U.S. patent application number 12/402232 was filed with the patent office on 2009-09-17 for pyrazolotriazole compound and electrophotographic toner.
This patent application is currently assigned to KONICA MINOLTA BUSINESS TECHNOLOGIES, INC.. Invention is credited to Koji DAIFUKU, Keiko ISHIDAI, Ryohei IWAMOTO, Issei NAKAHARA, Kaori ONO, Kimihiko OOKUBO.
Application Number | 20090233207 12/402232 |
Document ID | / |
Family ID | 40888143 |
Filed Date | 2009-09-17 |
United States Patent
Application |
20090233207 |
Kind Code |
A1 |
OOKUBO; Kimihiko ; et
al. |
September 17, 2009 |
PYRAZOLOTRIAZOLE COMPOUND AND ELECTROPHOTOGRAPHIC TONER
Abstract
A compound represented by Formula (X-1) is disclosed.
##STR00001## in the formula, Rx.sub.1, and Rx.sub.2 each
independently represents an alkyl group, Lx is a hydrogen atom or
an alkyl group, Gx.sub.1 is an alkyl group having 2 or more carbon
atoms, Gx.sub.2 is an alkyl group or an aromatic hydrocarbon group,
Gx.sub.3 is a hydrogen atom, a halogen atom, a Gx.sub.4-CO--NH--
group or a Gx.sub.5-N(Gx.sub.6)-CO-- group, Gx.sub.5 and Gx.sub.6
each independently represents a hydrogen atom or a substituent, and
Qx.sub.1, Qx.sub.2, Qx.sub.3, Qx.sub.4 and Qx.sub.5 each
independently represents a hydrogen atom or a substituent. An
electrophotographic toner containing the compound is also
disclosed.
Inventors: |
OOKUBO; Kimihiko; (Tokyo,
JP) ; IWAMOTO; Ryohei; (Tokyo, JP) ; DAIFUKU;
Koji; (Tokyo, JP) ; ISHIDAI; Keiko; (Tokyo,
JP) ; ONO; Kaori; (Tokyo, JP) ; NAKAHARA;
Issei; (Tokyo, JP) |
Correspondence
Address: |
LUCAS & MERCANTI, LLP
475 PARK AVENUE SOUTH, 15TH FLOOR
NEW YORK
NY
10016
US
|
Assignee: |
KONICA MINOLTA BUSINESS
TECHNOLOGIES, INC.
Tokyo
JP
|
Family ID: |
40888143 |
Appl. No.: |
12/402232 |
Filed: |
March 11, 2009 |
Current U.S.
Class: |
430/108.11 ;
430/108.21; 548/262.4 |
Current CPC
Class: |
C09B 23/04 20130101;
G03G 9/0924 20130101; G03G 9/0906 20130101 |
Class at
Publication: |
430/108.11 ;
548/262.4; 430/108.21 |
International
Class: |
G03G 9/09 20060101
G03G009/09; C07D 487/04 20060101 C07D487/04; G03G 9/087 20060101
G03G009/087 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 14, 2008 |
JP |
2008065484 |
Claims
1. A compound represented by Formula (X-1), ##STR00030## in the
formula, Rx.sub.1 and Rx.sub.2 each independently represents an
alkyl group, Lx is a hydrogen atom or an alkyl group, Gx.sub.1 is
an alkyl group having 2 or more carbon atoms, Gx.sub.2 is an alkyl
group or an aromatic hydrocarbon group, Gx.sub.3 is a hydrogen
atom, a halogen atom, a Gx.sub.4-CO--NH-- group or a
Gx.sub.5-N(Gx.sub.6)-CO-- group, Gx.sub.4 is a substituent,
Gx.sub.5 and Gx.sub.6 each independently represents a hydrogen atom
or a substituent, and Qx.sub.1, Qx.sub.2, Qx.sub.3, Qx.sub.4 and
Qx.sub.5 are each independently a hydrogen atom or a
substituent.
2. The compound of claim 1, wherein Gx.sub.1 is a branched alkyl
group.
3. The compound of claim 1, wherein Lx is a hydrogen atom.
4. The compound of claim 1, wherein Gx.sub.3 is a hydrogen
atom.
5. The compound of claim 1, wherein Gx.sub.1 is a tertiary alkyl
group.
6. The compound of claim 1, wherein Gx.sub.4 is an alkyl group or
an aryl group.
7. The compound of claim 1, wherein Gx.sub.5 and Gx.sub.6 is an
alkyl group.
8. The compound of claim 1, wherein Qx.sub.1, Qx.sub.2, Qx.sub.3,
Qx.sub.4 and each represents a hydrogen atom.
9. A color toner for an electrophotography comprising a resin and a
compound represented by formula (X-1) of claim 1, ##STR00031## in
the formula, Rx.sub.1 and Rx.sub.2 each independently represents an
alkyl group, Lx is a hydrogen atom or an alkyl group, Gx.sub.1 is
an alkyl group having 2 or more carbon atoms, Gx.sub.2 is an alkyl
group or an aromatic hydrocarbon group, Gx.sub.3 is a hydrogen
atom, a halogen atom, a Gx.sub.4-CO--NH-- group or a
Gx.sub.5-N(Gx.sub.6)-CO-- group, Gx.sub.4 is a substituent,
Gx.sub.5 and Gx.sub.6 each independently represents a hydrogen atom
or a substituent, and Qx.sub.1, Qx.sub.2, Qx.sub.3, Qx.sub.4 and
Qx.sub.5 each independently represents a hydrogen atom or a
substituent.
10. The color toner for an electrophotography of claim 9, which
further comprises a compound represented by Formula (1),
##STR00032## in the Formula (1) R.sub.1 is a hydrogen atom or a
substituent, R.sub.2 is an alky group, an alkenyl group, an alkynyl
group, an aryl group, a heterocyclic group, an alkoxycarbonyl
group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl
group, an alkylsulfonyl group, an arylsulfonyl group or a cyano
group, in which at least one of R.sub.1, and R.sub.2 is an electron
attractive group, and R.sub.3 is an alky group having 3 or more
carbon atoms, an alkenyl group, an alkynyl group, an aryl group or
a heterocyclic group, with proviso that number of carbon atoms in
one molecule of the ligand represented by formula (1) is 25 or
less.
11. The color toner for an electrophotography of claim 10, wherein
R.sub.1 is an alky group, an alkenyl group, an aryl group, a
heterocyclic group, an alkoxycarbonyl group, an acyl group, a
carbamoyl group or a cyano group.
12. The color toner for an electrophotography of claim 11, wherein
R.sub.1 is an alky group, an aryl group, a heterocyclic group or a
cyano group.
13. The color toner for an electrophotography of claim 12, wherein
R.sub.1 is a trifluoromethyl group or a trichloromethyl group.
14. The color toner for an electrophotography of claim 10, wherein
R.sub.2 is an alky group, a cyano group, a sulfinyl group, or
sulfonyl group.
15. The color toner for an electrophotography of claim 14, wherein
R.sub.2 is a cyano group, a sulfinyl group or a sulfonyl group.
16. The color toner for an electrophotography of claim 11, wherein
R.sub.3 is an alky group having 3 or more carbon atoms, an alkenyl
group, an alkynyl group, an aryl group or a heterocyclic group.
17. The color toner for an electrophotography of claim 16, wherein
R.sub.3 is an alky group having B or more carbon atoms.
Description
[0001] This application is based on Japanese Patent Application No.
2008-65484 filed on Mar. 14, 2008, in Japanese Patent Office, the
entire content of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The present invention relates to a compound having a
specific structure and further an electrophotographic toner
containing the compound.
[0004] 2. Description of Related Art
[0005] A substance of an organic compound is known as an organic
dye which gives a color to a material by absorption of visible
light. The organic dye is widely utilized in various fields such as
dying of fabrics, colorant for resin or paint, image forming
material for photography, printing, copying apparatus and printer,
and light absorbent of color filter by utilizing a function to give
a color to a material. Various image forming dyes are proposed for
forming color hard copy employing methods such as inkjet,
electrophotography, silver salt photography and thermal transfer.
Demands of dyes for a filter dye for a camera tube or a liquid
crystal color television, a light image recording medium employing
semiconductor laser, in accordance to a development of an
electronic imaging. Thus the fields utilizing the dye expand
recently. The dye is commonly expected to have the following
properties.
[0006] The properties include good hue for color reproduction,
optimum spectroscopic characteristics, image fastness against
light, heat, moisture and chemicals, and large molecular absorbancy
index.
[0007] The dye is usually used as an electrophotographic toner
wherein the dye is mixed and dispersed together with a medium such
as a binding resin in a color copying machine or a color printer
utilizing electrophotography. The dye used for the
electrophotographic toner is preferable to have properties
mentioned above. The other properties required for the
electrophotographic toner are color reproduction, transparency of
an image, inhibition or reduction of stain on a fixing roller
surface or inside of printer frame, minimized image blur in fixed
image, and Loners satisfying these properties are disclosed, for
example, Patent Documents 1 and 2.
[0008] A demand for larger amount production with shorter delivery
time is further enhanced since these toners attain the properties
mentioned above with high level and are very high performance.
Further improvement in dye is required in adaptation of a toner
production process in which the used dyes have several insufficient
matters.
[0009] Patent Document 1: JP A 2006-350300
[0010] Patent Document 2: JP A 2007-34264
SUMMARY
[0011] The present invention is practiced to dissolve these
problems mentioned above. An object of this invention is to provide
a compound more adaptable for a toner production process, and
another objection is to provide an electrophotographic toner having
excellent adaptability to the production process.
[0012] The present invention is described.
[0013] A compound represented by Formula (X-1).
##STR00002##
[0014] In the formula, Rx.sub.1 and R.sub.2 each independently
represent an alkyl group, Lx is a hydrogen atom or an alkyl group,
Gx.sub.1 is an alkyl group having 2 or more carbon atoms, Gx.sub.2
is an alkyl group or an aromatic hydrocarbon group, Gx.sub.3 is a
hydrogen atom, a halogen atom, a Gx.sub.4-CO--NH-- group or a
Gx.sub.5-N(Gx.sub.6)-CO-- group, Gx.sub.5 and Gx.sub.6 each
independently represent a hydrogen atom or a substituent, and
Qx.sub.1, Qx.sub.2, Qx.sub.3, Qx.sub.4 and Qx.sub.5 each
independently represent a hydrogen atom or a substituent.
[0015] The compound represented by Formula (X-1) is suitably
employed for an electrophotographic toner.
[0016] A compound more adaptable for a toner production process is
provided. An electrophotographic toner having excellent
adaptability to the production process is provided by the present
invention.
[0017] The compound represented by Formula X-1 is described
below.
[0018] In the formula, Rx.sub.1 and Rx.sub.2 are each independently
an alkyl group which may be a straight-chain alkyl group, a
branched-chain alkyl group or a cycloalkyl group, and the alkyl
groups represented by Rx.sub.1 or Rx.sub.2 may be the same or
different. In concrete, examples of the straight- and
branched-chain alkyl group include a methyl group, an ethyl group,
a propyl group, an isopropyl group, an n-butyl group, an isobutyl
group, a tert-butyl group, a pentyl group, an amyl group, an
isoamyl group, a hexyl group, an octyl group, a dodecyl group, a
tridecyl group, a tetradecyl group and a pentadecyl group, and
those of the cycloalkyl group include a cyclopropyl group, a
cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a
4-tert-butyl-cyclohexyl group. The straight-chain alkyl groups and
the branched-chain alkyl groups are preferred.
[0019] The alkyls group represented by Rx.sub.1 or Rx.sub.2 each
may have a substituent. The group substitutable on the alkyl group
is not specifically limited and examples of that include the above
described alkyl groups and cycloalkyl groups; an alkenyl group such
as a vinyl group and an allyl group; an alkynyl group such as a
ethynyl group and a propargyl group; an aromatic hydrocarbon group
such as a phenyl group and a naphthyl group; an aromatic
heterocyclic group such as a furyl group, a thienyl group, a
pyridyl group, a pyridazyl group, a pyrimidyl group, a pyrazyl
group, a triazyl group, an imidazolyl group, a pyrazolyl group, a
thiazolyl group, a benzimidazolyl group, a benzoxyazolyl group, a
quinazolyl group and a phthalazyl group, a heterocyclic group such
as a pyrrolidinyl group, an imidazolidinyl group, a morpholyl group
and an oxazolidinyl; an alkoxyl group such as a methoxy group, an
ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy
group, an octyloxy group and a dodecyloxy group; a cycloalkoxyl
group such as a cyclopentyloxy group and a cyclohexyloxy group; an
aryloxyl group such as a phenoxy group and a naphthyloxy group; an
alkylthio group such as a methylthio group, an ethylthio group, a
propylthio group, a pentylthio group, a hexylthio group, an
octylthio group and a dodecylthio group; a cycloalkylthio group
such as a cyclopentylthio group and a cyclohexylthio group; an
arylthio group such as a phenylthio group and a naphthylthio group;
an alkoxycarbonyl group such as a methyloxycarbonyl group, an
ethyloxycarbonyl group, a butyloxycarbonyl group, an
octyloxycarbonyl group and a dodecyloxycarbonyl group; an
aryloxycarbonyl group such as a phenyloxycarbonyl group and a
naphthyloxycarbonyl group; a phosphoryl such as a
dimethoxyphosphoryl group and a diphenylphosphoryl group; a
sulfamoyl group such as an aminosulfonyl group, a
methylaminosulfonyl group, a dimethylaminosulfonyl group, a
butylaminosulfonyl group, a hexylaminosulfonyl group, a
cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a
dodecylaminosulfonyl group, a phenylaminosulfonyl group, a
naphthylaminosulfonyl group and a 2-pyridylaminosulfonyl group; an
acyl group such as an acetyl group, an ethylcarbonyl group, a
propylcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl
group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a
dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl
group and a pyridylcarbonyl group; an acyloxy group such as an
acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy
group, an octylcarbonyloxy group, a dodecylcarbonyloxy group and a
phenylcarbonyloxy group; an amido group such as a
methylcarbonylamino group, an ethylcarbonylamino group, a
dimethylcarbonylamino group, a propylcarbonylamino group, a
pentylcarbonylamino group, a cyclohexylcarbonylamino group,
2-ethylhexylcarbonylamino group, an octylcarbonylamino group, a
dodecylcarbonylamino group, a phenylcarbonylamino group and a
naphthylcarbonylamino group; a carbamoyl group such as an
aminocarbonyl group, a methylaminocarbonyl group, a
dimethylaminocarbonyl group, a propylaminocarbonyl group, a
pentylaminocarbonyl group, a cyclohexylaminocarbonyl group, an
octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a
dodecylaminocarbonyl group, a phenylaminocarbonyl group, a
naphthylaminocarbonyl group and a 2-pyridylamino-carbonyl group; a
ureido group such as a methylureido group, an ethylureido group, a
pentylureido group, a cyclohexylureido group, an octylureido group,
a dodecylureido group, a phenylureido group, a naphthylureido group
and a 2-pyridylureido group, a sulfinyl group such as a
methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl
group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a
dodecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl
group and a 2-pyridylsulfinyl group; an alkylsulfonyl group such as
a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl
group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group and
a dodecylsulfonyl group; an arylsulfonyl group such as a
phenylsulfonyl group, a naphthylsulfonyl group and a
2-pyridylsulfonyl group; an amino group such as an amino group, an
ethylamino group, a dimethylamino group, a butylamino group, a
dibutylamino group, a cyclopentylamino group, a 2-ethylhexylamino
group, a dodecylamino group, an anilino group, a naphthylamino
group and a 2-pyridylamino group; an azo group such as a phenylazo
group; an alkylsulfonyloxy group such as a methanesulfonyloxy
group; a cyano group; a nitro group; a halogen atom such as a
fluorine atom, a chlorine atom and a bromine atom, and a hydroxyl
group.
[0020] These groups each may further have a substituent. Preferable
examples of the substituent capable of substituting on the alkyl
group represented by Rx.sub.1 or Rx.sub.2 are the aromatic
hydrocarbon group, alkoxyl group, cycloalkyl group, halogen atom
and hydroxyl group.
[0021] As the alkyl group represented by Rx.sub.1 or Rx.sub.2,
unsubstituted alkyl groups and those substituted by the alkoxyl
group are preferable and the unsubstituted alkyl groups are most
preferable.
[0022] The total number of carbon atoms contained in the alkyl
group represented by Rx.sub.1 and Rx.sub.2 is preferably not less
than 8 and more preferably not less than 12 and most preferably not
less than 16.
[0023] Lx is a hydrogen atom or an alkyl group, and preferably a
hydrogen atom. When Lx is an alkyl group, the alkyl group is
synonym for the alkyl group represented by Rx.sub.1 or Rx.sub.2 and
is preferably an alkyl group having 1 to 5 carbon atoms and more
preferably a methyl group or an ethyl group.
[0024] Gx.sub.1 represents an alkyl group having 2 or more carbon
atoms, and the alkyl group may be any of a straight-chain alkyl
group, a branched-chain alkyl group and a cycloalkyl group.
Concrete examples of the straight- and branched-chain alkyl group
include an ethyl group, a propyl group, an isopropyl group, an
n-butyl group, an isobutyl group, a tert-butyl group, a pentyl
group, an amyl group, an isoamyl group, a hexyl group, an octyl
group, a dodecyl group, a tridecyl group, a tetradecyl group and a
pentadecyl group, and those of the cycloalkyl group include a
cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a
cyclohexyl group and a 4-tert-butyl-cyclohexyl group. Among them,
the branched-alkyl groups are preferable and the tertiary alkyl
group is more preferable and the tert-butyl group is most
preferable.
[0025] Gx.sub.2 is an alkyl group or an aromatic hydrocarbon group,
the alkyl group is synonym for the alkyl group represented by
Rx.sub.1 and Rx.sub.2 and the aromatic hydrocarbon group is, for
example, a phenyl group or a naphthyl group, and is preferably the
alkyl group, more preferably the alkyl group having 1 to 5 carbon
atoms and further preferably a methyl group or an ethyl group.
[0026] Gx.sub.3 is a halogen atom, a Gx.sub.4-CO--NH-- group or a
Gx.sub.5-N(Gx.sub.6)-CO-- group and preferably a hydrogen atom.
Gx.sub.4 each represents a substituent. As the substituent, a group
synonym for the substituent capable of substituting on the alkyl
group represented by Rx.sub.1 and Rx.sub.2, and preferably a group
synonym for the alkyl group represented by Rx.sub.1 or Rx.sub.2 or
an aromatic hydrocarbon group.
[0027] Gx.sub.5 and Gx.sub.6 are each a hydrogen atom or a
substituent. As the substituent, groups synonym for the group
capable of substituting with the alkyl group represented by
Rx.sub.1 or Rx.sub.2 are cited, and the alkyl groups synonym for
the alkyl groups represented by Rx.sub.1 or Rx.sub.2 are
preferable.
[0028] Qx.sub.1, Qx.sub.2, Qx.sub.3, Qx.sub.4, Qx.sub.5 and
Qx.sub.6 are each independently a hydrogen atom or a substituent,
and the groups synonym for the groups represented by Gx.sub.1 can
be cited as the substituent. It is preferable that Qx.sub.1,
Qx.sub.2, Qx.sub.3, Qx.sub.4, Qx.sub.5 and Qx.sub.6 are each
independently a hydrogen atom, an alkyl group, a halogen atom or an
alkoxyl group and is most preferable that they are hydrogen
atoms.
[0029] Concrete examples of the compound represented by Formula X-1
are shown below. Isomers are included when they exist.
##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007##
##STR00008## ##STR00009##
[0030] The compound represented by formula (X-1) can be synthesized
by methods described, for example, following documents; JP A
S63-226653, JP A H10-193807, JP A H 11-78258, JP A H 6-250357, JP A
H 2-155693, JP A H01-110565, JP A H02-668, JP A H02-28264, JP A
H02-53865, JP A H02-53866, British Patent 1,252,418, JP A
S64-63194, JP A H02-208094, JP A H03-205189, JP A H 02-265791, JP A
H02-310087, JP A H02-53866, JP A H04-91987, JP A S63-205288, JP A
H03-226750, British Patent 1,183/515, JP A H04-190348, JP A
S63-113077, JP A H03-275767, JP A H04-13774, JP A H04-89287, JP A
H07-175187, JP A H10-60296, JP A H11-78258, JP A 2004-1138834, and
JP A 2006-350300.
[0031] Synthesis examples of the compounds represented by formula
(X-1) are described, and the other compounds may be synthesized by
a similar synthesis method. These can be synthesized by other
way.
SYNTHESIS EXAMPLE 1
Synthesis of Exemplified Compound DX-1
##STR00010##
[0033] Fifty milliliter of toluene and 0.35 g of morpholine were
added to 1.93 g of Intermediate 1 and 1.53 g of Intermediate 2
while stirring and heated and refluxed to make reaction for 8 hours
while dehydrating by using an esterifying tube. After finishing of
the reaction, the reacting liquid was concentrated and purified by
column chromatography and recrystallized from the ethyl
acetate/hexane mixed solvent to obtain 2.71 g of DX-1. It was
confirmed by MASS, .sup.1H-NMR and IR spectrum that the obtained
material was the objective substance. The maximum absorption
wavelength in visible light absorption spectrum (solvent: ethyl
acetate) was 535 nm and the mole absorbancy index was 71,000
(L/molecm).
SYNTHESIS EXAMPLE 2
Synthesis of Exemplified Compound DX-2
##STR00011##
[0035] Exemplified Compound DX-2 was obtained in the same manner as
in Synthesis Example 1 except that Intermediate 1 was replaced by
Intermediate 3 and Intermediate 2 was replaced by Intermediate 4,
and recrystallization solvent was replaced by methanol. The maximum
absorption wavelength in visible light absorption spectrum
(solvent: ethyl acetate) was 522 nm and the mole absorbancy index
was 53,000 (L/molecm).
SYNTHESIS EXAMPLE 3
Synthesis of Exemplified Compound DX-3
##STR00012##
[0037] Exemplified Compound DX-2 was obtained in the same manner as
in Synthesis Example 2 except that Intermediate 4 was replaced by
Intermediate 5 The maximum absorption wavelength in visible light
absorption spectrum (solvent: ethyl acetate) was 544 nm and the
mole absorbancy index was (L/molecm).
SYNTHESIS EXAMPLE 4
Synthesis of Exemplified Compound DX-4
##STR00013##
[0039] Exemplified Compound DX-4 was obtained in the same manner as
in Synthesis Example 1 except that Intermediate 2 was replaced by
Intermediate 6. The maximum absorption wavelength in visible light
absorption spectrum (solvent: ethyl acetate) was 532 nm and the
mole absorbancy index was 60,000 (L/molecm).
SYNTHESIS EXAMPLE 5
Synthesis of Exemplified Compound DX-5
##STR00014##
[0041] Exemplified Compound DX-5 having a melting point of from
96.5 to 97.5.degree. C. was obtained in the same manner as in
Synthesis Example 1 except that Intermediate 2 was replaced by
Intermediate 5 used in the Synthesis Example 3. The maximum
absorption wavelength in visible light absorption spectrum
(solvent: ethyl acetate) was 533 nm and the mole absorbancy index
was 66,600 (L/molecm).
SYNTHESIS EXAMPLE 6
Synthesis of Exemplified Compound DX-6
##STR00015##
[0043] Exemplified Compound DX-6 was obtained in the same manner as
in Synthesis Example 1 except that Intermediate 2 was replaced by
Intermediate 7. The maximum absorption wavelength in visible light
absorption spectrum (solvent: ethyl acetate) was 526 nm and the
mole absorbancy index was 61,000 (L/molecm).
SYNTHESIS EXAMPLE 7
Synthesis of Exemplified Compound DX7
##STR00016##
[0045] Exemplified Compound DX-7 was obtained in the sane manner as
in Synthesis Example 2 except that Intermediate 4 was replaced by
Intermediate 7 and recrystallization solvent was replaced by
mixture of ethylacetate and hexane. The maximum absorption
wavelength in visible light absorption spectrum (solvent: ethyl
acetate) was 523 nm and the mole absorbancy index was 56,000
(L/molecm).
SYNTHESIS EXAMPLE 8
Synthesis of Exemplified compound DX-9
##STR00017##
[0047] Exemplified Compound DX-9 was obtained in the same manner as
in Synthesis Example 1 except that Intermediate 1 was replaced by
Intermediate 9. The maximum absorption wavelength in visible light
absorption spectrum (solvent: ethyl acetate) was 533 nm.
SYNTHESIS EXAMPLE 9
Synthesis of Exemplified Compound DX-10
##STR00018##
[0049] Exemplified Compound DX-10 was obtained in the same manner
as in Synthesis Example 1 except that Intermediate 1 was replaced
by Intermediate 10. The maximum absorption wavelength in visible
light absorption spectrum (solvent: ethyl acetate) was 532 nm.
[0050] The color toner for an electrophotography of this invention
is preferably to further comprise a compound represented by Formula
(1).
##STR00019##
[0051] R.sub.1 is a hydrogen atom or a substituent, R.sub.2 is an
alky group, an alkenyl group, an alkynyl group, an aryl group, a
heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl
group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group,
an arylsulfonyl group and a cyano group, in which at least one of
R.sub.1 and R.sub.2 is an electron attractive group, and R.sub.3 is
an alky group having 3 or more carbon atoms, an alkenyl group, or
an alkynyl group, an aryl group or a heterocyclic group, with
proviso that number of carbon atoms in one molecule of the ligand
represented by formula (1) is 25 or less.
[0052] Metal containing compounds represented by formula (1) will
be described.
[0053] Metal containing compounds represented by formula (1) are
preferably those obtained by reacting the compounds represented by
formula (1) after their synthesis with a divalent copper compound.
The metal containing organic compound can be synthesized in
accordance of the description of "Chelate Chemistry (5) Complex
Chemistry Experiment Method [1], Nankodo edition" or so. The
divalent cupric compounds are copper chloride, and cupric acetate,
and cupric acetate is preferably employed.
##STR00020##
[0054] The metal containing compounds may have a neutral ligand if
necessary, representative example of which includes H.sub.2O and
NH.sub.3.
[0055] R.sub.1 is a hydrogen atom or a substituent in formula (1).
The substituent includes an alky group such as a methyl group, an
ethyl group, a propyl group, an isopropyl group, a tert-butyl
group, a pentyl group, a hexyl group, an octyl group, a dodecyl
group, a tridecyl group, a tetradecyl group and a pentadecyl group,
a chloromethyl group, a trifluoromethyl group, a tribromomethyl
group, a pentafluoroethyl group, and a methoxyethyl group; a
cycloalkyl group such as a cyclopentyl group and a cyclohexyl
group; an alkenyl group such as a vinyl group and an allyl group;
an alkynyl group such as an ethynyl group and a propargyl group; an
aryl group such as a phenyl group, a naphthyl group, a
p-nitrophenyl group, a p-fluorophenyl group, and a p-methoxy phenyl
group; a heterocyclic group such as a furyl group, a thienyl group,
a pyridyl group, pyridazyl group, pyrimidyl group, a pyrazyl group,
a triazyl group, an imidazolyl group, a pyrazolyl group, a
thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, a
quinazolyl group, a phthalazyl group, a pyrrolidinyl group, an
imidazolidinyl group, a morpholyl group, and an oxazolidinyl group;
an alkoxycarbonyl group such as a methyloxycarbonyl group, an
ethyloxycarbonyl group, a butyloxycarbonyl group, an
octyloxycarbonyl group and a dodecyloxycarbonyl group; an
aryloxycarbonyl group such as a phenyloxycarbonyl group and a
naphthyloxycarbonyl group; a sulfamoyl group such as an
aminosulfonyl group, a methylaminosulfonyl group, a
dimethylaminosulfonyl group, a butylaminosulfonyl group, a
hexylaminosulfonyl group, a cyclohexylaminosulfonyl group, an
octylaminosulfonyl group, a dodecylaminosulfonyl group, a
phenylaminosulfonyl group, a naphthylaminosulfonyl group and a
2-pyridylaminosulfonyl group; an acyl group such as an acetyl
group, an ethylcarbonyl group, a propylcarbonyl group, a
pentylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl
group, a 2-ethylheaxylcarbonyl group, a dodecylcarbonyl group, a
phenylcarbonyl group, a naphthylcarbonyl group and a
pyridylcarbonyl group; a carbamoyl group such as an aminocarbonyl
group, a methylaminocarbonyl group, a dimethylaminocarbonyl group,
a propylaminocarbonyl group, a pentylaminocarbonyl group, a
cyclohexylaminocarbonyl group, an octylaminocarbonyl group, a
2-ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a
phenylaminocarbonyl group, a naphthylaminocarbonyl group and a
2-pyridylaminocarbonyl group; a sulfinyl group such as a
methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl
group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a
dodecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl
group and a 2-pyridylsulfinyl group; an alkylsulfonyl group such as
a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl
group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group and
a dodecylsulfonyl group; an arylsulfonyl group such as a
phenylsulfonyl group, a naphthylsulfonyl group and
2-pyridylsulfonyl group; and a cyano group.
[0056] Preferable example of R.sub.1 is an alky group, an alkenyl
group, an aryl group, a heterocyclic group, an alkoxycarbonyl
group, an acyl group, a carbamoyl group and a cyano group. An alky
group, an aryl group, a heterocyclic group and a cyano group are
more preferable.
[0057] The substituent may be substituted by other substituent.
[0058] An alky group is most preferable and a trifluoromethyl group
and a trichloromethyl group are preferable.
[0059] R.sub.2 is an alky group, an alkenyl group, an alkynyl
group, an aryl group, a heterocyclic group, an alkoxycarbonyl
group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl
group, a sulfonyl group and a cyano group.
[0060] Practically, example of R.sub.2 includes an alky group such
as a methyl group, an ethyl group, a propyl group, an isopropyl
group, a tert-butyl group, a pentyl group, a hexyl group, an octyl
group, a dodecyl group, a tridecyl group, a tetradecyl group, a
pentadecyl group, a chloromethyl group, a trifluoromethyl group, a
tribromomethyl group, a pentafluoroethyl group, and a methoxyethyl
group; an alkenyl group such as a vinyl group and an allyl group;
an alkynyl group such as an ethynyl group and a propargyl group; an
aryl group such as a phenyl group, a naphthyl group, a
p-nitrophenyl group, a p-fluorophenyl group, and a p-methoxy phenyl
group; a heterocyclic group such as a furyl group, a thienyl group,
a pyridyl group, pyridazyl group, pyrimidyl group, a pyrazyl group,
a triazyl group, an imidazolyl group, a pyrazolyl group, a
thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, a
quinazolyl group, a phthalazyl group, a pyrrolidinyl group, an
imidazolidinyl group, a morpholyl group, and an oxazolidinyl group;
an alkoxycarbonyl group such as a methyloxycarbonyl group, an
ethyloxycarbonyl group, a butyloxycarbonyl group, an
octyloxycarbonyl group and a dodecyloxycarbonyl group; an
aryloxycarbonyl group such as a phenyloxycarbonyl group and a
naphthyloxycarbonyl group; a sulfamoyl group such as an
aminosulfonyl group, a methylaminosulfonyl group, a
dimethylaminosulfonyl group, a butylaminosulfonyl group, a
hexylaminosulfonyl group, a cyclohexylaminosulfonyl group, an
octylaminosulfonyl group, a dodecylaminosulfonyl group, a
phenylaminosulfonyl group, a naphthylaminosulfonyl group and a
2-pyridylaminosulfonyl group; a sulfinyl group such as a
methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl
group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a
dodecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl
group and a 2-pyridylsulfinyl group; and an alkylsulfonyl group
such as a methylsulfonyl group, an ethylsulfonyl group, a
butylsulfonyl group, a cyclohexylsulfonyl group, a
2-ethylhexylsulfonyl group and a dodecylsulfonyl group, and an
alkylsulfonyl group such as a phenylsulfonyl group, a
naphthylsulfonyl group and 2-pyridylsulfonyl group.
a cycloalkyl group such as a cyclopentyl group and a cyclohexyl
group;
[0061] Preferable example of R.sub.2 is an alky group, a cyano
group, a sulfinyl group, and sulfonyl group, and further
preferably, is a cyano group, a sulfinyl group and a sulfonyl
group.
[0062] The substituent may be substituted by other substituent.
[0063] R.sub.3 is an alky group having 3 or more carbon atoms, an
alkenyl group, or an alkynyl group, an aryl group or a heterocyclic
group. A good stability against water of the compound of (X-1) and
the compound of (1) is obtained when R.sub.3 has 3 or more carbon
atoms. It is remarkably displayed when R.sub.3 is an alky group
having 8 or more carbon atoms.
[0064] The alkyl group having 3 or more carbon atoms includes, for
example, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl,
dodecyl, tridecyl, tetradecyl, pentadecyl; the alkenyl group
includes, for example, vinyl and allyl; the alkynyl group includes,
for example, ethynyl and propargyl; the aryl group includes, for
example, phenyl, naphthyl, p-nitrophenyl, p-fluorophenyl and
p-methoxyphenyl; the heterocyclic group includes, for example,
furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl,
imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl,
quinazolyl, phthalazyl, pyrrolidyl, imidazolidyl, morpholyl and
oxazolidyl.
[0065] Those alkyl group having 3 or more carbon atoms, alkenyl
group, alkynyl group and aryl group may be substituted by a
substituent. R.sub.3 is preferably an alkyl group having 3 or more
carbon atoms or an aryl group.
[0066] R.sub.1 and R.sub.2 or R.sub.2 and R.sub.3 may combine with
each other to form a 5- or 6-membered ring.
[0067] The number of carbon atoms in one molecule of the ligand
represented by formula (1) is 25 or less. Good affinity and
compatibility of the metal containing compound represented by
formula (1) to the compound of (X-1) are obtained.
[0068] One of the R.sub.1 and R.sub.2 is an electron-attractive
group, and both of R.sub.1 and R.sub.2 is preferably an
electron-attractive group, and the total of .sigma.p values of
R.sub.1 and R.sub.2 is 0.2 to 2.0.
[0069] The electron attractive group is a substituent which may
have positive Hammett substituent constant .sigma..
[0070] When, in m- or p-substituted aromatic compounds, k.sub.0 and
k are respectively defined as reaction rate constants of an
unsubstituted compound and a substituted one, the Hammett
substituent constant is defined by the following Hammett
equation:
log(k/k.sub.0)=.rho..sigma.
where .sigma. is a substituent constant; and .rho. is a reaction
constant. In the foregoing Hammett equation, the dissociation
reaction of benzoic acid and its derivatives in an aqueous solution
at 25.degree. C. is defined as .rho.=1.
[0071] Hammett substituent constants are referred to Journal of
medicinal Chemistry, 1973, Vol. 16, No. 11, 1207-1216.
[0072] Specific examples of an electron-attractive-group include a
substituted alkyl group such as halogen-substituted alkyl; a
substituted alkenyl group such as cyanovinyl; a substituted or
unsubstituted alkynyl group such as trifluoromethylacetylenyl,
cyanoacetylenyl; a substituted aryl group such as cyanophenyl; a
substituted or unsubstituted heterocyclic group such as pyridyl,
triazinyl, benzoxazolyl; a halogen atom, cyano group, an acyl group
such as acetyl, trifluoroacetyl, formyl; a thicacetyl group such as
thioacetyl, thioformyl; an oxalyl such as methyloxalyl; an
oxyoxalyl group such as ethoxalyl; a thiooxalyl group such as
ethylthiooxalyl; an oxamoyl group such as methyloxamoyl; an
oxycarbonyl group such as ethoxycarbonyl; a carboxyl group; a
thiocarbonyl group such as ethylthiocarbonyl; a carbamoyl group; a
thiocarbamoyl group; a sulfonyl group; a sulfinyl group; an
oxysulfonyl group such as ethoxysulfonyl; a thiosulfonyl group such
as ethylthiosulfonyl; a sulfamoyl group; an oxysulfinyl group such
as methoxysulfinyl; a thiosufinyl group such as methylthiosulfinyl;
a sulfinamoyl group; a phosphoryl group; a nitro group; an imino
group; an N-carbonylimino group such as N-acetylimino; an
N-sulfonylimino group such as N-methanesulfonylimino; a
dicyanoethylene group; an ammonium group; a sulfonium group; a
phosphonium group; a pyrilium group and an immonium group.
[0073] Of the foregoing groups, a substituted alkyl group, a
substituted aryl group, a cyano group, an acyl group, an
oxycarbonyl group, a nitro group and a cyano group are preferred.
Practical examples thereof include a cyano group, a nitro group, a
trichloromethyl group, a dichloromethyl group, a chloromethyl
group, a tribromomethyl group, a dibromomethyl group, a bromomethyl
group, an alkoxyacyl group, an acyl group and an aromatic group
substituted by these substituent mentioned above.
[0074] It is preferable that log P of one molecule of ligands in
the compound represented by Formula (1) is 3 to 8. In this instance
an interaction between the compound represented by Formula (1) and
the compound represented by Formula (X-1) is sufficiently active,
and excellent stability against heat, light and particularly water
is obtained absorption is sharp with less subsidiary absorption and
further good solubility in an organic solvent is obtained.
[0075] The log P is a parameter expressing degree of the
hydrophilicity-hydrophobicity of the compound and higher value
corresponds to higher hydrophobicity and lower value corresponds to
higher hydrophilicity. The log P value is well known parameter of
compound and can be obtained by measurement or calculation.
[0076] The value of log P calculated by the following expression is
different a little from the value determined by measurement in some
cases. However, the difference is not so large and approximate
property of the compound can be sufficiently surmised by
measurement or calculation. The log P value is preferably
determined by the calculation when the value can be determined by
each of the methods. [0077] log P.sub.O/W [0078]
P.sub.O/W=S.sub.O/S.sub.W [0079] S.sub.O=Solubility of the organic
compound in n-octanol at 25.degree. C. [0080] S.sub.W=Solubility of
the organic compound in purified water at 25.degree. C.
[0081] For determining the log P value by calculation, some methods
such as a method based on molecular orbital calculation, a fragment
method basically utilizing data of Hansch and a method by HPLC are
applicable. In the invention, the calculation is preferably carried
out by using Project Leader contained in a molecular calculation
package CAChe manufactured by Fujitsu or ChemProp contained in a
chemical structure drawing software CS Chem Draw 8.0 manufactured
by Cambridge Soft, and the calculation by ChemProp in CS Chem Draw
8.0 or its later version is particularly preferable.
[0082] Practical examples of the compound represented by Formula
(1) are listed.
##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##
##STR00026## ##STR00027##
[0083] The color toner for an electrophotography according to this
invention will be described.
[0084] The color toner for an electrophotography comprises a resin
and the compound represented by the formula (X-1).
[0085] The compound represented by the formula (X-1) is preferably
an oil soluble dye when it is employed in a toner. The oil soluble
dye is usually a dye having no water soluble group such as a
carbonic acid or sulphonic acid group and soluble in an organic
solvent and not in water, however it includes a dye showing oil
solubility by forming a salt of the water soluble dye with a long
chain base in the present invention. When the compound is oil
soluble, toner may prepared via various methods to incorporate the
compound in a toner such that a solid dispersion of the compound is
prepared via submerged drying method and is incorporated in a
toner; the compound is added in a step of aggregating the
emulsified polymer by a coagulant to color a toner; and the
compound is added in step of polymerizing monomers and a toner is
prepared by polymerization. Good transparency of a toner color as
well as color of superposed toners can be obtained when the
compound is sufficiently compatible to a thermoplastic resin in a
toner, whereby the compound migrates in the thermoplastic resin to
form a colored area, a dye cloud, having larger than the minute
particle of the compound as itself.
[0086] The compound represented by the formula (X-1) may be used
singly or plurality thereof having different structures may be used
in an electrophotographic toner.
[0087] The compound represented by the formula (X-1) may be used in
combination with a conventional dye used for the electrophotography
as tar as the dye does not deteriorate the characteristics of the
compound represented by the formula (X-1).
(Dye Dispersion)
[0088] The toner according to this invention contains a compound
represented by the formula (X-1). The compound may be incorporated
in a toner as a solid dispersion in the following manners. The
compound singly or in combination with a resin, which may be
dispersed in water employing a dispersant such as a surfactant, is
dissolved or dispersed in a water-immiscible organic solvent such
as ethyl acetate or toluene, and further emulsified in water to
form an emulsion; the thus formed emulsion is subjected to
submerged drying to remove the organic solvent to obtain a
dispersion of colored particles; and the colored particles are
allowed to coagulate with a latex of a (thermoplastic) resin to
obtain toner particles. Emulsification is carried out using, for
example, an ultrasonic homogenizer or a high-speed stirring type
disperser.
[0089] A solid particle dispersion of the metal chelate dye is
comprised of microparticles, having a particle size of 10 to 2000
nm, and preferably 10 to 100 nm, more preferably 10 to 80 nm. The
solid particle dispersion is preferably comprised of monodisperse
microparticles, whereby light-scattering is reduced and
light-masking particles are reduced. Enhanced monochromatic
transparency of the toner results, leading to greatly enhanced
chroma (or colorfulness) per dye coverage.
[0090] Alternatively, a solid of the compound represented by the
formula (X-1) is mixed with a surfactant and pulverized by using a
medium type stirrer to obtain a dispersion of colored particles.
The colored particle dispersion is allowed to coagulated with a
latex of (thermoplastic) resin to obtain toner particles.
[0091] A solid particle dispersion obtained by the submerged drying
method is comprised of particles exhibiting a form close to a
sphere, resulting in enhanced adhesiveness to a binder and reduced
interfacial scattering.
[0092] The solid particle dispersion includes, as far as it
contains the compound represented by the formula (X-1) as a
colorant, minute particles composed of the compound represented by
the formula (X-1) as itself, minute particles composed of a
combination of the colorant and a surfactant, minute particles
composed of a combination of the colorant, a surfactant and a
resin, and further minute particles containing other additives.
Colored minute particles having various characteristics can be
obtained by employing a resin or an additive in addition to the dye
as the colorant component in combination.
[0093] (Surfactant)
[0094] A usual anionic emulsification agent (surfactant) and/or
nonionic emulsification agent (surfactant) can be used according to
necessity on the occasion of emulsification of the colored fine
particle as one of preferable embodiments of the invention.
[0095] As examples of nonionic surfactant, a polyoxyethylene alkyl
ether such as polyoxyethylene lauryl ether and polyoxyethylene
stearyl ether, a polyoxyethylene alkylphenyl ether such as
polyoxyethylene nonylphenyl ether, a sorbitan higher fatty acid
ester such as sorbitan monolaurate, sorbitan monostearate and
sorbitan trioleate, a polyoxyethylene higher fatty acid ester such
as polyoxyethylene monolaurate and polyoxyethylene monostearate, a
glycerol higher fatty acid ester such as oleic monoglyceride and
stearic monoglyceride and a polyoxyethylene-polyoxypropylene block
copolymer are cited.
[0096] As examples of the anionic surfactant, a higher fatty acid
salt such as sodium oleate, an alkylarylsulfonate such as sodium
dodecylbenzenesulfonate, an alkylsulfate such as sodium
laurylsulfate, a polyoxyethylene alkyl ether sulfate such as sodium
polyethoxyethylene lauryl ether sulfate, a polyoxyethylene
alkylaryl ether sulfate such as sodium polyoxyethylene nonylphenyl
ether sulfate, a salt of alkylsulfosuccinic ester salt such as
sodium monooctyl-sulfosuccinate, sodium dioctylsulfosuccinate and
sodium polyoxyethylene laurylsulfosuccinate and a derivative
thereof can be cited.
[0097] The compound represented by the formula (X-1) included in
the electrophotographic toner preferably is in the form of
particles having a particle size of 10 to 100 nm. The particles are
small size and monodisperse, whereby light-scattering is reduced
and light-masking particles are removed.
[0098] When the compound represented by formula (X-1) is not in the
state of a molecule but in the form of coagulated particles,
migration is inhibited, causing no concern of sublimation of a dye
during fixing or oil staining.
[0099] (Thermoplastic or Binder Resin)
[0100] As the thermoplastic resin to be contained in the
electrophotographic toner of the invention, one having high
contacting ability with the colored fine particle or the copper
complex fine particle which are one of the preferable embodiments
of the invention, and solvent-soluble one is particularly
preferred. A curable resin capable of forming a three dimensional
structure is usable when the precursor of the resin is solvent
soluble. As the thermoplastic resin, one usually used for toner can
be used without any limitation. Examples of the thermoplastic resin
include a styrene type resin, an acryl resin such as an alkyl
acrylate and alkyl methacrylate, a styrene-acryl type copolymer
resin, a polyester type resin, a silicone type resin, an olefin
type resin, an amide type resin and an epoxy type resin are
suitably used, and the resin having high transparency, low
viscosity in melted state and sharp melting property is required
for raising the transparency and the color reproducibility of the
overlapped image. Styrene type resin, acryl type resin and
polyester resin are suitable for the resin having such the
properties.
[0101] The resin having a number average molecular weight (Mn) of
from 3,000 to 6,000, preferably from 3,500 to 5,500, a ratio Mw/Mn
of weight average molecular weight Mw to number average molecular
weight Mn of from 2 to 6, preferably from 2.5 to 5.5, a glass
transition temperature of from 50 to 70.degree. C., preferably from
55 to 70.degree. C., and a softening point of from 90 to
110.degree. C., preferably from 90 to 105.degree. C. is desirably
used for the binder resin.
[0102] Fixing strength against folding is degraded and damages of
the image are caused by peeling off of the toner on the occasion of
folding a full color solid image when the number average molecular
weight of the binder resin is less than 3,000, and the fixing
strength is lowered accompanied with lowering in the thermal
melting ability on the occasion of fixing when the number average
molecular weight exceeds 6,000. Offset at high temperature is
easily caused when Mw/Mn is less than 2, and the sharp melt ability
at the time of fixing is lowered and light permeability and color
mixing ability on the occasion of full color image formation is
degraded when the ratio is more than 6. When the glass transition
point is lower than 50.degree. C., the heat resistivity of the
toner is made insufficient and coagulation of the toner during
storage tends to be caused and when the glass transition point is
higher than 70.degree. C., the toner is difficulty melted so that
the fixing ability and the color mixing ability on the occasion of
full color image formation are lowered. When the softening point is
lower than 90.degree. C., high temperature offset is easily caused
and when higher than 110.degree. C., light permeability, color
mixing ability and glossiness of full color image are lowered.
[0103] (Toner)
[0104] In the electrophotographic toner of the invention, a charge
controlling agent and an offset preventing agent can be added
additionally to the above thermoplastic resin and the colored fine
particle.
[0105] As the charge controlling agent to be used in the color
toner, a colorless, white or faint color charge controlling agent
which does not give bad influence on the tone and transparency of
the toner can be used. For example, complexes of metal such as zinc
and chromium with a derivative of salicylic acid, calixarene type
compounds, organic boron compounds and fluorine-containing
quaternary ammonium salt type compounds are suitably can be used.
For example, the salicylic acid metal complexes described in JP A
S53-127726 and 62-145255, the calixarene compounds described in JP
A H02-201378, the organic boron compounds described in JP A
H02-221967 and the fluorine-containing quaternary ammonium salt
type compounds described in 3-1162 are usable. When such the charge
controlling agent is used, the content of it is preferably from 0.1
to 10, and more preferably from 0.5 to 5.0, parts by weight to 100
parts by weight of the thermoplastic resin (binder resin).
[0106] The offset preventing agent is not specifically limited and
polyethylene wax, oxide type polyethylene wax, Carnauba wax,
polypropylene wax, oxide type polypropylene wax, Sasol wax, rice
wax, candelilla wax, jojoba oil wax and beeswax are usable for
example. The adding amount of such the wax is desirably from 0.5 to
5, preferably from 1 to 3, parts by weight to 100 parts by weight
of the thermoplastic (binder) resin. The effect of addition is made
insufficient when the adding amount is less than 0.5 parts by
weight, and the transparence and color reproduction ability is
lowered when the adding amount is more than 5 parts by weight.
[0107] The electrophotographic toner of the invention can be
produced by using the above-described thermoplastic resin, colored
fine particle and the other desirable additives, the fine particle
may be a mixture of several kinds thereof or single kind for each
of the particles, and by applying a method such as a knead and
crushing method, suspension polymerization method, emulsion
polymerization method, emulsified dispersion granule forming
method, and capsulation method.
[0108] Among these production methods, the emulsion polymerization
method is preferable from the viewpoint of the cost and stability
of the production considering the size down of the toner particle
accompanied with the improvement of image quality.
[0109] By the polymerization method, the toner particle is produced
as follows; thermoplastic resin emulsion prepared by emulsion
polymerization is mixed with the dispersion of another component of
toner particle such as the colored fine particles and the particles
are gradually coagulated while taking balance between the repulsion
force of the particle surface and the coagulation force caused by
the addition of electrolyte by pH control, and the fusion and shape
of the particles is controlled by heating and stirring the system
while controlling the diameter and distribution thereof. It is
preferable from the viewpoint of high definition reproduction of
image to control the volume average diameter of the
electrophotographic toner particle to 4 to 10 .mu.m, more
preferably to 6 to 9 .mu.m.
[0110] In the electrophotographic toner of the invention, a post
treatment agent can be added and mixed for providing fluidity and
improvement of cleaning suitability. As such the post treatment
agent, an inorganic oxide fine particle such as a silica fine
particle, an alumina fine particle and a titania fine particle, an
inorganic stearic acid compound such as aluminum stearate fine
particle and zinc stearate fine particle and an inorganic titanic
acid compound fine particle such as strontium titanate and zinc
titanate are usable. Such the fine particles may be used singly or
in combination with another kind of additive. It is desirable that
these fine particles are subjected to surface treatment by a silane
coupling agent, titanium coupling agent, higher fatty acid or
silicone oil and the adding amount of the fine particle is from
0.05 to 5 parts by weight, preferably from 0.1 to 3 parts by
weight, to 100 parts by weight of the toner.
[0111] The electrophotographic toner of the invention can be used
as the toner of a two-component developer together with a carrier
or a one-component developer without carrier.
[0112] As the carrier for two-component developer to be combined
with the electrophotographic toner of the invention, for example, a
carrier composed of a particle of magnetic substance such as iron
and ferrite, a resin coated carrier prepared by coating the
magnetic particle with a resin and a binder type carrier prepared
by dispersing the fine particles of the magnetic substance into a
binder resin are usable.
[0113] Among these carriers, a resin coat carrier using a silicone
type resin, a copolymer resin (graft resin) of organopolysiloxane
and a vinyl type monomer or a polyester type resin is preferably
used from the viewpoint of toner spending and a carrier coated with
a resin formed by reacting isocyanate to the copolymer resin of
organopolysiloxane and a vinyl type monomer is preferable from the
viewpoint of durability, environmental stability and ant-spending
property. As the above vinyl type monomer, a monomer having a
substituent reactive with isocyanate such as a hydroxyl group is
necessarily used. The carrier having a volume average diameter of
from 20 to 100 .mu.m and preferably from 20 to 60 .mu.m is
preferably used for holding high image quality and preventing
fog.
[0114] The color toner may comprise a metal-containing compound
represented by Formula (1). The compound represented by Formula (1)
is used in any content ratio to the compound represented by Formula
(X-1) according to an object, and preferably the ratio A/B is
between 0.5 and 2.5 and more preferably 0.8 and 2.0, wherein A is
total mole of the compound represented by Formula (X-1) added in
the toner and B is total mole of the metal-containing compound
represented by Formula (1).
EXAMPLES
Example 1
Evaluation of Handling of Dye Solid Powder (I)
[0115] Solid powder of DX-1 was dried well and pulverized properly
by using glass rod was reserved in a Petri dish for 24 hours in an
environment of 20.degree. C. and 55% RH.
[0116] Then about 10 g of the powder was taken on a 10 cm.times.10
cm paraffin paper, which was put into a 50 ml sample tube
carefully. Appearance of remaining powder on the paraffin paper and
scattered powder flew around was totally evaluated by visual
observation. The same procedure was conducted by three persons
separately, and their opinions were summarized to determine the
evaluation.
[0117] The evaluation was ranked as A, B, C and D, criteria of
which is described below. Ranks A and are practically acceptable.
The results are shown in Table 1.
Criteria
[0118] A: Residual powder was hardly observed on paraffin paper,
and powder scattered around was not observed. B: Residual powder
was hardly observed on paraffin paper, and powder scattered around
was observed slightly. C: Residual powder was observed partly on
paraffin paper, and powder scattered around was observed partly. D:
Residual powder was observed adhered to both front and back surface
of the paraffin paper, and powder scattered around was
observed.
Evaluation of Handling of Dye Solid Powder (II)
[0119] The same test was conducted in the same way as Evaluation of
Handling of Dye Solid Powder (I) except that the powder was
reserved in an environment of 30.degree. C. and 30% RH. The result
is shown in Table 1.
Evaluation of Handling of Dye Solid Powder (III)
[0120] The same test was conducted in the same way as Evaluation of
Handling of Dye Solid Powder (II) except that the powder was
reserved for more 24 hours. The result is shown in Table 1.
[0121] The same test was conducted by changing solid powder as
described in Table 1. The result is shown in Table 1.
TABLE-US-00001 TABLE 1 Evaluation Evaluation Evaluation No.
Compound (I) (II) (III) 1-1 DX-1 B B B 1-2 DX-3 A A B 1-3 DX-4 A B
B 1-4 DX-5 A A A 1-5 DX-7 A B B 1-6 DX-9 A B B 1-7 DX-10 A B B 1-8
DX-11 A A B 1-9 DX-12 A A A 1-10 DX-17 B B B 1-11 DX-18 B B B 1-12
DX-23 B B B 1-13 Dye A B C C 1-14 Dye B B C D
[0122] Dye A (Disclosed in JP A 2007-34264)
##STR00028##
[0123] Dye B (Disclosed in JP A 2006-350300)
##STR00029##
Example 2
Evaluation of Stability of Dye Solid Powder Dispersed in Water
<Preparation of Dispersion 2-1>
[0124] Each of 20 g of compounds shown in Table 2, was added in a
solution of 9.5 g of sodium dodecyl sulfate dissolved in 200 ml of
deionized water, the mixture was subjected to stirring and
ultrasonic dispersion. Dispersion process was terminated when
volume average particle diameter (diameter of particle at which
particles are accumulated to 50% from smaller diameter) reached
about 0.4 .mu.m, and aqueous dispersion was prepared
Ultrasonic dispersion apparatus: UH-600S manufactured by SMT Co.,
Ltd. Particle diameter Distribution analyzer: MICROTRACK MT3300EXII
manufactured by Nikkiso Co., Ltd
Evaluation of Stability of Dispersion
[0125] The aqueous dispersion was kept stand and period maintaining
stable dispersion state was measured.
[0126] Three dispersion were prepared for each dye solid powder and
average time maintaining stable dispersion state was obtained as
the index of the stability. Ranks A and B are practically good
stability.
[0127] The result is shown in Table 2.
Criteria
[0128] A: Stable for 15 minutes or more. B: Stable for 10 minutes
to less than 15 minutes. C: Stable for 5 minutes to less than 10
minutes. D: Stable for less than 5 minutes.
TABLE-US-00002 TABLE 2 (X-1) No. Compound Evaluation 2-1 DX-1 B 2-2
DX-3 A 2-3 DX-4 B 2-4 DX-5 A 2-5 DX-7 B 2-6 DX-9 B 2-7 DX-10 B 2-8
DX-11 A 2-9 DX-12 B 2-10 DX-17 B 2-11 DX-18 B 2-12 DX-23 B 2-13 Dye
A D 2-14 Dye B D
[0129] The result shown in Table 2 demonstrates the compounds
according to the present invention are excellent in dispersion
stability in comparison with Dyes A and B.
Example 3
Preparation of Toner
[0130] Toners were prepared by employing compounds shown in Table 3
and preparation method described below.
[0131] <Preparation Method 1, Pulverization Method>
[0132] One hundred parts by weight of polyester resin, 2 parts by
weight of colorant and the equimolar copper complex compound each
shown in Table 1 and 3 parts by weight of propylene resin VISCOL
550P, manufactured by Sanyo Chemical Industries, Ltd., were mixed,
kneaded, pulverized and classified to obtain a powder having an
average particle diameter of 8.5 .mu.m. Then 100 parts by weight of
the powder and 1.0 parts of silica fine particles 2805 having a
particle diameter of 12 nm and a hydrophobicity of 60, manufactured
by Nippon Aerosil Co., Ltd., was mixed by a Henschel mixer to
obtain a crushed toner.
<Preparation Method of Crushed Color Toner>
[0133] A solid dye powder according to this invention in an amount
of 20 g and a metal-containing compound (amount disclosed in Table
3) were added to a solution of 4.5 g of sodium dodecyl sulfate
dissolved in 200 ml of deionized water, the mixture was subjected
to stirring and ultrasonic dispersion to obtain colorant
dispersion. Emulsion dispersion was prepared by that low molecular
weigh polypropylene having number average molecular weight of 3,200
was added to it with heating and emulsified in water so that the
solid content became 30% by weight.
[0134] To the emulsion dispersion 60 g of low molecular weight
polypropylene emulsion dispersion was mixed and then 220 g of
styrene, 40 g of n-butylacrylate, 12 g of methacrylic acid, 5.4 g
of t-dodecylmercaptane as a chain transfer agent and 2,000 ml of
degassed deionized water were added. The emulsion polymerization
was conducted by stirring in nitrogen stream at 70.degree. C. for 3
hours.
[0135] To 1,000 ml of obtained resin fine particle dispersion
aqueous solution of sodium chloride was added to adjust pH of 7.0,
270 ml of 2.7 mol % aqueous solution of potassium chloride was
added and further solution of 160 ml of isopropyl alcohol and 9.0 g
of polyoxyethylene-octylphenylether having ethyleneoxide average
polymerization degree of 10, dissolved in 60 ml of deionized water,
was added. The mixture was subjected to reaction with stirring at
75.degree. C. for 6 hours. The obtained reaction product was
filtered and washed, and dried and pulverized to obtain colored
particles.
[0136] The colored particles and 1.0 parts of silica fine particles
R805, having particle diameter of 12 nm, hydrophobicity of 60,
manufactured by Nihon Aerosil, were mixed by Henschel mixer to
obtain polymerization method toner.
[0137] Production suitability was evaluated in view of processing
adaptability by 5 times production of toners in each production
method. Rank A is suitable.
Criteria
(Production Method 1)
[0138] A: Color stain was not observed at production area during
weighing and mixing. B: Color stain was observed t production area
by scattering solid powder during weighing and mixing.
(Production Method 1)
[0139] A: Color stain was not observed at production area during
weighing and preparation of emulsion dispersion was easy. B:
Scattering of solid powder was observed and speedy handling was
required prior to generation of precipitation of dispersion.
TABLE-US-00003 TABLE 3 Compound represented (X-1) by Formula (1)
Preparation No. Compound Compound Amount method Evaluation 3-1 DX-1
-- -- 1 A 3-2 DX-1 32 Equimolar 1 A to DX-1 3-3 DX-5 -- -- 2 A 3-4
DX-5 32 Equimolar 2 A to DX-5 3-5 DX-7 -- -- 1 A 3-6 DX-7 32
Equimolar 1 A to DX-7 3-7 DX-9 -- -- 1 A 3-8 DX-9 32 Equimolar 1 A
to DX-9 3-9 DX-12 -- -- 2 A 3-10 DX-12 32 Equimolar 2 A to DX-12
3-11 Dye A -- -- 1 B 3-12 Dye A 32 Equimolar 1 B to Dye A 3-13 Dye
B -- -- 2 B 3-14 Dye B 32 Equimolar 2 B to Dye B
[0140] The result demonstrates that the compounds of this invention
are good in handling in any preparation methods, less scattering
and reduced environmental contamination.
* * * * *