U.S. patent application number 14/549339 was filed with the patent office on 2015-03-19 for magenta toner containing compound having azo skeleton.
The applicant listed for this patent is CANON KAUBSHIKI KAISHA. Invention is credited to Waka Hasegawa, Yuki Hasegawa, Masashi Hirose, Masashi Kawamura, Ayano Mashida, Yasuaki Murai, Chiaki Nishiura, Masanori Seki, Takayuki Toyoda, Taiki Watanabe.
Application Number | 20150079515 14/549339 |
Document ID | / |
Family ID | 47720374 |
Filed Date | 2015-03-19 |
United States Patent
Application |
20150079515 |
Kind Code |
A1 |
Toyoda; Takayuki ; et
al. |
March 19, 2015 |
MAGENTA TONER CONTAINING COMPOUND HAVING AZO SKELETON
Abstract
A toner comprising toner particles, each of which contains a
binder resin, a compound in which a polymer portion is bound to an
azo skeleton structure, and a magenta pigment.
Inventors: |
Toyoda; Takayuki;
(Yokohama-shi, JP) ; Murai; Yasuaki;
(Kawasaki-shi, JP) ; Hasegawa; Waka;
(Kawasaki-shi, JP) ; Hasegawa; Yuki;
(Yokohama-shi, JP) ; Kawamura; Masashi;
(Yokohama-shi, JP) ; Watanabe; Taiki;
(Akishima-shi, JP) ; Seki; Masanori;
(Yokohama-shi, JP) ; Nishiura; Chiaki;
(Kawasaki-shi, JP) ; Mashida; Ayano;
(Kawasaki-shi, JP) ; Hirose; Masashi;
(Machida-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CANON KAUBSHIKI KAISHA |
Tokyo |
|
JP |
|
|
Family ID: |
47720374 |
Appl. No.: |
14/549339 |
Filed: |
November 20, 2014 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
13777764 |
Feb 26, 2013 |
8936894 |
|
|
14549339 |
|
|
|
|
Current U.S.
Class: |
430/108.22 |
Current CPC
Class: |
C09B 69/106 20130101;
G03G 9/08768 20130101; G03G 9/091 20130101; C09B 68/41 20130101;
C09B 67/0055 20130101; G03G 9/0906 20130101; G03G 9/0924 20130101;
G03G 9/08 20130101; G03G 9/092 20130101 |
Class at
Publication: |
430/108.22 |
International
Class: |
G03G 9/08 20060101
G03G009/08; G03G 9/09 20060101 G03G009/09 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 29, 2012 |
JP |
2012-043073 |
Claims
1. A magenta toner comprising toner particles, each of which
contains a binder resin; a compound and a magenta pigment the
compound has a structure, a polymer portion of which has a monomer
unit represented by formula (2) and is bound to a structure
represented by formula (5); ##STR00038## where, in formula (5),
each R.sub.1 independently represents a hydrogen atom, a halogen
atom, an alkyl group, an alkoxy group, a trifluoromethyl group, a
cyano group, or a hydroxyl group; R.sub.9 and R.sub.10 each
independently represent an alkyl group, a phenyl group, an OR.sub.4
group, or an NR.sub.5R.sub.6 group; R.sub.4 to R.sub.6
independently represent a hydrogen atom, an alkyl group, a phenyl
group, or an aralkyl group; R.sub.26 to R.sub.30 independently
represent a hydrogen atom, a COOR.sub.21 group, a
CONR.sub.22R.sub.23 group, a NHCOR.sub.24 group, or an OR.sub.25
group; R.sub.21 to R.sub.25 independently represent a hydrogen
atom, an alkyl group, an aryl group, or an aralkyl group; l
represents 4; and L represents a divalent linking group that binds
to the polymer portion, ##STR00039## where, in formula (2), R.sub.7
represents a hydrogen atom or an alkyl group; and R.sub.8
represents a phenyl group, a carboxyl group, a carboxylic acid
ester group, or a carboxylic acid amide group.
2. The magenta toner according to claim 1, where at least one of
R.sub.26 to R.sub.30 in formula (5) represents a COOR.sub.21 group
or a CONR.sub.22R.sub.23 group; R.sub.21 to R.sub.23 independently
represent a hydrogen atom, an alkyl group, an aryl group, or an
aralkyl group; and R.sub.1 represents a hydrogen atom.
3. The magenta toner according to claim 1, wherein the structure
represented by formula (5) is a structure represented by formula
(7) below ##STR00040## where, in formula (7), each R.sub.1
independently represents a hydrogen atom, a halogen atom, an alkyl
group, an alkoxy group, a trifluoromethyl group, a cyano group, or
a hydroxyl group; each R.sub.9 independently represents an alkyl
group, a phenyl group, an OR.sub.4 group, or an NR.sub.5R.sub.6
group; R.sub.4 to R.sub.6 each independently represent a hydrogen
atom, an alkyl group, a phenyl group, or an aralkyl group; p
represents an integer of 2 or 3; q represents an integer of 3 or 4;
p+q=6; and L represents a divalent linking group that binds to the
polymer portion.
4. The magenta toner according to claim 3, where R.sub.1 in formula
(7) represents a hydrogen atom and q represents 3 or 4.
5. The magenta toner according to claim 1, wherein the magenta
pigment is a pigment represented by formula (8): ##STR00041##
where, in formula (8), R.sub.31 to R.sub.38 independently represent
a hydrogen atom, a chlorine atom, or a methyl group.
6. The magenta toner according to claim 1, wherein the magenta
pigment is a pigment represented by formula (9): ##STR00042##
where, in formula (9), R.sub.39 to R.sub.44 independently represent
a hydrogen atom, a chlorine atom, a tert-butyl group, a cyano
group, or a phenyl group.
7. The magenta toner according to claim 1, wherein the toner
particles are prepared by a suspension polymerization method or a
suspension granulation method.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. patent
application Ser. No. 13/777,764 filed Feb. 26, 2013, which claims
priority to Japanese Patent Application No. 2012-043073 filed Feb.
29, 2012, each of which are hereby incorporated by reference herein
in their entireties.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a magenta toner for use in
electrophotography, electrostatic recording, electrostatic
printing, or toner jet recording, the magenta toner containing a
compound having an azo skeleton as a dispersant.
[0004] 2. Description of the Related Arts
[0005] Magenta pigments typically used as colorants for magenta
toners are difficult to disperse due to small pigment particle
size. If the pigment is not sufficiently dispersed in the toner
particles, the coloring power of the toner particles is degraded.
This has also led to other problems such as significant fluctuation
in charging properties due to environmental changes such as changes
in temperature and humidity and a high incidence of "fogging", that
is, development of the toner on background portions of images.
[0006] Japanese Patent Laid-Open No. 2006-30760 discloses a
technique for dispersing a pigment in a toner. According to this
technique, a particular polymer dispersant is used in combination
with a magenta pigment to enhance the dispersibility of the magenta
pigment and improve the coloring property and charging property of
the toner. Japanese Patent Laid-Open No. 11-231572 discloses a
method for satisfactorily dispersing a coloring material in a toner
by use of a pigment derivative and a polymer dispersant. Japanese
Patent Laid-Open No. 2003-202697 discloses a pigment dispersant in
which a quinacridone is covalently bonded to a polymer.
[0007] Japanese Patent Laid-Open No. 2-210459 proposes a method
that uses a diketopyrrolopyrrole-based pigment instead of a
quinacridone pigment in order to improve the charging stability of
the magenta toner and suppress fogging.
SUMMARY OF THE INVENTION
[0008] The polymer dispersant disclosed in Japanese Patent
Laid-Open No. 2006-30760 generally has poor compatibility with
hydrophobic binder resins (such as polystyrene) and has a problem
in that the pigment is not sufficiently dispersed.
[0009] The method that uses the pigment derivative and the polymer
dispersant disclosed in Japanese Patent Laid-Open No. 11-231572
results in formation of a highly polar salt on a pigment surface
because the pigment is dispersed by acid-base interaction. Thus,
when a toner is produced in water, the pigment localizes on the
toner surfaces and causes dispersion failure. This results in
instable charging, which has been a problem.
[0010] The method that uses a dispersant in which a quinacridone is
covalently bonded to a polymer disclosed in Japanese Patent
Laid-Open No. 2003-202697 needs further improvements since the
recent requirements for higher image quality are not sufficiently
met although a certain dispersing effect is exhibited for
quinacridone pigments.
[0011] According to the method disclosed in Japanese Patent
Laid-Open No. 2-210459, the dispersibility of the
diketopyrrolopyrrole-based pigment in the toner is still
insufficient and fogging on images has not been satisfactorily
prevented.
[0012] The present invention provides a magenta toner having high
coloring power in which the dispersibility of a magenta pigment in
the binder resin is improved. A magenta toner that suppresses
fogging and offers high transfer efficiency is also provided. A
magenta toner comprising toner particles, each of which includes a
binder resin, a compound and a magenta pigment,
the compound has a structure, a polymer portion of which has a
monomer unit represented by formula (2) and is bound to a structure
represented by formula (1);
##STR00001##
where, in formula (1), at least one of R.sub.2, R.sub.3, Ar.sub.1,
and Ar.sub.2 is bound to the polymer portion directly or through a
linking group, wherein each R.sub.1 independently represents a
hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a
trifluoromethyl group, a cyano group, or a hydroxyl group; R.sub.2
and R.sub.3 not bound to the polymer portion independently
represent a monovalent group selected from the group consisting of
an alkyl group, a phenyl group, an OR.sub.4 group, and an
NR.sub.5R.sub.6 group; R.sub.4 to R.sub.6 independently represent a
hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group;
Ar.sub.1 and Ar.sub.2 not bound to the polymer portion
independently represent an aryl group; wherein any one of R.sub.2
and R.sub.3 bound to the polymer portion independently represents a
divalent group, a hydrogen atom of which is removed from the
corresponding monovalent group of any one of R.sub.2 and R.sub.3;
any one of Ar.sub.1 and Ar.sub.2 bound to the polymer portion
independently represents a divalent group, a hydrogen atom of which
is removed from the corresponding aryl group of any one of Ar.sub.1
and Ar.sub.2; m represents an integer of 3 or 4; n represents an
integer of 1 or 2; and n+m=5,
##STR00002##
where, in formula (2), R.sub.7 represents a hydrogen atom or an
alkyl group; and R.sub.8 represents a phenyl group, a carboxyl
group, a carboxylic acid ester group, or a carboxylic acid amide
group.
[0013] Further features of the present invention will become
apparent from the following description of exemplary embodiments
(with reference to the attached drawings).
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a graph showing a .sup.1H NMR spectrum of a
compound (116) having an azo skeleton in CDCl.sub.3 at room
temperature at 400 MHz.
[0015] FIG. 2 is a graph showing a .sup.1H NMR spectrum of a
compound (129) having an azo skeleton in CDCl.sub.3 at room
temperature at 400 MHz.
[0016] FIG. 3 is a graph showing a .sup.1H NMR spectrum of a
compound (174) having an azo skeleton in CDCl.sub.3 at room
temperature at 400 MHz.
[0017] FIG. 4 is a graph showing a .sup.1H NMR spectrum of a
compound (176) having an azo skeleton in CDCl.sub.3 at room
temperature at 400 MHz.
DESCRIPTION OF THE EMBODIMENTS
[0018] The present invention will now be described in detail
through embodiments.
[0019] A toner according to the present invention comprises toner
particles, each of which includes a magenta pigment, a binder
resin, and a compound having a structure, a polymer portion of
which has a monomer unit represented by formula (2) and is bound to
a structure represented by formula (1) directly or through a
linking group,
##STR00003##
[In formula (1), at least one of R.sub.2, R.sub.3, Ar.sub.1, and
Ar.sub.2 is bound to the polymer portion directly or through a
linking group, wherein each R.sub.1 independently represents a
hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a
trifluoromethyl group, a cyano group, or a hydroxyl group; R.sub.2
and R.sub.3 not bound to the polymer portion independently
represent a monovalent group selected from the group consisting of
an alkyl group, a phenyl group, an OR.sub.4 group, and an
NR.sub.5R.sub.6 group; R.sub.4 to R.sub.6 independently represent a
hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group;
Ar.sub.4 and Ar.sub.2 independently represent an aryl group;
wherein any one of R.sub.2 and R.sub.3 bound to the polymer portion
independently represents a divalent group, a hydrogen atom of which
is removed from the corresponding monovalent group of any one of
R.sub.2 and R.sub.3; any one of Ar.sub.4 and Ar.sub.2 bound to the
polymer portion independently represents a divalent group, a
hydrogen atom of which is removed from the corresponding aryl group
of any one of Ar.sub.1 and Ar.sub.2; m represents an integer of 3
or 4; n represents an integer of 1 or 2; and n+m=5]
##STR00004##
[In formula (2), R.sub.7 represents a hydrogen atom or an alkyl
group; and R.sub.8 represents a phenyl group, a carboxyl group, a
carboxylic acid ester group, or a carboxylic acid amide group].
[0020] The present invention provides a magenta toner that
contains, as a dispersant, a compound in which a structure
represented by formula (1) is linked to a polymer portion having a
monomer unit represented by formula (2). This compound has affinity
to water-insoluble solvents, polymerizable monomers, and binder
resins for toners and high affinity to magenta pigments. Thus, when
this compound is used as a pigment dispersant, the magenta pigment
is satisfactorily dispersed in the binder resin and a magenta toner
having high coloring power is provided. Moreover, addition of the
compound to the magenta toner suppresses fogging and a magenta
toner that offers high transfer efficiency is provided.
[0021] The structure represented by formula (1) may also be
referred to as "azo skeleton structure". The compound in which the
azo skeleton structure is bonded to a polymer portion having a
monomer unit represented by formula (2) may also be referred to as
"compound having an azo skeleton structure". The polymer portion
having a monomer unit represented by formula (2) not bonded to the
azo skeleton structure may be simply referred to as "polymer
portion".
[0022] The present invention will now be described in detail.
[0023] First, the structure of the compound having an azo skeleton
structure is described. The compound having an azo skeleton
structure is constituted by an azo skeleton structure represented
by formula (1) above having high affinity to magenta pigments and a
polymer portion having a monomer unit represented by formula (2)
above having high affinity to water-insoluble solvents.
[0024] The azo skeleton structure is first described in detail.
[0025] Examples of the halogen atom for R.sub.1 in formula (1)
above include a fluorine atom, a chlorine atom, a bromine atom, and
an iodine atom.
[0026] Examples of the alkyl group for R.sub.1 in formula (1) above
include linear, branched, or cyclic alkyl groups such as a methyl
group, an ethyl group, an n-propyl group, an n-butyl group, an
n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl
group, a sec-butyl group, a tert-butyl group, and a cyclohexyl
group.
[0027] Examples of the alkoxy group for R.sub.1 in formula (1)
include linear or branched alkoxy groups such as a methoxy group,
an ethoxy group, an n-propoxy group, an n-butoxy group, and an
isopropoxy group.
[0028] R.sub.1 in formula (1) can be freely selected from the
above-listed substituents, a trifluoromethyl group, a cyano group,
a hydroxyl group, and a hydrogen atom but is preferably a hydrogen
atom in view of affinity to the magenta pigment.
[0029] Examples of the substitution positions of the acylacetamide
groups in formula (1) when m is 4 and n is 1 include cases where
the acylacetamide groups are ortho, meta, or para to each other.
The affinity to the magenta pigment is the same irrespective of
whether the positions are ortho, meta, or para. When m is 3 and n
is 2, the acylacetamide groups may be substituted in the 1, 2, and
3 positions, 1, 2, and 4 positions, or 1, 3, and 5 positions, for
example. The affinity to the magenta pigment is also the same
irrespective of whether the acylacetamide groups are substituted in
the 1, 2, and 3 positions, 1, 2, and 4 positions, or 1, 3, and 5
positions.
[0030] Examples of the alkyl group for R.sub.2 and R.sub.3 in
formula (1) include linear, branched, or cyclic alkyl groups such
as a methyl group, an ethyl group, an n-propyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an isopropyl group, an
isobutyl group, a sec-butyl group, a tert-butyl group, and a
cyclohexyl group.
[0031] The substituents R.sub.2 and R.sub.3 in formula (1) may be
further substituted with substituents as long as the affinity to
the magenta pigments is not significantly degraded. Examples of
such substituents include a halogen atom, a nitro group, an amino
group, a hydroxyl group, a cyano group, and a trifluoromethyl
group.
[0032] Examples of the alkyl group for R.sub.4 to R.sub.6 in
formula (1) include linear, branched, or cyclic alkyl groups such
as a methyl group, an ethyl group, an n-propyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an isopropyl group, an
isobutyl group, a sec-butyl group, a tert-butyl group, and a
cyclohexyl group.
[0033] Examples of the aralkyl group for R.sub.4 to R.sub.6 in
formula (1) include a benzyl group and a phenethyl group.
[0034] R.sub.4 to R.sub.6 in formula (1) can be freely selected
from the substituents listed above, a hydrogen atom, and a phenyl
group.
[0035] Ar.sub.1 and Ar.sub.e in formula (1) each represent an aryl
group such as a phenyl group or a naphthyl group. These
substituents may be further substituted with substituents as long
as the affinity to the magenta pigment is not significantly
degraded. Examples of such substituents include an alkyl group, an
alkoxy group, a halogen atom, a hydroxyl group, a cyano group, a
trifluoromethyl group, a carboxyl group, a carboxylic acid ester
group, and a carboxylic acid amide group.
[0036] At least one of R.sub.2, R.sub.3, Ar.sub.1, and Ar.sub.2 in
formula (1) is bound to the polymer portion directly or through a
linking group. At least one of R.sub.2, R.sub.3, Ar.sub.1, and
Ar.sub.2 in formula (1) is preferably bound to the polymer portion
through a linking group. Any one of R.sub.2 and R.sub.3 bound to
the polymer portion independently represents a divalent group, a
hydrogen atom of which is removed from the corresponding monovalent
group of any one of R.sub.2 and R.sub.3. Any one of Ar.sub.1 and
Ar.sub.2 bound to the polymer portion independently represents a
divalent group, a hydrogen atom of which is removed from the
corresponding aryl group of any one of Ar.sub.1 and Ar.sub.2. In
view of affinity to the magenta pigment, the structure represented
by formula (1) may be a structure represented by formula (3) below.
In other words, in formula (1), Ar.sub.1 and Ar.sub.2 may each
represent a phenyl group, and at least one of hydrogen atoms of the
phenyl groups may be substituted with a linking group to form a
link to the polymer portion.
##STR00005##
[In formula (3), R.sub.1 is the same as R.sub.1 in formula (1);
R.sub.9 and R.sub.10 independently represent an alkyl group, a
phenyl group, an OR.sub.4 group, or an NR.sub.5R.sub.6 group;
R.sub.4 to R.sub.6 are the same as R.sub.4 to R.sub.6 in formula
(1); R.sub.11 to R.sub.20 independently represent a linking group
or a monovalent group selected from the group consisting of a
hydrogen atom, a COOR.sub.21 group, a CONR.sub.22R.sub.23 group, a
NHCOR.sub.24 group, and an OR.sub.25 group; R.sub.21 to R.sub.25
each independently represent a hydrogen atom, an alkyl group, an
aryl group, or an aralkyl group; wherein at least one of R.sub.11
to R.sub.20 is the linking group that binds to the polymer portion;
m represents an integer of 3 or 4; n represents an integer of 1 or
2; and n+m=5].
[0037] In formula (3), R.sub.11 to R.sub.20 may each be freely
selected from a hydrogen atom, a COOR.sub.21 group, a
CONR.sub.22R.sub.23 group, a NHCOR.sub.24 group, and an OR.sub.25
group but preferably at least one of R.sub.11 to R.sub.20 is a
COOR.sub.21 group or a CONR.sub.22R.sub.23 group from the viewpoint
of affinity to the magenta pigment.
[0038] Examples of the alkyl group for R.sub.21 to R.sub.25 in
formula (3) include linear, branched, or cyclic alkyl groups such
as a methyl group, an ethyl group, an n-propyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an isopropyl group, an
isobutyl group, a sec-butyl group, a tert-butyl group, and a
cyclohexyl group.
[0039] Examples of the aryl group for R.sub.21 to R.sub.25 in
formula (3) include a phenyl group and a naphthyl group.
[0040] Examples of the aralkyl group for R.sub.21 to R.sub.25 in
formula (3) include a benzyl group and a phenethyl group.
[0041] R.sub.21 to R.sub.25 in formula (3) may be freely selected
from the substituents listed above and a hydrogen atom. From the
viewpoint of the affinity to the magenta pigment, R.sub.21 is
preferably a methyl group and R.sub.22 and R.sub.23 are preferably
each independently a methyl group or a hydrogen atom.
[0042] Examples of the alkyl group for R.sub.9 and R.sub.10 in
formula (3) include linear, branched, or cyclic alkyl groups such
as a methyl group, an ethyl group, an n-propyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an isopropyl group, an
isobutyl group, a sec-butyl group, a tert-butyl group, and a
cyclohexyl group.
[0043] The substituents R.sub.9 and R.sub.10 in formula (3) may be
further substituted with substituents as long as affinity to the
magenta pigment is not significantly degraded. Examples of such
substituents include a halogen atom, a nitro group, an amino group,
a hydroxyl group, a cyano group, and a trifluoromethyl group.
[0044] R.sub.9 and R.sub.10 in formula (3) can each be freely
selected from the substituents listed above but are preferably each
independently a methyl group from the viewpoint of affinity to the
magenta pigment.
[0045] The structure represented by formula (3) is more preferably
a structure represented by any one of formulae (4) to (7) below
from the viewpoint of affinity to the magenta pigment. In other
words, the azo skeleton structure portion is preferably bonded to
the polymer portion through a linking group L as shown in formulae
(4) to (7) below.
##STR00006##
[In formula (4), R.sub.1 is the same as R.sub.1 in formula (1);
R.sub.9 and R.sub.10 are the same as R.sub.9 and R.sub.10 in
formula (3); R.sub.26 to R.sub.30 independently represent a
hydrogen atom, a COOR.sub.21 group, a CONR.sub.22R.sub.23 group, a
NHCOR.sub.24 group, or an OR.sub.25 group; R.sub.21 to R.sub.25 are
the same as R.sub.21 to R.sub.25 in formula (3); 1 represents 4;
and L represents a divalent linking group that binds to the polymer
portion.]
##STR00007##
[In formula (5), R.sub.1 is the same as R.sub.1 in formula (1);
R.sub.9 and R.sub.10 are the same as R.sub.9 and R.sub.10 in
formula (3); R.sub.26 to R.sub.30 independently represent a
hydrogen atom, a COOR.sub.21 group, a CONR.sub.22R.sub.23 group, a
NHCOR.sub.24 group, or an OR.sub.25 group; R.sub.21 to R.sub.25 are
the same as R.sub.21 to R.sub.25 in formula (3); 1 represents 4;
and L represents a divalent linking group that binds to the polymer
portion.]
##STR00008##
[In formula (6), R.sub.1 is the same as R.sub.1 in formula (1);
R.sub.9 is the same as R.sub.9 in formula (3); p represents an
integer of 2 or 3; q represents an integer of 3 or 4; p+q=6; and L
represents a divalent linking group that binds to the polymer.]
##STR00009##
[In formula (7), R.sub.1 is the same as R.sub.1 in formula (1);
R.sub.9 is the same as R.sub.9 in formula (3); p represents an
integer of 2 or 3; q represents an integer of 3 or 4; p+q=6; and L
represents a divalent linking group that binds to the polymer
portion.].
[0046] L in formulae (4) to (7) above is a divalent linking group
and links the azo skeleton structure portion to the polymer
portion.
[0047] According to the structures represented by formulae (4) and
(6), the azo skeleton structure is linked to the polymer portion
through L at one position. According to the structures of formulae
(5) and (7), links are formed at two positions.
[0048] L in formulae (4) to (7) may be any divalent linking group
but preferably includes a carboxylic acid ester bond, a carboxylic
acid amide bond, or a sulfonic acid ester bond. This is because the
reaction that can induce formation of such bonds is convenient as
the reaction for linking the azo skeleton structure to the polymer
portion.
[0049] The substitution position of L in formulae (4) to (7) may be
that at least one L is in meta or para position with respect to the
hydrazo group from the viewpoint of the affinity to the magenta
pigment.
[0050] R.sub.26 to R.sub.30 in formula (4) or (5) may be selected
from a hydrogen atom, a COOR.sub.21 group, a CONR.sub.22R.sub.23
group, a NHCOR.sub.24 group, and an OR.sub.25 group. From the
viewpoint of affinity to the magenta pigment, at least one of
R.sub.26 to R.sub.30 is preferably a COOR.sub.21 group or a
CONR.sub.22R.sub.23 group.
[0051] The polymer portion will now be described in detail.
[0052] The alkyl group for R.sub.7 in formula (2) may be any alkyl
group. Examples thereof include linear, branched, or cyclic alkyl
groups such as a methyl group, an ethyl group, an n-propyl group,
an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl
group, an isobutyl group, a sec-butyl group, a tert-butyl group,
and a cyclohexyl group.
[0053] R.sub.7 in formula (2) may be freely selected from the
substituents listed above and a hydrogen atom but is preferably a
hydrogen atom or a methyl group from the viewpoint of
polymerizability of the monomer unit.
[0054] The carboxylic acid ester group for R.sub.8 in formula (2)
may be any carboxylic acid ester group. Examples thereof include
linear or branched ester groups such as a methyl ester group, an
ethyl ester group, an n-propyl ester group, an isopropyl ester
group, an n-butyl ester group, an isobutyl ester group, a sec-butyl
ester group, a tert-butyl ester group, a dodecyl ester group, a
2-ethylhexyl ester group, a stearyl ester group, a phenyl ester
group, a 2-hydroxyethyl ester group, an octyl ester group, a nonyl
ester group, a decyl ester group, an undecyl ester group, a dodecyl
ester group, a hexadecyl ester group, an octadecyl ester group, an
eicosyl ester group, and a behenyl ester group.
[0055] Examples of the carboxylic acid amide group for R.sub.8 in
formula (2) include amide groups such as a N-methylamide group, a
N,N-dimethylamide group, a N,N-diethylamide group, a
N-isopropylamide group, a N-tert-butylamide group, a N-phenylamide
group, a N-(2-ethylhexyl)amide group, and a
N,N-di(2-ethylhexyl)amide group.
[0056] The substituent R.sub.8 in formula (2) may be further
substituted as long as the polymerizability of the monomer unit is
not impaired and the solubility of the compound having the azo
skeleton structure is not significantly degraded. Examples of the
substituents include alkoxy groups such as a methoxy group and an
ethoxy group, amino groups such as N-methylamino group and a
N,N-dimethylamino group, acyl groups such as an acetyl group, and
halogen atoms such as a fluorine atom and a chlorine atom.
[0057] R.sub.8 in formula (2) may be freely selected from the
substituents listed above, a phenyl group, and a carboxyl group but
is preferably a phenyl group or a carboxylic acid ester group from
the viewpoints of the dispersibility of the compound having an azo
skeleton structure into the binder resin of the toner and the
compatibility between the compound and the binder resin.
[0058] The affinity of the polymer portion to the dispersion medium
can be controlled by changing the content of the monomer unit
represented by formula (2). When the dispersion medium is a
nonpolar solvent such as styrene, the content of the monomer unit
represented by formula (2) with R.sub.8 representing a phenyl group
may be increased from the viewpoint of affinity to the dispersion
medium. When the dispersion medium is a solvent that has a
particular degree of polarity such as an acrylic acid ester, the
content of the monomer unit represented by formula (2) with R.sub.8
representing a carboxyl group, a carboxylic acid ester group, or a
carboxylic acid amide group may be increased from the viewpoint of
affinity to the dispersion medium.
[0059] The number-average molecular weight of the polymer portion
may be 500 or more from the viewpoint of improving the
dispersibility of the magenta pigment. The larger the molecular
weight, the higher the effect of improving the dispersibility of
the magenta pigment. However, at an excessively high molecular
weight, the affinity to water-insoluble solvents tends to be
degraded. Thus, the number-average molecular weight of the polymer
portion is preferably up to 200000 and more preferably in the range
of 2000 to 50000 considering the ease of production.
[0060] As disclosed in PCT Japanese Translation Patent Publication
No. 2003-531001, the dispersibility can be improved by using a
polyoxyalkylene carbonyl-based dispersant having a branched
aliphatic chain introduced at a terminus. If the above-described
polymer portion can be made telechelic by a method such as atom
transfer radical polymerization (ATRP) described below, a branched
aliphatic chain can be introduced to a terminus and the
dispersibility may be improved in some cases.
[0061] The substitution positions of the azo skeleton structures in
the compound having the azo skeleton structure may be scattered at
random or may be localized to form one or more blocks at a
terminus.
[0062] The larger the number of azo skeleton structures substituted
in the compound having the azo skeleton structure, the higher the
affinity to the magenta pigment. However, if the number of the azo
skeleton structures is excessively large, affinity to
water-insoluble solvents is degraded. Thus, the number of the azo
skeleton structures is preferably within the range of 0.2 to 10 and
more preferably within the range of 0.2 to 5 per 100 of monomers
constituting the polymer portion.
[0063] The azo skeleton structure represented by formula (1) has
tautomers represented by formulae (10) and (11) below as shown
below. These tautomers are also within the range of the present
invention.
##STR00010##
[In formulae (10) and (11), R.sub.1 to R.sub.3, Ar.sub.1, Ar.sub.2,
m, and n are the same as R.sub.1 to R.sub.3, Ar.sub.1, Ar.sub.2, m,
and n in formula (1)].
[0064] Examples of the method for synthesizing the compound having
an azo skeleton structure include the following methods (i) to
(iv).
Method (i): An example scheme of method (i) is described below in
detail. First, an azo skeleton structure and a polymer portion are
separately synthesized in advance and then linked to each other by
condensation reaction or the like so as to synthesize a compound
having an azo skeleton structure.
##STR00011## ##STR00012##
[In formulae (12) to (21), R.sub.1 to R.sub.3, Ar.sub.1, m, and n
are the same as R.sub.1 to R.sub.3, Ar.sub.1, m, and n in formula
(1); Ar.sub.3 in formulae (20) and (21) represents an arylene
group; X.sub.1 in formula (13) and X.sub.2 in formula (18) each
represent a leaving group; P.sub.1 represents a polymer portion
having a monomer unit represented by general formula (2); X.sub.3
in formulae (20) and (21) represents a substituent that forms the
divalent linking group L by reacting with P.sub.1; and r represents
an integer of 1 or 2.]
[0065] In the scheme described as an example above, the compound
having an azo skeleton structure can be synthesized through step 1
of amidating a nitroaniline derivative represented by formula (12)
and an acetoacetic acid analog represented by formula (13) to
synthesize an intermediate (14) which is an acylacetanilide analog;
step 2 of performing diazo coupling of the intermediate (14) and an
aniline derivative (15) to synthesize an azo compound (16); step 3
of reducing the nitro groups in the azo compound (16) to synthesize
an intermediate (17) which is an aniline analog; step 4 of
amidating the intermediate (17) and an acetoacetic acid analog
represented by formula (18) to synthesize an intermediate (19)
which is an acylacetanilide analog; step 5 of performing diazo
coupling of the intermediate (19) and an aniline derivative (20) to
synthesize an azo compound (21); and step 6 of performing
condensation reaction of the azo skeleton and a polymer portion
P.sub.1.
[0066] First, step 1 is described. A common method may be employed
in step 1 (e.g., see Datta E. Ponde and four others, The Journal of
Organic Chemistry, (USA), American Chemical Society, 1998, vol. 63,
No. 4, pp. 1058-1063). When R.sub.2 in formula (14) is a methyl
group, synthesis is possible by using a diketone instead of the
material (13) (e.g., see Kiran Kumar Solingapuram Sai and two
others, The Journal of Organic Chemistry, (USA), American Chemical
Society, 2007, vol. 72, No. 25, pp. 9761-9764).
[0067] There are a wide variety of commercially available products
for the nitroaniline derivative (12) and the acetoacetic acid
analog (13). The nitroaniline derivative (12) and the acetoacetic
acid analog (13) are also easy to synthesize by common methods.
[0068] This step can be performed in the absence of any solvent but
is preferably performed in the presence of a solvent to suppress
rapid progress of the reaction. The solvent may be any solvent that
does not inhibit the reaction and examples thereof include alcohols
such as methanol, ethanol, and propanol, esters such as methyl
acetate, ethyl acetate, and propyl acetate, ethers such as diethyl
ether, tetrahydrofuran, and dioxane, hydrocarbons such as benzene,
toluene, xylene, hexane, and heptane, halogen-containing
hydrocarbons such as dichloromethane, dichloroethane, and
chloroform, amides such as N,N-dimethylformamide,
N-methylpyrrolidone, and N,N-dimethylimidazolidinone, nitriles such
as acetonitrile and propionitrile, acids such as formic acid,
acetic acid, and propionic acid, and water. Two or more of these
solvents may be used as a mixture. In blending the solvents, the
blend ratio may be freely determined depending on the solubility of
the substrate. The amount of the solvent used may be freely
determined but is preferably 1.0 to 20 times the amount of the
compound represented by formula (12) on a mass basis from the
viewpoint of the reaction rate.
[0069] This step is usually performed within the temperature range
of 0.degree. C. to 250.degree. C. and is usually completed within
24 hours.
[0070] Next, step 2 is described. In step 2, a common method may be
employed. For example, an aniline derivative (15) is reacted with a
diazotizing agent such as sodium nitrite or nitrosylsulfuric acid
in a methanol solvent in the presence of an inorganic acid such as
hydrochloric acid or sulfuric acid so as to synthesize a
corresponding a diazonium salt. This diazonium salt is coupled with
the intermediate (14) to synthesize the azo compound (16).
[0071] There are a wide variety of commercially available products
for the aniline derivative (15). The aniline derivative (15) is
also easy to synthesize by common methods.
[0072] This step can be performed in the absence of any solvent but
is preferably conducted in the presence of a solvent to suppress
rapid progress of the reaction. The solvent may be any solvent that
does not inhibit the reaction. Examples thereof include alcohols
such as methanol, ethanol, and propanol, esters such as methyl
acetate, ethyl acetate, and propyl acetate, ethers such as diethyl
ether, tetrahydrofuran, and dioxane, hydrocarbons such as benzene,
toluene, xylene, hexane, and heptane, halogen-containing
hydrocarbons such as dichloromethane, dichloroethane, and
chloroform, amides such as N,N-dimethylformamide,
N-methylpyrrolidone, and N,N-dimethylimidazolidinone, nitriles such
as acetonitrile and propionitrile, acids such as formic acid,
acetic acid, and propionic acid, and water. Two or more of these
solvents may be used as a mixture. In blending the solvents, the
blend ratio may be freely determined depending on the solubility of
the substrate. The amount of the solvent used may be freely
determined but is preferably 1.0 to 20 times the amount of the
compound represented by formula (15) on a mass basis from the
viewpoint of the reaction rate.
[0073] This step is usually performed within the temperature range
of -50.degree. C. to 100.degree. C. and is usually completed within
24 hours.
[0074] Step 3 will now be described. In step 3, a common method may
be employed (an example of a method that uses a metal compound and
the like is described in "Jikken Kagaku Kouza [Experimental
Chemistry]", published by Maruzen Publishing Co., Ltd., first
edition, vol. 17-2, pp. 162-179 and an example of a catalytic
hydrogenation method is described in "Jikken Kagaku Kouza
[Experimental Chemistry]", published by Maruzen Publishing Co.,
Ltd., first edition, vol. 15, pp. 390-448 or International
Publication No. 2009/060886 pamphlet).
[0075] This step can be performed in the absence of any solvent but
is preferably performed in the presence of a solvent to suppress
rapid progress of the reaction. The solvent may be any solvent that
does not inhibit the reaction and examples thereof include alcohols
such as methanol, ethanol, and propanol, esters such as methyl
acetate, ethyl acetate, and propyl acetate, ethers such as diethyl
ether, tetrahydrofuran, and dioxane, hydrocarbons such as benzene,
toluene, xylene, hexane, and heptane, and amides such as
N,N-dimethylformamide, N-methylpyrrolidone, and
N,N-dimethylimidazolidinone. Two or more of these solvents may be
used as a mixture. In blending the solvents, the blend ratio may be
freely determined. The amount of the solvent used may be freely
determined depending on the solubility of the substrate but is
preferably 1.0 to 20 times the amount of the compound represented
by formula (16) on a mass basis from the viewpoint of the reaction
rate.
[0076] This step is usually performed within the temperature range
of 0.degree. C. to 250.degree. C. and is usually completed within
24 hours.
[0077] Next, step 4 is described. In step 4, the same method as in
step 1 is employed to synthesize the intermediate (19) which is an
acylacetanilide analog.
[0078] Next, step 5 is described. In step 5, the same method as in
step 2 is employed to synthesize the azo compound (21).
[0079] There are a wide variety of commercially available products
for the aniline derivative (20). The aniline derivative (20) is
also easy to synthesize by common methods.
[0080] Next, a method for synthesizing the polymer portion P.sub.1
used in step 6 is described. A common polymerization method may be
employed in synthesizing the polymer portion P.sub.1 (e.g., see
Krzysztof Matyjaszewski and one other, Chemical Reviews, (USA),
American Chemical Society, 2001, vol. 101, pp. 2921-2990).
[0081] Specific examples thereof include radical polymerization,
cationic polymerization, and anionic polymerization. Preferably,
radical polymerization is employed due to ease of production.
[0082] Radical polymerization may be conducted by using a radical
polymerization initiator, by applying radiation, a laser beam, or
the like, by using a photopolymerization initiator and applying
light, or by heating, for example.
[0083] The radical polymerization initiator may be any that can
generate a radical and initiate polymerization reaction and may be
selected from among the compounds that generate radicals due to
heat, light, radiation, redox reaction, and the like. Examples
thereof include azo compounds, organic peroxides, inorganic
peroxides, organic metal compounds, and photopolymerization
initiators. Specific examples thereof include azo-based
polymerization initiators such as 2,2'-azobis(isobutyronitrile),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and
2,2'-azobis(2,4-dimethylvaleronitrile), organic peroxide-based
polymerization initiators such as benzoyl peroxide, di-tert-butyl
peroxide, tert-butylperoxyisopropyl carbonate, tert-hexylperoxy
benzoate, and tert-butylperoxy benzoate, inorganic peroxide-based
polymerization initiators such as potassium persulfate and ammonium
persulfate, and redox initiators such as those based on hydrogen
peroxide-ferrous iron, benzoyl peroxide-dimethylaniline, and
cerium(IV) salt-alcohol. Examples of the photopolymerization
initiator include benzophenones, benzoin ethers, acetophenones, and
thioxanthones. Two or more of these radical polymerization
initiators may be used in combination.
[0084] The amount of the polymerization initiator used may be
adjusted within the range of 0.1 to 20 parts by mass per 100 parts
by mass of the monomers so that a copolymer having a desired
molecular weight distribution is obtained.
[0085] The polymer portion represented by P.sub.1 can be prepared
by any method such as solution polymerization, suspension
polymerization, emulsion polymerization, dispersion polymerization,
precipitation polymerization, and bulk polymerization. Solution
polymerization in a solvent that can dissolve all the components
used in production is preferred. Examples of the solvent that can
be used include polar organic solvents such as alcohols, e.g.,
methanol, ethanol, and 2-propanol, ketones, e.g., acetone and
methyl ethyl ketone, ethers, e.g., tetrahydrofuran and diethyl
ether, ethylene glycol monoalkyl ethers or acetates thereof,
propylene glycol monoalkyl ethers or acetates thereof, and
diethylene glycol monoalkyl ethers; and, if appropriate, nonpolar
solvents such as toluene and xylene. These solvents can be used
alone or in combination. Preferably, solvents having a boiling
point within the range of 100.degree. C. to 180.degree. C. are used
alone or in combination among these solvents.
[0086] The polymerization temperature is not particularly limited
since a preferable temperature range differs depending on types of
initiators used. The temperature range for polymerization is
usually -30.degree. C. to 200.degree. C. and is preferably
40.degree. C. to 180.degree. C.
[0087] The molecular weight distribution and molecular structure of
the polymer portion represented by P.sub.1 can be controlled by
common methods. Examples of such methods include a method in which
an addition fragmentation type chain transfer agent is used (refer
to Japanese Patent Nos. 4254292 and 3721617), a nitroxide-mediated
polymerization (NMP) method in which dissociation and bonding of
amine oxide radicals are utilized [see Craig J. Hawker and two
others, Chemical Reviews, (USA), American Chemical Society, 2001,
vol. 101, pp. 3661-3688], an atom transfer radial polymerization
(ATRP) method in which polymerization is conducted by using a metal
catalyst, a ligand, and a halogen compound as a polymerization
initiator [see Masami Kamigaito and two others, Chemical Reviews,
(USA), American Chemical Society, 2001, vol. 101, pp. 3689-3746], a
reversible addition fragmentation chain transfer (RAFT) method that
uses a dithiocarboxylic acid ester, a xanthate compound, or the
like as a polymerization initiator (e.g., PCT Japanese Translation
Patent Publication No. 2000-515181), a MADIX (macromolecular design
via interchange of xanthates) method (e.g., see International
Publication No. 99/05099 pamphlet), and a degenerative transfer
(DT) method [for example, see Atsushi Goto and six others, Journal
of The American Chemical Society, (USA), American Chemical Society,
2003, vol. 125, pp. 8720-8721]. A polymer portion P.sub.1 with
controlled molecular weight distribution and molecular structure
can be produced by these methods.
[0088] Next, step 6 is described. In step 6, a common method may be
employed. For example, a polymer portion P.sub.1 having a carboxyl
group and an azo compound (21) with X.sub.3 representing a
substituent having a hydroxyl group may be used to synthesize a
compound having an azo skeleton structure with a linking group L
having a carboxylic acid ester bond. Alternatively, a polymer
portion P.sub.1 having a hydroxyl group and an azo compound (21)
with X.sub.3 representing a substituent having a sulfonic acid
group may be used to synthesize a compound having an azo skeleton
structure with a linking group L having a sulfonic acid ester bond.
Yet alternatively, a polymer portion P.sub.1 having a carboxyl
group and an azo compound (21) with X.sub.3 representing a
substituent having an amino group may be used to synthesize a
compound having an azo skeleton structure with a linking group L
having a carboxylic acid amide bond. Specific examples of such
methods include a method that uses a dehydration condensation
agent, e.g., 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
hydrochloride (for example, see Melvin S. Newman and one other, The
Journal of Organic Chemistry, (USA), American Chemical Society,
1961, vol. 26, No. 7, pp. 2525-2528) and a Schotten-Baumann method
(for example, see Norman O. V. Sonntag, Chemical Reviews, (USA),
American Chemical Society, 1953, vol. 52, No. 2, pp. 237-416).
[0089] This step can be performed in the absence of any solvent but
is preferably performed in the presence of a solvent to suppress
rapid progress of the reaction. The solvent may be any solvent that
does not inhibit the reaction and examples thereof include ethers
such as diethyl ether, tetrahydrofuran, and dioxane, hydrocarbons
such as benzene, toluene, xylene, hexane, and heptane,
halogen-containing hydrocarbons such as dichloromethane,
dichloroethane, and chloroform, amides such as
N,N-dimethylformamide, N-methylpyrrolidone, and
N,N-dimethylimidazolidinone, and nitriles such as acetonitrile and
propionitrile. Two or more of these solvents may be used as a
mixture depending on the solubility of the substrate. In blending
the solvents, the blend ratio may be freely determined. The amount
of the solvent used may be freely determined but is preferably 1.0
to 20 times the amount of the compound represented by formula (21)
on a mass basis from the viewpoint of the reaction rate.
[0090] This step is usually performed within the temperature range
of 0.degree. C. to 250.degree. C. and is usually completed within
24 hours.
[0091] Next, method (ii) is described in detail by using an example
scheme below. In method (ii), an azo compound having a
polymerizable functional group is prepared in advance and then
copolymerized with a polymerizable monomer that forms a monomer
unit represented by formula (2) to thereby synthesize the compound
having an azo skeleton structure.
##STR00013##
[In formula (21), R.sub.1 to R.sub.3, Ar.sub.1, Ar.sub.3, X.sub.3,
m, n, and r are the same as R.sub.1 to R.sub.3, Ar.sub.1, Ar.sub.3,
X.sub.3, m, n, and r in formula (21) in the scheme of method (i)
above; R.sub.45 in formula (22) represents a hydrogen atom or an
alkyl group; X.sub.4 represents a substituent that reacts with
X.sub.3 in formula (21) to give X.sub.5 in formula (23); R.sub.1 to
R.sub.3, R.sub.45, Ar.sub.1, Ar.sub.3, m, n, and r in formula (23)
are the same as those in formulae (21) and (22); and X.sub.5
represents a divalent linking group L formed by reaction between
X.sub.3 in formula (21) and X.sub.4 in formula (22).]
[0092] In the scheme illustrated above, a compound having an azo
skeleton structure is synthesized through step 7 of reacting an azo
compound (21) with a vinyl group containing compound represented by
formula (22) to synthesize an azo compound (23) having a
polymerizable functional group and step 8 of copolymerizing the azo
compound (23) having a polymerizable functional group and a
polymerizable monomer that forms the monomer unit represented by
formula (2).
[0093] First, step 7 is described. In step 7, the same method as in
step 6 of method (i) above is employed to synthesize an azo
compound (23) having a polymerizable functional group.
[0094] There are a wide variety of commercially available products
for the vinyl group containing compound (22). The vinyl group
containing compound (22) is also easy to synthesize by common
methods.
[0095] Next, step 8 is described. In step 8, the method for
synthesizing the polymer portion P.sub.1 in method (i) can be used
to synthesize a compound having an azo skeleton structure through
copolymerization of the azo compound (23) having a polymerizable
functional group and the polymerizable monomer that forms the
monomer unit represented by formula (2).
[0096] Next, method (ii) is described in detail by using an example
scheme below. In method (iii), an azo compound having a halogen
atom synthesized in advance is used as a polymerization initiator
and copolymerized with a polymerizable monomer that forms the
monomer unit represented by formula (2) so as to synthesize a
compound having the azo skeleton structure.
##STR00014##
[In formula (21), R.sub.1 to R.sub.3, Ar.sub.1, Ar.sub.3, X.sub.3,
m, n, and r are the same as R.sub.1 to R.sub.3, Ar.sub.1, Ar.sub.3,
X.sub.3, m, n, and r in formula (21) in method (i) above; X.sub.6
in formula (24) represents a substituent that reacts with X.sub.3
in formula (21) to give X.sub.7 in formula (25); A represents a
chlorine atom, a bromine atom, or an iodine atom; R.sub.1 to
R.sub.3, Ar.sub.1, Ar.sub.2, X.sub.3, m, n and r in formula (25)
are the same as those in formula (21); and X.sub.7 represents a
divalent linking group L formed by reaction between X.sub.3 in
formula (21) and X.sub.6 in formula (24).]
[0097] In the scheme illustrated above, a compound having an azo
skeleton structure is synthesized through step 9 of reacting an azo
compound (21) with a halogen atom-containing compound represented
by formula (24) to synthesize an azo compound (25) having a halogen
atom and step 10 of polymerizing the halogen atom-containing azo
compound (25) serving as a polymerizing initiator with a
polymerizable monomer that forms the monomer unit represented by
formula (2).
[0098] First, step 9 is described. In step 9, the same method as in
step 6 of method (i) above is employed to synthesize a halogen
atom-containing azo compound (25). For example, a halogen
atom-containing azo skeleton structure (25) having a linking group
L containing a carboxylic acid ester bond can be synthesized by
using a halogen atom-containing compound (24) having a carboxyl
group and an azo compound (21) with X.sub.3 representing a
substituent having a hydroxyl group. Alternatively, a halogen
atom-containing azo skeleton structure (25) having a linking group
L containing a sulfonic acid ester bond can be synthesized by using
a halogen atom-containing compound (24) having a hydroxyl group and
an azo compound (21) with X.sub.3 representing a substituent having
a sulfonic acid group. Yet alternatively, a halogen atom-containing
azo skeleton structure (25) having a linking group L containing a
carboxylic acid amide bond can be synthesized by using a halogen
atom-containing compound (24) having a carboxyl group and an azo
compound (21) with X.sub.3 representing a substituent having an
amino group.
[0099] Examples of the halogen atom-containing compound (24) having
a carboxyl group include chloroacetic acid, .alpha.-chloropropionic
acid, .alpha.-chlorobutyric acid, .alpha.-chloroisobutyric acid,
.alpha.-chlorovaleric acid, .alpha.-chloroisovaleric acid,
.alpha.-chlorocaproic acid, .alpha.-chlorophenylacetic acid,
.alpha.-chlorodiphenylacetic acid,
.alpha.-chloro-.alpha.-phenylpropionic acid,
.alpha.-chloro-.beta.-phenylpropionic acid, bromoacetic acid,
.alpha.-bromopropionic acid, .alpha.-bromobutyric acid,
.alpha.-bromoisobutyric acid, .alpha.-bromovaleric acid,
.alpha.-bromoisovaleric acid, .alpha.-bromocaproic acid,
.alpha.-bromophenylacetic acid, .alpha.-bromodiphenylacetic acid,
.alpha.-bromo-.alpha.-phenylpropionic acid,
.alpha.-bromo-.beta.-phenylpropionic acid, iodoacetic acid,
.alpha.-iodopropionic acid, .alpha.-iodobutyric acid,
.alpha.-iodoisobutyric acid, .alpha.-iodovaleric acid,
.alpha.-iodoisovaleric acid, .alpha.-iodocaproic acid,
.alpha.-iodophenylacetic acid, .alpha.-iododiphenylacetic acid,
.alpha.-iodo-.alpha.-phenylpropionic acid,
.alpha.-iodo-.beta.-phenylpropionic acid, .beta.-chlorobutyric
acid, .beta.-bromoisobutyric acid, iododimethylmethylbenzoic acid,
and 1-chloroethylbenzoic acid. Acid halides and acid anhydrides
thereof can also be used in the present invention.
[0100] Examples of the halogen atom-containing compound (24) having
a hydroxyl group include 1-chloroethanol, 1-bromoethanol,
1-iodoethanol, 1-chloropropanol, 2-bromopropanol,
2-chloro-2-propanol, 2-bromo-2-methylpropanol,
2-phenyl-1-bromoethanol, and 2-phenyl-2-iodoethanol.
[0101] Next, step 10 is described. In step 10, the ATRP method
described in method (i) above is used to synthesize a compound
having an azo skeleton structure by polymerizing a halogen
atom-containing azo skeleton structure (25) serving as a
polymerization initiator with a polymerizable monomer that forms
the monomer unit represented by formula (2) in the presence of a
metal catalyst and a ligand.
[0102] The metal catalyst used in the ATRP method is not
particularly limited but may be at least one transition metal
selected from groups 7 to 11 in the periodic table. For a redox
catalyst (redox conjugated complex) in which a low valence complex
and a high valence complex change reversibly, the low valence metal
specifically used is, for example, a metal selected from the group
consisting of Cu.sup.+, Ni.sup.0, Ni.sup.+, Ni.sup.2+, Pd.sup.0,
Pd.sup.+, Pt.sup.0, Pt.sup.+, Pt.sup.2+, Rh.sup.+, Rh.sup.2+,
Rh.sup.3+, Co.sup.+, Co.sup.2+, Ir.sup.0, Ir.sup.+, Ir.sup.2+,
Ir.sup.3+, Fe.sup.2+, Ru.sup.2+, Ru.sup.3+, Ru.sup.4+, Ru.sup.5+,
Os.sup.2+, Os.sup.3+, Re.sup.2+, Re.sup.3+, Re.sup.4+, Re.sup.6+,
Mn.sup.2+, and Mn.sup.3+. Among these, Cu.sup.+, Ru.sup.2+,
Fe.sup.2+, or Ni.sup.2+ is preferred and Cu.sup.+ is particularly
preferable due to its high availability. The monovalent copper
compound may be cuprous chloride, cuprous bromide, cuprous iodide,
or cuprous cyanide.
[0103] The ligand used in the ATRP method is typically an organic
ligand. Examples thereof include 2,2'-bipyridyl and derivatives
thereof, 1,10-phenanthroline and derivatives thereof,
N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'',N''-pentamethyldiethylenetriamine,
tris[2-(dimethylamino)ethyl]amine, triphenylphosphine, and
tributylphosphine. Considering the ease of production, aliphatic
polyamines such as N,N,N',N'',N''-pentamethyldiethylenetriamine may
be used.
[0104] Next, method (iv) is described in detail by using an example
scheme below. In method (iv), a polymer portion having a monomer
unit represented by formula (2) bonded to an amino group-containing
aryl group and an intermediate which is an acylacetanilide analog
are separately synthesized in advance and then subjected to diazo
coupling so as to form a compound having an azo skeleton
structure.
##STR00015##
[P.sub.1 is the same as P.sub.1 in the scheme of method (i) above;
R.sub.1 to R.sub.3, Ar.sub.1, m, and n in formula (19) are the same
as R.sub.1 to R.sub.3, Ar.sub.1, m, and n in formula (19) of the
scheme of method (i); Ar.sub.4 in formulae (26) to (28) represents
an arylene group; X.sub.8 in formula (26) represents a substituent
that reacts with P.sub.1 to give X.sub.9 in formula (27); r
represents 1 or 2; and X.sub.9 in formulae (27) and (28) represents
a divalent linking group L formed by the reaction between X.sub.8
in formula (26) and P.sub.1.]
[0105] In the scheme illustrated above, a compound having an azo
skeleton structure is synthesized through step 11 of introducing a
nitro group-containing arylene group (26) into the polymer portion
P.sub.1 to synthesize a polymer portion (27) having a nitro
group-containing arylene group, step 12 of reducing the polymer
portion (27) having a nitro group-containing arylene group to
synthesize a polymer portion (28) having an amino group-containing
arylene group, and step 13 of performing diazo coupling of the
polymer portion (28) having an amino group-containing arylene group
and an intermediate (19) which is an acylacetanilide analog.
[0106] First, step 11 is described. In step 11, the same method as
in step 6 of method (i) above is employed to synthesize a polymer
portion (27) having a nitro group-containing arylene group. For
example, a polymer portion (27) having a nitro group-containing
arylene group with a carboxylic acid ester bond serving as a
linking group can be synthesized by reacting a polymer portion
P.sub.1 having a carboxyl group with a nitro group-containing
arylene group (26) with X.sub.8 representing a hydroxyl
group-containing substituent. A polymer portion (27) having a nitro
group-containing arylene group with a sulfonic acid ester bond
serving as a linking group can be synthesized by reacting a polymer
portion P.sub.1 having a hydroxyl group with a nitro
group-containing arylene group (26) with X.sub.8 representing a
substituent containing a sulfonic acid. A polymer portion (27)
having a nitro group-containing arylene group with a carboxylic
acid amide bond serving as a linking group can be synthesized by
reacting a polymer portion P.sub.1 having a carboxyl group with a
nitro group-containing arylene group (26) with X.sub.8 representing
a substituent containing an amino group.
[0107] There are a wide variety of commercially available products
for the nitro group-containing arylene group (26). The nitro
group-containing arylene group (26) is also easy to synthesize by
common methods.
[0108] Next, step 12 is described. In step 12, the same method as
step 3 in method (i) above is applied to synthesize a polymer
portion (28) having an amino group-containing arylene group.
[0109] Next, step 13 is described. In step 13, the same method as
step 2 in method (i) above is applied to synthesize a compound
having an azo skeleton structure.
[0110] The compounds having an azo skeleton structure obtained in
the steps of the synthetic methods illustrated above and the
compounds represented by formulae (14), (16), (17), (19), (21),
(23), (25), (27), and (28) can be purified through a typical
isolation or purifying method for organic compounds. Examples of
the isolation or purifying method include a recrystallization
method and a reprecipitation method that use organic solvents, and
column chromatography using silica gel and the like. One or a
combination of two or more of these methods may be used to purify
the compounds and obtain high-purity compounds.
[0111] The compounds represented by formulae (14), (16), (17),
(19), (21), (23), and (25) obtained in the steps of the synthetic
methods illustrated above were identified and analyzed to determine
the purity by nuclear magnetic resonance spectroscopy (ECA-400
produced by JEOL Ltd.), ESI-TOF MS (LC/MSD TOF produced by Agilent
Technologies), and HPLC analysis (LC-20A produced by Shimadzu
Corporation).
[0112] The compounds having an azo skeleton structure obtained by
the synthetic methods illustrated above and the polymer portions
represented by formulae (27) and (28) were identified and analyzed
to determine the molecular weight by size exclusion chromatography
(SEC) (HLC8220GPC produced by Tosoh Corporation), nuclear magnetic
resonance spectroscopy (ECA-400 produced by JEOL Ltd.), and acid
value measurement according to Japanese Industrial Standard (JIS)
K-0070 (automatic titrator COM-2500 produced by Hiranuma Sangyo
Corporation).
[0113] Next, the binder resin of the toner of the present invention
is described.
[0114] Examples of the binder resin of the toner of the present
invention include commonly used binder resins such as
styrene-methacrylic acid copolymers, styrene-acrylic acid
copolymers, polyester resins, epoxy resins, and styrene-butadiene
copolymers. In a method of directly obtaining toner particles by
polymerization, monomers that form the binder resin are used.
Examples thereof include styrene-based monomers such as styrene,
.alpha.-methylstyrene, .alpha.-ethylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene,
and p-ethylstyrene; methacrylate-based monomers such as methyl
methacrylate, ethyl methacrylate, propyl methacrylate, butyl
methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl
methacrylate, behenyl methacrylate, 2-ethylhexyl methacrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
methacrylonitrile, and amide methacrylate; acrylate-based monomers
such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl
acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate,
behenyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl
acrylate, diethylaminoethyl acrylate, acrylonitrile, and amide
acrylate; and olefin-based monomers such as butadiene, isoprene,
and cyclohexene. These are used alone or as a mixture of two or
more so that the theoretical glass transition temperature (Tg)
thereof is within the range of 40.degree. C. to 75.degree. C.
(refer to J. Brandrup, E. H. Immergut (editor), Polymer Handbook,
(USA), third edition, John Wiley & Sons, 1989, pp. 209-277).
When the theoretic glass transition temperature is less than
40.degree. C., the storage stability and durability stability of
the toner may be degraded. When the theoretic glass transition
temperature exceeds 75.degree. C., transparency is degraded when
the toner is used to form full color images.
[0115] The binder resin of the toner of the present invention may
be constituted by a nonpolar resin such as polystyrene and a polar
resin such as a polyester resin or a polycarbonate resin so that
the in-toner distribution of additives such as a colorant, a charge
controller, and a wax can be controlled. For example, in the case
where toner particles are directly produced by suspension
polymerization or the like, the polar resin is added during a
polymerization reaction performed in the dispersing step through
the polymerization step. The polar resin is added depending on the
balance of polarity between a water-based medium and the
polymerizable monomer composition that forms toner particles. In
this manner, the resin concentration can be controlled to
continuously change from the toner particle surface toward the
toner particle center, because, for example, a thin layer of the
polar resin can be formed on the surfaces of toner particles. The
polar resin used here may be a polar resin that can interact with
the compound having an azo skeleton structure, a colorant, and a
charge controller so that the state of presence of the colorant in
the toner particles can be controlled as desired.
[0116] Examples of the magenta pigments that can be used in the
toner of the present invention include magenta pigments (for
example, quinacridone-based pigments, monoazonaphthol-based
pigments, disazonaphthol-based pigments, perylene-based pigments,
thioindigo-based pigments, and diketopyrrolopyrrole-based pigments)
described in Organic Pigments Handbook published in 2006 (written
by Isao Hashimoto) and the magenta pigment may be appropriately
selected from these. In particular, quinacridone-based pigments and
diketopyrrolopyrrole-based pigments are preferred since they have
high affinity to the pigment dispersant of the present invention
and offer magenta toners with high coloring properties.
[0117] Quinacridone-based pigments and diketopyrrolopyrrole-based
pigments for use as a colorant of the toner of the present
invention are preferably represented by formulae (8) and (9) below
from the viewpoint of affinity to the pigment dispersant of the
present invention:
##STR00016##
[In formula (8), R.sub.31 to R.sub.38 independently represent a
hydrogen atom, a chlorine atom, or a methyl group.]
##STR00017##
[In formula (9), R.sub.39 to R.sub.44 independently represent a
hydrogen atom, a chlorine atom, a tert-butyl group, a cyano group,
or a phenyl group.]
[0118] In formula (8), R.sub.31 to R.sub.38 may each be freely
selected from the substituents listed above. From the viewpoint of
coloring power, R.sub.31 to R.sub.32, R.sub.34 to R.sub.36, and
R.sub.38 each preferably represent a hydrogen atom. More
preferably, R.sub.33 and R.sub.37 each represent a hydrogen atom, a
chlorine atom or a methyl group.
[0119] In formula (9), R.sub.39 to R.sub.44 may each be freely
selected from the substituents listed above. From the viewpoint of
coloring power, R.sub.39, R.sub.41 and R.sub.42, and R.sub.44 each
preferably represent a hydrogen atom. More preferably, R.sub.40 and
R.sub.43 each represent a hydrogen atom or a phenyl group.
[0120] Specific examples of the quinacridone-based pigments
represented by formula (8) include C.I. Pigment Red 202, C.I.
Pigment Red 122, C.I. Pigment Red 192, and C.I. Pigment Red 209.
Specific examples of diketopyrrolopyrrole-based pigments
represented by formula (9) include C.I. Pigment Red 255, C.I.
Pigment Red 254, and C.I. Pigment Red 264.
[0121] In order to obtain a magenta toner having higher coloring
power, the magenta pigment used in combination with the compound
having an azo skeleton structure of the present invention is
preferably C.I. Pigment Red 122, C.I. Pigment Red 202, C.I. Pigment
Red 255, or C.I. Pigment Red 264.
[0122] These magenta pigments may be used alone or in
combination.
[0123] The ratio of the content of the magenta pigment to the
content of the compound having an azo skeleton structure on a mass
basis is preferably in the range of 100:0.1 to 100:100. More
preferably, when the specific surface area of the magenta pigment
is 300 m.sup.2/g or less, this ratio is in the range of 100:0.5 to
100:20 from the viewpoint to dispersibility of the magenta
toner.
[0124] One or more of the magenta pigments need to be used as the
colorant of the toner of the present invention but other colorants
may additionally be used as long as the dispersibility of the
magenta pigment is not inhibited.
[0125] Examples of such colorants that can be additionally used
include common magenta colorants.
[0126] Examples of the magenta colorant that can be additionally
used include fused azo compounds, anthraquinone, basic dye lake
compounds, naphthol compounds, benzimidazolone compounds,
thioindigo compounds, and perylene compounds. Specific examples
thereof include C.I. Pigment Red 2, C.I. Pigment Red 3, C.I.
Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment
Red 23, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment
Red 48:4, C.I. Pigment Red 57:1, C.I. Pigment Red 81:1, C.I.
Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 150, C.I.
Pigment Red 166, C.I. Pigment Red 169, C.I. Pigment Red 177, C.I.
Pigment Red 184, C.I. Pigment Red 185, C.I. Pigment Red 220, C.I.
Pigment Red 221, C.I. Pigment Red 238, and C.I. Pigment Red
269.
[0127] The amount of these colorants used differs depending on the
type of the colorants. The total colorant content is 0.1 to 60
parts by mass and more preferably 0.5 to 50 parts by mass relative
to 100 parts by mass of the binder resin.
[0128] During the synthesis of the binder resin, a crosslinking
agent may be used to enhance the mechanical strength of the toner
particles and control the molecular weight of the molecules
constituting the particles.
[0129] Examples of the crosslinking agent used in toner particles
of the present invention include difunctional crosslinking agents.
Examples of the difunctional crosslinking agents include
divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene
glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol
diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate,
neopentyl glycol diacrylate, diethylene glycol diacrylate,
triethylene glycol diacrylate, tetraethylene glycol diacrylate,
diacrylates of polyethylene glycol #200, #400, and #600,
dipropylene glycol diacrylate, polypropylene glycol diacrylate,
polyester-type diacrylate, and dimethacrylates of these
diacrylates.
[0130] Examples of the multifunctional crosslinking agent include
pentaerythritol triacrylate, trimethylolethane triacrylate,
trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
oligo ester acrylate, and methacrylates thereof,
2,2-bis(4-methacryloxyphenyl)propane, diallyl phthalate, triallyl
cyanurate, triallyl isocyanurate, and triallyl trimellitate.
[0131] These crosslinking agents are preferably used in an amount
in the range of 0.05 to 10 parts by mass and more preferably in an
amount in the range of 0.1 to 5 parts by mass relative to 100 parts
by mass of the monomer from the viewpoints of fixability of the
toner and offset resistance.
[0132] A wax component may also be used during synthesis of the
binder resin in order to prevent adhesion of the toner to the
fixing member.
[0133] Examples of the wax component that can be used include
petroleum waxes such as paraffin wax, microcrystalline wax, and
petrolatum and derivatives thereof, montan wax and derivatives
thereof, hydrocarbon wax produced by Fischer-Tropsch processes and
derivatives thereof, polyolefin wax such as polyethylene and
derivatives thereof, and natural wax such as carnauba wax and
candelilla wax and derivatives thereof. Derivatives may refer to
oxides, block copolymers with vinyl monomers, and graft modified
products. Further examples thereof include alcohols such as higher
aliphatic alcohols, fatty acids such as stearic acid and palmitic
acid, fatty acid amides, fatty acid esters, hydrogenated castor oil
and derivatives thereof, vegetable wax, and animal wax. These may
be used alone or in combination.
[0134] The total amount of the wax component added is preferably
within the range of 2.5 to 15.0 parts by mass and more preferably
within the range of 3.0 to 10.0 parts by mass relative to 100 parts
by mass of the binder resin. If the amount of wax is smaller than
2.5 parts by mass, oil-less fixing becomes difficult. When the
amount exceeds 15.0 parts by mass, the amount of the wax component
in the toner particles becomes excessively large, and large
quantities of excess wax component may be present on the toner
particles surfaces, possibly adversely affecting charging
properties.
[0135] A charge controller can be blended to the toner of the
present invention as needed. The optimum triboelectric charge
amount for the development system can be controlled with the charge
controller.
[0136] Any common charge controller may be used. A charge
controller that has high charging speed and is capable of stably
retaining a particular amount of charge is preferred. In the case
where toner particles are formed directly by polymerization, a
charge controller that rarely inhibits polymerization and that is
substantially free of matter soluble in water-based dispersion
media is particularly preferable.
[0137] Examples of the charge controller that negatively charges
the toner include polymers or copolymers having a sulfonic acid
group, a sulfonic acid base, or a sulfonic acid ester group,
salicylic acid derivatives and metal complexes thereof, monoazo
metal compounds, acetylacetone metal compounds, aromatic
oxycarboxylic acids, aromatic mono- or polycarboxylic acids and
metal salts, anhydrides, and esters thereof, phenol derivatives
such as bisphenol, urea derivatives, metal-containing naphthoic
acid-based compounds, boron compounds, quaternary ammonium salts,
calixarene, and resin-based charge controllers. Examples of the
charge controller that positively charges the toner include
nigrosin and nigrosin products modified with fatty acid metal salts
or the like, guanidine compounds, imidazole compounds,
tributylbenzylammonium-1-hydroxy-4-naphtholsulfonic acid salts,
quaternary ammonium salts such as tetrabutylammonium
tetrafluoroborate, onium salts such as phosphonium salts of analogs
of the foregoing and lake pigments thereof, triphenyl methane dyes
and lake pigments thereof (examples of the laking agent include
phosphotungstic acid, phosphomolybdic acid, phosphotungstic
molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide,
and ferrocyanide), metal salts of higher fatty acids, diorganotin
oxides such as dibutyltin oxide, dioctyltin oxide, and
dicyclohexyltin oxide, diorganotin borates such as dibutyltin
borate and dioctyltin borate, and resin-based charge controllers.
These may be used alone or in combination.
[0138] An inorganic fine powder serving as a flowing agent may be
added to the toner particles of the toner of the present invention.
Examples of the inorganic fine powder include silica, titanium
oxide, alumina, a complex oxide thereof, and a surface-treated fine
powder thereof.
[0139] Examples of the method for producing toner particles
constituting the toner of the present invention include a grinding
method, a suspension polymerization method, a suspension
granulation method, and an emulsion polymerization method. From the
viewpoints of environmental load during production and
controllability of particle size, a production method with which
particles are formed in water-based media, such as a suspension
polymerization method or a suspension granulation method, is
preferred.
[0140] In the method for producing toner of the present invention,
a compound having an azo skeleton structure and a magenta pigment
may be mixed in advance to prepare a pigment composition. In this
manner, the dispersibility of the magenta pigment can be
improved.
[0141] The pigment composition can be produced by a dry process or
a wet process. Considering that the compound having an azo skeleton
structure has high affinity to water-insoluble solvents, a wet
process is preferred since a homogeneous pigment composition can be
easily produced. An example of such a method is as follows. A
compound having an azo skeleton structure and, if needed, a resin
are added to a dispersion medium. A magenta pigment powder is
slowly added to the mixture under stirring so that the magenta
pigment powder is thoroughly mixed with the dispersion medium. Then
mechanical shear force is applied to the resulting mixture with a
disperser such as a kneader, a roll mill, a ball mill, a paint
shaker, a dissolver, an attritor, a sand mill, or a high-speed
mill. As a result, the magenta pigment can be stably and uniformly
dispersed into fine particles.
[0142] The dispersion medium that can be used in the pigment
composition may be any. In order for the compound having an azo
skeleton structure to achieve high pigment dispersing effect, the
dispersion medium is preferably a water-insoluble solvent. Examples
of the water-insoluble solvent include esters such as methyl
acetate, ethyl acetate, and propyl acetate, hydrocarbons such as
hexane, octane, petroleum ethers, cyclohexane, benzene, toluene,
and xylene, and halogen-containing hydrocarbon such as carbon
tetrachloride, trichloroethylene, and tetrabromoethane.
[0143] The dispersion medium that can be used in the pigment
composition may be a polymerizable monomer. Examples thereof
include styrene, .alpha.-methylstyrene, .alpha.-ethylstyrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene,
p-methoxystyrene, p-phenylstyrene, p-chlorostyrene,
3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene,
p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene,
p-n-dodecylstyrene, ethylene, propylene, butylene, isobutylene,
vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide,
vinyl acetate, vinyl propionate, vinyl benzoate, methacrylic acid,
methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl
methacrylate, n-octyl methacrylate, dodecyl methacrylate,
2-ethylhexyl methacrylate, stearyl methacrylate, behenyl
methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl methacrylate, acrylic acid, methyl acrylate,
ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl
acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl
acrylate, stearyl acrylate, behenyl acrylate, 2-chloroethyl
acrylate, phenyl acrylate, vinyl methyl ether, vinyl ethyl ether,
vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone,
methyl isopropenyl ketone, vinyl naphthalene, acrylonitrile,
methacrylonitrile, and acrylamide.
[0144] Examples of the resin that can be used in the pigment
composition are the same as those that can be used as the binder
resin for the toner of the present invention. Examples thereof
include styrene-methacrylic acid copolymers, styrene-acrylic acid
copolymers, polyester resins, epoxy resins, and styrene-butadiene
copolymers. Two or more of these dispersion media may be mixed and
used. The pigment composition can be isolated by a common method,
for example, filtration, decantation, or centrifugation. The
solvent may be removed by washing.
[0145] An auxiliary agent may be added to the pigment composition
during production. Examples of the auxiliary agent include a
surfactant, a dispersant, a filler, a standardizer, a resin, a wax,
a defoaming agent, an antistatic agent, an antidust agent, an
extender, a shading colorant, a preservative, a drying inhibitor, a
rheology controller, a humectant, an antioxidant, a UV absorber, a
photostabilizer, and any combination of these. The compound having
an azo skeleton structure may be added in advance during production
of the bulk pigment.
[0146] Toner particles are produced by a suspension polymerization
method in the following manner, for example. The pigment
composition described above, a polymerizable monomer, a wax
component, a polymerization initiator, and the like are mixed to
prepare a polymerizable monomer composition. Then the polymerizable
monomer composition is dispersed in a water-based medium to form
particles of the polymerizable monomer composition. Then the
polymerizable monomer in the particles of the polymerizable monomer
composition is polymerized in the water-based medium so as to
obtain toner particles.
[0147] The polymerizable monomer composition in the above-described
step may be prepared by mixing a dispersion prepared by dispersing
the pigment composition in a first polymerizable monomer with a
second polymerizable monomer. In other words, the pigment
composition is thoroughly dispersed in the first polymerizable
monomer and then mixed with the second polymerizable monomer along
with other toner materials so that the magenta pigment can be more
satisfactorily dispersed in the toner particles.
[0148] Commonly used polymerization initiators can be used as the
polymerization initiator used in the suspension polymerization
method described above. Examples thereof include azo compounds,
organic peroxides, inorganic peroxides, organic metal compounds,
and photopolymerization initiators. Specific examples thereof
include azo-based polymerization initiators such as
2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile), and
dimethyl-2,2'-azobis(isobutyrate), organic peroxide-based
polymerization initiators such as benzoyl peroxide, di-tert-butyl
peroxide, tert-butyl peroxyisopropyl monocarbonate,
tert-hexylperoxy benzoate, and tert-butylperoxy benzoate, inorganic
peroxide-based polymerization initiators such as potassium
persulfate and ammonium persulfate, and initiators based on
hydrogen peroxide-ferrous iron, BPO-dimethylaniline, and cerium(IV)
salt-alcohol. Examples of the photopolymerization initiator include
acetophenones, benzoin ethers, and ketals. These polymerization
initiators may be used alone or in combination.
[0149] The concentration of the polymerization initiator is
preferably 0.1 to 20 parts by mass and more preferably 0.1 to 10
parts by mass relative to 100 parts by mass of the polymerizable
monomer. The type of the polymerization initiator depends on the
polymerization method. One or a mixture of two or more
polymerization initiators is used by considering the 10 hour
half-life temperature.
[0150] The water-based medium used in the suspension polymerization
method above may contain a dispersion stabilizer. Any common
inorganic or organic dispersion stabilizer can be used as the
dispersion stabilizer. Examples of the inorganic dispersion
stabilizer include calcium phosphate, magnesium phosphate, aluminum
phosphate, zinc phosphate, magnesium carbonate, calcium carbonate,
calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium
metasilicate, calcium sulfate, barium sulfate, bentonite, silica,
and alumina. Examples of the organic dispersion stabilizer include
polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl
cellulose, ethyl cellulose, sodium salts of carboxymethyl
cellulose, and starch. A nonionic, anionic, or cationic surfactant
can also be used. Examples thereof include sodium dodecyl sulfate,
sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl
sulfate, sodium oleate, sodium laurate, potassium stearate, and
calcium oleate.
[0151] Of the dispersion stabilizers listed above, sparingly
water-soluble inorganic dispersion stabilizers soluble in acids are
preferably used in the present invention. In preparing a
water-based dispersion medium by using a sparingly water-soluble
inorganic dispersion stabilizer in the present invention, 0.2 to
2.0 parts by mass of the dispersion stabilizer may be used relative
to 100 parts by mass of the polymerizable monomer from the
viewpoint of stability of droplets of the polymerizable monomer
composition in the water-based medium. In the present invention,
300 to 3000 parts by mass of water may be used relative to 100
parts by mass of the polymerizable monomer composition to prepare a
water-based medium.
[0152] In preparing a water-based medium in which the sparingly
water-soluble inorganic dispersion stabilizer is dispersed, a
commercially available dispersion stabilizer may be directly used
to conduct dispersion. However, it is preferable that the sparingly
water-soluble inorganic dispersion stabilizer is generated in water
under high speed stirring. In this case, dispersion stabilizer
particles, that are fine and have uniform particle size, can be
obtained. For example, when calcium phosphate is used as the
dispersion stabilizer, an aqueous sodium phosphate solution and an
aqueous calcium chloride solution may be mixed and stirred at high
speed to form fine particles of calcium phosphate. As a result, a
desired dispersion stabilizer can be obtained.
[0153] Toner particles of the present invention can also be
obtained by a suspension granulation method. Since the production
process of the suspension granulation method does not include a
heating step, the resin and the wax component are suppressed from
becoming compatible to each other which would otherwise be the case
when a low melting point wax is used, and the decrease in glass
transition temperature of the toner caused by becoming compatible
can be prevented. The suspension granulation method allows a wide
range of options of toner materials for the binder resin and it is
easy to use a polyester resin, which is generally considered as
offering good fixability, as a main component. Accordingly, the
suspension granulation method is advantageous in producing a toner
that has a resin composition not suitable for a suspension
polymerization method.
[0154] Toner particles are produced by the suspension granulation
method described above in the following manner. First, the pigment
composition, a binder, resin, a wax component, and the like are
mixed in a solvent to prepare a solvent composition. The solvent
composition is dispersed in a water-based medium to form particles
of the solvent composition and to thereby obtain a toner particle
suspension. The suspension is heated or evacuated to remove the
solvent to obtain toner particles.
[0155] The solvent composition in the above-described step may be
prepared by mixing a dispersion prepared by dispersing the pigment
composition in a first solvent with a second solvent. In other
words, the pigment composition is thoroughly dispersed in the first
solvent and then mixed with the second solvent along with other
toner materials so that the magenta pigment can be more
satisfactorily dispersed in the toner particles.
[0156] Examples of the solvent that can be used in the suspension
granulation method include hydrocarbons such as toluene, xylene,
and hexane, halogen-containing hydrocarbons such as methylene
chloride, chloroform, dichloroethane, trichloroethane, and carbon
tetrachloride, alcohols such as methanol, ethanol, butanol, and
isopropyl alcohol, polyhydric alcohols such as ethylene glycol,
propylene glycol, diethylene glycol, and triethylene glycol,
cellosolves such as methyl cellosolve and ethyl cellosolve, ketones
such as acetone, methyl ethyl ketone, and methyl isobutyl ketone,
ethers such as benzyl alcohol ethyl ether, benzyl alcohol isopropyl
ether, and tetrahydrofuran, and esters such as methyl acetate,
ethyl acetate, and butyl acetate. These may be used alone or as a
mixture of two or more. Among these, a solvent that has a low
boiling point and is capable of sufficiently dissolving the binder
resin is preferred in order to facilitate removal of the solvent
from the toner particle suspension.
[0157] The amount of the solvent used is preferably in the range of
50 to 5000 parts by mass and more preferably in the range of 120 to
1000 parts by mass relative to 100 parts by mass of the binder
resin.
[0158] The water-based medium used in the suspension granulation
method described above may contain a dispersion stabilizer. Any
common inorganic or organic dispersion stabilizer can be used as
the dispersion stabilizer. Examples of the inorganic dispersion
stabilizer include calcium phosphate, calcium carbonate, aluminum
hydroxide, calcium sulfate, and barium carbonate. Examples of the
organic dispersion stabilizer include surfactants such as polyvinyl
alcohol, methyl cellulose, hydroxyethyl cellulose, ethyl cellulose,
sodium salts of carboxymethyl cellulose, water-soluble polymers
such as polysodium acrylate and polysodium methacrylate, anionic
surfactants such as sodium dodecylbenzenesulfonate, sodium
octadecyl sulfate, sodium oleate, sodium laurate, and potassium
stearate, cationic surfactants such as lauryl amine acetate,
stearyl amine acetate, and lauryl trimethyl ammonium chloride,
amphionic surfactants such as lauryldimethylamine oxide, and
nonionic surfactants such as polyoxyethylene alkyl ether,
polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl
amine.
[0159] Relative to 100 parts by mass of the binder resin, 0.01 to
20 parts by mass of the dispersant may be used from the viewpoint
of stability of the droplets of the solvent composition in the
water-based medium.
[0160] The weight-average particle size (hereinafter "D4) of the
toner of the present invention is within the range of 3.00 to 15.0
.mu.m and more preferably within the range of 4.00 to 12.0 .mu.m. A
high-definition image can be easily obtained while maintaining
charge stability if the particle size is within this range.
[0161] The ratio of D4 of the toner to the number-average particle
size (hereinafter "D1") (hereinafter this ratio is referred to as
D4/D1) is 1.35 or less and preferably 1.30 or less in order to
suppress fogging and improve transfer efficiency while maintaining
high resolution.
[0162] D4 and D1 of the toner of the present invention are adjusted
in different ways depending on the method for producing the toner
particles. In the case where a suspension polymerization method is
used to produce toner particles, D4 and D1 can be adjusted by
controlling, for example, the dispersant concentration used in
preparing the water-based dispersion medium, the rate of stirring
during the reaction, and the time of stirring during the
reaction.
[0163] The toner of the present invention may be magnetic or
nonmagnetic. If a magnetic toner is to be used, a magnetic material
may be mixed with the toner particles of the toner of the present
invention. Examples of the magnetic material include iron oxides
such as magnetite, maghemite, and ferrite, iron oxides containing
other metal oxides, metals such as Fe, Co, and Ni, and alloys and
mixtures of these metals with Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb,
Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V. The magnetic material most
suited for the purposes of the present invention is fine powder of
triiron tetraoxide or .gamma.-diiron trioxide.
[0164] These magnetic materials preferably have an average particle
size of 0.1 to 2 .mu.m and more preferably 0.1 to 0.3 .mu.m, and
preferably exhibit a coercive force of 1.6 to 12 kA/m, a saturation
magnetization of 5 to 200 Am.sup.2/kg and more preferably 50 to 100
Am.sup.2/kg, and a residual magnetization of 2 to 20 Am.sup.2/kg
under application of a 795.8 kA/m magnetic field from the viewpoint
of development properties of the toner.
[0165] To 100 parts by mass of the binder resin, 10 to 200 parts by
mass and preferably 20 to 150 parts by mass of the magnetic
material is used.
EXAMPLES
[0166] The present invention will now be described in further
detail by using Examples and Comparative Examples. The present
invention is not limited by the examples below. In the description
below, "part" and "%" are on a mass basis unless otherwise
noted.
[0167] The measurement methods employed in the synthetic examples
are as follows.
(1) Determination of Molecular Weight
[0168] The molecular weight of a compound having a polymer portion
and an azo skeleton structure was calculated on a polystyrene basis
by size exclusion chromatography (SEC). The molecular weight was
determined by SEC as follows.
[0169] A sample was added to an eluent described below so that the
sample concentration was 1.0% to prepare a solution. The solution
was left standing still for 24 hours at room temperature and
filtered through a solvent-resistant membrane filter with a 0.2
.mu.m pore size to prepare a sample solution. The sample solution
was measured under the following conditions.
Instrument: High speed GPC device HLC-8220GPC [produced by Tosoh
Corporation] Column: Two column combination of LF-804
Eluant: THF
[0170] Flow rate: 1.0 ml/min Oven temperature: 40.degree. C. Amount
of injected sample: 0.025 ml
[0171] In calculating the molecular weight of the sample, molecular
weight calibration curves obtained from standard polystyrene resins
[products of Tosoh Corporation, TSK standard polystyrene F-850,
F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000,
A-2500, A-1000, and A-500] were used.
(2) Acid Value Measurement
[0172] The acid value of the compound having a polymer portion and
an azo skeleton structure was determined by the following
method.
[0173] The basic procedure was carried out according to JIS
K-0070.
1) First, 0.5 to 2.0 g of the sample is accurately weighed. This
mass is assumed to be M (g). 2) The sample is placed in a 50 ml
beaker and dissolved by addition of 25 ml of a
tetrahydrofuran/ethanol (2:1) mixed solution. 3) Titration is
conducted with a potentiometric titrator by using a 0.1 mol/l
ethanol solution of KOH. For example, automatic titrator COM-2500
produced by Hiranuma Sangyo Corporation can be used. 4) The amount
of the KOH solution used in this step is assumed to be S (ml). At
the same time, the blank is measured and the amount of the KOH
solution used is assumed to be B (ml). 5) The acid value is
calculated by the following formula where f represents a factor of
the KOH solution.
Acid value [ mg KOH / g ] = ( S - B ) .times. f .times. 5.61 M
##EQU00001##
(3) Composition Analysis
[0174] The structure of the compound having a polymer portion and
an azo skeleton structure is identified by using the following
instrument.
[0175] .sup.1H NMR
[0176] ECA-400 produced by JEOL Ltd. (solvent used: deuterated
chloroform)
Example 1
[0177] A compound having an azo skeleton was obtained through the
following method.
Production Example of Compound (116)
[0178] A compound (116) having an azo skeleton represented by
structural formula below was produced by the following scheme.
##STR00018## ##STR00019##
[0179] First, 3.11 parts of p-nitroaniline (29) was added to 30
parts of chloroform, the mixture was cooled with ice to 10.degree.
C. or lower, and 1.89 parts of diketene (30) was added thereto,
followed by stirring for 2 hours at 65.degree. C. After completion
of the reaction, chloroform extraction and condensation were
performed to obtain 4.70 parts (yield: 94.0%) of a compound
(31).
[0180] Next, 40.0 parts of methanol and 5.29 parts of concentrated
hydrochloric acid were added to 4.25 parts of dimethyl
2-aminoterephthalate (32) and the mixture was cooled with ice to
10.degree. C. or lower. To the resulting solution, 2.10 parts of
sodium nitrite dissolved in 6.00 parts of water was added and the
reaction was carried out at the same temperature for 1 hour. Next,
0.990 parts of sulfamic acid was added thereto, followed by
stirring for 20 minutes (diazonium salt solution). To 70.0 of
methanol, 4.51 parts of the compound (31) was added. The mixture
was cooed with ice to 10.degree. C. or lower and the diazonium salt
solution was added to the mixture. Thereto, 5.83 parts of sodium
acetate dissolved in 7.00 parts of water was added and the reaction
was carried out for 2 hours at 10.degree. C. or lower. After
completion of the reaction, 300 parts of water was added and
stirring was conducted for 30 minutes. Solid matter was filtered
out and purified by a recrystallization method in
N,N-dimethylformamide. As a result, 8.71 parts (yield: 96.8%) of a
compound (33) was obtained.
[0181] Next, 8.58 parts of the compound (33) and 0.40 parts of
palladium-active carbon (5% palladium) were added to 150 parts of
N,N-dimethylformamide and the resulting mixture was stirred in a
hydrogen gas atmosphere (reaction pressure: 0.1 to 0.4 MPa) at
40.degree. C. for 3 hours. After completion of the reaction, the
solution was filtered and condensed to obtain 6.99 parts (yield:
87.5%) of a compound (34).
[0182] Next, 6.50 parts of the compound (34) was added to 30.0
parts of chloroform and the resulting mixture was cooled with ice
to 10.degree. C. or lower. To the mixture, 0.95 parts of diketene
(30) was added, followed by stirring at 65.degree. C. for 2 hours.
After completion of the reaction, chloroform extraction and
condensation were conducted to obtain 7.01 parts (yield: 94.2%) of
an azo compound intermediate (35).
[0183] Next, 15.0 parts of methanol and 1.48 parts of concentrated
hydrochloric acid were added to 1.78 parts of
2-(4-aminophenyl)ethanol (36) and the resulting mixture was cooed
with ice to 10.degree. C. or lower. To the resulting solution, 1.08
parts of sodium nitrite dissolved in 3.00 parts of water was added
and the reaction was carried out at the same temperature for 1
hour. To the resulting solution, 0.380 parts of sulfamic acid was
added, followed by further stirring for 20 minutes (diazonium salt
solution). To 70.0 parts of N,N-dimethylformamide, 7.18 parts of
potassium carbonate dissolved in 7.00 parts of water and 6.50 parts
of the compound (35) were added. The resulting mixture was cooled
with ice to 10.degree. C. or lower and the diazonium salt solution
was added thereto. The reaction was carried out for 2 hours at
10.degree. C. or lower. After completion of the reaction, 300 parts
of water was added, followed by stirring for 30 minutes. Solid
matter was filtered out and purified by a recrystallization method
from N,N-dimethylformamide. As a result, 7.62 parts (yield: 91.0%)
of a compound (37) was obtained.
[0184] Next, 2.00 parts of the compound (37) was added to 20.0
parts of chloroform. The resulting mixture was cooled with ice to
10.degree. C. or lower and 0.855 parts of 2-bromoisobutyrylbromide
(38) was added thereto, followed by stirring at 65.degree. C. for 2
hours. After completion of the reaction, chloroform extraction and
condensation were conducted to obtain 2.26 parts (yield: 92.0%) of
an intermediate (39).
[0185] Next, 0.684 parts of the compound (39), 27.3 parts of
styrene (40), 0.305 parts of
N,N,N',N'',N''-pentamethyldiethylenetriamine, and 0.124 parts of
copper(I) bromide were added to 10.0 parts of
N,N-dimethylformamide. Then stirring was conducted in a nitrogen
atmosphere at 100.degree. C. for 7.5 hours. After completion of the
reaction, chloroform extraction and purification through methanol
reprecipitation were conducted to obtain 8.50 parts (yield: 85.0%)
of a compound (116).
[0186] The product obtained as such was analyzed by the instruments
described above to confirm the structure. The analytic results are
as follows.
Analytic Results of the Compound (116) Having an Azo Skeleton
[0187] [1] Results of molecular weight measurement (GPC)
Weight-average molecular weight (Mw)=15117, number-average
molecular weight (Mn)=12910 [2] Results of acid value measurement 0
mgKOH/g [3] Results of .sup.1H NMR (400 MHz, CDCl.sub.3, room
temperature) (see FIG. 1)
[0188] .delta. [ppm]=15.65 (s, 1H), 14.77 (s, 1H), 11.40 (s, 1H),
11.41 (s, 1H), 8.62 (s, 1H), 8.15 (d, 1H), 7.79 (d, 1H), 7.74 (d,
2H), 7.64 (d, 2H), 7.37-6.27 (m, 738H), 4.07 (s, 3H), 3.98 (s, 3H),
3.73 (br, 2H), 2.72-2.52 (m, 9H), 2.47-1.05 (m, 458H), 1.01-0.78
(m, 6H)
Production Example of Compound (129)
[0189] A compound (129) having an azo skeleton was produced by the
following scheme.
##STR00020##
[0190] First, 100 parts of propylene glycol monomethyl ether was
heated under nitrogen purge and refluxed at a liquid temperature of
120.degree. C. or higher. Thereto, a mixture of 190 parts of
styrene (40), 10.0 parts of acrylic acid (41), and 1.00 part of
tert-butylperoxybenzoate [organic peroxide-based polymerization
initiator produced by NOF Corporation, trade name: PERBUTYL Z] was
added dropwise for 3 hours. After completion of the dropwise
addition, the solution was stirred for 3 hours and distilled at
normal pressure while heating the solution to a liquid temperature
of 170.degree. C. After reaching the liquid temperature of
170.degree. C., distillation was conducted at a reduced pressure of
1 hPa for 1 hour to remove the solvent and obtain a resin solid
product. The solid product was dissolved in tetrahydrofuran and
purified by reprecipitation in n-hexane to obtain 185 parts (yield:
92.5%) of a compound (42).
[0191] To 15.0 parts of chloroform, 3.00 parts of the compound (42)
and 184 parts of oxalyl chloride were added, followed by stirring
in a nitrogen gas atmosphere at room temperature for 5 hours. To
the resulting solution, 0.644 parts of p-phenylenediamine (43)
dissolved in 10.0 parts of chloroform and 5.00 parts of
N,N-dimethylformamide was added dropwise, followed by stirring in a
nitrogen gas atmosphere at room temperature for 2 hours. After
completion of the reaction, the solution was fractionated with
chloroform/water, condensed, and purified through reprecipitation
in methanol. As a result, 2.98 parts (yield: 90.3%) of a compound
(44) was obtained.
[0192] Next, 10.0 parts of tetrahydrofuran and 0.252 parts of
concentrated hydrochloric acid were added to 1.00 part of the
compound (44) and the resulting mixture was cooled with ice to
0.degree. C. or lower. To this solution, 0.0900 parts of sodium
nitrite dissolved in 0.270 parts of water was added and the
reaction was carried out at the same temperature for 1 hour. Then
0.063 parts of sulfamic acid was added, followed by further
stirring for 20 minutes (diazonium salt solution). To 15.0 parts of
N,N-dimethylformamide, 0.446 parts of potassium carbonate dissolved
in 1.50 parts of water and 0.354 parts of the compound (35) were
added. The resulting mixture was cooled with ice to 10.degree. C.
or lower, the diazonium salt solution was added thereto, and the
reaction was carried out at 10.degree. C. or lower for 4 hours.
After completion of the reaction, 300 parts of water was added,
followed by stirring for 30 minutes. Solid matter was filtered out,
dissolved in chloroform, and purified through reprecipitation in
methanol. As a result, 0.970 parts (yield: 97.0%) of a compound
(129) was obtained.
[0193] The product obtained as such was analyzed by the instruments
described above to confirm the structure. The analytic results are
as follows.
Analytic Results of the Compound (129) Having an Azo Skeleton
[0194] [1] Results of molecular weight measurement (GPC)
Weight-average molecular weight (Mw)=32442, number-average
molecular weight (Mn)=18329 [2] Results of acid value measurement 0
mgKOH/g [3] Results of .sup.1H NMR (400 MHz, CDCl.sub.3, room
temperature) (see FIG. 2)
[0195] .delta. [ppm]=15.57 (s, 1H), 14.70 (s, 1H), 11.44 (s, 1H),
11.33 (s, 1H), 8.54 (s, 1H), 8.07 (d, 1H), 7.71 (d, 1H), 7.65 (d,
2H), 7.56 (d, 2H), 7.19-6.43 (m, 136H), 4.00 (s, 3H), 3.91 (s, 3H),
2.61 (s, 3H), 2.50 (s, 3H), 1.76-0.81 (m, 97H)
Production Example of Compound (174)
[0196] A compound (174) having an azo skeleton was produced by the
following scheme.
##STR00021## ##STR00022##
[0197] To 0.395 parts of methyl 2-bromopropionate (45), 60.0 parts
of styrene (40), 1.47 parts of
N,N,N',N'',N''-pentamethyldiethylenetriamine, and 0.493 parts of
copper(I) bromide were added, followed by stirring in a nitrogen
gas atmosphere at 100.degree. C. for 5 hours. After completion of
the reaction, chloroform extraction and purification through
reprecipitation in methanol were conducted. As a result, 52.4 parts
(yield: 81.9%) of a compound (46) was obtained.
[0198] To 150 parts of dioxane, 1.00 parts of the compound (46) was
added. The resulting mixture was stirred at 110.degree. C. and a
mixture of 5.00 parts of concentrated hydrochloric acid and 30
parts of dioxane was added thereto, followed by stirring in a
nitrogen gas atmosphere at 110.degree. C. for 5 hours. After
completion of the reaction, chloroform extraction and purification
through reprecipitation in methanol were conducted. As a result,
0.98 parts (yield: 98.0%) of a compound (47) was obtained.
[0199] Next, 1.00 parts of the compound (47) and 0.0160 parts of
oxalyl chloride were added to 5.00 parts of chloroform and the
resulting mixture was stirred in a nitrogen gas atmosphere at room
temperature for 5 hours. To the resulting solution, 0.0670 parts of
p-phenylenediamine (43) dissolved in 10.0 of chloroform and 5.00
parts of N,N-dimethylformamide was added dropwise, followed by
stirring in a nitrogen gas atmosphere at 60.degree. C. for 2 hours.
After completion of the reaction, the solution was fractionated
with chloroform/water, condensed, and purified through
reprecipitation in methanol. As a result, 0.970 parts (yield:
97.0%) of a compound (48) was obtained.
[0200] Next, 50.0 parts of p-phenylenediamine (43) and 35.0 parts
of acetone were added to 300 parts of chloroform. The resulting
mixture was cooled with ice to 10.degree. C. or lower and 72.0
parts of diketene (30) was added thereto, followed by stirring at
65.degree. C. for 2 hours. After completion of the reaction,
chloroform extraction and condensation were conducted to obtain 121
parts (yield: 97.4%) of a compound (49).
[0201] Next, to 4.00 parts of the compound (49), 40.0 parts of THF
and 0.127 parts of concentrated hydrochloric acid were added, and
the resulting mixture was cooled with ice to 10.degree. C. or
lower. To the resulting solution, 0.005 parts of sodium nitrite
dissolved in 1.70 parts of water was added and the reaction was
carried out at the same temperature for 1 hour. Then 0.0320 parts
of sulfamic acid was added, followed by further stirring for 20
minutes (diazonium salt solution). To 70.0 parts of methanol, 0.230
parts of the potassium sulfate dissolved in 1.00 part of water, and
0.0460 parts of the compound (48) were added and the resulting
mixture was cooled with ice to 10.degree. C. or lower. The
diazonium salt solution was added thereto and the reaction was
carried out at 10.degree. C. or lower for 2 hours. After completion
of the reaction, 300 parts of water was added thereto, followed by
stirring for 30 minutes. Solid matter was filtered out and purified
through reprecipitation in methanol. As a result, 3.80 parts
(yield: 95.0%) of a compound (174) was obtained.
Analytic Results of the Compound (174) Having an Azo Skeleton
[0202] [1] Results of molecular weight measurement (GPC)
Weight-average molecular weight (Mw)=31686, number-average
molecular weight (Mn)=22633 [2] Results of acid value measurement 0
mgKOH/g [3] Results of .sup.1H NMR (400 MHz, CDCl.sub.3, room
temperature) (see FIG. 3)
[0203] .delta. [ppm]=14.78 (s, 2H), 11.50 (s, 2H), 7.63 (d, 4H),
7.29-6.37 (m, 1192H), 2.56 (s, 6H), 2.18-0.99 (m, 839H)
Production Example of Compound (176)
[0204] A compound (176) having an azo skeleton represented by a
structure below was produced by the following scheme.
##STR00023##
[0205] First, a compound (48) was obtained by the same operation as
Production Example of compound (174).
[0206] Next, to 10.0 parts of N,N-dimethylformamide, 0.500 parts of
1,3,5-triaminobenzene (50) and 0.345 parts of triethylamine were
added, followed by stirring at room temperature. Next, 0.949 parts
of diketene (30) was added thereto, followed by stirring at
50.degree. C. for 2 hours. After completion of the reaction, 300
parts of water was added, followed by stirring for 30 minutes and
solid matter was filtered out. As a result, 1.41 parts (yield:
92.8%) of a compound (51) was obtained.
[0207] Next, to 4.00 of the compound (48), 20 parts of DMF, 20.0
parts of THF, and 0.130 parts of concentrated hydrochloric acid
were added. The resulting mixture was cooled with ice to 10.degree.
C. or lower. To this solution, 0.0450 parts of sodium nitrite
dissolved in 0.136 parts of water was added and the reaction was
carried out at the same temperature for 1 hour. Thereto, 0.0320
parts of sulfamic acid was added, followed by further stirring for
20 minutes (diazonium salt solution). To 15.0 of DMF, 0.225 parts
of potassium acetate dissolved in 1.00 part of water and 0.0440
parts of the compound (51) were added and the resulting mixture was
cooled with ice to 10.degree. C. or lower. Thereto, the diazonium
salt solution was added and the reaction was carried out at
10.degree. C. or lower for 2 hours. After completion of the
reaction, 300 parts of water was added, followed by stirring for 30
minutes, and solid matter was filtered out and purified through
recrystallization in N,N-dimethylformamide so as to obtain 3.78
parts (yield: 94.5%) of a compound (176).
Analytic Results of the Compound (176) Having an Azo Skeleton
[0208] [1] Results of molecular weight measurement (GPC)
Weight-average molecular weight (Mw)=48989, number-average
molecular weight (Mn)=28481 [2] Results of acid value measurement 0
mgKOH/g [3] Results of .sup.1H NMR (400 MHz, CDCl.sub.3, room
temperature) (see FIG. 4)
[0209] .delta. [ppm]=14.73 (s, 3H), 11.53 (s, 3H), 7.79 (s, 3H),
7.27-6.31 (m, 2175H), 2.52 (s, 9H), 2.12-0.81 (m, 1461H)
[0210] The same operation as the synthetic example of the compounds
(116), (129), (174), and (176) having azo skeletons was performed
to produce compounds (101) to (115), (117) to (128), (130) to
(173), (175), and (177) to (179) having azo skeletons.
[0211] The polymer portion is shown in Table 1 and the compounds
having azo skeletons are shown in Tables 2-1 to 2-4 below.
TABLE-US-00001 TABLE 1 Polymer Sequential portion arrangement No.
No. No. No. number of monomers of X of Y.sub.1 of Y.sub.2 of Z
R.sub.46 R.sub.47 R.sub.48 R.sub.49 R.sub.50 R.sub.51 R-1
.alpha.-W-polyX 95 0 0 0 H -- -- -- -- -- R-2 .alpha.-W-polyX 149 0
0 0 H -- -- -- -- -- R-3 .alpha.-W-polyY.sub.1 0 101 0 0 -- H
COOC.sub.4H.sub.9(n) -- -- -- R-4 .alpha.-W-poly(X-co-Y.sub.1) 71
18 0 0 H H COOC.sub.4H.sub.9(n) -- -- -- R-5
.alpha.-W-poly(X-co-Y.sub.1) 18 88 0 0 H H COOC.sub.4H.sub.9(n) --
-- -- R-6 .alpha.-W-poly(X-co-Y.sub.1) 71 18 0 0 H H CONH.sub.2 --
-- -- R-7 .alpha.-W-poly(X-co-Y.sub.1) 71 18 0 0 H H COOCH.sub.3 --
-- -- R-8 .alpha.-W-poly(X-co-Y.sub.1) 71 18 0 0 H H COOBn -- -- --
R-9 poly(X-co-Y.sub.1-co-Z) 141 30 0 11 H H COOC.sub.4H.sub.9(n) --
-- H R-10 poly(X-co-Y.sub.1-co-Z) 15 11 0 7 CH.sub.3 CH.sub.3
COOC.sub.4H.sub.9(n) -- -- H R-11 poly(X-co-Y.sub.1-co-Z) 220 4 0 4
H -- COOCH.sub.3 -- -- H R-12 poly(X-co-Y.sub.1-co-Z) 57 5 0 3 H H
COOCH.sub.2CH(C.sub.2H.sub.5)C.sub.4H.sub.9 -- -- H R-13
poly(X-co-Y.sub.1-co-Z) 49 4 0 2 H H COOC.sub.18H.sub.37(n) -- -- H
R-14 poly(X-co-Y.sub.1-co-Z) 58 3 0 3 H H COOC.sub.22H.sub.45(n) --
-- H R-15 poly 75 13 3 3 H H COOCH.sub.3 H COOC.sub.22H.sub.45(n) H
(X-co-Y.sub.1-co-Y.sub.2-co-Z) R-16 poly 59 28 4 3 H H
COOC.sub.4H.sub.9(n) H COOC.sub.22H.sub.45(n) H
(X-co-Y.sub.1-co-Y.sub.2-co-Z) R-17 poly(X-co-Z) 220 0 0 8 H -- --
-- -- H R-18 poly(X-co-Z) 1174 0 0 384 H -- -- -- -- H R-19
poly(Y.sub.1-co-Z) 0 90 0 10 -- H COOC.sub.4H.sub.9(n) -- -- H R-20
polyX-b-polyZ 84 0 0 5 H -- -- -- -- H R-21
poly(X-co-Y.sub.1)-b-polyZ 74 14 0 2 H H COOC.sub.4H.sub.9(n) -- --
H
In Table 1, the prefix .alpha. represents the terminal group on the
left of the structure. W represents a COOH group. X, Y.sub.1,
Y.sub.2, and Z respectively represent structures indicated below.
Bn represents an unsubstituted benzyl group. (n) indicates that the
alkyl group is linear.
##STR00024##
[in formula (X), R.sub.46 represents a hydrogen atom or an alkyl
group]
##STR00025##
[in formula (Y.sub.1), R.sub.47 represents a hydrogen atom or an
alkyl group and R.sub.48 represents a carboxylic acid ester group
or a carboxylic acid amide group]
##STR00026##
[in formula (Y.sub.2), R.sub.49 represents a hydrogen atom or an
alkyl group and R.sub.50 represents a carboxylic acid ester group
or a carboxylic acid amide group]
##STR00027##
[in formula (Z), R.sub.51 represents a hydrogen atom or an alkyl
group]
TABLE-US-00002 TABLE 2-1 Linking Substitution position to Number of
positions of Polymer polymer introduced acetamide Compound portion
portion m n units groups R.sub.1 R.sub.9 R.sub.10 R.sub.11 101 R-1
W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 102 R-3 W 4 1
1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 103 R-4 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 104 R-5 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 105 R-6 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 106 R-7 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 107 R-8 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 108 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 109 R-4 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 110 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 111 R-4 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 112 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 113 R-4 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 114 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 115 R-4 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 116 R-2 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 117 R-4 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 118 R-9 Z 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 119 R-9 Z 4 1 11 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 120 R-10 Z 4 1 2 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 Compound R.sub.12 R.sub.13
R.sub.14 R.sub.15 R.sub.16 R.sub.17 R.sub.18 R.sub.19 R.sub.20 101
H H COOCH.sub.3 H H H L.sub.1 H H 102 H H COOCH.sub.3 H H H L.sub.1
H H 103 H H COOCH.sub.3 H H H L.sub.1 H H 104 H H COOCH.sub.3 H H H
L.sub.1 H H 105 H H COOCH.sub.3 H H H L.sub.1 H H 106 H H
COOCH.sub.3 H H H L.sub.1 H H 107 H H COOCH.sub.3 H H H L.sub.1 H H
108 H H COOCH.sub.3 H H H L.sub.2 H H 109 H H COOCH.sub.3 H H H
L.sub.2 H H 110 H H COOCH.sub.3 H H H L.sub.3 H H 111 H H
COOCH.sub.3 H H H L.sub.3 H H 112 H H COOCH.sub.3 H H H L.sub.4 H H
113 H H COOCH.sub.3 H H H L.sub.4 H H 114 H H COOCH.sub.3 H H H
L.sub.5 H H 115 H H COOCH.sub.3 H H H L.sub.5 H H 116 H H
COOCH.sub.3 H H H L.sub.6 H H 117 H H COOCH.sub.3 H H H L.sub.6 H H
118 H H COOCH.sub.3 H H H L.sub.7 H H 119 H H COOCH.sub.3 H H H
L.sub.7 H H 120 H H COOCH.sub.3 H H H L.sub.7 H H
TABLE-US-00003 TABLE 2-2 Linking Substitution position to Number of
positions of Polymer polymer introduced acetamide Compound portion
portion m n units groups R.sub.1 R.sub.9 R.sub.10 R.sub.11 121 R-10
Z 4 1 7 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 122 R-11 Z 4 1
4 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 123 R-12 Z 4 1 3
1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 124 R-13 Z 4 1 2 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 125 R-14 Z 4 1 3 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 126 R-15 Z 4 1 3 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 127 R-16 Z 4 1 3 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 128 R-11 Z 4 1 6 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 129 R-11 Z 4 1 8 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 130 R-12 Z 4 1 197 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 131 R-13 Z 4 1 8 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 132 R-14 Z 4 1 5 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 133 R-15 Z 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 134 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 135 R-1 W 4 1 1 1,4-
2,3,5,6-H C.sub.6CH.sub.13(n) Ph COOCH.sub.3 136 R-1 W 4 1 1 1,4-
2-OH CH.sub.3 CH.sub.3 COOCH.sub.3 3,6-H 5-Cl 137 R-1 W 4 1 1 1,4-
2-OCH.sub.3 CH.sub.3 CH.sub.3 COOCH.sub.3 3,5,6-H 138 R-1 W 4 1 1
1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOCH.sub.3 139 R-1 W 4 1 1 1,4-
2-CF.sub.3 CH.sub.3 CH.sub.3 COOCH.sub.3 3,5,6-H 140 R-1 W 4 1 1
1,4- 2-CN CH.sub.3 CH.sub.3 COOCH.sub.3 3,5,6-H Compound R.sub.12
R.sub.13 R.sub.14 R.sub.15 R.sub.16 R.sub.17 R.sub.18 R.sub.19
R.sub.20 121 H H COOCH.sub.3 H H H L.sub.7 H H 122 H H COOCH.sub.3
H H H L.sub.7 H H 123 H H COOCH.sub.3 H H H L.sub.7 H H 124 H H
COOCH.sub.3 H H H L.sub.7 H H 125 H H COOCH.sub.3 H H H L.sub.7 H H
126 H H COOCH.sub.3 H H H L.sub.7 H H 127 H H COOCH.sub.3 H H H
L.sub.7 H H 128 H H COOCH.sub.3 H H H L.sub.7 H H 129 H H
COOCH.sub.3 H H H L.sub.7 H H 130 H H COOCH.sub.3 H H H L.sub.7 H H
131 H H COOCH.sub.3 H H H L.sub.7 H H 132 H H COOCH.sub.3 H H H
L.sub.7 H H 133 H H COOCH.sub.3 H H H L.sub.7 H H 134 H H
COOCH.sub.3 H H H L.sub.7 H H 135 H H COOCH.sub.3 H H H L.sub.8 H H
136 H H COOCH.sub.3 H H H L.sub.8 H H 137 H H COOCH.sub.3 H H H
L.sub.8 H H 138 H H COOCH.sub.3 H H H L.sub.8 H H 139 H H
COOCH.sub.3 H H H L.sub.8 H H 140 H H COOCH.sub.3 H H H L.sub.8 H
H
TABLE-US-00004 TABLE 2-3 Linking Substitution position to Number of
positions of Polymer polymer introduced acetamide Compound portion
portion m n units groups R.sub.1 R.sub.9 R.sub.10 R.sub.11 141 R-1
W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 CH.sub.3 142 R-1 W 4 1 1
1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H 143 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 H 144 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3
CH.sub.3 H 145 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOH
146 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOC.sub.2H.sub.5
147 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOPr(n) 148 R-1 W
4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 COOPr(i) 149 R-1 W 4 1 1
1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 CONH.sub.2 150 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 CONHCH.sub.3 151 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 CONHC.sub.2H.sub.5 152 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 CONHPr(i) 153 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 CONHPr(n) 154 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 CON(C.sub.2H.sub.5).sub.2 155 R-4 W 4 1
1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H 156 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 CONH.sub.2 157 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 H 158 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3
CH.sub.3 H 159 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H 160
R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H Compound R.sub.12
R.sub.13 R.sub.14 R.sub.15 R.sub.16 R.sub.17 R.sub.18 R.sub.19
R.sub.20 141 H Cl H H H H L.sub.8 H H 142 CF.sub.3 H H H H H
L.sub.8 H H 143 H OCH.sub.2CH.sub.3 H H H H L.sub.8 H H 144 CN H H
H H H L.sub.8 H H 145 H H COOH H H H L.sub.8 H H 146 H H
COOC.sub.2H.sub.5 H H H L.sub.8 H H 147 H H COOPr(n) H H H L.sub.8
H H 148 H H COOPr(i) H H H L.sub.8 H H 149 H H CONH.sub.2 H H H
L.sub.8 H H 150 H H CONHCH.sub.3 H H H L.sub.8 H H 151 H H
CONHC.sub.2H.sub.5 H H H L.sub.8 H H 152 H H CONHPr(i) H H H
L.sub.8 H H 153 H H CONHPr(n) H H H L.sub.8 H H 154 H H
CON(C.sub.2H.sub.5).sub.2 H H H L.sub.8 H H 155 CONH.sub.2 H H H H
H L.sub.8 H H 156 H H H H H H L.sub.8 H H 157 CONH.sub.2 H H H H H
L.sub.8 H H 158 H CONH.sub.2 H H H H L.sub.8 H H 159 CONH.sub.2 H H
OCH3 H H L.sub.8 H H 160 CONHC.sub.6H.sub.5 H H OCH3 H H L.sub.8 H
H
TABLE-US-00005 TABLE 2-4 Linking Substitution position to Number of
positions of Polymer polymer introduced acetamide Compound portion
portion m n units groups R.sub.1 R.sub.9 R.sub.10 R.sub.11 161 R-1
W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H 162 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 H 163 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 H 164 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3
CH.sub.3 H 165 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3
COOCH.sub.3 166 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H 167
R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3 CH.sub.3 H 168 R-1 W 4 1 1 1,4-
2,3,5,6-H CH.sub.3 CH.sub.3 H 169 R-1 W 4 1 1 1,3- 2,3,5,6-H
CH.sub.3 CH.sub.3 COOCH.sub.3 170 R-1 W 4 1 1 1,2- 2,3,5,6-H
CH.sub.3 CH.sub.3 COOCH.sub.3 171 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 COOCH.sub.3 172 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 COOCH.sub.3 173 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 COOCH.sub.3 174 R-1 W 4 1 1 1,4- 2,3,5,6-H
CH.sub.3 CH.sub.3 H 175 R-1 W 4 1 1 1,4- 2,3,5,6-H CH.sub.3
CH.sub.3 H 176 R-1 W 3 2 1 1,3,5- 2,4,6-H CH.sub.3 CH.sub.3 H 177
R-1 W 3 2 1 1,2,3- 4,5,6-H CH.sub.3 CH.sub.3 H 178 R-1 W 3 2 1
1,2,5- 2-CH.sub.3 CH.sub.3 CH.sub.3 H 6-H 179 R-1 W 3 2 1 1,3,5-
2,6-H CH.sub.3 CH.sub.3 H Compound R.sub.12 R.sub.13 R.sub.14
R.sub.15 R.sub.16 R.sub.17 R.sub.18 R.sub.19 R.sub.20 161
CONHC.sub.6H.sub.5 H H H H H L.sub.8 H H 162 CONHCH.sub.3 H H H H H
L.sub.8 H H 163 NHCOCH.sub.3 H H H H H L.sub.8 H H 164 CONH.sub.2 H
H OH H H L.sub.8 H H 165 H H H H H H L.sub.8 H H 166 COOCH.sub.3 H
H H H H L.sub.8 H H 167 H COOCH.sub.3 H H H H L.sub.8 H H 168
COOCH.sub.3 H COOCH.sub.3 H H H L.sub.8 H H 169 H H COOCH.sub.3 H H
H L.sub.8 H H 170 H H COOCH.sub.3 H H H L.sub.8 H H 171 H H
COOCH.sub.3 H H L.sub.8 H H H 172 H H COOCH.sub.3 H L.sub.8 H H H H
173 H H COOCH.sub.3 H H L.sub.8 H L.sub.8 H 174 H L.sub.8 H H H H
L.sub.8 H H 175 L.sub.8 H L.sub.8 H H L.sub.8 H L.sub.8 H 176 H
L.sub.8 H H H H L.sub.8 H H 177 H L.sub.8 H H H H L.sub.8 H H 178 H
L.sub.8 H H H H L.sub.8 H H 179 L.sub.8 H L.sub.8 H H L.sub.8 H
L.sub.8 H
[0212] In Tables 2-1 to 2-4, m, n, R.sub.1, and R.sub.9 to R.sub.20
respectively represent m, n, R.sub.1 and R.sub.9 to R.sub.20 in
formula (3) below; Pr represents an unsubstituted propyl group; Ph
represents an unsubstituted phenyl group; (n) and (i) respectively
represent a linear alkyl group and a branched alkyl group; a
compound in which the bonding portion to the polymer portion is "W"
forms a linking group L by bonding with a COOH group represented by
W in the polymer portion shown in Table 1; a compound in which the
"linking moiety to the polymer portion" is indicated by "W" forms a
linking group L by bonding with a COOH group represented by "W" in
the polymer portion described in Table 1 and a compound in which
the linking moiety to the polymer portion is indicated by "Z" forms
a linking group L by bonding with a COOH group in the monomer "Z"
in the polymer portion described in Table 1; L.sub.1 to L.sub.8 in
Table 2 each represent a linking group L to the polymer resin and
are represented by the structural formula below:
##STR00028##
[in formula (L.sub.1), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00029##
[in formula (L.sub.2), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00030##
[in formula (L.sub.3), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00031##
[in formula (L.sub.4), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00032##
[in formula (L.sub.5), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00033##
[in formula (L.sub.6), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00034##
[in formula (L.sub.7), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)]
##STR00035##
[in formula (L.sub.8), "*" represents a linking moiety linking to
the polymer portion indicated in Table 1 and "**" represents a
linking moiety in the azo skeleton structure represented by formula
(1)].
Example 2
[0213] A magenta pigment dispersion containing a magenta pigment
and a compound having an azo skeleton was prepared by the following
method in a toner production process that involves a suspension
polymerization method.
Preparation Example 1 of Magenta Pigment Dispersion
[0214] Mixed were 30.0 parts of a pigment represented by formula
(52) below serving as a colorant, 3.0 parts of the compound (101)
having an azo skeleton structure, 180 parts of styrene as a
water-insoluble solvent, and 130 parts of glass beads (1 mm in
diameter). The resulting mixture was dispersed in an attritor
(produced by Nippon Coke & Engineering Co., Ltd.) for 3 hours
and filtered through a mesh to obtain a magenta pigment dispersion
(DIS1).
##STR00036##
Preparation Example 2 of Magenta Pigment Dispersion
[0215] Magenta pigment dispersions (DIS2) to (DIS79) were obtained
as in Preparation Example 1 of magenta pigment dispersion except
that the compound (101) having an azo skeleton structure was
changed to compounds (102) to (179) having azo skeleton
structures.
Preparation Example 3 of Magenta Pigment Dispersion
[0216] Magenta pigment dispersions (DIS80), (DIS81), and (DIS82)
were obtained as in Preparation Example 1 of magenta pigment
dispersion except that the pigment represented by formula (52)
above was changed to pigments represented by formulae (53), (54),
and (55) below.
##STR00037##
Comparative Example 1
[0217] A magenta pigment dispersion that serves as a standard of
evaluation and a magenta pigment dispersion for comparison were
prepared by the following method.
Preparation Example 1 of Magenta Pigment Dispersion for
Standard
[0218] A magenta pigment dispersion (DIS83) for standard was
obtained as in Preparation Example 1 of magenta pigment dispersion
in Example 2 except that the compound (101) having an azo skeleton
structure was not added.
Preparation Example 2 of Magenta Pigment Dispersion for
Standard
[0219] Magenta pigment dispersions (DIS84) to (DIS86) were obtained
as in Preparation Example 3 of magenta pigment dispersion in
Example 2 except that the compound (101) having an azo skeleton
structure was not added.
Preparation Example 1 of Magenta Pigment Dispersion for
Comparison
[0220] A magenta pigment dispersion (DIS87) was obtained as in
Preparation Example 1 of magenta pigment dispersion of Example 2
except that the compound (101) having an azo skeleton structure was
changed to DA-703-50 (product of produced by Kusumoto Chemicals
Ltd.) (comparative compound 1) described in Japanese Patent
Laid-Open No. 2006-30760.
Preparation Example 2 of Magenta Pigment Dispersion for
Comparison
[0221] Magenta pigments dispersions (DIS88) to (DIS90) for
comparison were obtained as in Preparation Example 3 of magenta
pigment dispersion of Example 2 except that the compound (101)
having an azo skeleton structure was changed to comparative
compound 1.
Example 3
[0222] The magenta pigment dispersions prepared as above were
evaluated by the following method.
Evaluation of Dispersibility in Magenta Pigment Dispersion
[0223] The magenta pigment dispersibility of the compound having an
azo skeleton structure of the present invention was evaluated by
performing a gloss test on coating films of magenta pigment
dispersions. That is, a magenta pigment dispersion taken in a
syringe was discharged on a sheet of super art paper (SA Kinfuji
180 kg, 80.times.160 produced by Oji Holdings Corporation) so as to
draw a straight line and spread with a wire bar (#10) to evenly
coat the art paper. The gloss after drying (angle of reflection:
75.degree.) was measured with a Gloss Meter VG7000 (produced by
Nippon Denshoku Industries Co., Ltd.) and evaluated based on the
standard below. The flatness and the gloss of the coating film
improve as the magenta pigment is dispersed more finely.
[0224] The gloss improvement rates for the magenta pigment
dispersions (DIS1) to (DIS79) and (DIS87) that used a magenta
pigment represented by formula (52) as a colorant were determined
on the basis of the gloss value of the magenta pigment dispersion
(DIS83) for standard.
[0225] The gloss improvement rates for the magenta pigment
dispersions (DIS80) and (DIS88) that used a magenta pigment
represented by formula (53) as a colorant were determined on the
basis of the gloss value of the magenta pigment dispersion (DIS84)
for standard.
[0226] The gloss improvement rates for the magenta pigment
dispersions (DIS81) and (DIS89) that used a magenta pigment
represented by formula (54) as a colorant were determined on the
basis of the gloss value of the magenta pigment dispersion (DIS85)
for standard.
[0227] The gloss improvement rates for the magenta pigment
dispersions (DIS82) and (DIS90) that used a magenta pigment
represented by formula (55) as a colorant were determined on the
basis of the gloss value of the magenta pigment dispersion (DIS86)
for standard.
[0228] The evaluation standard for the pigment dispersions is as
follows.
A: The gloss value improvement rate was 30% or more. B: The gloss
value improvement rate was 20% or more but less than 30%. C: The
gloss value improvement rate was 10% or more but less than 20%. D:
The gloss value improvement rate was less than 10%.
[0229] The magenta pigment dispersibility was evaluated as
satisfactory as long as the gloss rate improvement rate was 10% or
more.
[0230] The evaluation results for the magenta pigment dispersions
are shown in Table 3.
TABLE-US-00006 TABLE 3 Magenta Gloss pigment Magenta (gloss
dispersion Compound pigment value) DIS1 101 Formula(52) A(70) DIS2
102 Formula(52) A(72) DIS3 103 Formula(52) A(74) DIS4 104
Formula(52) A(73) DIS5 105 Formula(52) A(69) DIS6 106 Formula(52)
A(75) DIS7 107 Formula(52) A(74) DIS8 108 Formula(52) A(76) DIS9
109 Formula(52) A(71) DIS10 110 Formula(52) A(71) DIS11 111
Formula(52) A(70) DIS12 112 Formula(52) A(73) DIS13 113 Formula(52)
A(74) DIS14 114 Formula(52) A(75) DIS15 115 Formula(52) A(70) DIS16
116 Formula(52) A(76) DIS17 117 Formula(52) A(71) DIS18 118
Formula(52) A(70) DIS19 119 Formula(52) A(75) DIS20 120 Formula(52)
A(71) DIS21 121 Formula(52) A(70) DIS22 122 Formula(52) A(74) DIS23
123 Formula(52) A(73) DIS24 124 Formula(52) A(75) DIS25 125
Formula(52) A(72) DIS26 126 Formula(52) A(76) DIS27 127 Formula(52)
A(70) DIS28 128 Formula(52) A(75) DIS29 129 Formula(52) A(74) DIS30
130 Formula(52) A(65) DIS31 131 Formula(52) A(73) DIS32 132
Formula(52) A(70) DIS33 133 Formula(52) A(70) DIS34 134 Formula(52)
A(72) DIS35 135 Formula(52) A(72) DIS36 136 Formula(52) A(74) DIS37
137 Formula(52) A(71) DIS38 138 Formula(52) A(73) DIS39 139
Formula(52) A(69) DIS40 140 Formula(52) A(75) DIS41 141 Formula(52)
A(67) DIS42 142 Formula(52) A(64) DIS43 143 Formula(52) A(66) DIS44
144 Formula(52) A(64) DIS45 145 Formula(52) A(70) DIS46 146
Formula(52) A(72) DIS47 147 Formula(52) A(66) DIS48 148 Formula(52)
A(65) DIS49 149 Formula(52) A(77) DIS50 150 Formula(52) A(71) DIS51
151 Formula(52) A(70) DIS52 152 Formula(52) A(65) DIS53 153
Formula(52) A(65) DIS54 154 Formula(52) A(64) DIS55 155 Formula(52)
A(67) DIS56 156 Formula(52) A(66) DIS57 157 Formula(52) A(78) DIS58
158 Formula(52) A(72) DIS59 159 Formula(52) A(77) DIS60 160
Formula(52) A(76) DIS61 161 Formula(52) A(64) DIS62 162 Formula(52)
A(70) DIS63 163 Formula(52) A(65) DIS64 164 Formula(52) A(77) DIS65
165 Formula(52) A(71) DIS66 166 Formula(52) A(73) DIS67 167
Formula(52) A(74) DIS68 168 Formula(52) A(70) DIS69 169 Formula(52)
A(72) DIS70 170 Formula(52) A(73) DIS71 171 Formula(52) A(73) DIS72
172 Formula(52) A(77) DIS73 173 Formula(52) A(72) DIS74 174
Formula(52) A(65) DIS75 175 Formula(52) A(67) DIS76 176 Formula(52)
A(66) DIS77 177 Formula(52) A(68) DIS78 178 Formula(52) A(64) DIS79
179 Formula(52) B(67) DIS80 101 Formula(53) A(69) DIS81 101
Formula(54) A(80) DIS82 101 Formula(55) A(75) DIS83 None
Formula(52) Standard(42) DIS84 None Formula(53) Standard(45) DIS85
None Formula(54) Standard(42) DIS86 None Formula(55) Standard(39)
DIS87 Comparative Formula(52) B(54) compound 1 DIS88 Comparative
Formula(53) B(55) compound 1 DIS89 Comparative Formula(54) C(48)
compound 1 DIS90 Comparative Formula(55) B(50) compound 1
Example 4
[0231] A toner of the present invention was produced by the
following suspension polymerization method.
Toner Production Example 1
[0232] To a 2 L four neck flask equipped with a high speed stirrer
T.K. Homomixer (produced by PRIMIX Corporation), 710 parts of ion
exchange water and 450 parts of a 0.1 mol/l aqueous
Na.sub.3PO.sub.4 solution were added. The speed of rotation was
adjusted to 12000 rpm and the mixture was heated to 60.degree. C.
Thereto, 68 parts of a 1.0 mol/l aqueous CaCl.sub.2 solution was
slowly added to prepare a water-based medium containing fine
sparingly water-soluble dispersion stabilizer
Ca.sub.3(PO.sub.4).sub.2. Then the composition below was heated to
60.degree. C. and evenly dissolved and dispersed in a high sped
stirrer T.K. Homomixer (produced by PRIMIX Corporation) at 5000
rpm.
TABLE-US-00007 magenta pigment dispersion (DIS1) 132 parts styrene
monomer 46 parts n-butyl acrylate monomer 34 parts polar resin
[saturated polyester resin (terephthalic acid- 10 parts propylene
oxide-modified bisphenol A, acid value: 15, peak molecular weight:
6000)] ester wax (maximum endothermic peak in DSC = 70.degree. 25
parts C., Mn = 704) aluminum salicylate compound [produced by
Orient 2 parts Chemical Industries Co., Ltd., trade name: BONTRON
E-108] divinylbenzene monomer 0.1 parts
[0233] To this composition, 10 parts of
2,2'-azobis(2,4-dimethylvaleronitrile) serving as a polymerization
initiator was added and the resulting mixture was placed in the
water-based medium and formed into particles while retaining a
rotation speed of 12000 rpm for 15 minutes. Then the high speed
stirrer was changed to an impeller stirrer equipped with a stirring
blade, the polymerization was continued at a liquid temperature of
60.degree. C. for 5 hours, and then the liquid temperature was
increased to 80.degree. C. The polymerization was continued for 8
hours. After termination of the polymerization, the remaining
monomers were distilled away at a reduced pressure at 80.degree. C.
and the reaction product was cooled to 30.degree. C. As a result, a
polymer fine particle dispersion was obtained.
[0234] The polymer fine particle dispersion obtained was placed in
a washing container. Thereto, diluted hydrochloric acid was added
under stirring. Stirring was conducted for 2 hours at pH of 1.5, a
compound of calcium and a phosphoric acid containing
Ca.sub.3(PO.sub.4).sub.2 was dissolved in the dispersion, and the
resulting mixture was filtered to conduct solid liquid separation.
As a result, polymer fine particles were obtained. The polymer fine
particles were again placed in water to again form a dispersion.
Then the dispersion was separated into solid and liquid through a
filter. This re-dispersing of the polymer fine particles in water
and solid liquid separation were repeated until the compound of
phosphoric acid and calcium containing Ca.sub.3(PO.sub.4).sub.2 was
satisfactorily removed. Then polymer fine particles after final
solid liquid separation were thoroughly dried with a drier to
obtain toner particles.
[0235] In a Henschel mixer, (produced by Nippon Coke &
Engineering Co., Ltd.), 100 parts of the toner particles obtained,
1.0 parts of hydrophobic silica fine powder surface-treated with
hexamethyldisilazane (number-average particle size of primary
particles: 7 nm), 0.15 parts of rutile-type titanium oxide fine
powder (number-average particle size of primary particles: 45 nm),
and 0.5 parts of a rutile-type titanium oxide fine powder
(number-average particle size of primary particles: 200 nm) were
dry-mixed for 5 minutes. As a result, a toner (TNR1) was
obtained.
Toner Production Example 2
[0236] Toners (TNR2) to (TNR79) of the present invention were
obtained as in Toner Production Example 1 except that the magenta
pigment dispersion (DIS1) in Toner Production Example 1 was changed
to magenta pigment dispersions (DIS2) to (DIS79).
Toner Production Example 3
[0237] Toners (TNR80) to (TNR82) of the present invention were
obtained as in Toner Production Example 1 except that the magenta
pigment dispersion (DIS1) in Toner Production Example 1 was changed
to magenta pigment dispersions (DIS80) to (DIS82).
Comparative Example 2
[0238] A toner used as the standard for evaluation and a toner for
comparison for the toners of the present invention produced in
Example 4 were produced by the following method.
Production Example 1 of Toner for Standard
[0239] A toner (TNR83) for standard was obtained as in Toner
Production Example 1 except that the magenta pigment dispersion
(DIS1) in Toner Production Example 1 was changed to magenta pigment
dispersion (DIS83).
Production Example 2 of Toner for Standard
[0240] Toners (TNR84) to (TNR86) for standard were obtained as in
Toner Production Example 1 except that the magenta pigment
dispersion (DIS1) in Toner Production Example 1 was changed to
magenta pigment dispersions (DIS84) to (DIS86).
Production Example 1 of Toner for Comparison
[0241] A toner (TNR87) for comparison was obtained as in Toner
Production Example 1 except that the magenta pigment dispersion
(DIS1) in Toner Production Example 1 was changed to magenta pigment
dispersion (DIS87).
Production Example 2 of Toner for Comparison
[0242] Toners (TNR88) to (TNR90) for comparison were obtained as in
Toner Production Example 1 except that the magenta pigment
dispersion (DIS1) in Toner Production Example 1 was changed to
magenta pigment dispersions (DIS88) to (DIS90).
Example 5
[0243] A toner of the present invention was produced by the
following suspension granulation method.
Toner Production Example 4
[0244] Mixed were 180 parts of ethyl acetate, 30 parts of Pigment
Red 122, 3.0 parts of the compound (101) having a azo skeleton
structure, and 130 parts of glass beads (1 mm in diameter). The
resulting mixture was dispersed in an attritor (produced by Nippon
Coke & Engineering Co., Ltd.) for 3 hours and filtered through
a mesh to obtain a magenta pigment dispersion.
[0245] The composition below was dispersed in a ball mill for 24
hours to obtain 200 parts of a toner composition mixed liquid.
TABLE-US-00008 magenta pigment dispersion 96.0 parts polar resin
[saturated polyester resin (a polycondensate of 85.0 parts
propylene oxide-modified bisphenol A and phthalic acid, Tg =
75.9.degree. C., Mw = 11000, Mn = 4200, acid value: 11)]
hydrocarbon wax (Fischer-Tropsch wax, maximum 9.0 parts endothermic
peak in DSC: = 80.degree. C., Mw = 750) aluminum salicylate
compound [BONTRON E-108 2.0 parts produced by Orient Chemical
Industries Co., Ltd.] ethyl acetate (solvent) 10.0 parts
[0246] The following composition was dispersed in a ball mill for
24 hours to dissolve carboxy methyl cellulose and obtain a
water-based medium.
TABLE-US-00009 calcium carbonate (coated with acrylic acid-based
20.0 parts copolymer) carboxy methyl cellulose [CELLOGEN BS-H,
produced 0.5 parts by Daiichi Kogyo Seiyaku Co., Ltd.] ion exchange
water 99.5 parts
[0247] In a high speed stirrer T.K. Homomixer (produced by PRIMIX
Corporation), 1200 parts of the water-based medium was placed and
1000 parts of the toner composition mixed liquid was added thereto
while stirring the content with a rotating blade at a peripheral
velocity of 20 m/sec. Stirring was conducted for 1 minute while
retaining 25.degree. C. so as to obtain a suspension.
[0248] While stirring 2200 parts of the suspension with FULLZONE
impeller (produced by KOBELCO ECO-SOLUTIONS Co., Ltd.) at a
peripheral velocity of 45 m/min, the liquid temperature was
retained constant at 40.degree. C. and the gas phase on the
suspension surface was forcibly suctioned through a blower to start
removing the solvent. Fifteen minutes after start of solvent
removal, 75 parts of ammonia water diluted to 1% as an ionic
substance was added; 1 hour after start of solvent removal, 25
parts of the ammonia water was added; 2 hours after start of
solvent removal, 25 parts of the ammonia water was added; and
lastly 3 hours after start of solvent removal, 25 parts of the
ammonia water was added so that the total amount of the ammonia
water added was 150 parts. The liquid temperature was retained at
40.degree. C. for 17 hours after start of the solvent removal. As a
result, a toner dispersion obtained by removing the solvent (ethyl
acetate) from the suspended particles was obtained.
[0249] To 300 parts of the toner dispersion obtained by the solvent
removal step, 80 parts of 10 mol/l hydrochloric acid was added. The
resulting mixture was neutralized with a 0.1 mol/l aqueous sodium
hydroxide solution and washed four times with ion exchange water by
suction filtration to obtain a toner cake. The toner cake was dried
in a vacuum drier and passed through a 45 .mu.m sieve to obtain
toner particles. The subsequent operation was the same as Toner
Production Example 1 and a toner (TNR91) was obtained.
Toner Production Example 5
[0250] Toners (TNR92) to (TNR169) of the present invention were
obtained as in Toner Production Example 4 except that the compound
(101) having an azo skeleton structure was changed to compounds
(102) to (179).
Toner Production Example 6
[0251] Toners (TNR170) to (TNR172) of the present invention were
obtained as in Toner Production Example 5 except that the magenta
pigment represented by formula (52) was changed to those
represented by formulae (53) to (55).
Comparative Example 3
[0252] A toner used as the standard for evaluation and a toner for
comparison for the toners of the present invention produced in
Example 5 were produced by the following method.
Production Example 3 of Toner for Standard
[0253] A toner (TNR173) for standard was obtained as in Toner
Production Example 4 except that the compound (101) having an azo
skeleton structure was not added.
Production Example 4 of Toner for Standard
[0254] Toners (TNR174) to (TNR176) for standard were obtained as in
Toner Production Example 6 except that the compound (101) having an
azo skeleton structure was not added.
Production Example 3 of Toner for Comparison
[0255] A toner (TNR177) for comparison was obtained as in Toner
Production Example 4 except that the compound (101) having an azo
skeleton structure was changed to DA-703-50 (product of produced by
Kusumoto Chemicals Ltd.) described in Japanese Patent Laid-Open No.
2006-30760.
Production Example 4 of Toner for Comparison
[0256] Toners (TNR178) to (TNR180) for comparison were obtained as
in Production Example 3 of toner for comparison except that the
magenta pigment represented by formula (52) in Production Example 3
of toner for comparison was changed to those represented by
formulae (53) to (55).
Example 6
[0257] Toners obtained in the present invention were evaluated by
the following method.
[0258] The toners (TNR1) to (TNR90) and (TNR91) to (TNR180) were
used to output image samples and the image properties described
below were compared and evaluated. In comparing the image
properties, a modified model of LBP-5300 (produced by Canon
Kabushiki Kaisha) was used as an image forming apparatus
(hereinafter referred to as LBP) to feed paper. The apparatus was
modified by changing a development blade in a process cartridge
(referred to as CRG hereinafter) to a SUS blade having a thickness
of 8 .mu.m. The apparatus was also modified to apply a blade bias
of -200 V relative to development bias applied to a development
roller, which served as a toner bearing member.
Measurement of Weight-Average Particle Size D4 and Number-Average
Particle Size D1 of Toner
[0259] Coulter Multisizer (produced by Beckman Coulter Inc.) was
used and an interface (produced by Nikkaki Bios Co., Ltd.) for
outputting number distribution and volume distribution and a
personal computer were connected thereto. The electrolyte used was
a 1% aqueous NaCl solution using sodium chloride. For example,
ISOTON R-II (produced by Beckman Coulter Inc.) can be used. A
specific measurement procedure is described in catalog (February
2002 version) of Coulter Multisizer published by Coulter and
operation manuals for analyzers. For example, the procedure may be
as follows.
[0260] To 100 to 150 ml of the aqueous electrolyte solution, 2 to
20 mg of a measurement sample was added. The electrolyte in which
the sample was suspended was dispersed with an ultrasonic disperser
for about 1 to 3 minutes and the volume and number of the toner
particles 2.0 .mu.m or more and 64.0 .mu.m or less in size were
measured by using 100 .mu.m apertures of Coulter Multisizer. The
obtained data was distributed into 16 channels to determine the
weight-average particle size D4, the number-average particle size
D1, and the D4/D1 ratio.
Evaluation of Coloring Power of Toner
[0261] In a normal temperature, normal humidity (N/N (23.5.degree.
C., 60% RH)) environment, a solid image with a toner amount of 0.5
mg/cm.sup.2 on a transfer paper (75 g/m.sup.2 paper) was formed. A
reflection densitometer Spectrolino (produced by GretagMacbeth) was
used to measure the density of the solid image. The coloring power
of the toner was evaluated on the basis of the solid image density
improvement rate.
[0262] The solid image density improvement rate for the toners
(TNR1) to (TNR82) was determined on the basis of the solid image
density for the toners (TNR83) to (TNR86) for evaluation.
[0263] The solid image density improvement rate for the toners
(TNR90) to (TNR172) was determined on the basis of the solid image
density for the toners (TNR173) to (TNR176) for evaluation.
[0264] The evaluation standard of the solid image density
improvement rate is as follows.
A: The solid image density improvement rate was 20% or more. B: The
solid image density improvement rate was 10% or more but less than
20%. C: The solid image density improvement rate was 5% or more but
less than 10%. D: The solid image density improvement rate was less
than 5%.
[0265] The coloring power was considered satisfactory as long as
the solid image density improvement rate was 5% or more.
[0266] The results of coloring power evaluation of the toners
prepared by suspension polymerization are shown in Tables 4-1 and
4-2 and the results of coloring power evaluation of the toners
prepared by suspension granulation are shown in Tables 5-1 and
5-2.
Evaluation of Toner Fogging
[0267] In a normal temperature, normal humidity (N/N (23.5.degree.
C., 60% RH)) environment and in a high-temperature, high-humidity
(H/H (30.degree. C., 80% RH)) environment, an image output test of
making 10,000 printouts of an image having a printing ratio of 2%
was conducted on transfer paper (75 g/m.sup.2 paper). At the end of
the test, an image having a white background portion was output.
The whiteness (reflectance Ds (%)) of the white background portion
of the printout image was measured with REFLECTMETER MODEL TC-6DS
(produced by Nippon Denshoku Industries Co., Ltd.) and the
difference between this whiteness and the whiteness (average
reflectance Dr (%)) of the transfer paper was determined [=Dr
(%)-Ds (%)] and assumed to be the fogging density (%). The fogging
at the end of the test was evaluated.
A: Less than 1.0% B: 1.0% or more but less than 2.0% C: 2.0% or
more but less than 3.0% D: 3.0% or more
[0268] The fogging density was evaluated as practically acceptable
as long as the fogging density was less than 3%.
[0269] The evaluation results concerning fogging of the toners
produced by suspension polymerization are shown in Tables 4-1 and
4-2 and the evaluation results concerning fogging of the toners
produced by suspension granulation are shown in Tables 5-1 and
5-2.
Evaluation of Toner Transfer Efficiency
[0270] In a high-temperature, high-humidity (H/H (30.degree. C.,
80% RH)) environment, an image output test of making 10,000
printouts of an image having a printing ratio of 2% was conducted
on transfer paper (75 g/m.sup.2 paper). At the end of the test, the
transfer efficiency was confirmed. A solid image having a toner
amount of 0.65 mg/cm.sup.2 was developed on a drum and then
transferred to a sheet of transfer paper (75 g/m.sup.2 paper) to
obtain an unfixed image. The transfer efficiency was determined on
the basis of the difference in mass between the amount of the toner
on the drum and the amount of the toner on the transfer paper. The
transfer efficiency was assumed to be 100% when all of the toner on
the drum was transferred onto the transfer paper. The evaluation
standard for the transfer efficiency was as follows.
A: The transfer efficiency was 95% or more. B: The transfer
efficiency was 90% or more but less than 95%. C: The transfer
efficiency was 80% or more but less than 90%. D: The transfer
efficiency was less than 80%.
[0271] The transfer efficiency was considered satisfactory if the
transfer efficiency was 80% or more.
[0272] The evaluation results of transfer efficiency of the toners
produced by suspension polymerization are shown in Tables 4-1 and
4-2 and the evaluation results of transfer efficiency of the toners
produced by suspension granulation are shown in Tables 5-1 and
5-2.
Comparative Example 5
[0273] The coloring power, fogging, and transfer efficiency of the
toners (TNR87) to (TNR90), (TNR177) to (TNR180) for comparison were
evaluated as in Example 6.
[0274] The solid image density improvement rate of the toners
(TNR87) to (TNR90) for comparison was evaluated on the basis of the
solid image density of the toners (TNR83) to (TNR86) for
standard.
[0275] The solid image density improvement rate of the toners
(TNR177) to (TNR180) for comparison was evaluated on the basis of
the solid image density of the toners (TNR173) to (TNR176) for
standard.
[0276] The evaluation results for the toners for comparison
prepared by suspension polymerization are shown in Tables 4-1 and
4-2 and the evaluation results for the toners for comparison
prepared by suspension granulation are shown in Tables 5-1 and
5-2.
TABLE-US-00010 TABLE 4-1 Toner particles Pigment Magenta D4
Coloring Fogging Fogging Transfer Toner dispersion Compound pigment
[.mu.m] D4/D1 power [N/N] [H/H] property TNR1 DIS1 101 Formula(52)
6.30 1.17 A A A A TNR2 DIS2 102 Formula(52) 6.27 1.13 A A A A TNR3
DIS3 103 Formula(52) 6.19 1.19 A A A A TNR4 DIS4 104 Formula(52)
6.27 1.16 A A A A TNR5 DIS5 105 Formula(52) 6.15 1.20 A A A A TNR6
DIS6 106 Formula(52) 6.32 1.23 A A A A TNR7 DIS7 107 Formula(52)
6.28 1.19 A A A A TNR8 DIS8 108 Formula(52) 6.42 1.22 A A A A TNR9
DIS9 109 Formula(52) 6.29 1.22 A A A A TNR10 DIS10 110 Formula(52)
6.32 1.18 A A A A TNR11 DIS11 111 Formula(52) 6.23 1.21 A A A A
TNR12 DIS12 112 Formula(52) 6.21 1.20 A A A A TNR13 DIS13 113
Formula(52) 6.09 1.18 A A A A TNR14 DIS14 114 Formula(52) 6.14 1.20
A A A A TNR15 DIS15 115 Formula(52) 6.36 1.18 A A A A TNR16 DIS16
116 Formula(52) 6.11 1.22 A A A A TNR17 DIS17 117 Formula(52) 6.35
1.20 A A A A TNR18 DIS18 118 Formula(52) 6.28 1.17 A A A A TNR19
DIS19 119 Formula(52) 6.06 1.15 A A A A TNR20 DIS20 120 Formula(52)
6.13 1.15 A A A A TNR21 DIS21 121 Formula(52) 6.25 1.18 A A A A
TNR22 DIS22 122 Formula(52) 6.04 1.20 A A A A TNR23 DIS23 123
Formula(52) 6.12 1.16 A A A A TNR24 DIS24 124 Formula(52) 6.19 1.18
A A A A TNR25 DIS25 125 Formula(52) 6.13 1.15 A A A A TNR26 DIS26
126 Formula(52) 6.08 1.19 A A A A TNR27 DIS27 127 Formula(52) 6.05
1.14 A A A A TNR28 DIS28 128 Formula(52) 6.38 1.21 A A A A TNR29
DIS29 129 Formula(52) 6.10 1.23 A A A A TNR30 DIS30 130 Formula(52)
6.44 1.28 B B B B TNR31 DIS31 131 Formula(52) 6.24 1.12 A A A A
TNR32 DIS32 132 Formula(52) 6.09 1.15 A A A A TNR33 DIS33 133
Formula(52) 6.36 1.21 A A A A TNR34 DIS34 134 Formula(52) 6.32 1.15
A A A A TNR35 DIS35 135 Formula(52) 6.16 1.18 A A A A TNR36 DIS36
136 Formula(52) 6.09 1.23 A A A A TNR37 DIS37 137 Formula(52) 6.17
1.20 A A A A TNR38 DIS38 138 Formula(52) 6.26 1.18 A A A A TNR39
DIS39 139 Formula(52) 6.16 1.12 A A A A TNR40 DIS40 140 Formula(52)
6.27 1.20 A A A A TNR41 DIS41 141 Formula(52) 6.42 1.26 B B B B
TNR42 DIS42 142 Formula(52) 6.39 1.29 B B B B TNR43 DIS43 143
Formula(52) 6.62 1.24 B B B B TNR44 DIS44 144 Formula(52) 6.36 1.25
B B B B TNR45 DIS45 145 Formula(52) 6.26 1.21 A A A A
TABLE-US-00011 TABLE 4-2 Toner particles Pigment Magenta D4
Coloring Fogging Fogging Transfer Toner dispersion Compound pigment
[.mu.m] D4/D1 power [N/N] [H/H] property TNR46 DIS46 146
Formula(52) 6.29 1.19 A A A A TNR47 DIS47 147 Formula(52) 6.33 1.17
B B B B TNR48 DIS48 148 Formula(52) 6.19 1.18 B B B B TNR49 DIS49
149 Formula(52) 6.27 1.20 A A A A TNR50 DIS50 150 Formula(52) 6.22
1.15 A A A A TNR51 DIS51 151 Formula(52) 6.35 1.18 A A A A TNR52
DIS52 152 Formula(52) 6.22 1.32 B B B B TNR53 DIS53 153 Formula(52)
6.38 1.25 B B B B TNR54 DIS54 154 Formula(52) 6.20 1.23 B B B B
TNR55 DIS55 155 Formula(52) 6.48 1.30 B B B B TNR56 DIS56 156
Formula(52) 6.27 1.29 B B B B TNR57 DIS57 157 Formula(52) 6.17 1.18
A A A A TNR58 DIS58 158 Formula(52) 6.08 1.21 A A A A TNR59 DIS59
159 Formula(52) 6.21 1.16 A A A A TNR60 DIS60 160 Formula(52) 6.47
1.23 A A A A TNR61 DIS61 161 Formula(52) 6.48 1.30 B B B B TNR62
DIS62 162 Formula(52) 6.21 1.17 A A A A TNR63 DIS63 163 Formula(52)
6.39 1.31 B B B B TNR64 DIS64 164 Formula(52) 6.18 1.15 A A A A
TNR65 DIS65 165 Formula(52) 6.28 1.19 A A A A TNR66 DIS66 166
Formula(52) 6.26 1.15 A A A A TNR67 DIS67 167 Formula(52) 6.17 1.24
A A A A TNR68 DIS68 168 Formula(52) 6.30 1.18 A A A A TNR69 DIS69
169 Formula(52) 6.26 1.22 A A A A TNR70 DIS70 170 Formula(52) 6.31
1.26 A A A A TNR71 DIS71 171 Formula(52) 6.27 1.19 A A A A TNR72
DIS72 172 Formula(52) 6.13 1.21 A A A A TNR73 DIS73 173 Formula(52)
6.30 1.25 A A A A TNR74 DIS74 174 Formula(52) 6.40 1.29 B B B B
TNR75 DIS75 175 Formula(52) 6.37 1.23 B B B B TNR76 DIS76 176
Formula(52) 6.44 1.25 B B B B TNR77 DIS77 177 Formula(52) 6.11 1.28
B B B B TNR78 DIS78 178 Formula(52) 6.30 1.22 B B B B TNR79 DIS79
179 Formula(52) 6.14 1.28 B B B B TNR80 DIS80 101 Formula(53) 6.06
1.18 A A A A TNR81 DIS81 101 Formula(54) 6.25 1.22 A A A A TNR82
DIS82 101 Formula(55) 6.11 1.18 A A A A TNR83 DIS83 None
Formula(52) 6.82 1.32 D D D D TNR84 DIS84 None Formula(53) 6.51
1.25 D D D D TNR85 DIS85 None Formula(54) 6.68 1.29 D D D D TNR86
DIS86 None Formula(55) 6.60 1.23 D D D D TNR87 DIS87 Comparative
Formula(52) 7.25 1.38 D D D D compound 1 TNR88 DIS88 Comparative
Formula(53) 6.92 1.33 D D D D compound 1 TNR89 DIS89 Comparative
Formula(54) 7.01 1.31 D D D D compound 2 TNR90 DIS90 Comparative
Formula(55) 6.73 1.34 D D D D compound 3
TABLE-US-00012 TABLE 5-1 Toner particles Magenta D4 Coloring
Fogging Fogging Transfer Toner Compound pigment [.mu.m] D4/D1 power
[N/N] [H/H] property TNR91 101 Formula(52) 6.19 1.21 A A A A TNR92
102 Formula(52) 6.34 1.24 A A A A TNR93 103 Formula(52) 6.30 1.17 A
A A A TNR94 104 Formula(52) 6.27 1.20 A A A A TNR95 105 Formula(52)
6.13 1.22 A A A A TNR96 106 Formula(52) 6.31 1.21 A A A A TNR97 107
Formula(52) 6.39 1.19 A A A A TNR98 108 Formula(52) 6.32 1.20 A A A
A TNR99 109 Formula(52) 6.38 1.21 A A A A TNR100 110 Formula(52)
6.22 1.19 A A A A TNR101 111 Formula(52) 6.27 1.20 A A A A TNR102
112 Formula(52) 6.20 1.19 A A A A TNR103 113 Formula(52) 6.13 1.18
A A A A TNR104 114 Formula(52) 6.08 1.22 A A A A TNR105 115
Formula(52) 6.19 1.24 A A A A TNR106 116 Formula(52) 6.16 1.18 A A
A A TNR107 117 Formula(52) 6.25 1.17 A A A A TNR108 118 Formula(52)
6.22 1.24 A A A A TNR109 119 Formula(52) 6.14 1.21 A A A A TNR110
120 Formula(52) 6.33 1.18 A A A A TNR111 121 Formula(52) 6.21 1.19
A A A A TNR112 122 Formula(52) 6.11 1.17 A A A A TNR113 123
Formula(52) 6.13 1.15 A A A A TNR114 124 Formula(52) 6.08 1.16 A A
A A TNR115 125 Formula(52) 6.04 1.19 A A A A TNR116 126 Formula(52)
6.02 1.17 A A A A TNR117 127 Formula(52) 6.08 1.15 A A A A TNR118
128 Formula(52) 6.36 1.24 A A A A TNR119 129 Formula(52) 6.19 1.22
A A A A TNR120 130 Formula(52) 6.24 1.32 B B B B TNR121 131
Formula(52) 6.33 1.27 A A A A TNR122 132 Formula(52) 6.07 1.21 A A
A A TNR123 133 Formula(52) 6.30 1.20 A A A A TNR124 134 Formula(52)
6.24 1.24 A A A A TNR125 135 Formula(52) 6.19 1.26 A A A A TNR126
136 Formula(52) 6.26 1.19 A A A A TNR127 137 Formula(52) 6.28 1.26
A A A A TNR128 138 Formula(52) 6.11 1.19 A A A A TNR129 139
Formula(52) 6.23 1.23 A A A A TNR130 140 Formula(52) 6.30 1.24 A A
A A TNR131 141 Formula(52) 6.25 1.29 B B B B TNR132 142 Formula(52)
6.49 1.30 B B B B TNR133 143 Formula(52) 6.52 1.31 B B B B TNR134
144 Formula(52) 6.32 1.33 B B B B TNR135 145 Formula(52) 6.33 1.21
A A A A
TABLE-US-00013 TABLE 5-2 Toner particles Magenta D4 Coloring
Fogging Fogging Transfer Toner Compound pigment [.mu.m] D4/D1 power
[N/N] [H/H] property TNR136 146 Formula(52) 6.35 1.21 A A A A
TNR137 147 Formula(52) 6.47 1.28 B B B B TNR138 148 Formula(52)
6.39 1.30 B B B B TNR139 149 Formula(52) 6.09 1.18 A A A A TNR140
150 Formula(52) 6.39 1.22 A A A A TNR141 151 Formula(52) 6.31 1.24
A A A A TNR142 152 Formula(52) 6.13 1.33 B B B B TNR143 153
Formula(52) 6.27 1.30 B B B B TNR144 154 Formula(52) 6.22 1.28 B B
B B TNR145 155 Formula(52) 6.38 1.27 B B B B TNR146 156 Formula(52)
6.43 1.30 B B B B TNR147 157 Formula(52) 6.32 1.16 A A A A TNR148
158 Formula(52) 6.14 1.21 A A A A TNR149 159 Formula(52) 6.23 1.28
A A A A TNR150 160 Formula(52) 6.36 1.19 A A A A TNR151 161
Formula(52) 6.31 1.32 B B B B TNR152 162 Formula(52) 6.30 1.27 A A
A A TNR153 163 Formula(52) 6.24 1.29 B B B B TNR154 164 Formula(52)
6.26 1.26 A A A A TNR155 165 Formula(52) 6.25 1.25 A A A A TNR156
166 Formula(52) 6.32 1.21 A A A A TNR157 167 Formula(52) 6.11 1.25
A A A A TNR158 168 Formula(52) 6.32 1.26 A A A A TNR159 169
Formula(52) 6.32 1.28 A A A A TNR160 170 Formula(52) 6.14 1.19 A A
A A TNR161 171 Formula(52) 6.22 1.26 A A A A TNR162 172 Formula(52)
6.17 1.22 A A A A TNR163 173 Formula(52) 6.14 1.19 A A A A TNR164
174 Formula(52) 6.30 1.25 B B B B TNR165 175 Formula(52) 6.29 1.31
B B B B TNR166 176 Formula(52) 6.41 1.30 B B B B TNR167 177
Formula(52) 6.37 1.32 B B B B TNR168 178 Formula(52) 6.44 1.31 B B
B B TNR169 179 Formula(52) 6.58 1.32 B B B B TNR170 101 Formula(53)
6.12 1.23 A A A A TNR171 101 Formula(54) 6.28 1.29 A A A A TNR172
101 Formula(55) 6.11 1.18 A A A A TNR173 None Formula(52) 6.69 1.35
D D D D TNR174 None Formula(53) 6.53 1.33 D D D D TNR175 None
Formula(54) 6.48 1.30 D D D D TNR176 None Formula(55) 6.42 1.27 D D
D D TNR177 Comparative Formula(52) 6.38 1.29 D D D D compound 1
TNR178 Comparative Formula(53) 6.40 1.27 D D D D compound 1 TNR179
Comparative Formula(54) 6.59 1.34 D D D D compound 1 TNR180
Comparative Formula(55) 6.61 1.30 D D D D compound 1
[0277] Table 3 clearly shows that the dispersibility of the magenta
pigment into the binder resin is improved by using a compound
having an azo skeleton structure.
[0278] Tables 4-1 and 4-2 clearly show that use of a compound
having an azo skeleton structure improves dispersibility of the
magenta pigment into the binder resin and thus a magenta toner with
satisfactory coloring power is provided. Use of a compound having
an azo skeleton structure also suppresses fogging and a magenta
toner that has high transfer efficiency is provided. Tables 5-1 and
5-2 clearly show that even when suspension granulation is employed,
the dispersibility of the magenta pigment into the binder resin is
improved, fogging is suppressed, and a toner having satisfactory
coloring power as well as high transfer efficiency is provided.
[0279] While the present invention has been described with
reference to exemplary embodiments, it is to be understood that the
invention is not limited to the disclosed exemplary embodiments.
The scope of the following claims is to be accorded the broadest
interpretation so as to encompass all such modifications and
equivalent structures and functions.
[0280] This application claims the benefit of Japanese Patent
Application No. 2012-043073 filed Feb. 29, 2012, which is hereby
incorporated by reference herein in its entirety.
* * * * *