoxycarbonyl or
t-butyloxycarbonyl), a heterocyclooxy group (e.g.,
1-phenyltetrazole-5-oxy or 2-tetrahydropyranyloxy), an azo group
(e.g., phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, or
2-hydroxy-4-propanoylphenylazo), an acyloxy group (e.g., acetoxy),
a carbamoyloxy group (e.g., N-methylcarbamoyloxy or
N-phenylcarbamoyloxy), a silyloxy group (e.g., trimethylsilyloxy or
dibutylmethylsilyloxy), an aryloxycarbonylamino group (e.g.,
phenoxycarbonylamino), an imide group (e.g., N-succinimide or
N-phthalimide), a heterocyclothio group (e.g.,
2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, or
2-pyridylthio), a sulfinyl group (e.g., 3-phenoxypropylsulfinyl), a
phosphonyl group (e.g., phenoxyphosphonyl, octyloxyphosphonyl, or
phenylphosphonyl), an aryloxycarbonyl group (e.g.,
phenoxycarbonyl), an acyl group (e.g., acetyl, 3-phenylpropanoyl,
or benzoyl), and an ionic hydrophilic group (e.g., carboxyl, sulfo,
or quaternary ammonium).
[0030] The aryl groups represented by R.sub.1 include an aryl group
having a substituent and an aryl group having no substituent. The
aryl groups are preferably aryl groups having 6 to 12 carbon atoms.
Examples of the substituent include an alkyl group, an alkoxy
group, a halogen atom, an alkylamino group, and an ionic
hydrophilic group. Examples of the aryl groups include phenyl,
p-tolyl, p-methoxyphenyl, o-chlorophenyl, p-chlorophenyl, and
2,4,6-trimethylphenyl.
[0031] The heterocyclic groups represented by R.sub.1 include a
heterocyclic group having a substituent and a heterocyclic group
having no substituent. The heterocyclic groups are preferably 5- or
6-membered heterocyclic groups. Examples of the substituent include
an ionic hydrophilic group. Examples of the heterocyclic groups
include a 2-pyridyl group, a 3-pyridyl group, a 2-thienyl group,
and a 3-furyl group.
[0032] In the general formula (I), R.sub.2 represents a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted cycloalkyl
group, a substituted or unsubstituted alkenyl group, a substituted
or unsubstituted aralkyl group, or a substituted or unsubstituted
heterocyclic group.
[0033] R.sub.2 may further have a substituent selected, for
example, from the groups represented by R.sub.1.
[0034] The alkyl groups represented by R.sub.2 include an alkyl
group having a substituent and an alkyl group having no
substituent. Preferably, the alkyl groups are alkyl groups having 1
to 12 carbon atoms. More preferably, the alkyl groups are alkyl
groups having 1 to 6 carbon atoms. Examples of the substituent
include a hydroxyl group, an alkoxy group, a cyano group, a halogen
atom, and an ionic hydrophilic group. Examples of the alkyl group
include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl,
methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, and
4-sulfobutyl.
[0035] The aryl groups represented by R.sub.2 include an aryl group
having a substituent and an aryl group having no substituent. The
aryl groups are preferably aryl groups having 6 to 12 carbon atoms.
Examples of the substituent include an alkyl group, an alkoxy
group, a halogen atom, an alkylamino group, and an ionic
hydrophilic group. Examples of the aryl groups include phenyl,
p-tolyl, p-methoxyphenyl, and p-chlorophenyl.
[0036] The cycloalkyl groups represented by R.sub.2 include a
cycloalkyl group having a substituent and a cycloalkyl group having
no substituent. The cycloalkyl groups are preferably cycloalkyl
groups having 5 to 12 carbon atoms. Examples of the substituent
include an ionic hydrophilic group. Examples of the cycloalkyl
groups include a cyclohexyl group.
[0037] The alkenyl groups represented by R.sub.2 include an alkenyl
group having a substituent and an alkenyl group having no
substituent. The alkenyl groups are preferably alkenyl groups
having 2 to 12 carbon atoms. Examples of the substituent include an
ionic hydrophilic group. Examples of the alkenyl groups include a
vinyl group and an allyl group.
[0038] The aralkyl groups represented by R.sub.2 include an aralkyl
group having a substituent and an aralkyl group having no
substituent. The aralkyl groups are preferably aralkyl groups
having 7 to 12 carbon atoms. Examples of the substituent include an
ionic hydrophilic group. Examples of the aralkyl groups include a
benzyl group and a 2-phenethyl group.
[0039] The heterocyclic groups represented by R.sub.2 include a
heterocyclic group having a substituent and a heterocyclic group
having no substituent. The heterocyclic groups are preferably 5- or
6-membered heterocyclic groups. Examples of the substituent include
an ionic hydrophilic group. Examples of the heterocyclic groups
include a 2-pyridyl group, a 2-thienyl group, and a 2-fury
group.
[0040] In the general formula (I), R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 each independently represents 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 amide 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 heterocyclooxy group, an azo
group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an
aryloxycarbonyl group, an aryloxycarbonylamino group, an imide
group, a heterocyclothio group, a sulfinyl group, a phosphoryl
group, an acyl group, or an ionic hydrophilic group.
[0041] Among the groups listed above, a hydrogen atom, a halogen
atom, an alkyl group, an aryl group, a cyano group, an alkoxy
group, an amide group, a ureido group, an alkoxycarbonylamino
group, a sulfonamide group, a carbamoyl group, a sulfamoyl group,
and an alkoxycarbonyl group are preferable.
[0042] Further, a hydrogen atom, a halogen atom, an alkyl group, an
alkoxy group, an amide group, a ureido group, a sulfonamide group,
a carbamoyl group, and a sulfamoyl group are particularly
preferable.
[0043] R.sub.3, R.sub.4, R.sub.5, and R.sub.6 may further have a
substituent selected, for example, from the groups represented by
R.sub.1.
[0044] The halogen atoms represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include a fluorine atom, a chlorine atom, and a bromine
atom.
[0045] The alkyl groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an alkyl group having a substituent and an alkyl
group having no substituent. The alkyl groups are preferably alkyl
groups having 1 to 12 carbon atoms. Examples of the substituent
include a hydroxyl group, an alkoxy group, a cyano group, a halogen
atom, and an ionic hydrophilic group. Examples of the alkyl groups
include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl,
methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, and
4-sulfobutyl.
[0046] The cycloalkyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a cycloalkyl group having a substituent
and a cycloalkyl group having no substituent. The cycloalkyl groups
are preferably cycloalkyl groups having 5 to 12 carbon atoms.
Examples of the substituent include an ionic hydrophilic group.
Examples of the cycloalkyl groups include a cyclohexyl group.
[0047] The alkenyl groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an alkenyl group having a substituent and an
alkenyl group having no substituent. The alkenyl groups are
preferably alkenyl groups having 2 to 12 carbon atoms. Examples of
the substituent include an ionic hydrophilic group. Examples of the
alkenyl groups include a vinyl group and an allyl group.
[0048] The aralkyl groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an aralkyl group having a substituent and an
aralkyl group having no substituent. The aralkyl groups are
preferably aralkyl groups having 7 to 12 carbon atoms. Examples of
the substituent include an ionic hydrophilic group. Examples of the
aralkyl groups include a benzyl group and a 2-phenethyl group.
[0049] The aryl groups represented by R.sub.3, R.sub.4, R.sub.5, or
R.sub.6 include an aryl group having a substituent and an aryl
group having no substituent. The aryl groups are preferably aryl
groups having 7 to 12 carbon atoms. Examples of the substituent
include an alkyl group, an alkoxy group, a halogen atom, an
alkylamino group, and an ionic hydrophilic group. Examples of the
aryl groups include phenyl, p-tolyl, p-methoxyphenyl,
o-chlorophenyl, and m-(3-sulfopropylamino)phenyl.
[0050] The heterocyclic groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a heterocyclic group having a
substituent and a heterocyclic group having no substituent. The
heterocyclic groups are preferably 5- or 6-membered heterocyclic
groups. Examples of the substituent include an ionic hydrophilic
group. Examples of the heterocyclic groups include a 2-pyridyl
group, a 2-thienyl group, and a 2-fury group.
[0051] The alkylamino groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include an alkylamino group having a
substituent and an alkylamino group having no substituent. The
alkylamino groups are preferably alkylamino groups having 1 to 6
carbon atoms. Examples of the substituent include an ionic
hydrophilic group. Examples of the alkylamino groups include a
methylamino group and a diethylamino group.
[0052] The alkoxy groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an alkoxy group having a substituent and an
alkoxy group having no substituent. The alkoxy groups are
preferably alkoxy groups having 1 to 12 carbon atoms. Examples of
the substituent include an alkoxy group, a hydroxyl group, and an
ionic hydrophilic group. Examples of the alkoxy groups include a
methoxy group, an ethoxy group, an isopropoxy group, a
methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy
group.
[0053] The aryloxy groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an aryloxy group having a substituent and an
aryloxy group having no substituent. The aryloxy groups are
preferably aryloxy groups having 6 to 12 carbon atoms. Examples of
the substituent include an alkoxy group and an ionic hydrophilic
group. Examples of the aryloxy groups include a phenoxy group, a
p-methoxyphenoxy group, and an o-methoxyphenoxy group.
[0054] The amide groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an amide group having a substituent and an amide
group having no substituent. The amide groups are preferably amide
groups having 2 to 12 carbon atoms. Examples of the substituent
include an ionic hydrophilic group. Examples of the amide groups
include an acetamide group, a propionamide group, a benzamide
group, and a 3,5-disulfobenzamide group.
[0055] The arylamino groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include an arylamino group having a substituent
and an arylamino group having no substituent. The arylamino groups
are preferably arylamino groups having 6 to 12 carbon atoms.
Examples of the substituent include a halogen atom and an ionic
hydrophilic group. Examples of the arylamino groups include an
anilino group and a 2-chloroanilino group.
[0056] The ureido groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include a ureido group having a substituent and a ureido
group having no substituent. The ureido groups are preferably
ureido groups having 1 to 12 carbon atoms. Examples of the
substituent include an alkyl group and an aryl group. Examples of
the ureido groups include a 3-methylureido group, a
3,3-dimethylureido group, and a 3-phenylureido group.
[0057] The sulfamoylamino groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a sulfamoylamino group having a
substituent and a sulfamoylamino group having no substituent.
Examples of the substituent include an alkyl group. Examples of the
sulfamoylamino groups include an N,N-dipropylsulfamoylamino
group.
[0058] The alkylthio groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include an alkylthio group having a substituent
and an alkylthio group having no substituent. The alkylthio groups
are preferably alkylthio groups having 1 to 12 carbon atoms.
Examples of the substituent include an ionic hydrophilic group.
Examples of the alkylthio groups include a methylthio group and an
ethylthio group.
[0059] The arylthio groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include an arylthio group having a substituent
and an arylthio group having no substituent. The arylthio groups
are preferably arylthio groups having 6 to 12 carbon atoms.
Examples of the substituent include an alkyl group and an ionic
hydrophilic group. Examples of the arylthio groups include a
phenylthio group and a p-tolylthio group.
[0060] The alkoxycarbonylamino groups represented by R.sub.3,
R.sub.4, R.sub.5, or R.sub.6 include an alkoxycarbonylamino group
having a substituent and an alkoxycarbonylamino group having no
substituent. The alkoxycarbonylamino groups are preferably
alkoxycarbonylamino groups having 2 to 12 carbon atoms. Examples of
the substituent include an ionic hydrophilic group. Examples of the
alkoxycarbonylamino groups include an ethoxycarbonylamino
group.
[0061] The sulfonamide groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a sulfonamide group having a
substituent and a sulfonamide group having no substituent. The
sulfonamide groups are preferably sulfonamide groups having 1 to 12
carbon atoms. Examples of the substituent include an ionic
hydrophilic group. Examples of the sulfonamide groups include a
methanesulfonamide group, a benzenesulfonamide group, and a
3-carboxybenzenesulfonamide group.
[0062] The carbamoyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a carbamoyl group having a substituent
and a carbamoyl group having no substituent. Examples of the
substituent include an alkyl group. Examples of the carbamoyl
groups include a methylcarbamoyl group and a dimethylcarbamoyl
group.
[0063] The sulfamoyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a sulfamoyl group having a substituent
and a sulfamoyl group having no substituent. Examples of the
substituent include an alkyl group. Examples of the sulfamoyl
groups include a dimethylsulfamoyl group and a
di-(2-hydroxyethyl)sulfamoyl group.
[0064] The sulfonyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a methanesulfonyl group and a
phenylsulfonyl group.
[0065] The alkoxycarbonyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include an alkoxycarbonyl group having a
substituent and an alkoxycarbonyl group having no substituent. The
alkoxycarbonyl groups are preferably alkoxycarbonyl groups having 2
to 12 carbon atoms. Examples of the substituent include an ionic
hydrophilic group. Examples of the alkoxycarbonyl groups include a
methoxycarbonyl group and an ethoxycarbonyl group.
[0066] The heterocyclooxy groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a heterocyclooxy group having a
substituent and a heterocyclooxy group having no substituent. The
heterocyclooxy groups are preferably heterocyclooxy groups having a
5- or 6-membered heterocycle. Examples of the substituent include a
hydroxyl group and an ionic hydrophilic group. Examples of the
heterocyclooxy groups include a 2-tetrahydropyranyloxy group.
[0067] The azo groups represented by R.sub.3, R.sub.4, R.sub.5, or
R.sub.6 include an azo group having a substituent and an azo group
having no substituent. Examples of the azo groups include a
p-nitrophenyl azo group.
[0068] The acyloxy groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an acyloxy group having a substituent and an
acyloxy group having no substituent. The acyloxy groups are
preferably acyloxy groups having 1 to 12 carbon atoms. Examples of
the substituent include an ionic hydrophilic group. Examples of the
acyloxy groups include an acetoxy group and a benzoyloxy group.
[0069] The carbamoyloxy groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a carbamoyloxy group having a
substituent and a carbamoyloxy group having no substituent.
Examples of the substituent include an alkyl group. Examples of the
carbamoyloxy groups include an N-methylcarbamoyloxy group.
[0070] The silyloxy groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a silyloxy group having a substituent
and a silyloxy group having no substituent. Examples of the
substituent include an alkyl group. Examples of the silyloxy groups
include a trimethylsilyloxy group.
[0071] The aryloxycarbonyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include an aryloxycarbonyl group having a
substituent and an aryloxycarbonyl group having no substituent. The
aryloxycarbonyl groups are preferably aryloxycarbonyl groups having
7 to 12 carbon atoms. Examples of the substituent include an ionic
hydrophilic group. Examples of the aryloxycarbonyl groups include a
phenoxycarbonyl group.
[0072] The aryloxycarbonylamino groups represented by R.sub.3,
R.sub.4, R.sub.5, or R.sub.6 include an aryloxycarbonylamino group
having a substituent and an aryloxycarbonylamino group having no
substituent. The aryloxycarbonylamino groups are preferably
aryloxycarbonylamino groups having 7 to 12 carbon atoms. Examples
of the substituent include an ionic hydrophilic group. Examples of
the aryloxycarbonylamino groups include a phenoxycarbonylamino
group.
[0073] The imide groups represented by R.sub.3, R.sub.4, R.sub.5,
or R.sub.6 include an imide group having a substituent and an imide
group having no substituent. Examples of the imide groups include
an N-phthalimide group and an N-succinimide group.
[0074] The heterocyclothio groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a heterocyclothio group having a
substituent and a heterocyclothio group having no substituent. The
heterocyclothio groups preferably have a 5- or 6-membered
heterocycle. Examples of the substituent include an ionic
hydrophilic group. Examples of the heterocyclothio groups include a
2-pyridylthio group.
[0075] The sulfinyl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a sulfinyl group having a substituent
and a sulfinyl group having no substituent. Examples of the
sulfinyl groups include a phenylsulfinyl group.
[0076] The phosphoryl groups represented by R.sub.3, R.sub.4,
R.sub.5, or R.sub.6 include a phosphoryl group having a substituent
and a phosphoryl group having no substituent. Examples of the
phosphoryl groups include a phenoxyphosphoryl group and a
phenylphosphoryl group.
[0077] The acyl groups represented by R.sub.3, R.sub.4, R.sub.5, or
R.sub.6 include an acyl group having a substituent and an acyl
group having no substituent. The acyl groups are preferably acyl
groups having 1 to 12 carbon atoms. Examples of the substituent
include an ionic hydrophilic group. Examples of the acyl groups
include an acetyl group and a benzoyl group.
[0078] The ionic hydrophilic groups represented by R.sub.3,
R.sub.4, R.sub.5, or R.sub.6 include a carboxyl group, a sulfo
group, and a quaternary ammonium group. The ionic hydrophilic
groups are preferably a carboxyl group and a sulfo group and
particularly preferably a sulfo group. The carboxyl group and sulfo
group may each be in a state of a salt. Examples of the counter ion
that forms the salt include alkali metal ions (e.g., sodium ion and
potassium ion) and organic cations (e.g., tetramethylguanidinium
ion).
[0079] In the general formula (I), R.sub.1 and R.sub.2, R.sub.3 and
R.sub.1, and R.sub.2 and R.sub.5 may each form a ring. If the ring
is formed, preferred examples of the ring are given below. 7
[0080] In the general formula (I), W represents a group of atoms
necessary for forming a nitrogen-containing, 5- to 6-membered
heterocycle (this ring may be condensed with other ring to form a
condensed ring).
[0081] Preferred examples of the nitrogen-containing heterocycle,
which is made up of W, and the condensed ring of the heterocycle in
the general formula (I) include imidazole, benzimidazole, pyrazole,
triazole, thiazole, benzothiazole, isothiazole, benzisothiazole,
oxazole, benzoxazole, thiadiazole, 3H-pyrrole, 3H-indole,
isoxazole, and benzisoxazole. Pyrazole, triazole, isothiazole, and
thiadiazole are preferable. Pyrazole is particularly
preferable.
[0082] In the azo dyes represented by the general formula (I)
preferable combinations of the substituents are as follows. R.sub.1
is preferably an aryl group or a heterocyclic group (which may have
an ionic hydrophilic group as a substituent) and is particularly
preferably an aryl group. R.sub.2 is preferably an alkyl group or
an aryl group (which may have an ionic hydrophilic group as a
substituent) and is particularly preferably an aryl group. R.sub.3,
R.sub.4, and R.sub.5 are each a hydrogen atom. R.sub.6 is an amide
group, a ureido group, a sulfamoylamino group, an
alkoxycarbonylamino group, or a sulfonamide group, more preferably
an amide group, a ureido group, or a sulfonamide group, and is
particularly preferably an amide group (which may have an ionic
hydrophilic group as a substituent). The nitrogen-containing
heterocycle made up of W is preferably pyrazole, triazole,
isothiazole, or thiadiazole and is particularly preferably
pyrazole.
[0083] The preferred combinations of the substituents of the
compound represented by the general formula (I) are as follows. The
compound in which at least one of the substituents is the
preferable group described above is preferable; the compound in
which more of the substituents are the preferable groups described
above is more preferable; and compound in which all of the
substituents are the preferable groups described above is most
preferable.
[0084] Among the azo compounds represented by the general formula
(I), the azo compounds having the structures represented by the
following general formula (II) are preferable. The azo compounds
represented by the general formula (II) of the present invention
are explained in detail below. 8
[0085] In the general formula (II), R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, and R.sub.6 are defined in the same way as
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 in the
general formula (I), respectively. The same applies to the
preferred examples of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
and R.sub.6.
[0086] In the general formula (II), X represents an
electron-withdrawing group whose Hammett substitution constant
.sigma..sub.p is 0.20 or greater and preferably 0.30 or greater.
The upper limit of the constant is 1.0 for the electron-withdrawing
group.
[0087] Specific examples of the electron-withdrawing group X which
has a Hammett's constant .sigma..sub.p of 0.20 or greater include
an acyl group, an acyloxy group, a carbamoyl group, an
alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a
nitro group, a dialkylphosphono group, a diarylphosphono group, a
diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl
group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy
group, an acylthio group, a sulfamoyl group, a thiocyanate group, a
thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy
group, a halogenated aryloxy group, a halogenated alkylamino group,
a halogenated alkylthio group, an aryl group substituted with other
electron-withdrawing group having a .sigma..sub.p value of 0.20 or
greater, a heterocyclic group, a halogen atom, an azo group, and a
selenocyanate group.
[0088] X may further have a substituent, and examples of the
substituent include those listed as the examples of R.sub.1.
[0089] Preferred examples of X include an acyl group having 2 to 12
carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a
carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl
group having 2 to 12 carbon atoms, an aryloxycarbonyl group having
7 to 18 carbon atoms, a cyano group, a nitro group, an
alkylsulfinyl group having 1 to 12 carbon atoms, an arylsulfinyl
group having 6 to 18 carbon atoms, an alkylsulfonyl group having 1
to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon
atoms, a sulfamoyl group having 0 to 12 carbon atoms, a halogenated
alkyl group having 1 to 12 carbon atoms, a halogenated alkyloxy
group having 1 to 12 carbon atoms, a halogenated alkylthio group
having 1 to 12 carbon atoms, a halogenated aryloxy group having 7
to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms and
substituted with two or more other electron-withdrawing groups each
having a .sigma..sub.p value of 0.20 or greater, and a 5- to
8-membered heterocyclic group having a nitrogen, oxygen, or sulfur
atom and 1 to 18 carbon atoms.
[0090] More preferred examples of X are an alkyloxycarbonyl group
having 2 to 12 carbon atoms, a nitro group, a cyano group, an
alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl
group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12
carbon atoms, and a halogenated alkyl group having 1 to 12 carbon
atoms. Particularly preferred examples of X are a cyano group, an
alkylsulfonyl group having 1 to 12 carbon atoms, and an
arylsulfonyl group having 6 to 18 carbon atoms. The most preferred
example of X is a cyano group.
[0091] In the general formula (II), Y represents a substituted or
unsubstituted secondary or tertiary alkyl group, a substituted or
unsubstituted aryl group, or a substituted or unsubstituted
heterocyclic group. Preferably, Y represents a secondary or
tertiary alkyl group, or an aryl group. Most preferably, Y
represents a tertiary alkyl group. Specifically, Y represents an
isopropyl group, a t-butyl group, a phenyl group, or a
benzothiazolyl group. Most preferably, Y represents a tertiary
alkyl group. These substituents may further have substituents which
include a hydroxyl group, an alkoxy group, a cyano group, a halogen
atom, and an ionic hydrophilic group.
[0092] In the general formula (II), A represents a group made up of
nonmetallic atoms necessary for forming a 5- to 8-membered ring
which may have a substituent and may be a saturated ring or may
have an unsaturated bond. Preferred examples of the nonmetallic
atoms include a nitrogen atom, an oxygen atom, a sulfur atom, and a
carbon atom.
[0093] Examples of the ring made up of A include a benzene ring, a
cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a
cyclooctane ring, a cyclohexene ring, a pyridine ring, a piperazine
ring, an oxane ring, and a thiane ring. These rings may further
have substituents such as those listed as examples of the
substituents R.sub.3, R.sub.4, R.sub.5, and R.sub.6.
[0094] The ring made up of A is preferably one of the substituents
(III-1 to III-9) represented by any one of the following general
formulae (III): 9
[0095] In the general formulae (III), Z.sub.1, Z.sub.2, Z.sub.3,
Z.sub.4, and Z.sub.5 each independently represents 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 amide
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 heterocyclooxy group, an
azo group, an acyloxy group, a carbamoyloxy group, a silyloxy
group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an
imide group, a heterocyclothio group, a sulfinyl group, a
phosphoryl group, an acyl group, or an ionic hydrophilic group.
[0096] Specific examples of Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, and
Z.sub.5 include the groups such as those listed as examples of the
substituents R.sub.3, R.sub.4, R.sub.5, and R.sub.6 in the general
formula (I).
[0097] Preferred examples of Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4,
and Z.sub.5 are each a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a cyano group, a nitro group, an alkoxy
group, an amide group, a ureido group, a sulfamoylamino group, an
alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group,
a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an
acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl
group, a phosphoryl group, an acyl group, and an ionic hydrophilic
group. Further, preferably at least two of Z.sub.1, Z.sub.2,
Z.sub.3, Z.sub.4, and Z.sub.5 are substituted with substituents
whose sum of the values of .sigma..sub.p is 0.4 or greater.
[0098] Furthermore, most preferably Z.sub.1, Z.sub.2, Z.sub.3,
Z.sub.4, and Z.sub.5 are each a hydrogen atom, a halogen atom, a
cyano group, a nitro group, an alkoxy group, an amide group, a
ureido group, a sulfamoylamino group, an alkoxycarbonylamino group,
a sulfonamide group, a sulfonyl group, or an ionic hydrophilic
group. Furthermore, most preferably at least two of Z.sub.1,
Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5 are substituted with
substituents whose sum of the values of .sigma..sub.p is 0.4 or
greater.
[0099] Z.sub.6 and Z.sub.9 each independently represents
--NR.sub.7--, an oxygen atom, or a sulfur atom, where R.sub.7
represents a hydrogen atom or a substituent.
[0100] Examples of the substituent R.sub.7 are the same as R.sub.3
to R.sub.6 in the general formula (I) and preferred examples of the
substituent R.sub.7 are also the same as those of R.sub.3 to
R.sub.6.
[0101] Z.sub.7, Z.sub.8, Z.sub.10, Z.sub.11, Z.sub.12, Z.sub.13,
Z.sub.14, Z.sub.15, Z.sub.16, Z.sub.17, Z.sub.18, Z.sub.19,
Z.sub.20, Z.sub.21, Z.sub.22, Z.sub.23, Z.sub.24, Z.sub.25, and
Z.sub.26 are defined in the same way, respectively, as R.sub.3,
R.sub.4, R.sub.5, and R.sub.6 in the general formula (II).
[0102] Preferably, Z.sub.7, Z.sub.8, Z.sub.10, Z.sub.11, Z.sub.12,
Z.sub.13, Z.sub.14, Z.sub.15, Z.sub.16, Z.sub.17, Z.sub.18,
Z.sub.19, Z.sub.20, Z.sub.21, Z.sub.22, Z.sub.23, Z.sub.24,
Z.sub.25, and Z.sub.26 are each a hydrogen atom, a halogen atom, an
alkyl group, a cyano group, a nitro group, an alkoxy group, an
amide group, a ureido group, a sulfamoylamino group, an
alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group,
a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an
acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl
group, a phosphoryl group, an acyl group, or an ionic hydrophilic
group.
[0103] More preferably, Z.sub.7, Z.sub.8, Z.sub.10, Z.sub.11,
Z.sub.12, Z.sub.13, Z.sub.14, Z.sub.15, Z.sub.16, Z.sub.17,
Z.sub.18, Z.sub.19, Z.sub.20, Z.sub.21, Z.sub.22, Z.sub.23,
Z.sub.24, Z.sub.25, and Z.sub.26 are each a hydrogen atom, a
halogen atom, a cyano group, a nitro group, an alkoxy group, an
amide group, a ureido group, a sulfamoylamino group, an
alkoxycarbonylamino group, a sulfonamide group, a sulfonyl group,
or an ionic hydrophilic group.
[0104] Among the azo compounds represented by the general formula
(II), the azo compounds having the structures represented by the
general formulae (VI) are preferable. 10
[0105] In the azo dyes represented by the general formula (II),
particularly preferable combinations of the substituents are as
follows. X is a cyano group, an alkylsulfonyl group having 1 to 12
carbon atoms, or an arylsulfonyl group having 6 to 18 carbon atoms,
and is particularly preferably a cyano group. Y is a secondary or
tertiary alkyl, an aryl group, or a heterocyclic group and is
particularly preferably a t-butyl group. R.sub.1 is an aryl group
or a heterocyclic group (which may have an ionic hydrophilic group
as a substituent) and is particularly preferably an aryl group.
R.sub.2 is an alkyl group or an aryl group (which may have an ionic
hydrophilic group as a substituent) and is particularly preferably
an aryl group. R.sub.6 is an amide group, a ureido group, a
sulfamoylamino group, an alkoxycarbonylamino group, or a
sulfonamide group, more preferably an amide group, a ureido group,
or a sulfonamide group, and is particularly preferably an amide
group (which may have an ionic hydrophilic group as a substituent).
Z.sub.1 and Z.sub.2 are each a halogen atom or an alkyl group.
Z.sub.4 is a hydrogen atom, a halogen atom, an amide group, a
sulfonamide group, a carbamoyl group, a sulfamoyl group, an
alkoxycarbonyl group, or an ionic hydrophilic group, and is
particularly preferably an ionic hydrophilic group or an amide
group.
[0106] The preferable combinations of the substituents of the
compound represented by the general formula (II) are as follows. A
compound in which at least one of the substituents is the
preferable group described above is preferable; a compound in which
more of the substituents are the preferable groups described above
is more preferable; and a compound in which all of the substituents
are the preferable groups described above is most preferable.
[0107] A detailed description of the pyrazolylaniline azo dye
derivative represented by the general formula (IV) of the present
invention is given below. The compound represented by the general
formula (IV) is a compound having a novel structure hitherto
unknown. This compound is useful as a water-soluble dye for ink jet
printing ink or as an intermediate for synthesis of the
water-soluble dye and can be an intermediate for useful chemical,
medical, or agricultural organic chemical compounds. 11
[0108] In the general formula (IV), X, Y, A, R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are defined in the same way
as X, Y, A, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 in the general formula (II), respectively. The same applies
to the preferred examples of X, Y, A, R.sub.1, R.sub.2, R.sub.3,
R.sub.4, and R.sub.6.
[0109] Among the azo compounds represented by the general formula
(IV), the azo compounds having the structures represented by the
general formulae (VII) are more preferable. 12
[0110] In the general formula (VII), X, Y, R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, Z.sub.1, Z.sub.2, Z.sub.3,
Z.sub.4, Z.sub.5, Z.sub.6, Z.sub.7, Z.sub.8, Z.sub.9, Z.sub.10,
Z.sub.11, Z.sub.12, Z.sub.13, Z.sub.14, Z.sub.15, Z.sub.16,
Z.sub.17, Z.sub.18, Z.sub.19, Z.sub.20, Z.sub.21, Z.sub.22,
Z.sub.23, Z.sub.24, Z.sub.25, and Z.sub.26 are defined in the same
way as X, Y, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, Z.sub.5, Z.sub.6, Z.sub.7,
Z.sub.8, Z.sub.9, Z.sub.10, Z.sub.11, Z.sub.12, Z.sub.13, Z.sub.14,
Z.sub.15, Z.sub.16, Z.sub.17, Z.sub.18, Z.sub.19, Z.sub.20,
Z.sub.21, Z.sub.22, Z.sub.23, Z.sub.24, Z.sub.25, and Z.sub.26 in
the general formula (VI). The same applies to the preferred
examples thereof.
[0111] The preferable combinations of the substituents of the
compound represented by the general formula (VII) are as follows.
The compound in which at least one of the substituents is the
preferable group described above is preferable; the compound in
which more of the substituents are the preferable groups described
above is more preferable; and compound in which all of the
substituents are the preferable groups described above is most
preferable.
[0112] Specific examples (exemplary compounds 101 to 130) of the
azo dyes represented by the general formulae (I), (II), and (IV)
are given below. However, it should be noted that the azo dyes that
can be used in the present invention are not limited to these
examples. 13
[0113] Specific synthesis examples of the heterylaniline azo dye
derivatives of the present invention are given below.
[0114] The azo dyes represented by the general formula (I), (II),
or (IV) can be synthesized by a diazo coupling reaction between a
coupling component, i.e., an aniline derivative represented by the
following general formula (i) and a diazo component, i.e., a
heterocyclic amine derivative (e.g., 5-amino-pyrazole) represented
by the following general formula (ii). Typical examples of the
synthetic routes for making the azo dyes (azo dye (I) and (II))
represented by the general formula (I), (II), or (IV) are shown
below. 14
[0115] The diazo component, i.e., {e.g., 3-(secondary or tertiary
alkyl)-4-cyano-5-aminopyrazole or 3-aryl-4-cyano-5-aminopyrazole}
as a starting material for use in the present invention, can be
synthesized by making reference to the methods described in U.S.
Pat. No. 3,336,285, Heterocycles, 20, 519(1983), and Japanese
Patent Application Publication (JP-B) No. 6-19036. Typical examples
are given below. 15
[0116] The aniline coupler component as a starting material for use
in the present invention can be synthesized by making reference,
for example, to the method described in Tetrahedron Letter Vol. 37,
No. 51, pp. 9207-9210 (1996). Typical examples are given below.
16
[0117] In the preparation of the diazonium salt of the heterocyclic
amine derivative (5-amino-pyrazole or the like), an organic solvent
(e.g., an aliphatic acid-based solvent such as acetic acid,
propionic acid, and isobutyric acid, an alcoholic solvent such as
methanol, ethanol, and isopropyl alcohol, an amide-based solvent
such as N,N-dimethylacetamide, N,N-dimethylformamide, and
1-methyl-2-pyrrolidone, a sulfone-based solvent such as sulfolane,
a sulfoxide-based solvent such as dimethyl sulfoxide, a
ureido-based solvent such as tetramethylurea, a halide-based
solvent such as dichloromethane, chloroform, and
1,2-dichloroethane, an ester-based solvent such as ethyl acetate
and butyl acetate, and an ether-based solvent such as diethyl ether
and tetrahydrofuran) can be used as a reaction solvent. These
organic solvents can be used singly or as a mixture of two or more.
Further, a mixture of an organic solvent and water can be used.
Furthermore, water as a single solvent can be used. Among these
solvents, an aliphatic acid-based solvent, an ester-based solvent,
and an ether-based solvent are preferable. Mixtures of these
solvents with alcoholic solvents or water are also preferable. The
most preferred solvent is a single organic solvent, i.e., an
aliphatic acid-based solvent or an ester-based solvent, a mixture
of such solvent with water, or water as a single solvent.
[0118] Examples of the acid that can be used include hydrochloric
acid, nitric acid, sulfuric acid, methanesulfonic acid,
trifluoromethanesulfoni- c acid, heptadecafluorooctanesulfonic
acid, acetic acid, trifluoroacetic acid, propionic acid, and a
mixture of these acids. Among these acids, sulfuric acid,
trifluoromethanesulfonic acid, and heptadecafluorooctanesu- lfonic
acid are preferable. Sulfuric acid and
heptadecafluorooctanesulfoni- c acid are most preferable.
[0119] Examples of the diazotizing agent that can be used include,
sodium nitrite, an aqueous sodium nitrite solution, potassium
nitrite, an aqueous potassium nitrite solution, isoamyl nitrite,
and nitrosyl sulfate (a sulfuric acid solution). Among these
diazotizing agents, an aqueous sodium nitrite solution, isoamyl
nitrite, and nitrosyl sulfate (a sulfuric acid solution) are
preferable. The most preferred diazotizing agents are isoamyl
nitrite and nitrosyl sulfate (a sulfuric acid solution).
[0120] The diazotization reaction temperature is within the range
of -78 to 50.degree. C., preferably within the range of -20 to
20.degree. C., and particularly preferably within the range of -20
to 10.degree. C.
[0121] Examples of the solvent that can be used as a reaction
solvent in the diazo coupling reaction (i.e., conversion into an
azo dye) include an organic solvent (e.g., an aliphatic acid-based
solvent such as acetic acid, propionic acid, and isobutyric acid,
an alcoholic solvent such as methanol, ethanol, and isopropyl
alcohol, an amide-based solvent such as N,N-dimethylacetamide,
N,N-dimethylformamide, and 1-methyl-2-pyrrolidone, sulfone-based
solvent such as sulfolane, a sulfoxide-based solvent such as
dimethyl sulfoxide, a ureido-based solvent such as tetramethylurea,
a halide-based solvent such as dichloromethane, chloroform, and
1,2-dichloroethane, an ester-based solvent such as ethyl acetate
and butyl acetate, an ether-based solvent such as diethyl ether and
tetrahydrofuran, and a pyridine-based solvent such as pyridine,
.alpha.-picoline, and 2,6-lutidine). These organic solvents can be
used singly or as a mixture of two or more. Further, a mixture of
an organic solvent and water can be used. Furthermore, water as a
single solvent can be used. Among these solvents, an aliphatic
acid-based solvent, an amide-based solvent, an ester-based solvent,
and an ether-based solvent are preferable. Mixtures of these
solvents with alcoholic solvents or water are also preferable. In
particular, an aliphatic acid-based solvent or an amide-based
solvent as a single solvent and a mixture of such solvent with an
alcoholic solvent or water are preferable.
[0122] Examples of the base that can be used include an organic
base (e.g., an aliphatic amine such as a triethylamine aqueous
solution, triethylamine, tripropylamine, diisopropylethylamine,
triethanolamine, and diethanolamine, an aromatic amine such as
N,N-dimethylaniline and N,N-diethylaniline, and a
nitrogen-containing unsaturated heterocycle such as pyridine,
.alpha.-picoline, 2,6-lutidine, pyridazine, and N-imidazole) and an
inorganic base (e.g., an acetate such as potassium acetate and
sodium acetate, a carbonate such as potassium carbonate, sodium
carbonate, sodium hydrogencarbonate, and potassium
hydrogencarbonate, and a metal hydroxide such as sodium hydroxide
and potassium hydroxide). Among these bases, aliphatic amines,
nitrogen-containing unsaturated heterocycles, and acetates are
preferable. In particular, aliphatic amines and acetates are
preferable.
[0123] The reaction temperature for the diazo coupling reaction
(i.e., conversion into an azo dye) is within the range of -78 to
50.degree. C., preferably within the range of -20 to 20.degree. C.,
and particularly preferably within the range of -20 to 15.degree.
C.
[0124] The product obtained by any of these reactions is
post-treated according to an ordinary method employed in organic
synthesis and is used after being purified or without being
purified. That is, the reaction product liberated from the reaction
system can be used without purification. Otherwise, the reaction
product liberated from the reaction system may be subjected to a
process or a combination of processes which include
recrystallization, column chromatography, or the like.
Alternatively, after the completion of the reaction, the reaction
product, after removal of the reaction solvent by distillation or
without the reaction solvent being removed by distillation, is
poured into water or onto ice. After that, the separated product,
after being neutralized or without being neutralized, may be
subjected to a process or a combination of processes which include
recrystallization, column chromatography, or the like. Further,
after the completion of the reaction, the reaction product, after
removal of the reaction solvent by distillation or without the
reaction solvent being removed by distillation, is poured into
water or onto ice. After that, the resulting mixture, after being
neutralized or without being neutralized, may be extracted with an
organic solvent. The extract may be used without being purified, or
the extract may be subjected to a process or a combination of
processes which include crystallization, column chromatography, or
the like.
[0125] Typical azo dye derivatives of the present invention can be
easily synthesized by making reference to the following synthetic
schemes. 17 18
[0126] That is, according to the synthetic routes, a heterocyclic
amine derivative, a diazo component compound (A) and an aniline
derivative as a coupler component or compound (W) or (X) were
synthesized as the intermediates of synthesis of the exemplary
compounds. The intermediates were subjected to the diazo coupling
reaction for making dyes and to a subsequent reaction (such as a
nucleophilic substitution reaction, Michael addition reaction and
the like). In this way, the exemplary compounds (101) and (102)
were obtained.
[0127] [Synthesis Example 1] (Synthesis of the Specific Exemplary
Compound (101))
[0128] Synthesis of the Compound (A)
[0129] (a) Synthesis of an intermediate compound (Y) of the diazo
component
[0130] Pivaloyl chloride (60 g) and malononitrile (33 g) were
dissolved in methylene chloride (500 mL), and the solution was
placed in a flask equipped with a stirrer and a dropping funnel.
While the internal temperature was kept at 5.degree. C. or below,
triethylamine (100 g) was gradually added to the solution in the
flask over a period of 60 minutes. After that, while the resulting
reaction solution was gradually heated, the reaction solution was
stirred until the solution interior reached room temperature. Next,
after the triethylamine hydrochloride that was formed was removed,
the filtrate was concentrated until methylene chloride disappeared.
The concentrated liquid was poured onto ice and the liquid was
strongly acidified with concentrated sulfuric acid. The deposited
crystals were collected by filtration and were then washed
sufficiently with water. After that, the crystals were dried
overnight at 50.degree. C. The amount of the reaction product
obtained was 51.2 g and the yield was 68.4%.
[0131] (b) Synthesis of an intermediate compound (Z) of the diazo
component
[0132] The pivaloyl malononitrile intermediate (Y) (51 g) thus
obtained was placed in methylene chloride (500 mL) and mildly
stirred so that a suspension was formed. To the suspension was
added phosphorus pentachloride (78 g) gradually. The reaction
solution was continuously stirred for 16 hours at room temperature.
Sulfur dioxide was introduced into the solution for 20 minutes and
the solvent was distilled off under a reduced pressure by means of
a rotary evaporator. The residue was poured onto ice and the
deposited crystals were collected by filtration. The reaction
product thus obtained was not subjected to further
purification.
[0133] (c) Synthesis of the diazo component compound (A)
[0134] Hydrazine monohydrate (15 g) was dissolved in ethanol (50
mL), and the solution was placed in a flask equipped with a
condenser, a dropping funnel, a thermometer, and a magnetic
stirrer. While the solution was stirred, an ethanol solution (200
mL) of the intermediate (Z) (51 g) that was obtained above was
added to the solution in the flask at such a rate that did not
allow the temperature of the solution in the flask to become higher
than 35.degree. C. After that, the reaction mixture was refluxed
mildly for 90 minutes and part of the solvent was removed. The
residue was treated with water. The reaction product was then dried
overnight at 50.degree. C. The 44 g of crude crystals thus obtained
were purified by recrystallization using a 2/1 mixture of ethyl
acetate/n-hexane. The amount of the reaction product obtained was
35.3 g and the yield was 71.7%.
[0135] Synthesis of the Coupler Component Compound (W)
[0136] (d) Synthesis of an intermediate (W-1) of the coupler
component
[0137] m-nitroaniline (13.8 g) was suspended in o-dichlorobenzene
(200 mL) and mildly stirred. To the suspension were gradually added
potassium carbonate (36.4 g) and copper powder (2 g) while being
stirred. Further, p-methyliodobenzene (98.12 g) was added. The
reaction liquid was then gradually heated to reflux temperature.
After that, reaction liquid was continuously stirred for 12 hours
at the reflux temperature. Next, after the reaction liquid was
cooled to room temperature, the reaction liquid underwent Celite
filtration (i.e., removal of inorganic substance). The filtrate was
subjected to distillation under a reduced pressure to remove the
solvent. The residue (oily substance) was purified by means of
silica gel column chromatography (CH.sub.2Cl.sub.2/n-hexane). After
that, the crude product was purified by recrystallization from
CH.sub.2Cl.sub.2/CH.sub.3OH. In this way, the coupler component
compound (W-1) was obtained. The amount of the product was 23 g and
the yield was 72.2%.
[0138] (e) Synthesis of an intermediate (W-2) of the coupler
component
[0139] The intermediate (W-1) obtained above (16 g) was suspended
in ethanol (200 mL). To the suspension was added 10% Pd-C (1 g) and
the suspension was stirred at room temperature. Next, hydrazine
monohydrate (10 mL) was added dropwise over a period of 5 minutes
while paying attention to the foaming. After that, the reaction
mixture was continuously stirred for 20 minutes at reflux
temperature, and, while hot, the reaction mixture underwent Celite
filtration. Warm water was added to the filtrate and, while being
stirred, the mixture was allowed to cool down to room temperature.
The aqueous solution was removed by decantation from the deposited
solid substance and the solid substance was dissolved in ethyl
acetate. The solution underwent drying by MgSO.sub.4, filtration,
and removal of ethyl acetate by distillation under a reduced
pressure using a rotary evaporator. The amount of the product was
14.4 g and the yield was 100%.
[0140] (f) Synthesis of coupler component (W)
[0141] The intermediate (W-2) obtained above (14.4 g) was dissolved
in acetonitrile (100 mL). To the solution was added acetic
anhydride (5.7 mL) dropwise. The reaction mixture was stirred for
15 minutes at reflux temperature. Next, the acetonitrile was
removed by distillation under a reduced pressure using a rotary
evaporator. To the oily substance obtained was added n-hexane that
had been warmed in advance and the resulting solution was stirred
while hot. While being stirred, the solution was allowed to cool
down gradually to room temperature. After that, the deposited
crystals were collected by filtration and dried overnight at room
temperature. The amount of the product was 14.5 g and the yield was
87.8%.
[0142] (g) Synthesis of dye (101-A)
[0143] A reaction liquid composed of the diazo component A obtained
above (3.3 g), concentrated hydrochloric acid (6 mL), and water (20
mL) was stirred at an internal temperature of 5.degree. C. To the
reaction liquid was added sodium nitrite (1.5 g) in aliquots over a
period of 5 minutes. The reaction liquid was continuously stirred
for 15 minutes to thereby prepare a diazonium salt. Next, the
diazonium salt prepared above was dropped over a period of 10
minutes into a 3-neck flask which had been charged with the coupler
component (W) (6.6 g), sodium acetate (20 g), acetic acid (100 mL),
and propionic acid (50 mL) and had been cooled so that the internal
temperature was kept at 5.degree. C. After the addition of the
diazonium salt, the reaction liquid was continuously stirred for 30
minutes. After that, ethyl acetate and water were introduced into
the reaction liquid for separatory extraction. The ethyl acetate
layer was washed with a saturated sodium chloride aqueous solution
and thereafter dried by MgSO.sub.4. The ethyl acetate was removed
by distillation under a reduced pressure using a rotary evaporator.
The crude product was purified by recrystallization from
CH.sub.2Cl.sub.2/methanol. The dye (101-A) that was deposited was
isolated by suction filtration. The amount of the product was 8.58
g and the yield was 84.8%.
[0144] (h) Synthesis of dye (101-B)
[0145] The dye (101-A) (5.1 g) was dissolved in DMAc (50 mL) at
room temperature. To the solution was added potassium carbonate
(2.1 g) and then 3,5-dichloro-4-nitrobenzene (4.1 g). The reaction
liquid was stirred for 2 hours at 100.degree. C. The reaction
liquid was cooled to room temperature. After that, the reaction
liquid was poured into water while being stirred. The deposited dye
(101-B) was isolated by suction filtration. The crude crystals were
purified by recrystallization from CH.sub.2Cl.sub.2/methanol. In
this way, the dye (101-B) was obtained. The amount of the product
was 6.0 g and the yield was 86.2%.
[0146] (i) Synthesis of dye (101-C)
[0147] Sodium hydrosulfide (0.56 g) was added to a mixture that was
composed of the dye (101-B) (2.8 g), ethanol (100 mL), and water
(15 mL) and was being stirred at room temperature. The resulting
reaction mixture was heated at reflux temperature for 30 minutes.
Upon completion of the reaction, the deposited crystals were
collected by filtration. Next, ethyl acetate and a 1 mol/L
hydrochloric acid aqueous solution were added to the crude crystals
obtained above for separatory extraction. The ethyl acetate layer
was washed with a saturated sodium chloride aqueous solution and
thereafter dried by MgSO.sub.4. After suction filtration, the ethyl
acetate was removed by distillation under a reduced pressure using
a rotary evaporator. In this way, the dye (101-C) was obtained. The
amount of the product was 1.92 g and the yield was 71.9%.
[0148] (j) Specific exemplary compound: Synthesis of dye 101
[0149] Acetyl chloride (0.21 mL) was gradually added dropwise to a
solution that was composed of the dye (101-C) (1.3 g) dissolved in
DMAc (15 mL) and was being stirred at an internal temperature of
5.degree. C. The resulting reaction liquid was continuously stirred
for 30 minutes. After that, ethyl acetate and a dilute hydrochloric
acid aqueous solution were added to the reaction liquid for
separatory extraction. The ethyl acetate layer was washed with a
saturated sodium chloride aqueous solution and thereafter dried by
MgSO.sub.4. After suction filtration, the ethyl acetate was removed
by distillation under a reduced pressure using a rotary evaporator.
In this way, a crude dye (101) was obtained. The crude dye was
purified by silica gel column chromatography
(CH.sub.2Cl.sub.2/n-hexane). According to the procedure described
above, the exemplary compound: dye (101) was obtained. The amount
of the product was 1.35 g and the yield was 95.5%.
.lambda..sub.max=548.9 nm; .epsilon..sub.max=4.80.times.10.sup.4
(DMF solution)
[0150] [Synthesis Example 2] (Synthesis of Specific Exemplary
Compound 102)
[0151] Synthesis of the Coupler Component Compound (X)
[0152] (k) Synthesis of an intermediate (X-1) of coupler
component
[0153] m-nitro-N-ethylaniline (16.6 g) was suspended in
o-dichlorobenzene (100 mL) and stirred. To the suspension being
stirred were added potassium carbonate (18.0 g) and copper powder
(2 g) gradually. Further, p-chloroiodobenzene (47.7 g) was added.
The reaction liquid was then gradually heated to reflux
temperature. After that, the reaction liquid was continuously
stirred for 63 hours at the reflux temperature. Next, after the
reaction liquid was cooled to room temperature, the reaction liquid
underwent Celite filtration (i.e., removal of inorganic substance).
The filtrate was subjected to distillation under a reduced pressure
to remove the solvent. The residue (oily substance) was purified by
means of silica gel column chromatography (ethyl acetate/n-hexane).
In this way, the intermediate (X-1) of coupler component in an oily
state was obtained. The amount of the product was 23.5 g and the
yield was 85.1%.
[0154] (1) Synthesis of an Intermediate (X-2) of Coupler
Component
[0155] The intermediate (X-1) obtained above (13.8 g) was suspended
in ethanol (150 mL). To the suspension was added 10% Pd-C (1 g) and
the suspension was stirred at room temperature. Next, hydrazine
monohydrate (10 mL) was added dropwise over a period of 5 minutes
while paying attention to the foaming. After that, the reaction
mixture was continuously stirred for 20 minutes at reflux
temperature, and, while hot, the reaction mixture underwent Celite
filtration. Warm water was added to the filtrate and, while being
stirred, the mixture was allowed to cool down to room temperature.
The aqueous solution was removed by decantation from the deposited
solid substance and the solid substance was dissolved in ethyl
acetate. The solution underwent drying by MgSO.sub.4, filtration,
and removal of ethyl acetate by distillation under a reduced
pressure using a rotary evaporator. The amount of the product was
12.3 g and the yield was 100%.
[0156] (m) Synthesis of Coupler Component (X)
[0157] The intermediate (X-2) obtained above (12.3 g) was dissolved
in acetonitrile (150 mL). To the solution was added acetic
anhydride (7.1 mL) dropwise. The reaction mixture was stirred for
60 minutes at reflux temperature. Next, the acetonitrile was
removed by distillation under a reduced pressure using a rotary
evaporator. To the oily product obtained was added n-hexane that
had been warmed in advance and the resulting solution was stirred
while hot. While being stirred, the solution was then allowed to
cool down gradually to room temperature. After that, the deposited
crystals were collected by filtration and dried overnight at room
temperature. The amount of the product was 11.8 g and the yield was
81.8%.
[0158] (n) Synthesis of dye (102-A)
[0159] A reaction liquid composed of the diazo component A obtained
above (4.9 g), concentrated hydrochloric acid (11 mL), and water
(40 mL) was stirred at an internal temperature of 5.degree. C. To
the reaction liquid was added sodium nitrite (2.2 g) in aliquots
over a period of 5 minutes. The reaction liquid was continuously
stirred for 15 minutes to thereby prepare a diazonium salt. Next,
the diazonium salt prepared above was dropped over a period of 10
minutes into a 3-neck flask which had been charged with the coupler
component (X) (9 g), sodium acetate (37 g), acetic acid (100 mL),
and propionic acid (50 mL) and had been cooled so that the internal
temperature was kept at 5.degree. C. After the addition of the
diazonium salt, the reaction liquid was continuously stirred for 30
minutes. After that, ethyl acetate and water were introduced into
the reaction liquid for separatory extraction. The ethyl acetate
layer was washed with a saturated sodium chloride aqueous solution
and thereafter dried by MgSO.sub.4. The ethyl acetate was removed
by distillation under a reduced pressure using a rotary evaporator.
The crude product was purified by recrystallization from warm
methanol. The dye (102-A) that was deposited was isolated by
suction filtration. The amount of the product was 11.5 g and the
yield was 82.7%.
[0160] (o) Synthesis of dye (102-B)
[0161] The dye (102-A) (9.3 g) was dissolved in DMAc (100 mL) at
room temperature. To the solution was added potassium carbonate
(4.1 g) and then 3,5-dichloro-4-nitrobenzene (9.5 g). The reaction
liquid was stirred for 2 hours at 100.degree. C. The reaction
liquid was cooled to room temperature. After that, the reaction
liquid was poured into water while being stirred. Next, ethyl
acetate was introduced into the reaction liquid for separatory
extraction. The ethyl acetate layer was washed with a saturated
sodium chloride aqueous solution and thereafter dried by
MgSO.sub.4. The ethyl acetate was removed by distillation under a
reduced pressure using a rotary evaporator. The crude product was
purified by recrystallization from CH.sub.2Cl.sub.2/methanol. In
this way, the dye (101-B) was obtained. The amount of the product
was 10.6 g and the yield was 80.9%.
[0162] (p) Synthesis of dye (102-C)
[0163] Sodium hydrosulfide (1.4 g) was added to a mixture that was
composed of the dye (102-B) (6.5 g), ethanol (300 mL), and water
(50 mL) and was being stirred at room temperature. The resulting
reaction mixture was heated at reflux temperature for 30 minutes.
Upon completion of the reaction, the ethyl acetate was removed by
distillation under a reduced pressure using a rotary evaporator.
Next, ethyl acetate and a 1 mol/L hydrochloric acid aqueous
solution were added to the distillation residue for separatory
extraction. The ethyl acetate layer was washed with a saturated
sodium chloride aqueous solution and thereafter dried by
MgSO.sub.4. After suction filtration, the ethyl acetate was removed
by distillation under a reduced pressure using a rotary evaporator
to thereby obtain a crude dye. The crude dye was purified by
recrystallization from CH.sub.2Cl.sub.2/methanol. In this way, the
dye (102-C) was obtained. The amount of the product was 5.65 g and
the yield was 90.6%.
[0164] (q) Specific exemplary compound: Synthesis of dye 102
[0165] 2-ethylhexanoyl chloride (1.5 mL) was gradually added
dropwise to a solution that was composed of the dye (102-C) (3.12
g) dissolved in DMAc (50 mL) and was being stirred at an internal
temperature of 5.degree. C. The resulting reaction liquid was
continuously stirred for 30 minutes. After that, ethyl acetate and
a dilute hydrochloric acid aqueous solution were added to the
reaction liquid for separatory extraction. The ethyl acetate layer
was washed with a saturated sodium chloride aqueous solution and
thereafter dried by MgSO.sub.4. After suction filtration, the ethyl
acetate was removed by distillation under a reduced pressure using
a rotary evaporator. In this way, a crude dye (102) was obtained.
The crude dye was purified by silica gel column chromatography
(ethyl acetate/n-hexane). According to the procedure described
above, the specific exemplary compound: dye (102) was obtained. The
amount of the product was 3.39 g and the yield was 90.3%.
.lambda..sub.max=533.1 nm; .epsilon..sub.max=4.38.times.10.sup.4
(DMF solution).
[0166] [Synthesis Example 3] (Synthesis of the Specific Exemplary
Compound 122)
[0167] (r) Specific exemplary compound: Synthesis of dye 122
[0168] m-Chlorosulfonylbenzoyl chloride (1.4 g) was gradually added
to a solution that was composed of the dye (102-C) (3.12 g)
dissolved in DMAc (50 mL) and was being stirred at an internal
temperature of 5.degree. C. The resulting reaction liquid was
continuously stirred for 30 minutes. Next, a saturated sodium
hydrogencarbonate aqueous solution was added to the reaction liquid
and the reaction liquid was stirred for 30 minutes. Upon completion
of the reaction, a saturated sodium chloride aqueous solution was
added to the reaction liquid and the deposited crystals were
collected by filtration. The crude dye underwent a desalting
treatment and was thereafter purified by recrystallization from
methanol. According to the procedure described above, the specific
exemplary compound: dye (122) was obtained. The amount of the
product was 3.4 g and the yield was 82.5%. .lambda..sub.max=534.2
nm; .epsilon..sub.max=4.40.times.10.sup.4 (DMF solution).
[0169] [Ink-jet Recording Ink]
[0170] The image-recording material containing the dye of the
present invention may be any material for forming images, in
particular color images. More specifically, the image-recording
material containing the dye of the present invention may be an
ink-jet recording material, a heat-sensitive transfer-type
image-recording material, a pressure-sensitive recording material,
an electrophotographic recording material, a transfer-type silver
halide photosensitive material, a printing ink, a recording pen, or
the like. Among these materials, the image-recording material
containing the dye of the present invention is preferably an
ink-jet recording material, a heat-sensitive transfer-type
image-recording material, or an electrophotographic image-recording
material, and more preferably an ink-jet recording material.
[0171] The ink-jet recording ink can be prepared by dissolving
and/or dispersing the azo dye in an aqueous medium. If necessary,
additives such as a surfactant, a drying-preventing agent (a
humidifier), a stabilizer, an antiseptic, and the like can be
added. In the case where the azo dye is dispersed in an aqueous
medium, it is preferable to disperse colored particles comprising
the azo dye and an oil-soluble polymer in an aqueous medium, to
disperse the azo dye dissolved in a high-boiling organic solvent in
an aqueous medium, or to disperse the azo in a solid state in an
aqueous medium to thereby produce a dispersion of fine particles.
At the time of dispersing, a dispersant or a surfactant can be
used. Examples of the dispersing equipment that can be used include
a simple stirrer or impeller, an in-line mixer, a mill (e.g., a
colloid mill, a ball mill, a sand mill, an attritor, a roller mill,
or an agitator mill), an ultrasonic disperser, and a high-pressure
emulsifying disperser (high-pressure homogenizer: gorille
homogenizer, micro-fluidizer, DeBEE 2000, etc. as commercially
available machines). The details of the methods of preparing the
ink-jet recording ink are described in JP-A Nos. 5-148436,
5-295312, 7-97541, 7-82515, 7-118584, and 11-286637, and Japanese
Patent Application No. 2000-87539. These methods can also be
utilized in the preparation of the ink-jet recording ink of the
present invention.
[0172] The aqueous medium described above can be a mixture composed
of water as a main component and a water-miscible organic solvent
as an optional component. Examples of the water-miscible organic
solvent include alcohols (e.g., methanol, ethanol, propanol,
isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol,
hexanol, cyclohexanol, and benzylalcohol), polyhydric alcohols
(e.g., ethylene glycol, diethylene glycol, triethylene glycol,
polyethylene glycol, propylene glycol, dipropylene glycol,
polypropylene glycol, butylene glycol, hexanediol, pentanediol,
glycerin, hexanetriol, and thiodiglycol), glycol derivatives (e.g.,
ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
ethylene glycol monobutyl ether, diethylene glycol monomethyl
ether, diethylene glycol monobutyl ether, propylene glycol
monomethyl ether, propylene glycol monobutyl ether, dipropylene
glycol monomethyl ether, triethylene glycol monomethyl ether,
ethylene glycol diacetate, ethylene glycol monomethyl ether
acetate, triethylene glycol monomethyl ether, triethylene glycol
monoethyl ether, and ethylene glycol monophenyl ether), amines
(e.g., ethanolamine, diethanolamine, triethanolamine,
N-methyldiethanolamine, N-ethyldiethanolamine, morpholine,
N-ethylmorpholine, ethylenediamine, diethylenetriamine,
triethylenetetramine, polyethyleneimine, and
tetramethylpropylenediamine), and other polar solvents (e.g.,
formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl
sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone,
N-vinyl-2-pyrrolidone, 2-oxazolidone,
1,3-dimethyl-2-imidazolidinone, acetonitrile, and acetone). These
water-miscible organic solvents may be used in combinations of two
or more.
[0173] It is preferable that the azo dye in an amount of 0.2 parts
by weight or more and 10 parts by weight or less is incorporated in
100 parts by weight of the jet-recording ink of the present
invention. The jet-recording ink of the present invention may
contain other dyes together with the azo dye described above. In
the case where two kinds or more of dyes are used, it is preferable
that the total content of the dyes falls within the above-described
range.
[0174] The viscosity of the ink-jet recording ink of the present
invention is preferably 40 cp or less. The surface tension of the
ink-jet recording ink of the present invention is preferably 200
.mu.N/cm or more and 1000 .mu.N/cm or less. The viscosity and the
surface tension can be controlled by the addition of additives such
as a viscosity-controlling agent, a surface tension-controlling
agent, a specific resistance-controlling agent, a film-controlling
agent, an ultraviolet absorber, an antioxidant, a browning
inhibitor, a mildew-proofing agent, a corrosion inhibitor, a
dispersant, and a surfactant.
[0175] The ink-jet recording ink of the present invention can be
used not only for the formation of single-color images but also for
the formation of full-color images. For the formation of full-color
images, a magenta-colored ink, a cyan-colored ink, and a
yellow-colored ink can be used. In addition, for the adjustment of
colors, a black-colored ink may also be used.
[0176] [Ink-jet Recording Method]
[0177] The ink-jet recording method according to the present
invention comprises applying an energy to the ink-jet recording ink
so that images are recorded on a conventionally known
image-receiving material. Examples of the image-receiving material
include plain paper, resin-coated paper such as paper exclusively
for ink-jet recording described, for example, in JP-A Nos.
8-169172, 8-27693, 2-276670, 7-276789, 9-323475, 62-238783,
10-153989, 10-217473, 10-235995, 10-337947, 10-217597, and
10-337947, films, paper for both electrophotography and ink-jet
recording, fabrics, glass, metals, and ceramics.
[0178] The recording paper and recording films, which are to be
used for ink-jet printing using the ink of the present invention,
are described below. The supports for use in the recording paper
and recording films may be those produced by such equipment as a
long-screen paper machine and a circular-screen paper machine and
from pulps such as chemical pulps, e.g., LBKP and NBKP, mechanical
pulps, e.g., GP, PGW, RMP, TMP, CTMP, CMP, and CGP, waste paper
pulp, e.g., DIP, and, if necessary, additives such as
conventionally known pigments, binders, sizing agents, fixing
agents, cationic agents, and fortifiers may be included. Besides
these materials, the supports may be synthetic paper or plastic
film sheets. The thickness of the support is preferably 10 to 250
.mu.m, and the weight is preferably 10 to 250 g/m.sup.2. An
ink-receiving layer and a back coat layer may be formed directly on
the support. Alternatively, an ink-receiving layer and a back coat
layer may be formed after a size press or anchor coat layer, which
is made from starch, polyvinyl alcohol, or the like, is provided on
the support. The support may be flattened by means of a calender
such as a machine calender, a TG calender, or a soft calender. The
support that is preferably used in the present invention is a paper
whose both sides are laminated with a polyolefin (e.g.,
polyethylene, polystyrene, polyethylene terephthalate, polybutene,
or a copolymer thereof or a plastic film. It is preferable that the
polyolefin contains a white pigment (e.g., titanium oxide, zinc
oxide, or the like) or a bluing dye (e.g., cobalt blue, ultramarine
blue, neodymium oxide, or the like).
[0179] The ink-receiving layer provided on the support contains a
pigment and an aqueous binder. The pigment is preferably a white
pigment. Examples of the white pigment include inorganic pigments
such as calcium carbonate, kaolin, talc, clay, diatomaceous earth,
synthetic amorphous silica, aluminum silicate, magnesium silicate,
calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite,
barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide,
and zinc carbonate and organic pigments such as a styrene-based
pigment, an acryl-based pigment, a urea resin, and a melamine
resin. The white pigment to be incorporated in the ink-receiving
layer is preferably a porous inorganic pigment. Synthetic amorphous
silica or the like having a high proportion of porous area is
particularly preferable. The synthetic amorphous silica that can be
used may be silicic acid anhydride produced by a dry process or
hydrous silicic acid produced by a wet process. The use of hydrous
silicic acid is particularly preferable.
[0180] Examples of the aqueous binder to be incorporated in the
ink-receiving layer include water-soluble polymers such as
polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch,
cationized starch, casein, gelatin, carboxymethyl cellulose,
hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide,
and derivatives of polyalkylene oxide and aqueous dispersions of
polymers such as a styrene/butadiene latex and an acrylic emulsion.
These aqueous binders may be used singly or in combinations of two
or more. Among these aqueous binders, polyvinyl alcohol and
silanol-modified polyvinyl alcohol are advantageously used in the
present invention from the standpoint of adhesion to the pigment
and peel resistance of the ink-receiving layer.
[0181] In addition to the pigment and aqueous binder, the
ink-receiving layer may contain a mordant, a water-proofing agent,
a lightfastness enhancer, a surfactant, and other additives.
[0182] It is preferable that the mordant to be incorporated in the
ink-receiving layer is immobilized. Accordingly, a polymeric
mordant is preferably used.
[0183] The polymeric mordants are described in JP-A Nos. 48-28325,
54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23851,
60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940,
60-122941, 60-122942, 60-235134, and 1-161236, and U.S. Pat. Nos.
2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386,
4,193,800, 4,273,853, 4,282,305, and 4,450,224. The image-receiving
materials containing the polymeric mordants described in JP-A No.
1-161236, pp. 212.about.215, are particularly preferable. The use
of the polymeric mordant described in this patent makes it possible
to obtain images having excellent qualities and to improve the
lightfastness of images.
[0184] The water-proofing agent is effective in increasing the
water resistance of images. The water-proofing agent is preferably
a cationic resin. Examples of the cationic resin include
polyamide/polyamine/epichlo- rohydrin, polyethylene imine,
polyamine sulfone, dimethyldiallylammonium chloride polymers,
cationic polyacrylamide, and colloidal silica. Among these cationic
resins, polyamide/polyamine/epichlorohydrin is preferable. The
content of the cationic resin is preferably 1 to 15% by weight,
more preferably 3 to 10% by weight, based on the total solid
components of the ink-receiving layer.
[0185] Examples of the lightfastness enhancer include zinc sulfate,
zinc oxide, hindered amine-based antioxidants, and
benzotriazole-based ultraviolet light absorbers such as
benzophenone. Among these substances, zinc sulfate is particularly
preferable.
[0186] The surfactant functions as a coating aid, a
peelability-improving agent, a slidability-improving agent, or an
antistatic agent.
[0187] The surfactants are described in JP-A Nos.62-173463 and
62-183457. An organofluorine compound may be used in place of the
surfactant. Preferably, the organofluorine compound is hydrophobic.
Examples of the organofluorine compound include a fluorine-based
surfactant, an oily fluorine-based compound (e.g., fluorine-based
oil), and a solid fluorine-based resin (e.g., tetrafluoroethylene
resin). The organofluorine compounds are described in JP-B No.
57-9053 (columns 8 to 17), and JP-A Nos. 61-20994 and 62-135826.
Examples of other additives which may be added to the ink-receiving
layer include a pigment dispersant, a thickener, a defoaming agent,
a dye, a fluorescent brightener, an antiseptic, a pH controlling
agent, a matting agent, a film hardener, and others. The
ink-receiving layer may have a single-layer construction or a
double-layer construction.
[0188] The recording paper or recording film may have a back coat
layer. This layer may contain a white pigment, an aqueous binder,
and other components. Examples of the white pigment to be
incorporated in the back coat layer include white inorganic
pigments such as light calcium carbonate, heavy calcium carbonate,
kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide,
zinc oxide, zinc sulfide, zinc carbonate, titanium white, aluminum
silicate, diatomaceous earth, calcium silicate, magnesium silicate,
synthetic amorphous silica, colloidal silica, colloidal alumina,
quasi-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,
hydrated halloysite, magnesium carbonate, and magnesium hydroxide,
and organic pigments such as styrene-based plastic pigments,
acryl-based plastic pigments, polyethylene, microcapsules, urea
resins, and melamine resins.
[0189] Examples of the aqueous binder to be incorporated in the
back coat layer include water-soluble polymers such as a
styrene/maleic salt copolymer, a styrene/acrylic salt copolymer,
polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch,
cationized starch, casein, gelatin, carboxymethyl cellulose,
hydroxyethyl cellulose, and polyvinylpyrrolidone, and aqueous
dispersions of polymers such as a styrene/butadiene latex and an
acrylic emulsion. Other components which may be incorporated in the
back coat layer include a defoaming agent, a foaming inhibitor, a
dye, a fluorescent brightener, an antiseptic, a water-proofing
agent, and others.
[0190] The layers constituting the ink-jet recording paper or
recording film (including a back layer) may contain a polymer
latex. The polymer latex is used for improvement of film physical
properties such as dimension stabilization, curling prevention,
adhesion prevention, and prevention of film cracking. The polymer
latices are described in JP-A Nos. 62-245258, 62-131668, and
62-110066. The incorporation of a polymer latex having a low glass
transition temperature (i.e., 40.degree. C. or below) in the layer
containing a mordant can prevent the cracking and curling of the
layer. The incorporation of a polymer latex having a high glass
transition temperature in the back layer can also prevent the
cracking and curling of the layer.
[0191] The ink-jet recording methods using the ink of the present
invention are not limited and conventionally known methods can be
used. Examples of the methods include a charge-controlling method
in which ink is ejected by use of electrostatic attraction, a
drop-on-demand method (pressure pulse method) in which vibratory
pressure of a piezoelectric element is used, an acoustic ink-jet
method in which electric signals are converted into acoustic beams
and the ink is irradiated with the acoustic beams so that the ink
is ejected by use of the radiation pressure, and a thermal ink-jet
method in which bubbles are formed by heating the ink and the
pressure thus created is used. The ink-jet recording methods
include a method in which many droplets, each made up of a small
volume of a so-called photo-ink having a low concentration, are
ejected, a method in which image quality is improved by use of
plural kinds of ink each having substantially the same color but a
different concentration, and a method in which colorless
transparent ink is used.
EXAMPLES
[0192] The present invention is explained by way of the following
examples. It should be noted that the present invention is not
limited to these examples.
Example 1
Preparation of Water-based Ink
[0193] While being heated at 30.about.40.degree. C., the following
components were stirred for 1 hour. After that, the liquid was
subjected to pressurized filtration through a micro-filter having
an average pore diameter of 0.8 .mu.m and a diameter of 47 mm. In
this way, an ink liquid A was prepared.
1 Azo dye (specific exemplary compound 122) 4 parts by weight
Diethylene glycol 9 parts by weight Tetraethylene glycol monobutyl
ether 9 parts by weight Glycerin 7 parts by weight Diethanolamine 1
part by weight Water 70 parts by weight
[0194] Ink liquids B.about.H were prepared in the same way as in
the preparation of the ink liquid A, except that the azo dye was
changed as shown in the following Table 1.
[0195] (Image Recording and Assessment)
[0196] Using each of the ink liquids A.about.H prepared above,
images were recorded on photographic glossy paper (SUPER
PHOTOGRADE, i.e., ink jet paper manufactured by Fuji Photo Film
Co., Ltd.) by means of an ink-jet printer (PM-700C manufactured by
Seiko-Epson Co., Ltd.).
[0197] Hue and lightfastness of the images obtained were assessed.
As to the hue, the assessment was visually conducted and the
results were expressed in 3 ratings of "Excellent", "Good", and
"Poor". The results are shown in Table 1. In Table 1, .largecircle.
indicates that the hue was excellent; .DELTA.: indicates that the
hue was good; and X indicates that the hue was poor. The
lightfastness assessment was conducted in the following way.
Immediately after recording, the image density Ci was measured.
After that, the image was irradiated with xenon light (85,000 lux)
by means of a weather-o-meter (Atlas C. 165) for 7 days and again
the image density Cf was measured. Using the difference in image
density before and after the irradiation with xenon light, the dye
retention rate ({(Ci-Cf)/Ci}.times.100%) was calculated and used
for the assessment. The image density was measured using a
reflection densitometer (X-Rite 310TR). The dye retention rate was
measured at 3 points of reflection densities, i.e., 1, 1.5, and
2.0. The ratings are shown in Table 1. In Table 1, .largecircle.
indicates that the dye retention rate was 80% or more at all of the
densities; .DELTA.: indicates that the dye retention rate was less
than 80% at two of the densities; and X indicates that the dye
retention rate was less than 80% at all of the densities. The ozone
gas resistance test was conducted in the following way. The image
immediately after being recorded was placed in a box in which the
ozone gas concentration was set to 0.5 ppm for 24 hours. Before and
after the exposure to the ozone gas, the image densities were
measured using a reflection densitometer (X-Rite 310TR) and the
ozone gas resistance was assessed based on the dye retention rate.
The dye retention rate was measured at 3 points of reflection
densities, i.e., 1, 1.5, and 2.0. The ozone gas concentration
inside the box was set by means of an ozone gas monitor (Model:
OZG-EM-01) manufactured by APPLICS. The assessment results were
expressed in 3 ratings. That is, .largecircle. indicates that the
dye retention rate was 70% or more at all of the densities;
.DELTA.: indicates that the dye retention rate was less than 70% at
one or two of the densities; and X indicates that the dye retention
rate was less than 70% at all of the densities.
2TABLE 1 ozone ink lightfastness resistance liquid dye hue (rating)
rating rating A azo dye 122 magenta (.largecircle.) .largecircle.
.largecircle. B azo dye 123 magenta (.largecircle.) .largecircle.
.largecircle. C azo dye 125 magenta (.largecircle.) .largecircle.
.largecircle. D azo dye 126 magenta (.largecircle.) .largecircle.
.largecircle. E comparative dye (A)* magenta (.DELTA.) X
.largecircle. F comparative dye (B)* magenta (X) .DELTA. X G
comparative dye (C)* magenta (X) .DELTA. X H comparative dye (D)*
magenta (X) .DELTA. X *Comparative dyes (A) to (D) are indicated
below. (Comparative dye A) 19 (Comparative dye B) 20 (Comparative
dye C) 21 (Comparative dye D) 22
[0198] As can be seen from the results shown in Table 1, the
magenta images formed from the ink liquids A.about.D were clearer
than the magenta images formed from the ink liquids E.about.H. The
images formed by using the ink liquids A.about.D exhibited superior
lightfastness.
[0199] Further, using each of the ink liquids A.about.D, images
were recorded on special use super fine glossy paper for special
purpose (MJA4S3P manufactured by Seiko-Epson Co., Ltd.) by means of
an ink-jet printer (PM-700C manufactured by Seiko-Epson Co., Ltd.).
Assessment of the hue and lightfastness of the images obtained gave
the same results as those of Table 1.
Example 2
Preparation of Sample 101
[0200] 5.63 g of an azo dye (specific exemplary compound 101: an
oil-soluble dye), 7.04 g of sodium dioctylsulfosuccinate, 4.22 g of
a high-boiling organic solvent (S-2) shown below and 5.63 g of a
high-boiling organic solvent (S-11) shown below were dissolved in
50 mL of ethyl acetate at 70.degree. C. After that, 500 mL of
deionized water was added to the solution, which was being stirred
by means of a magnetic stirrer, so as to prepare an oil-in-water
type, coarse dispersion. The coarse dispersion thus obtained was
passed through a micro-fluidizer (MICROFLUIDEX INC.) 5 times under
a pressure of 600 bar so as to obtain an emulsion having finer
particles. Next, the emulsion underwent a solvent-removing
treatment by means of a rotary evaporator until the smell of ethyl
acetate was lost. In this way, a fine emulsion of a hydrophobic dye
was obtained. Then, 140 g of diethylene glycol, 50 g of glycerin, 7
g of SURFYNOL 465 (Air Products & Chemicals Inc.), and 900 mL
of deionized water were added to the fine emulsion to thereby
prepare ink Sample 101. 23
Preparation of Samples 102.about.110
[0201] Samples 102.about.110 were prepared in the same way as in
the preparation of Sample 101, except that the azo dye (specific
exemplary compound 101: an oil-soluble dye) was replaced by the azo
dyes (oil-soluble dyes) as shown in the following Table 2. The
volume-average particle sizes of the emulsified dispersions of ink
Samples 101.about.110 were measured by means of MICROTRACK UPA
(Nikkisou Co., Ltd.). The results are shown in Table 2.
[0202] (Image Recording and Assessment)
[0203] The ink samples 101.about.110 and the comparative ink sample
underwent the following assessment. The results are shown in Table
2.
[0204] In Table 2, "color", "paper dependence", "water resistance",
and "lightfastness" are the test results of the images which were
recorded on photographic glossy paper (PHOTOGRADE, i.e., ink jet
paper manufactured by Fuji Photo Film Co., Ltd.) by means of an
ink-jet printer (PM-700C manufactured by Epson Co., Ltd.).
[0205] <Color>
[0206] Reflection spectra of the recorded image were measured in a
390 to 730 nm region at an interval of 10 nm and a* and b* were
calculated according to CIE L*a*b* color space. Preferable colors
as magenta were defined as follows.
[0207] Preferable a*: 76 or more
[0208] Preferable b*: -30 or more and 0 or less
[0209] A: both a* and b* are inside the preferable region
[0210] B: either a* or b* is inside the preferable region
[0211] C: both a* and b* are outside the preferable region
[0212] <Paper Dependence>
[0213] Comparison was made between the image formed on the
photographic glossy paper and the image formed on PPC plain paper.
If the difference between the two images was small, it was graded
as A (good), whereas, if the difference between the two images was
large, it was graded as B (poor). In this way, the difference was
assessed according to the two grades.
[0214] <Water resistance>
[0215] After an image was formed on the photographic glossy paper,
the paper was dried for one hour at room temperature. After that,
the paper was immersed in water for 30 seconds and thereafter left
to dry naturally at room temperature. The blur on the paper was
inspected. The blur was expressed by the following 3 ratings. A:
free from blur; B: slight blur; C: significant blur.
[0216] <Lightfastness>
[0217] The photographic glossy paper having an image formed thereon
was irradiated with xenon light (85,000 lx) by means of a
weather-o-meter (Atlas C. 165) for 3 days. Before and after the
xenon irradiation, the image densities were measured using a
reflection densitometer (X-Rite 310TR) and the values obtained were
used for the calculation of the dye retention rate. The measurement
was made at 3 points of reflection densities, i.e., 1, 1.5, and
2.0.
[0218] The dye retention rate was expressed by the following 3
ratings: A indicates that the dye retention rate was 70% or more at
all of the densities; B indicates that the dye retention rate was
less than 70% at one or two of the densities; and C indicates that
the dye retention rate was less than 70% at all of the
densities.
[0219] <Ozone Gas Resistance>
[0220] The photographic glossy paper having an image formed thereon
was placed in a box in which the ozone gas concentration was set to
0.5 ppm for 24 hours. Before and after the exposure to the ozone
gas, the image densities were measured using a reflection
densitometer (X-Rite 310TR) and the ozone gas resistance was
assessed based on the dye retention rate. The measurement was made
at 3 points of reflection densities, i.e., 1, 1.5, and 2.0. The
ozone gas concentration inside the box was set by means of an ozone
gas monitor (Model: OZG-EM-01) manufactured by APPLICS.
[0221] The ozone gas resistance was expressed by the following 3
ratings: A indicates that the dye retention rate was 70% or more at
all of the densities; B indicates that the dye retention rate was
less than 70% at one or two of the densities; and C indicates that
the dye retention rate was less than 70% at all of the
densities.
3TABLE 2 particle paper water Light- ozone Sample No. dye diameter
(nm) color dependence resistance fastness resistance comparative
Comparative -- B B B B C sample dye D sample 101 101 58 A A A A A
sample 102 102 50 A A A A A sample 103 103 62 A A A A A sample 104
105 61 A A A A A sample 105 106 59 A A A A A sample 106 107 63 A A
A A A sample 107 110 69 A A A A A sample 108 113 67 A A A A A
sample 109 114 83 A A A A A sample 110 121 79 A A A A A
[0222] As can be seen from Table 2, the jet printing ink of the
present invention exhibits excellent color developability,
excellent color, little dependence on paper, superior water
resistance, and superior lightfastness.
Example 3
[0223] The ink prepared in Example 2 was loaded into a cartridge of
an ink-jet printer BJ-F850 (manufactured by Canon Inc.). Using the
printer and photographic glossy paper GP-301 manufactured by Canon
Inc., images were printed. The prints underwent the same
assessments as in Example 2 and the same results as in Example 2
were obtained.
[0224] The present invention makes it possible (1) to provide a
novel heterylaniline azo dye derivative having a specific structure
which is useful as a dye for ink jet printing ink or as an
intermediate for synthesis of the dye, and can be an intermediate
for useful chemical, medical, or agricultural organic chemical
compounds and (2) to provide an ink-jet recording ink and an
ink-jet recording method which, by use of the heterylaniline azo
dye derivative, enable the formation of images having excellent hue
and excellent durability to light and ozone gas.
* * * * *