Title of Invention

TONER, AND DEVELOPER, DEVELOPING APPARATUS, PROCESS CARTRIDGE, IMAGE FORMING APPARATUS AND IMAGE FORMING METHOD

Abstract The present invention provides the following: a toner which comprises toner base particles comprising a binder resin and a colorant where the toner base particles have a surface roughness (Ra) of 18 nm to 50 nm and a standard deviation (RMS) of the surface roughness of 0.5 nm to 9.9 nm; a developer comprising the toner; a developing apparatus; a process cartridge; an image forming apparatus; and an image forming method using the developer.
Full Text WO 2006/075534 PCT/JP2005/024210
DESCRIPTION
TONER, AND DEVELOPER, DEVELOPING APPARATUS, PROCESS
CARTRIDGE, IMAGE FORMING APPARATUS AND IMAGE FORMING
METHOD
Technical Field
The present invention relates to a toner used for image formation
by an electrostatic copying process such as copying machine, facsimile .
and printer, as well as a developer comprising the toner, a developing
apparatus, a process cartridge, an image forming apparatus and an
image forming method using the developer.
Background Art
An image forming method by electrographic process generally
comprises: a charging process of charging by electric discharge the
surface of a photoconductor which is an image bearing member,' an
exposing process of forming a latent electrostatic image by exposing the
charged photoconductor surface; a developing process of developing a
toner image by supplying a toner to the latent electrostatic image formed
on the photoconductor surface; a transferring process of transferring the
toner image on the photoconductor surface onto the surface of a
transferring member," a fixing process of fixing the toner image on the
surface of the transferring member; and a cleaning process of removing
the toner left on the surface of the image bearing member after the
transferring process.
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Recently, in association with the broad propagation of color image
forming apparatuses using the electrographic process and easily
available digitized images, it is desired to make an image to be printed
with higher definition. While higher resolution and gradation of images
are being examined, regarding the improvement of a toner which
visualizes a latent image, it has been studied to further ensphere the
toner and reduce the particle size in order to form an image with high
definition. Since the toners produced by pulverizing methods have
limited properties thereof, polymerized toners produced by a suspension
polymerization method, an emulsification polymerization method and a
dispersion polymerization method capable of ensphering the particles
and reducing the particle size are being employed.
A toner with high sphericity is easily affected by electric lines of
force in an electrostatic development method, and a toner image is
closely developed along the electric lines of force of the latent
electrostatic image on the photoconductor. The toner is easily arranged
densely and uniformly, and the reproducibility a thin line becomes high
when a latent image of fine dots is reproduced. In addition, since the
toner has high particulate flowability due to its smooth surface and small
adhesive strength among the toner particles or between the toner
particles and the photoconductor; Therefore, the electrostatic
transferring method has high transfer ability since the toner is easily
affected by the electric lines of force, and the transfer is easily performed
faithfully along the electric lines of force.
However, the toner with high degree of sphericity has a smaller
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surface area compared to an amorphous toner of the same particle
diameter. This means that the surface available for factional charge by
contact with a fractional charging member such as a magnetic carrier and
developer regulation member is small. When, the toner is spherical, it
easily slides on the surface of the above frictional charging member.
Thus, the charging speed and the charging level are low. Therefore, more
than a certain amount of a charge controller is required on the surface of
the toner.
Additionally, the smaller the toner particle diameter is for
enhancing the reproducibility of a fine dot, the more the frictional charge
property is reduced. Thus, it is a critical issue to simultaneously satisfy
the charge property, developing property and transfer property.
Regarding the spherical toner and the toner having a small
particle diameter, various proposals to control their shapes have been
made. Shape Factors SF-1 and SF-2 are often used as indicators
representing the toner shape. The shape factor SF-1 is an indicator that
represents the degree of roundness of a toner particle, and SF-2 is an
indicator that represents the degree of convexoconcave of a toner particle.
For example, Patent Literatures 1 to 3 attempt to control the shape of
the particles by defining the ranges of the shape factors SF-1 and/or SF-2
in order to simultaneously satisfy the charge property, developing
property, transfer property, or cleaning property even with a spherical
toner and a toner having small particle diameter.
Patent Literature 4 describes a technology which defines the
range of the shape factor of toner particles as well as a surface area ratio
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represented by the following formula:
Surface area ratio = p xD50p x S
where p is a specific gravity (g/cm3) of the toner particles, D50p is a
number average particle diameter (m) of the toner particles, and S is
BET specific surface area (m2/g) of the toner particles.
This surface area ratio is a different measure that represents the
degree of convexoconcave of the toner particle from the foregoing shape
factor. When the value of the surface area ratio exceeds a given range,
the degree of convexoconcave on the surface of the toner particle becomes
large. This allows an external additive added externally with time to the
toner particles to enter in the depressing portions of the toner particles,
and thus it becomes impossible to maintain the charge property and the
transfer property over a long period of time.
In Patent Literature 5, the toner surface is defined by an atomic
force microscope. However, the degree of convexoconcave in Patent
Literature 5, i.e., the degree of surface roughness (Ra), the degree of
standard deviation of Ra (RSM) and the number of protective portions
having difference of elevation of 20 nm or more, is not sufficient for a
cleaning system with higher durability and stability. It was desired that
more enhanced cleaning property, by further increasing the degree of
convexoconcave in the toner shape reduced cleaning blade abrasion and
hence improved the image stability in printing with time.
The technology described in Patent Literature 5 is characterized
by having a fine convexoconcave on the toner surface for the purpose of
particularly improving the charge property, developing property and
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transfer property. However, the irregular shape property (large
convexoconcave) of the toner as a whole is not sufficient since fine
particles such as organosilica are not suitably used for changing the
shape. Therefore, it was absolutely insufficient for solving a problem of
an stability of the cleaning over time.
As described above, despite many attempts to enhance the charge
property, developing property, transfer property or cleaning property by
controlling the shapes of the toner particles, a toner having sufficiently
satisfactory performance and the related technology have not yet been
provided because all the attempts only have a rough view of the surface
shape of the toner particle, and none of them grasps the microscopic state
of concavoconvex for simultaneously satisfying the charge property,
developing property, transfer property and cleaning stability with time.
Patent Literature 1 Japanese Patent Application Laid-Open
(JP-A) No. H09-179331
Patent Literature 2 JP-A No. H10-142835
Patent Literature 3 JP-ANo. H11-327197
Patent Literature 4 JP-A No. 2001-51444
Patent Literature 5 JP-A No. 2004-246344
Disclosure of Invention
The present invention aims at providing a toner capable of
simultaneously satisfying a charge property, a developing property, a
transfer property and a cleaning stability over time even in the spherical
shape or with a small particle diameter by controlling the degree of the
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microscopic concavoconvex on the surface of toner base particles, as well
as a developer, a developing apparatus, a process cartridge, an image
forming apparatus and an image forming method using the developer.
The toner of the present invention comprises toner base particles
comprising a binder resin and a colorant,
wherein the toner base particles has a surface roughness (Ra) of
18 nm to 50 nm and a standard deviation (RMS) of the surface roughness
of 0.5 nm to 9.9 nm.
In the present invention, the foEowing are preferable: an aspect
where the surface roughness (Rz) of the toner base particles is 30 nm to
200 nm; an aspect where inorganic particulates are contained inside the
toner base particles; an aspect where an average circularity of the toner
base particles is 0.93 to 1.00; an aspect where a volume average particle
diameter (Dv) of the toner base particles is 2.0 mm to 6.0 urn and a ratio
(Dv/Dn) thereof to a number average particle diameter (Dn) is 1.00 to
1.40; an aspect where a ratio Ra (nm)/Dv (mm) of the surface roughness
(Ra) to the volume average particle diameter (Dv) is 0.3 to 17.0; an aspect
where a shape coefficient SF-2 of the toner base particles is 100 to 140
and a ratio (Ra/SF-2) of the surface roughness (Ra) to the shape
coefficient SF-2 is 0.008 to 0.500; an aspect where the toner is obtained
by being granulated in a liquid medium; an aspect where the surface of
the toner base particles has a different resin from the binder resin; an
aspect where a releasing agent is contained in the toner base particles;
an aspect where a dissolution or a dispersion in which a toner material
comprising inorganic particulates has been dissolved or dispersed in an
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organic solvent is granulated in an aqueous medium followed by
removing the organic solvent; an aspect where the toner is obtained by
dissolving or dispersing a toner material comprising a polyester
prepolymer having a functional group comprising a nitrogen atom, a
polyester resin, a colorant and a releasing agent in an organic solvent,
subsequently dispersing a dissolution or a dispersion in an aqueous
medium and performing at least either one of a crosslinking reaction or
an extension reaction, and the like.
The developer of the present invention comprises the above toner
of the present invention. The developer of the present invention
preferably has an aspect of either one-component developer or two-
component developer.
In the developing apparatus of the present invention, the
developer is borne and delivered by a latent image bearing member, an
alternating electric field is applied at a position opposite to the latent
image bearing member, and a latent electrostatic image is developed on
the latent image bearing member; the above developer is the developer of
the present invention.
The process cartridge of the present invention comprises a latent
image bearing member and a developing unit where the latent
electrostatic image formed on the latent image bearing member is
developed using the developer of the present invention to form a visible
image. ;
The image forming apparatus of the present invention comprises,
in a first embodiment, a latent image bearing member, a latent
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electrostatic image forming unit where a latent electrostatic image is
formed on the latent image bearing member, a developing unit where the
latent electrostatic image is developed using the developer of the present
invention to form a visible image, a transferring unit where the visible
image is transferred onto a recording medium, and a fixing unit where a
transfer image transferred onto the recording medium is fixed.
The image forming apparatus of the present invention comprises,
in a second embodiment, a latent image bearing member, a latent
electrostatic image forming unit where a latent electrostatic image is
formed on the latent image bearing member, a developing unit where the
latent electrostatic image is developed using the developer to form a
visible image, a transferring unit where the visible image is transferred
onto a recording medium and a fixing unit where a transfer image
transferred onto the recording medium is fixed; the developing unit is the
foregoing developing apparatus of the present invention.
The image forming method of the present invention comprises a
latent electrostatic image forming process where a latent electrostatic
image is formed on a latent image bearing member, a developing process
where the latent electrostatic image is developed using the developer of
the present invention to form a visible image, a transferring process
where the visible image is transferred onto a recording medium, and a
fixing process where a transfer image transferred onto the recording
medium is fixed.
Brief Description of Drawings
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Fig. 1 is a schematic diagram showing one example of a process
cartridge of the present invention.
Fig. 2 is a schematic diagram showing one example of an image
forming apparatus of the present invention.
Fig. 3 is a schematic diagram showing another example of an
image forming apparatus of the present invention.
Fig. 4 is a schematic diagram showing one example of a tandem
type image forming apparatus of the present invention.
Fig. 5 is a partially enlarged view of Fig. 4.
Fig. 6 is a diagram showing the relationship of a surface
roughness (Ra) with a standard deviation (RMS) in toners of the present
invention and conventional toners.
Fig. 7 is a view showing one example of an SEM photograph of a
toner base particle in the toner of the present invention.
Fig. 8 is a view showing one example of a surface concavoconvex
of a toner base particle in the toner of the present invention by 3D-SEM.
Fig. 9 is a view showing one example a surface concavoconvex of a
toner base particle in the toner of the present invention by 3D-SEM as a
topogram.
Fig. 10 is a collection of graphs showing one example of
quantitative results of analyzing the roughness of toner base particles in
the toner of the present invention.
Fig. 11 is a schematic diagram showing another example of an
image forming apparatus of the present invention.
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Best Modes for Carrying Out the Invention
(Toner)
The toner of the present invention comprises toner base particles
comprising a binder resin and a colorant, and further contains other
ingredients as needed.
A toner base particles has a surface roughness (Ra) of 18 nm to 50
nm and a standard deviation (RMS) of the surface roughness of 0.5 nm to
9.9 nm; the surface roughness Ra is large, and the standard deviation
RMS of the surface roughness is small (convexo-concave cycle is short).
Since the toner base particles of conventional toners obtained by
suspension polymerization and dissolution suspension are spherical and
thus have almost no convexoconcave. Therefore, Ra is reduced (region
where RMS is small or large) and is out of the above range.
Conventional emulsification aggregation toners have small Ra and large
RMS, which are out of this range even if they are modified in shape.
Furthermore, conventional toners obtained by pulverization has large Ra
and large RMS, which are also out of this range.
Surface characteristics of the toner base particles can be analyzed,
for example, using an atomic force microscope (AFM). However, a probe
top enters into a concave portion of the concavoconvex when the shape
having larger surface concavoconvex is measured,, and thus the
concavoconvex can not be correctly measured in some cases. Therefore, it
is preferable to use a 3D-SEM (3D-scanning electron microscope, field
emission electron beam three dimensional roughness analyzer) capable of
measuring without contact.
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A measurement principle is sometimes different depending on
manufacturing corporations, and for example, ERA-8900FE,
manufactured by Elionix Co., Ltd., equips multiple, or four, secondary
electron detectors with different placement, and it quantitatively detects
the amount of secondary electron signals which enter the detector and
calculates the angle of gradient for X-Y of a sample. A three dimensional
shape can be measured with this apparatus without severe damage to
the sample because the shape is evaluated using secondary electron. In
addition, a horizontal direction can be measured with high resolution. In
the present embodiment, the surface characteristics of the toner base
particles were defined by measuring the toner particle surface having 4
mm square.
The surface roughness Ra is defined by a three dimensional
average roughness for a center plane (i.e., the plane which divides the
concavo-convex volume equally in above and below this plane) and is
represented by the following formula I:

where Zcp represents the Z value of the center plane, Zi represents the Z
value in each data point, and N represents the number of the data points.
The standard deviation RMS of the surface roughness is the
standard deviation of Z values of all data points and is represented by
the following formula II:

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where Zave represents the mean of all Z values, Zi represents the Z value
of each data point, and N represents the number of the data points.
The surface roughness (Ra) is defined by an average length of the
highest 5 points from peaks and the lowest 5 points from bottoms
selected for each reference length.
The surface roughness (Ra) is an average surface roughness and
is identical when the volumes of the concavoconvex made by the center
plane and the surface shape are equal even whether the particles have a
rough concavoconvex or a fine concavoconvex. Meanwhile, the value of
the standard deviation (RMS) becomes large when the fine
concavoconvex is dominant. Thus, the standard deviation can represent
roughness and fineness of the concavoconvex.
Regarding the toner of the present invention, the surface
-roughness (Ra) of the toner base particles is 18 nm to 50 nm, and more
preferably 18 nm to 30 nm. When the surface roughness is less than 18
nm, the concavo-convex size on the surface of the toner base particle is
excessively small, a cleaning ability is reduced. A blade wearing property
after long use (after printing several hundred thousand sheets), largely
contributed by the reduction of the fine cleaning ability, is reduced, which
is not preferable. Also, since the frictional charging state is reduced, the
charge performance under an environment at high temperature and high
humidity or at low temperature and low humidity is reduced, which is
not preferable. When the surface roughness (Ra) exceeds 50 nm, the
concavo-convex sizes on the surface of the toner base particles are large,
which reduces the flowability of the toner as well as the charge property
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and the transfer property. The sharpness of the image is also reduced.
The standard deviation (RMS) of the surface roughness of the
toner base particles is 0.5 nm to 9.9 run, and preferably 2 nm to 8 nm. In
particular, the concavo-convex cycle is very important when the
microscopic cleaning ability involved in the cleaning blade wearing
property is discussed. A cleaning effect can not be sufficiently exerted
when the cycle is excessively large or small. By having a concavo-convex
cycle in this range, a dam effect can be formed on the blade with being
capable of preventing toner tumble in the cleaning blade while assuring
the toner transfer property. A trace amount of the toner scraping
through is reduced; and consequently the blade wearing caused by
thereof can be prevented. When the standard deviation (RMS) of the
surface roughness in the blade is less than 0.5 nm, the surface
concavoconvex of the toner base particles becomes excessively rough, and
the favorable factional charging by the contact with the frictional
charging member can not be performed. Furthermore, the transfer
property as well as the fine cleaning ability is reduced, which increases
in the amount of the toner left upon transferring. When RMS exceeds
9.9 nm, the surface concavoconvex of the toner base particles becomes
dense, the flowability of the toner, is reduced, and a tumble prevention
effect of the toner is reduced as well, which consequently reduces the
cleaning ability.
The surface roughness (Rz) of the toner base particles is
preferably 30 nm to 200 nm, and more preferably 50 nm to 150 nm in
terms of cleaning stability and charge stability. The surface roughness
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(Rz) is an indicator which represents the peak height of a concavoconvex
after noise rejection. The larger Rz is, the larger the degree, of
concavoconvex is. The smaller Rz is, the smaller the degree of
concavoconvex is. When Rz is less than 30 nm, the degree of
concavoconvex is excessively small, reducing the cleaning ability as well
as the blade wearing property after printing several hundred thousand
sheets, which is not preferable. Rz exceeding 200 run tends not only to
impair the toner charge stability but also to cause cracks in the convex
portions, which then easily causes the increase of fine powder ingredients
in a developing machine after long use for printing, which is not
preferable.
The toner of the present invention is toner base particles having
the above-mentioned surface characteristics, and it is more preferable
that inorganic particulates are internally added to the toner. Internal
addition of the inorganic particulates not only enables the formation of
the concavoconvex derived from the concavoconvex of the inorganic
particulates on the toner surface but also is effective, particularly when
the toner produced in a process comprising granulation in a liquid
medium, for the following reason. A polymer toner production comprises
a desolvation process, where the resin generally shrinks. Meanwhile, ,
hardness around the inorganic particulates is enhanced in particular
when the internally added inorganic particulates are present in the
vicinity of the surface, which causes a difference in the hardness from
that at the portion without organic particulates. Thus, a discrepancy in
the shrinking speed occurs, and consequently a deep concavoconvex
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having a dimple shape is formed on the toner surface.
Regarding the enhancement of the flowability, the charge
property and the environmental charge property, it is preferable to
externally add the inorganic particulates by combining those of equal or
different types.
Examples of the inorganic particulates includes silica,
organosilica sol, alumina, titanium oxide, barium titanate, magnesium
titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide,
quartz sand, clay, mica, wollastonite, diatomaceous earth, chromium
oxide, cerium oxide, colcothar, antimony trioxi.de, magnesium oxide,
zirconium oxide, barium sulfate, barium carbonate, calcium carbonate,
silicon carbide and silicon nitride. By using any of them individually or
some inorganic particulates in combination, it is possible to enhance the
shape, the flowability, developing property and the charge property of the
toner base particles.
The primary particle diameter of this inorganic particulate is
preferably 5 x 10'3 um to 2 fan, and more preferably 5 x 10"3 um to 0.5 (am.
It is preferable that the specific surface area by BET method is 20 m2/g to
500 m2/g. The percentage of this inorganic p articulate to be used is
preferably 0.01 % to 5 % by mass, and in particular preferably 0.01 % to
2.0 % by mass.
It is preferable that an average circularity of the toner base
particles is 0.93 to 1.00 in the light of obtaining high image quality
because an excellent dot reproducibility and favorable transfer property
may be obtained with the above circularity. The toner having such a
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high average circularity easily slides on the surface of the frictional
charging member such as magnetic carrier, and it is disadvantageous in
terms of charging speed and charging level. However, by having the
surface characteristics of the toner base particle of the present invention,
it is possible to obtain a toner with sufficient frictional charge property
as well as excellent developing property and transfer property.
When the average circularity is less than 0.93, i.e. the shape of
the toner is far from spherical, it is difficult to obtain a sufficient transfer
property or a high quality image with no dust. Such amorphous particles
have many contact points with medium having a smooth surface such as
photoconductor. Also, such particles have larger Van der Waals1 force and
image force than relatively spherical particles since charges are
concentrated at the top of a prominence; hence its adhesive force is also
larger. Thus, in a toner where amorphous particles and spherical
particles are mixed, the spherical particles selectively move to cause
image missing in a text section and a line section in an electrostatic
transferring process. The remaining toner must be removed for the
subsequent developing process, and there are problems such as a
cleaning apparatus is required and that a toner yield (percentage of the
toner used for the image formation) is low.
The average circularity of a toner is a value obtained by optically
detecting the particles and dividing the circumference of the projection
area by the circumference of a circle having the same area as the
projection area. Specifically, the particle is measured using a flow mode
particle image analyzer (FPIA-2000, manufactured by Sysmex
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Corporation). In a given vessel, 100 mL to 150 mL of water from which
solid impurities have been previously removed is placed. As a dispersant,
0.1 mL to 0.5 mL of a surfactant is added, and about 0.1 g to 9.5 g of a
sample to be measured is further added. A suspension in which the
sample has been dispersed is treated in an ultrasonic dispersion
apparatus for about 1 to 3 minutes to make the concentration of the
dispersion 3,000 to 10,000 particles/uL, and the shape and the
distribution of the toner are measured.
The toner preferably has a volume average particle diameter (Dv)
of 2.0 urn to 6.0 urn and a ratio (Dv/Dn) of the volume average particle
diameter (Dv) to a number average particle diameter (Dn) of 1.00 to 1.40.
More suitably, the volume average particle diameter is 3.0 jim to 6.0 urn,
and Dv/Dn is 1.00 to 1.15. Such a toner has excellent heat resistant
storage stability, low-temperature fixing property and hot offset
resistance. Especially, an excellent luster property of the image is
obtained when used with a full-color copying machine.
In general, the smaller the particle diameter of the toner is, the
more advantageous it is for obtaining the image with high resolution and
high quality. However, in contrast, it is disadvantageous in terms of the
transfer property and the cleaning ability. When the volume average
particle diameter is below the range of the present invention, the toner is
fused to the surface of the magnetic carrier in a prolonged stirring in the
developing apparatus to reduce the charge performance of the magnetic
carrier with a two-component developer. In the case of one-component
developer, filming of the toner to the developing roller and fusion of the
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toner to a member such as blade for thin filming of the toner tend to
occur.
These phenomena are largely dependent on the content of fine
powder. In particular, the content of the particles with a particle
diameter of 3 mm or less exceed 10 % works against the adhesion to the
magnetic carrier and the high-level charge stability.
Conversely, when the volume average particle diameter of the
toner is above the range of the present invention, it becomes difficult to
obtain an image with high resolution and high quality. In addition, the
variation of the particle diameter in the toner often becomes large when
the toner in the developer is balanced.
When Dv/Dn exceeds 1.40, a charge distribution becomes wide,
and resolution is reduced, which is not preferable.
The average particle diameter and particle size distribution of a
toner can be measured using Coulter Counter TA-II or Coulter Multisizer
(both are manufactured by Coulter). In the present invention,
measurements were performed using Coulter Counter TA-II connected
with an interface that output a number distribution and a volume
distribution (manufactured by The Institute of Japanese Union of
Scientists & Engineers) and . with PC9801 personal computer
(manufactured by NEC Corporation).
It is also preferable that the ratio of the surface roughness (Ra) to
the volume average particle diameter (Dv), i.e. Ra (nm)/Dv (mm), is 0.3 to
10.0. When the above ratio is less than 0.3, the toner base particles
easily slide on the surface of the frictional charging member since the
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degree of concavoconvex is small for the particle diameter of the toner
base particle. Therefore, the charge property is reduced, and the
cleaning ability is also reduced. Meanwhile, when the above ratio
exceeds 10.0, the toner base particles are strongly rubbed with the
frictional charging member and easily spent since the degree of
concavoconvex is large for the particle diameter of the toner base particle.
Thus, the charge performance is reduced.
Preferably, the toner base particles have a shape coefficient SF-2
of 100 to 140 and the ratio of the surface roughness (Ra) thereto, i.e. Ra
(nm)/SF-2, of 0.008 to 0.500.
The shape coefficient SF-2 indicates the degree of concavoconvex
of the toner shape as shown in Formula III below. SF-2 is a value
obtained by dividing the square of the peripheral length (PERI) of a
shape obtained by projecting the toner to a two dimensional plane by the
area (AREA) of the shape, and multiplying 100/471:

where PERI represents the peripheral length of the shape obtained by
projecting the toner base particle to a two dimensional plane; AREA
represents the area of the shape obtained by projecting the toner base
particle to the two dimensional plane.
When the value of SF-2 is 100, no macroscopic concavoconvex is
present in the toner shape. The larger the value of SF-2 is, the more the
concavoconvex in the toner shape becomes remarkable.
The value of SF-2 can be calculated by observing and saving the
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images of one hundred randomly selected toner particles by a scanning
electron microscope (FE-SEM S-4800, manufactured by Hitachi, Ltd.)
and by analyzing these images by an image analyzer (LUSEX AP, Nireco
Corporation). The analysis is more on the macroscopic concavoconvex of
the toner base particle compared to the surface roughness Ra.
When the value of SF'2 exceeds 140, the toner is scattered on the
image, and the image quality is reduced. Thus, the value of SF-2 is
preferably in the range of 100 to 140.
It is preferable that the ratio of the surface roughness Ra, which
represents the fineness of the surface concavoconvex of the toner base
particle, to the shape coefficient SF-2, which represents the macroscopic
concavoconvex on the shape of the toner base particle, i.e. Ra (nm)/SF-2,
is in the range of 0.008 to 0.500. The toner that has the ratio within this
range has suitably fine concavoconvex on the toner base particles, and
thus the frictional charge property is favorable. In addition, the toner is
excellent in developing property and transfer property since the shape of
the toner base particle is nearly spherical, and the image with high
quality can be provided.
The toner of the present invention can be produced by
granulating in a liquid medium. The toner of the present invention can
be obtained more suitably by dissolving/dispersing a toner material
containing inorganic particulates using an organic solvent, ' and
granulating in an aqueous medium followed by desolvation.
The toner produced by dry pulverization method has an
amorphous shape, and moreover it tends to have a wide particle diameter
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distribution. Therefore, it is preferable to produce by granulating in the
liquid medium in order to narrow the circularity distribution and the
particle diameter distribution and to narrow the charge distribution of
the toner. Specifically, it is possible to use a granulation method by
forming liquid drops in a liquid medium using a method such as
suspension polymerization, emulsification polymerization and dispersion
polymerization.
To control the surface roughness Ra of the toner base particles, it
is easy and preferable to use a method in which a different resin from the
toner binding resin is adhered to the surface of the toner base particles.
Regarding the different resin from the toner binding resin, it is possible
to use a resin capable of forming an aqueous dispersion, and the resin
may be a thermoplastic resin or a thermosetting resin. Examples of the
resin includes vinyl based resins, polyurethane resins, epoxy resins,
polyester resins, polyamide resins, polyimide resins, silicon based resins,
phenol resins, melamine resins, urea resins, aniline resins, ionomer
resins, and. polycarbonate resins. The resin may be used alone or in
combination of two or more.
Among them, the vinyl based resins, the polyurethane resins, the
epoxy resins and the polyester resins, and combinations thereof are
preferable in respect that the aqueous dispersion member of fine
spherical resin particles are easily obtained. For example, the vinyl
based resins include polymers obtained by homopolymerization or
copolymerization of vinyl based monomers, e.g., resins such as styrene-
(meth)acrylic acid ester copolymers, styrene-butadiene copolymers,
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(meth) acrylic acid-acrylic acid ester copolymers, styrene-acrylonitrile
copolymers, styrene-maleic acid ardiydrate copolymers and styrene-
(meth)acrylic acid copolymers.
When a toner composition, in which the above resin component is
dissolved or dispersed in an organic solvent is dispersed in an aqueous
medium, the resin component adheres as particulates to peripheries of oil
drops present to prevent the coalescence of the oil drops, and the oil
drops having uniform particle diameter are produced. This phenomenon
contributes to stabilization of the dispersion. The surface roughness Ra
of the toner base particles can be controlled by controlling the amount of
the resin component to be added and the particle diameter of the resin
particulates to be formed.
A method of adding a releasing agent in the toner may be given
as a means to prevent the hot offset of the toner, which is a problem in
the fixing process of the image forming process. The releasing agent
comprised in the toner appears on the toner surface to develop a
releasing property from a fixing member in association with deformation
of the toner by receiving heat and pressure upon fixing. It is preferable
that such releasing agent is enclosed without being exposed on the
surface of the toner base particles because the wax exposed on the
surface adheres to the surface of the frictional discharging member such
as magnetic carrier to reduce the frictional charge property of the toner
and exhibits an aggregation property to reduce the flowability of the
toner.
Furthermore, the use of the method for adhering the foregoing
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WO 2006/075534 PCT/JP2005/024210
resin particulates onto the surface of the toner base particles enables the
releasing agent enclosed in the toner base particles to bleed only upon
fixing, and the defects such as reduction of the toner charge property can
be resolved in addition to the control of the surface roughness.
Regarding the releasing agent, a wax having a low melting point
of 50 °C to 120 °C works effectively between a fixing roller and a toner
boundary surface as the releasing agent in the dispersion with the binder
resin, which is effective for a high-temperature offset without an
application of a releasing agent such as oil on the fixing roller. Such wax
components include the following. Examples of waxes include plant
based waxes such as carnauba wax, cotton wax, tree wax and rice wax;
animal based waxes such as bee wax and lanolin; mineral based waxes
such as ozokerite and selsyn; and petroleum based waxes such as
paraffin, microcrystalline and petrolatum. In addition to these natural
waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch waxes and
polyethylene waxes, and synthetic waxes such as ester, ketone and ether
are included. Furthermore, it is possible to use fatty acid amide such as
12-hydroxystearic acid amide, stearic acid amide, phthalic acid
anhydrate imide and chlorinated hydrocarbon, and crystalline polymers
having a long alkyl group in a side chain such as homopolymers and
copolymers (e.g., copolymer of n-stearyl acrylate-ethyl methacrylate) of
polyn-stearyl methacrylate, polyn-lauryl methacrylate which" are
crystalline polymer resins having low molecular weights.
The toner of the present invention is a toner obtained by
dispersing in an aqueous medium a toner material, in which at least
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WO 2006/075534 PCT/JP2005/024210
polyester prepolymer having a functional group comprising a nitrogen
atom, polyester, a colorant and a releasing agent are dispersed in an
organic solvent and by performing a Crosslin king reaction and/or an
extension reaction. Materials that compose the toner and suitable
methods for production are described below.
(Polyester)
Polyester is obtained by polymerizing and condensing a
polyvalent alcohol compound and a polyvalent carboxylic acid compound.
Examples of a polyvalent alcohol (PO) includes a divalent alcohol
(DIO) and an trivalent or highervalent alcohol (TO). DIO alone or a
mixture of DIO with a small amount of TO is preferable. Divalent
alcohols (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol); alkylene
ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol,
polyethylene glycol, polypropylene glycol and polytetramethylene ether
glycol); alicyclic diol (l,4-cyclohexane dimethanol and hydrogenated
bisphenol A); bisphenols (bisphenol A, bisphenol F and bisphenol S);
alkylene oxide adducts of the above alicyclic diol (ethylene oxide,
propylene oxide and butylene oxide); and alkylene oxide adducts of the
above bisphenols (ethylene oxide, propylene oxide and butylene oxide).
Among them, alkylene oxide adducts of alkylene glycol having 2 to 12
carbons and bisphenols are preferred. Particularly preferred are
alkylene oxide adducts of bisphenols, and combinations of alkylene glycol
having 2 to 12 carbons therewith. Alcohols with three or more valence
(TO) include trivalent to octavalent or higher-valent polyvalent aliphatic
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WO 2006/075534 PCT/JP2005/024210
alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol
and sorbitol)," trivalent or more phenols (tris phenol PA, phenol novolack
and cresol novolack); and alkylene oxide adducts of the above trivalent or
highervalent polyphenols.
Polyvalent carboxylic acid (PC) includes bivalent carboxylic acid
(DIC) and trivalent or highervalent carboxylic acid (TC). DIC alone or a
mixture of DIC with TC in a small amount is preferable. Bivalent
carboxylic acid DIC includes alkylene dicarboxylic acids (succinic acid,
adipic acid and sebacic acid); alkenylene dicarboxylic acids (maleic acid,
fumaric acid); aromatic dicarboxylic acids (phthalic acid, isophthalic acid,
terephthalic acid and naphthalene dicarboxylic acid). Among them,
alkenylene dicarboxylic acids having 4 to 20 carbons and aromatic
dicarboxylic acids having 8 to 20 carbons are preferred. Trivalent or
higher-valent carboxylic acids (TC) include aromatic polyvalent
carboxylic acids (trimellitic acid, pyromellitic acid) having 9 to 20 carbons.
As polyvalent carboxylic acid (PC), acid anhydrate or lower alkyl ester
(methyl ester, ethyl ester and isopropyl ester) of the above may be used to
react with polyvalent alcohol (PO).
The ratio of polyvalent alcohol (PO) to polyvalent carboxylic acid
(PC) is typically 2/1 to 1/1, preferably 1.5/1 to 1/1, and more preferably
1.3/1 to 1.02/1 as an equivalent ratio of a hydroxyl group [OH] to a
carboxyl group [COOH], i.e. [OH]/[COOH].
In the polymerization and condensation reaction, a polyvalent
alcohol (PO) and a polyvalent carboxylic acid (PC) are heated to 150 °C to
280 °C under the presence of a heretofore known esterification catalyst
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WO 2006/075534 PCT/JP2005/024210
such as tetrabutoxy titanate or dibutyltin oxide and distilling off
produced water under reducing pressure if necessary to produce. a
polyester comprising a hydroxyl group. The hydroxyl value of the
polyester is preferably 5 (mg KOH/g) or greater, and the acid value of the
polyester is typically 1 to 30 (mg KOH/g), and preferably 5 to 20. The
acid value gives the toner a negative charge property, and further the
favorable affinity between recording paper and the. toner improves the
low-temperature fixing property an affinity between recording paper and
the toner. However, when the acid value exceeds 30, the stability of the
charging is prone to deteriorate with environmental variation.
A weight average molecular weight is 10,000 to 400,000, and
preferably 20,000 to 200,000. The weight average molecular weight of
less than 10,000 is not preferable because the hot offset resistance is
reduced. When it exceeds 400,000, it is not preferable because the low-
temperature fixing property is reduced.
(Polyester prepolymer with a functional group comprising a nitrogen
atom (A))
The polyester preferably comprises a polyester modified with
urea in addition to an unmodified polyester obtained by the above
polymerization and condensation reaction. The urea modified polyester
is obtained by reacting a polyvalent isocyanate compound (PIC) with a
carboxyl group or a hydroxyl group at an end of the polyester obtained by
the above polymerization and condensation reaction to yield a polyester
prepolymer (A) comprising an isocyanate group, and reacting amines
therewith to crosslink and/or extend the molecular chain.
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WO 2006/075534 PCT/JP2005/024210
Examples of the polyvalent isocyanate compound (PIC) include
aliphatic polyvalent isocyanate (tetramethylene diisocyanate,
hexamethylene diisocyanate and 2,6-diisocyanatomethyl caproate):
alicyclic polyisocyanate (isophorone diisocyanate and cyclohexylmethane
diisocyanate); aromatic diisocyanate (trilene diisocyanate and
diphenylmethane diisocyanate) ; aromatic aliphatic diisocyanate
(a,a,a',a'-tetramethylxylylene diisocyanate) ; isocyanates; compounds
obtained by blocking the above polyisocyanate with a phenol derivative,
oxime, or caprolactam; and combinations of two or more thereof.
The ratio of the polyvalent isocyanate compound (PIC) is typically
5/1 to 1/1, preferably 4/1 to 2/1 and more preferably 2.5/1 to 1.5/1 as the
equivalent ratio of isocyanate groups [NCO] to hydroxyl groups [OH] of
polyester having the hydroxyl groups, i.e. [NCO]/[OH]. When
[NCO]/[OHl exceeds five, the low-temperature fixing property is reduced.
When the molar ratio of [NCO] is less than one, the contained amount of
urea portion becomes low with the use of the urea modified polyester,
which consequently reduces the hot offset resistance.
The composition of isocyanate compound (PIC) in the polyester
prepolymer (A) comprising an isocyanate group is typically 0.5 % to 40 %
by mass, preferably 1 % to 30 % by mass and more preferably 2 % to 20 %
by mass. When the amount is less than 0.5 % by mass, the hot offset
resistance is reduced, and at the same time, it is disadvantageous in
terms of both heat-resistant storage stability and low-temperature fixing
property. When it exceeds 40 % by mass, the low-temperature fixing
property is reduced.
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WO 2006/075534 PCT/JP2005/024210
The number of the isocyanate group comprised in one molecule of
the polyester prepolymer (A) comprising an isocyanate groups is typically
one or more, preferably an average of 1.5 to 3, and more preferably an
average of 1.8 to 2.5. When the number of the isocyanate group is less
than one per molecule, the molecular weight of the urea modified
polyester is small, which reduces the hot offset resistance.
Examples of amines (B) to be reacted with the polyester
prepolymer (A) comprising an isocyanate group include bivalent amine
compounds (Bl), trivalent or higher-valent amine compounds (B2), amino
alcohol (B3), aminomercaptan (B4), amino acids (B5) and those obtained
by blocking the amino groups in Bl to B5 (B6).
Examples of the bivalent amine compounds (Bl) include aromatic
diamine (phenylene diamine, diethyltoluene diamine and 4,4'-
diaminodiphenylmethane); alicyclic diamine, (4,4'-diamino-3,3'-
dimethyldicyclohexylmethane, diamine cyclohexane and isophorone
diamine); and aliphatic diamine (ethylenediamine,
tetramethylenedia mine and hexamethylenediamine).
Examples of trivalent or higher-valent amine compounds (B2)
include diethylenetriamine and triethylenetetraamine.
Examples of amino alcohols (B3) include ethanol amine and
hydroxyethylaniline.
Examples of aminomercaptan (B4) include aminoethylmercaptan
and aminopropylmercaptan.
Examples of amino acids (B5) include aminopropionic acid and
aminocaproic acid.
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Those obtained by blocking the amino group in Bl to B5 (B6)
include ketimine compounds and oxazolidine compounds obtained from
amines and ketones (acetone, methyl ethyl ketone and methyl isobutyl
ketone) of the above Bl to B5. Among these amines, Bl and a mixture of
Bl with a small amount of B2 are preferred.
The ratio of amines (B) is typically 1/2 to 2/1, preferably 1.5/1 to
1/1.5 and more preferably 1.2/1 to 1/1.2 as the equivalent ratio of the
isocyanate groups [NCO] in the polyester prepolymer (A) comprising an
isocyanate group to the amino groups [NHx] in amines (B), i.e.
[NCOMNHx].
When [NCO]/[NHx] is greater than two or is less than 1/2, the
molecular weight of the urea modified polyester becomes low, and the hot
offset resistance is reduced.
The urea modified polyester may also comprise a urethane bond
as well as a urea bond. The molar ratio of the urea bonds to the
urethane bonds to be contained is typically 100/0 to 10/90, preferably
80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio
of the urea bond is less than 10 %, the hot offset resistance is reduced.
The urea modified polyester is produced by a one-shot method.
A polyester comprising a hydroxyl group is obtained by heating
polyvalent alcohol (PO) and polyvalent carboxylic acid (PC) to 150 °C to
280 °C under the presence of a heretofore known esterification catalyst
such as tetrabutoxy titanate or dibutyltin oxide and distilling off the
produced water under reducing pressure if necessary. Then, this is
reacted with polyvalent isocyanate (PIC) at 40 °C to 140 °C to yield the
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WO 2006/075534 PCT/JP2005/024210
polyester prepolymer (A) comprising an isocyanate group. Furthermore,
amines (B) is reacted this (A) at 0 °C to 140 °C to yield the urea modified
polyester.
A solvent can also be used as needed in the reaction of PIC or in
the reaction of the polyester prepolymer (A) and amines (B). Examples of
a usable solvent include those such as aromatic solvents such as toluene
and xylenel ketones such as acetone, methyl ethyl ketone and methyl
isobutyl ketone! esters such as ethyl acetate; amides such as
dimethylformamide and dimethylacetamide; and ethers such
astetrahydrofuran, which are inert for isocyanate (PIC).
The molecular weight of the resulting urea modified polyester can
be adjusted with a reaction terminator if necessary in the crosslinking
reaction and/or the extension reaction of the polyester prepolymer (A)
and amines (B). Examples of the reaction terminator include monoamine
such as diethylamine, dibutylamine, butylamine and laurylamine," and
those obtained by "blocking them such as ketimine compounds.
The weight average molecular weight of the urea modified
polyester is typically 10,000 or more, preferably 20,000 to 10,000,000 and
more preferably 30,000 to 1,000,000. When it is less than 10,000, the hot
offset resistance is reduced. The number average molecular weight of
the urea modified polyester is not particularly limited when the above
unmodified polyester is used, and the number average molecular weight
may be adjusted so that the above weight average molecular weight is
easily obtained. When the urea modified polyester is used alone, the
number average molecular weight thereof is typically 2,000 to 20,000,
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WO 2006/075534 PCT/JP2005/024210
preferably 2,000 to 10,000 and more preferably 2,000 to 8,000. When it
exceeds 20,000, the lowtemperature fixing property and the luster
property for a full-color apparatus are reduced.
Since the lowtemperature fixing property and the luster property
for a full-color apparatus are enhanced by combining the unmodified
polyester with the urea modified polyester, the combination is more
preferable than the case of using the urea modified polyester alone. The
unmodified polyester may comprise a polyester modified with chemical
bonds other than urea bonds.
It is preferable in terms of low-temperature fixing property and
hot offset resistance that the unmodified polyester and the urea modified
polyester are at least partially compatible. Therefore, it is preferable
that the unmodified polyester and the urea modified polyester have
similar compositions.
The mass ratio of the unmodified polyester to the urea modified
polyester is typically 20/80 to 95/5, preferably 70/30 to 95/5, more
preferably 75/25 to 95/5 and particularly preferably 80/20 to 93/7. When
the mass ratio of the urea modified polyester is less than 5 %, the hot
offset resistance is reduced, and at the same time it is disadvantageous
in terms of balancing the heat resistant storage stability and the low-
temperature fixing property.
The glass transition point (Tg) of the binder resin comprising the
unmodified polyester and the urea modified polyester is typically 45 °C to
65 °C, and preferably 45 °C to 60 °C. When it is lower than 45 °C, the
toner heat resistance is reduced; whereas when it is higher than 65 °C,
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WO 2006/075534 PCT/JP2005/024210
the low-temperature fixing property is insufficient.
The urea modified polyester tends to present on the surface of the
resulting toner base particles. Therefore, even when the glass transition
point is lower compared to a heretofore known polyester based toner, the
heat resistant storage stability is favorable.
-Colorants-
Regarding the colorants, heretofore known dyes and pigments
such as the following may be used: carbon black, nigrosine dyes, iron
black, naphthol yellow S, hanza yellow (10G, 5G, G), cadmium yellow,
yellow iron oxide, yellow ocher, chrome yellow, titanium yellow, polyazo
yellow, oil yellow, hanza yellow (GR, A, RN, R), pigment yellow L,
benzidine yeEow (G, GR), permanent yellow (NCG), Balkan fast yellow
(5G, R), tartrazine lake, quinoline yellow lake, anthrazane yellow BGL,
isoindolinone yellow, colcothar, red lead, lead vermillion, cadmium red,
cadmium mercury red, antimony vermilhon, permanent red 4R, parared,
faicer red, parachloroorthonitroaniline red, lithol fast scarlet G, brilliant
fast scarlet, brilliant carmine BS, permanent red (F2R, F4R, FRL, FRLL,
F4RH), fast scarlet VD, Balkan fast rubine B, brilliant scarlet G, lithol
rubine GX, permanent red F5R, brilliant carmine 6B, pigment scarlet 3B,
Bordeaux 5B , toluidine maroon, permanent Bordeaux F2K, helio
Bordeaux BL, Bordeaux 10B, bon maroon light, bon maroon medium,
eosin lake, rhodamine lake B, rhodamine lake Y, alizarin lake, thioindigo
red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red,
polyazo red, chrome vermilion, benzidine orange, perinone orange, oil
orange, cobalt blue, cerulean blue, alkali blue lake, peacock blue lake,
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WO 2006/075534 PCT/JP2005/024210
Victoria blue lake, non-metallic phthalocyanine blue, phthalocyanine
blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine blue,
Prussian blue, anthraquinone blue, fast violet B, methyl violet lake,
cobalt violet, manganese violet, dioxane violet, anthraquinone violet,
chrome green, zinc green, chromium oxide, pyridian, emerald green,
pigment green B, naphthol green B, green gold, acid green lake,
malachite green, phthalocyanine green, anthraquinone green, titanium
oxide, zinc flower, lithopone and mixtures thereof.
The content of the above colorant is typically 1 % to 15 % by mass,
and preferably 3 % to 10 % by mass based on the toner.
The above colorants may be used as a master batch which is a
complex with the resin. Examples of a binder resin used for producing
the master batch or kneaded with the master batch includes the
following: polymers of styrene and derivative thereof such as polystyrene,
poly-p-chlorostyrene and polyvinyl toluene, or copolymers of vinyl
compounds therewith, polymethyl methacrylate, polybutyl methacrylate,
polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene,
polyester, epoxy resins, epoxy polyol resins, polyurethane, polyamide,
polyvinyl butyral,- polyacrylic acid resins, rosin, modified rosin, terpene
resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum
resins, chlorinated paraffin and paraffin wax. These may be used alone
or in combination.
-Charge controller-
A heretofore known charge controller may be used, and examples
thereof include nigrosine based dyes, triphenylmethane based dyes,
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WO 2006/075534 PCT/JP2005/024210
chromium containing metal complex dyes, molybdic acid chelated
pigments, rhodamine based dyes, alkoxy based a mine, quaternary
ammonium salts (including fluorine modified quaternary ammonium
salts), alkylamide, a single substance or compounds of phosphorous, a
single substance or compounds of tungsten, fluorine based activator,
metal salts such as salicylate metal salts and salicylate derivatives.
Specifically, Bontron 03 which is the nigrosine based dye, Bontron P-51
which is the quaternary ammonium salt, Bontron S-34 which is a metal
containing azo dye, E-82 which is an oxynaphthoic acid based metal
complex, E-84 which is a salicylic acid based metal complex and E-89
which is a phenol based condensate which are manufactured by Orient
Chemical Industries Ltd., TP-302 and TP-415 which are quaternary
ammonium salt molybdate complexes, which are manufactured by
Hodogaya Chemical Co., Ltd., Copy Charge PSY VP2038 which is the
quaternary ammonium salt, Copy Blue PR which is a triphenylmethane
derivative, Copy Charge NEG VP2036 and Copy Charge NX VP434
which are the quaternary ammonium salts, which are manufactured by
Hoechst AG, LR.-147 which is a boron complex (manufactured by Japan
Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo
based pigments) and additionally polymer compounds having a
functional group such as sulfonate, carboxyl groups and quaternary
ammonium salts. Among them, a substance which controls the toner to
negative polarity is preferably used.
The amount of the charge controller to be used depends on the
toner production method including the type of the binder resin, the
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WO 2006/075534 PCT/JP2005/024210
presence or absence of the optionally used additives and the dispersion
method. The amount is not clearly defined, but it is preferably in the
range of 0.1 parts to 10 parts by mass based on 100 parts by mass of the
binder resin. Preferably, it is in the range of 0.2 parts to 5 parts by mass.
When the amount exceeds 10 parts by mass, the charge property of the
toner is excessively large, the effect of the charge controller is reduced,
and the electrostatic suction power to the development roller is increased,
resulting in flowability reduction of the developer and reduction of an
image density in some cases.
Releasing agent-
As a releasing agent, a wax having a low melting point of 50 °C to
120 °C works effectively between a fixing roller and a toner boundary
surface as the releasing agent, in the dispersion with the binder resin,
and this is effective for a high-temperature offset without an application
of a releasing agent such as oil on the fixing roller. Examples of such
wax component includes plant based waxes such as carnauba wax, cotton
wax, tree wax and rice wax," animal based waxes such as bee wax and
lanolini mineral based waxes such as ozokerite and selsyn; and
petroleum based waxes such as paraffin, microcrystalline and petrolatum.
In addition to these natural waxes, synthetic hydrocarbon waxes such as
Fischer-Tropsch waxes and polyethylene waxes, and synthetic waxes of
ester, ketone and. ether are included. Furthermore, it is possible to use a
fatty acid amide such as 12"hydroxystearic acid amide, stearic acid amide,
phthalic acid anhydrate imide and chlorinated hydrocarbon, and
crystalline polymers having a long alkyl group in a side chain such as
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WO 2006/075534 PCT/JP2005/024210
homopolymers and copolymers (e.g., copolymer of n-stearyl acrylate"ethyl
methacrylate) of poly n-stearyl methacrylate, poly-n-lauryl methacrylate
which, are crystalline polymer resins having low molecular weights.
The charge controller and the releasing agent can be melted and
kneaded with the master batch and the binder resin, or they may also be
added when dissolved and dispersed in the organic solvent. Substances
described above may be used for the releasing agent and the inorganic
particulates.
(Method for producing toner)
Subsequently, the method for producing the toner is described.
Herein, a preferable production method is described, but this is not to be
construed as limiting a production method of the present invention.
(l) A toner material solution is made by dispersing a colorant, an
unmodified polyester, a polyester prepolymer comprising an isocyanate
group and a releasing agent in an organic solvent.
It is preferable that the organic solvent is volatile with a boiling
point lower than 100 °C in terms of an easy removal after forming toner
base particles. Specifically, water-insoluble or water-immiscible
compounds such as toluene, xylene, benzene, carbon tetrachloride,
methylene chloride, 1,2-dichloroethane, trichloroethylene, chloroform,
monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate,
methyl ethyl ketone and methyl isobutyl ketone may be used alone or in
combination of two or more. In particular, aromatic solvents such as
toluene and xylene, and halogenated hydrocarbon such as methylene
chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are
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WO 2006/075534 PCT/JP2005/024210
preferable. The amount of the organic solvent to be used is typically 0
parts to 300 parts by mass, preferably 0 parts to 100 parts by mass and
more preferably 25 parts to 70 parts by mass based on 100 parts by mass
of the polyester prepolymer.
Herein, it is preferable to disperse inorganic particulates inside
the toner, more preferably in the vicinity of the surface in order to control
toner shapes. It is possible to make the shape of the toner surface
concavoconvex by taking advantage of the shape of the inorganic
particulates or the difference of the shrinking speed within the toner in
an emulsification desolvation process. The inorganic particulates and
the desolvation are particularly effective for enlarging the cycle (i.e.
reducing the value of RMS of the degree of concavoconvex), i.e. 'further
deepening a depth of the concave portion of the concavoconvex,' as well as
enlarging the surface roughness (Ra). The substances described above
may be used for the inorganic particulates; among these, inorganic
particulates such as silica and more preferably organosilica are more
preferable in terms of shape control or charge stability over timeor
environmental charge stability.
(2) The toner material solution is emulsified in an aqueous
medium under the presence of a surfactant and resin particulates.
The aqueous medium may be water alone or water comprising an
organic solvent such as alcohol (methanol, isopropyl alcohol and ethylene
glycol), dimethylformamide, tetrahydrofuran, cellsolves (methyl cellsolve)
and lower ketones (acetone and methyl ethyl ketone).
The amount of the aqueous medium to be used is typically 50
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WO 2006/075534 PCT/JP2005/024210
parts to 2,000 parts by mass and preferably 100 parts to 1,000 parts by
mass based on 100 parts by mass of the toner material solution. When
the amount is less than 50 parts by mass, the toner material solution is
not dispersed well, and the toner base particles having given particle
diameter are not obtained. When it exceeds 2,000 parts by mass, it is not
economical.
Dispersants such as surfactant and resin p articulates are
optionally added in order to well disperse toner material liquid drops
(crosslinked or extended during a dispersion process) in the aqueous
medium..
Example of the surfactant include anionic surfactants such as
alkylbenzenesulfonate salts, ocolefin sulfonate salts and phosphate ester,
cationic surfactants such as amine salt types such as alkylamine salts,
amino alcohol fatty acid derivatives, polyamine, fatty acid derivatives
and imidazoline, and quaternary ammonium salt types such as
alkyltrimethylammonium salts, dialkyldimethylammonium salts,
altyldimethylbenzylammonium salts, pyridinium salts,
alkylisoquinolinium salts and benzethonium chloride, nonionic
surfactants such as fatty acid amide derivatives and polyvalent alcohol
derivatives, and ampholytic surfactant such as alanine,
dodecyldi(aminoethyl)glycine, di(octylaminoethyl)glycine and N-alkyl"
N,N-dimethylammonium betaine.
A surfactant comprising a fluoroalkyl group is advantageous
since the use of an extremely small amount of the surfactant is effective.
The preferably used anionic surfactants comprising a fluoroalkyl group
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WO 2006/075534 PCT/JP2005/024210
include fluoroalkyl carboxylic acids having 2 to 10 carbons and metal
salts thereof, disodium perfluorooctanesulfonyl glutamate, sodium 3-[or
fhioroalkyl (6 to 11 carbons)oxy]-l-alkyl (3 to 4 carbons) sulfonate, sodium
3-[ar£luoroaIkanoyl (6 to 8 carbons)-N-ethylamono]-l-propane sulfonate,
fluoroalkyl (11 to 20 carbons) carboxylic acids and metal salts thereof,
perfluoroalkyl carboxylic acids (7 to 13 carbons) and metal salts thereof,
perfLuoroalkyl (4 to 12) sulfonic acids and metal salts thereof,
perfluorooctane sulfonic acid diethanol amide, N-propyl"N-(2-
hydroxyethyOperfluorooctane sulfone amide, perfLuoroalkyl (6 to 10
carbons) sulfone amide propyltrimethyl ammonium salts, perfluoroalkyl
(6 to 10 carbons)-N-ethylsulfonyl glycine salts and perfluoroalkyl (6 to 16
carbons) ethyl phosphate ester. Trade names thereof include Surflon S-
111, S-112 and S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorad
FC-93, FC-95, Fc98 and FC-129 (manufactured by Sumitomo Three M
Co., Ltd.), Unidain DS-101 and DS-102 (manufactured by Daikin
Industries Ltd.), Megafac F-110, F-120, F-113, F-191, F-812 and F-833
(manufactured by Dainippon Ink And Chemicals, Incorporated), EFTOP
EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201 and 204
(manufactured by Tohchem Products Co., Ltd.) and FTAKGENT F-100
and F-105 (manufactured by Neos Co., Ltd.).
The cationic surfactants include aliphatic primary secondary or
tertiary amic acids having fluoroalkyl groups, aliphatic quaternary
ammonium salts such as perfluoroalkyl (6 to 10 carbons) sulfonamide
propyltrimethyl ammonium salts, and benzalkonium salts,
benzethonium chloride, pyridinium salts, imidazolium salts, and as the
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WO 2006/075534 PCT/JP2005/024210
trade names, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.),
Fluorad FO135 (manufactured by Sumitomo Three M Co., Ltd.), Unidain
DS-202 (manufactured by Daikin Industries Ltd.), Megafac F-150 and F-
824 (manufactured by Dainippon Ink And Chemicals, Incorporated),
EFTOP EF-132 (manufactured by Tohchem Products Co., Ltd.), and
FTARGENT F-300 (manufactured by Neos Co., Ltd.).
The resin particulates (organic particulates) are added in order to
stabilize the toner base particles formed in the aqueous medium and to
provide the surface roughness.
The effect on the concavoconvex of the toner surface varies
depending on the particle diameter of the resin particulates and the
adhering conditions (embedment, planar deformation or partial
desorption (by acid, alkali, solvent or mechanical treatment) of the resin
particulates on the toner surface. Ra as well as RMS is large when the
resin particulates having a larger particle diameter are adhered to the
surface of the spherical toner while maintaining the shape of the resin
particulates. On the other hand, Ra as well as RMS becomes small when
the resin particulates are small or the toner has embedment, planar
deformation or a partial desorption inside the toner. Meanwhile, the
value of RMS is easily affected by the shape having a large cycle as well
as the resin particulates. Thus, it is often difficult to control the value of
RMS by solely controlling the organic particulates. The large cycle may
be easily modified by taking advantage of the inorganic particulates and
additionally the shrinkage of the desolvation.
It is preferable to add the resin particulates so that the fraction of
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WO 2006/075534 PCT/JP2005/024210
resin particulates coating over the surface of the toner base particles is in
the range of 10 % to 90 %. Examples thereof include polymethacrylic
acid methyl particulates of 1 urn and 3 urn, polystyrene particulates of
0.2 mrn and 2 urn, poly(styrene-acrylonitrile) particulates of 1 urn, and as
the trade names, PB-200H (manufactured by Kao Corporation), SGP
(manufactured by Soken Chemical & Engineering Co., Ltd.),
Technopolymer SB (manufactured by Sekisui Plastics Co., Ltd.), SGP-3G
(manufactured by Soken Chemical & Engineering Co., Ltd.) and
Micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).
Inorganic compound dispersants such as tricalcium phosphate,
calcium carbonate, titanium oxide, colloidal silica and hydroxyapatite
can also be used.
Polymer based protection colloid may be used as a dispersant (or
dispersion stabilizer) to stabilize the dispersed liquid drops in
combination with the foregoing resin particulates and inorganic
compound dispersant. Examples thereof include homopolymers or
copolymers of the following compounds; acids such as acrylic acid,
methacrylic acid, a-cyanoacrylic acid, a-cyanomethacrylic acid, itaconic
acid, crotonic acid, fumaric acid, maleic acid and maleic acid anhydrate;
(meth)acrylic monomers comprising a hydroxyl group such as acrylic
acid-p-hydroxylethyl, methacrylic acid-p-hydroxylethyl, acrylic acid-p-
hydroxylpropyl, methacrylic acid-p-hydroxylpropyl, acrylic acid-y-
hydroxylpropyl, methacrylic acid-yhydroxylpropyl, acrylic acid-3-chloro-
2-hydroxylpropyl, methacrylic acid-3-chloro-2-hydroxylpropyl, diethylene
glycol monoacrylate ester, diethylene glycol monomethacrylate ester,
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WO 2006/075534 PCT/JP2005/024210
glycerin monoacrylate ester, glycerin monomethacrylate ester and N-
metliylol methacrylamide; vinyl alcohols or ethers with vinyl alcohol such
as vinyl methyl ether, vinyl ethyl ether and vinyl propyl ether; esters of
vinyl alcohol with a compound comprising a carboxylic group such as
vinyl acetate, vinyl propionate and vinyl butyrate; acrylamide,
methacrylami.de, diacetone acrylamide, and methylol compounds thereof
acid chlorides such as acrylate chloride and methacrylate chloride,"
nitrogen-containing compounds such as vinyl pyridine, vinyl pyrrolidone,
vinyl imidazole and ethylene inline," and those comprising a heterocyclic
ring thereof. More examples of the polymer based protection colloid
include polyoxyethylenes such as polyoxyethylene, polyoxypropylene,
polyoxyethylene alkylamine, polyoxypropylene alkylamine,
polyoxyethylene alkylamide, polyoxypropylene alkylamide,
polyoxyethylene nonylphenyl ether, polyoxyethylene laurylphenyl ether,
polyoxyethylene stearylphenyl ether and polyoxyethylene nonylphenyl
ester, and celluloses such as methylcellulose, hydroxyethylcellulose and
hydroxypropylcellulose.
The method of dispersion is not particularly limited, and
heretofore known equipments such as low-speed shearing method, high-
speed shearing method, high-pressure jet method and ultrasonic method
may be applied. Among them, the high-speed searing method, is
preferable for making the particle diameter of the dispersion 2 mm to 20
mm. The rotational frequency of a high speed shearing dispersion
machine is not particularly limited, but it is typically 1,000 rpm to 30,000
rpm and preferably 5,000 rpm to 20,000 rpm. The dispersion time period
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WO 2006/075534 PCT/JP2005/024210
is not particularly limited, but it is typically 0.1 minutes to 5 minutes in
the case of a batch mode. The temperature during dispersion is typically
0 °C to 150 °C (under pressure) and preferably 40 °C to 98 °C.
The releasing agent can be comprised in the aqueous medium
phase because it can transfer to the organic solvent phase due to its
lipophilicity even if it is initially comprised in the aqueous medium phase.
However, it is more preferable that the releasing agent is comprised in
the organic solvent phase.
(3) Amines (B) is added simultaneously with the production of an
emulsified liquid to react with the polyester prepolymer (A) comprising
an isocyanate group.
This reaction accompanies crosslinking and/or extension of the
molecular chain. The duration of the reaction is selected based on the
reactivity of amines with the isocyanate group structure of the polyester
prepolymer (A). It is typically 10 minutes to 40 hours, and preferably 2
hours to 24 hours. The reaction temperature is typically 0 °C to 150 °C,
and preferably 40 °C to 98 °C. A heretofore known catalyst can be used
as needed. Examples of the catalyst includes dibutyltin laurate and
dioctyltin laurate.
(4) After the reaction is completed, the organic solvent is removed
from an emulsified dispersion (reactant), and the emulsified dispersion is
then washed and dried to yield toner base particles.
The entire system is gradually heated with laminar stirring," a
strong agitation is given at a certain temperature range followed by
desolvation to removed the organic solvent, which as a result produces
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WO 2006/075534 PCT/JP2005/024210
spindle-shaped toner base particles. When a compound which may
dissolve in acid and alkali solution such as calcium phosphate salt is
used as a dispersion stabilizer, the calcium phosphate salt is removed
from the toner base particles by dissolving the salt with acid such as
hydrochloric acid and then washing with water. Additionally, the
dispersion stabilizer can be removed by decomposition with an enzyme.
(5) A charge controller is added to the toner base particles
obtained above, and then inorganic particulates such as silica
particulates and titanium oxide particulates are added externally to
obtain the toner.
The addition of the charge controller and the external addition of
the inorganic particulates are performed by heretofore known methods
using a mixer.
By this a toner with small particle diameter and sharp particle
diameter distribution is easily obtained. In addition, the shape can be
controlled from a pearl shape to a spindle shape by strong agitation in
the process of removing the organic solvent, and furthermore, surface
morphology can be controlled from a smooth shape to a dimple shape.
(Developer)
A developer of the present invention comprises the toner of the
present invention and optionally selected other components such as
carrier. The developer may be a one-component developer or a two-
component developer, and the two-component developer is preferable in
terms of enhanced lifetime when used for high speed printers compatible
with the recent enhancement in information processing speed.
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WO 2006/075534 PCT/JP2005/024210
In the case of the one-component developer with the toner of the
present invention, there is little variation in the toner particle diameter
even though the toner is balanced. Since there is no filming of the toner
to a developing roller and no fusion of the toner to a member such as
blade that makes the toner a thin layer, favorable and stable developing
property and images are achieved during the prolonged use (stirring) of
the developing unit. Regarding the two-component developer with the
toner of the present invention, there is little variation of toner particle
diameter in the developer even though the toner is balanced over a
prolonged period of time, and favorable and stable developing property
are obtained in stirring in the developing unit for a prolonged period of
time.
The foregoing carrier is not particularly limited and can be
optionally selected depending on the purpose, but those having a core
material and a resin layer which coats the core material are preferable.
Materials for the core material are not particularly limited, and
can be optionally selected from those heretofor known. For example,
manganese-strontium (Mn-Sr) based materials and manganese-
magnesium (Mn-Mg) based materials of 50 emu/g to 90 emu/g are
preferable. In terms of assuring the image density, highly magnetized
materials such as iron powder (100 emu/g or greater) and magnetite (75
emu/g to 120 emu/g) are preferable. Weakly magnetized materials such
as copper-zinc (Cu-Zn) based materials (30 emu/g to 80 emu/g) are
preferable in the respect that the contact of the toner in a spike-standing
state with the photoconductor can be softened and that it is
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WO 2006/075534 PCT/JP2005/024210
advantageous for making the image have high quality. These may be
used alone or in combination of two or more.
Regarding the particle diameter of the core material, an average
particle diameter, i.e. the volume average particle diameter (D50), is
preferably 10 mrn to 200 mrn, and more preferably 40 mm to 100 mm.
When the average particle diameter, i.e. volume average particle
diameter (D50), is less than 10 urn, the fraction of fine powder increases,
and magnetization per particle becomes low to cause carrier scattering in
some cases. When it exceeds 200 mm, the specific surface area is reduced
to cause toner scattering in some cases, and in particular, affect the
reproduction of solid images in a full-color printing comprising many
solid images.
Materials for the resin layer are not particularly limited and can
be optionally selected from heretofore known resins depending on the
purpose. Examples thereof include amino based resins, polyvinyl based
resins, polystyrene based resins, halogenated olefin resins, polyester
based resins, polycarbonate based resins, polyethylene resins,
polyfluorovinyl resins, polyfhiorovinylidene resins, polytrifLuoroetbylene
resins, polyhexafluoropropylene resins, copolymers of fluorovinylidene
and acryl monomer, copolymers of fluorovinylidene and fhiorovinyl,
fluoroterpolymer such as terpolymer of tetrafhioroethylene and
fluorovinylidene and non-fluoride monomer and silicone resins. These
may be used alone or in combination of two or more.
The amino based resins include, for example, urea-formaldehyde
resins, melamine resins, benzoguanamine resins, urea resins, polyamide
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WO 2006/075534 PCT/JP2005/024210
resins and epoxy resins. The polyvinyl based resins include, for example,
acryl resins, polymethyl methacrylate resins, polyacrylonitrile resins,
polyvinyl acetate resins, polyvinyl alcohol resins and polyvinyl butyral
resins. The polystyrene based resins include, for example, polystyrene
resins and styrene-acryl copolymer resins. The halogenated olefin resins
include, for example, polyvinyl chloride. The polyester based resins
include, for example, polyethylene terephthalate resins and polybutylene
terephthalate resins.
Conductive powder may be comprised in the resin layer as needed,
and the conductive powder includes, for example, metal powder, carbon
black, titanium oxide, tin oxide and zinc oxide. The average particle
diameter of these conductive powder is preferably 1 urn or less. When
the average particle diameter exceeds 1 mm, it becomes difficult to control
the electric resistance in some cases.
The resin layer can be formed by dissolving a silicone resin in the
solvent to prepare a coating solution, subsequently applying the coating
solution uniformly on the surface of the core material by a heretofore
known coating method and drying followed by calcination. The coating
method includes, for example, a dipping method, a spraying method and
a brushing method.
The above solvent is not particularly limited can be optionally
selected depending on the purpose. Examples thereof include toluene,
xylene, methyl ethyl ketone, methyl isobutyl ketone and cellsolve butyl
acetate.
The method of calcination is not particularly limited," it may be an
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WO 2006/075534 PCT/JP2005/024210
external heating method or an internal heating method. Examples
thereof include methods using a fixed electric furnace, a fluid electric
furnace, a rotary electric furnace and a burner furnace; and a method
using microwaves.
The amount of the resin layer in the carrier is preferably 0.01 %
to 5.0 % by mass. When the amount is less than 0.01 % by mass, the
uniform resin layer can not be formed on the surface of the core material
in some cases. When it exceeds 5.0 % by mass, the resin layer becomes
excessively thick to cause granulation within the carrier, and thus
uniform carrier particles can not be obtained in some cases.
When the developer is a two-component developer, the content of
the carrier in the two-component developer is not particularly limited
and can be optionally selected depending on the purpose. For example, it
is preferably 90 % to 98 % by mass and more preferably 93 % to 97 % by
mass.
In general, the mixing ratio of the toner to the carrier in the two-
component developer is preferably 1 parts to 10.0 parts by mass of the
toner based on 100 parts by mass of the carrier.
The developer of the present invention comprises the toner of the
present invention. Therefore, the occurrence of photoconductor filming
can be prevented, there is, and it is possible to stably form an excellent
and sharp images having high quality and no variation in" the
unevenness of image.
(Process cartridge)
The process cartridge of the present invention comprises a latent
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WO 2006/075534 PCT/JP2005/024210
image bearing member which bears a latent electrostatic image and a
developing unit in which the latent electrostatic image borne on the
latent image bearing member is developed using a toner to form a visible
image; it further comprises other units optionally selected as needed
such as a charging unit, developing unit, transferring unit, cleaning unit
and neutralizing unit.
The developing unit comprises a developer container in which the
toner or the developer of the present invention is held and a developer
bearing member which bears and delivers the toner or the developer held
in the developer container, and it may further comprises a layer
thickness controlling member for controlling the layer thickness of the
borne toner.
The process cartridge of the present invention can be detachably
provided for various electrograph apparatuses, facsimiles and printers,
and preferably, it is detachably provided for the image forming apparatus
of the present invention described hereinafter.
Herein, the process cartridge, for example as shown in Fig. 1,
comprises a built-in photoconductor 101, a charging unit 102, a
developing unit 104, a transferring unit 108 and a cleaning unit 107; it
further comprises other units as needed. In Fig. 1, 103 and 105
represent exposure by an exposing unit and a recording medium,
respectively.
The photoconductor 101 may be the one similar to that employed
by the image forming apparatus described later. An optional charging
member is used for the charging unit 102.
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WO 2006/075534 PCT/JP2005/024210
Next, an image forming process by the process cartridge shown in
Fig. 1 is described. A latent electrostatic image corresponding to, an
exposure image is formed on the surface of the photoconductor 101
rotating in the direction of the arrow, with charging by the charging unit
102 and exposure 103 by the exposing unit (not shown in the figure).
This latent electrostatic image is toner-developed in the developing unit
104. The tonerdeveloped image is transferred by the transferring unit
108 onto the recording medium 105 and printed out. Then, the
photoconductor surface after transferring the image is cleaned by the
cleaning unit 107 and further neutralized by the neutralizing unit (not
shown in the figure). The above operations are repeated again.
Regarding the image forming apparatus of the present invention,
the latent image bearing member and constituent elements such as
developing section and cleaning section are integrated into the process
cartridge, and this unit may detachably constitute the main body of the
apparatus. Alternatively, the process cartridge may be formed by
integrating at least one of a charging section, an image exposing section,
the developing section, a transferring or separating section and the
cleaning section with the latent image bearing member to make a
detachable single unit in the main body of the apparatus, and the single
unit may be made detachable guiding units such as rails in the main
body of the apparatus.
(Image forming apparatus and image forming method)
The image forming apparatus of the present invention comprises
a latent image bearing member, a latent electrostatic image forming unit,
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WO 2006/075534 PCT/JP2005/024210
a developing unit, a transferring unit and a fixing unit; it further
comprises other units such as a neutralizing unit, cleaning unit,
recycling unit and controlling unit optionally selected as needed.
The image forming method of the present invention comprises a
latent electrostatic image forming process, a developing process, a
transferring process and a fixing process; and it further comprises other
processes such as a neutralizing process, cleaning process, recycling
process and controlling process optionally selected as needed.
The image forming method of the present invention can be
favorably carried out by the image forming apparatus of the present
invention; the latent electrostatic image forming process can be carried
out by the latent electrostatic image forming unit; the developing process
can be carried out by the developing unit; the transferring process can be
carried out by the transferring unit; the fixing process can be carried out
by the fixing unit; and the other processes can be carried out by the other
units.
-Latent electrostatic image forming process and latent electrostatic
image forming unit-
The latent, electrostatic image forming process is a process of
forming a latent electrostatic image on the latent image bearing member.
The latent image bearing member (sometimes referred to as
an 'electrographic photoconductor' or a 'photoconductor') is not
particularly limited in terms of material, shape, structure and size, and
it can be appropriately selected from those heretofore known. However,
the shape is favorably a drum shape, and the materials thereof include
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WO 2006/075534 PCT/JP2005/024210
inorganic photoconductors such as amorphous silicon and selenium, and
organic photoconductors such as polysilane and phthalopolymethine.
Among them, amorphous silicon is preferable in terms of long lifetime.
Regarding the amorphous silicon photoconductor, it is possible to
use a photoconductor having a photoconductive layer composed of a-Si
(sometimes referred to as an 'a-Si based photoconductor'), obtained by
heating a support to 50 °C to 400 °C and making the layer on the support
by a film forming method such as vacuum deposition method, spattering
method, ion plating method, thermal CVD method, photo-assisted CVD
method and plasma CVD method. Among them, the plasma CVD method,
i.e. the method in which a source gas is decomposed by direct current,
high frequency or microwave glow discharge to form an a"Si deposition
film on the support, is favorable.
The latent electrostatic image can be formed by charging the
surface of the latent image bearing member and subsequently exposing
according to the image; it can be performed with the latent electrostatic
image forming unit.
The latent electrostatic image forming unit comprises the
charging section which charges the surface of the latent image bearing
member and the exposing section which exposes the surface of the latent
image bearing member according to the image.
The charging can be performed by applying a voltage onto the
surface of the latent image bearing member using the charging section.
The charging section is not particularly limited, and it can be
optionally selected depending on the purpose. Examples thereof include
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WO 2006/075534 PCT/JP2005/024210
contact charging sections per se heretofore known comprising a
conductive or semi-conductive roller, brush, film and rubber blade; and
non-contact charging section that uses corona discharge such as corotron
and scorotron.
The shape of the charging member may be of any form such as
magnetic brush and fur brush in addition to roller, and it can be selected
in concert with the specification and the form of the electrograph
apparatus. When the magnetic brush is used, the magnetic brush uses
various ferrite particles such as Zn-Cu ferrite as the charging member
and is composed of a non-magnetic conductive sleeve for supporting the
particles and a magnet roll enclosed in the sleeve. Also, when a brush is
used, for example, a fur conductively treated with carbon, copper sulfide,
metal or metal oxide is used as the material of the fur brush, and the
charging section is made by looping or attaching the fur to a metal or
other conductively treated core grids.
The charging section is not limited to the above contact type
charging sections. However, it is preferable to use a contact type
charging section since an image forming apparatus with reduced ozone
generated from the charging section is obtained.
The exposure can be performed by exposing the surface of the
latent image bearing member according to the image using the exposing
section.
The exposing section is not particularly limited as long as the
exposure can be performed according to the image on the surface of the
latent image bearing member charged by the charging section, and it can
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WO 2006/075534 PCT/JP2005/024210
be optionally selected depending on the purpose. Examples thereof
include various exposing sections such as replicating optical, rod lens
alley based, laser optical and liquid-crystal shutter optical exposing
sections.
In the present invention, a back-lighting method in which the
exposure is performed according to the image from the backside of the
latent image bearing member may be employed.
-Developing process and developing unit-
The developing process is a process of developing the latent
electrostatic image using the toner or the developer of the present
invention to form a visible image.
The formation of the visible image can be performed by
developing the latent electrostatic image using the toner or the developer
of the present invention, and it can be performed by the developing unit.
The developing unit is not particularly limited as long as the
development can be performed using the toner or the developer of the
present invention. It can be optionally selected from those heretofore
known, and suitable examples include those comprising a developing
section which holds the toner or the developer of the present invention
and can impart the toner or the developer of the present invention to the
latent electrostatic image with or without contact. A developing section
comprising a vessel with the toner of the present invention is more
preferable.
In the developing unit, the developer is borne and delivered by
the latent image bearing member. An alternating electric field is applied
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WO 2006/075534 PCT/JP2005/024210
at a position opposite to the latent image bearing member, and the latent
electrostatic image on the latent image bearing member is developed,
where the developer of the present invention is used as the developer.
The developing section may be a dry developing system or a wet
developing system,' moreover, it may be a single-color development
section or a multi-color developing section. Suitable examples thereof
include those having a stirring section which charges the toner or the
developer by rubbing and stirring; and those having a rotatable magnet
roller.
In the developing section, the toner and the carrier are mixed and
stirred, for example, where the toner is charged by friction and
maintained in a spike-standing state on the surface of a rotating magnet
roller to form a magnetic brush. The magnet roller is disposed in the
vicinity of the latent image bearing member (photoconductor). Thus, a
part of the toner which composes the magnetic brush formed on the
surface of the magnet roller transfers to the surface of the latent image
bearing member (photoconductor) by electrical attractive force. As a
result, the latent electrostatic image is developed by the toner, and a
visible image by the toner is formed on the latent image bearing member
(photoconductor).
The developer held in the developing section is a developer
comprising the toner of the present invention. The developer may be a
one-component developer or a two-component developer. The toner
comprised in the developer is the toner of the present invention.
-Transferring process and transferring unit-
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The transferring process is a process that transfers the visible
image to a recording medium. A preferable aspect is where, by
employing an intermediate transferring member, the visible image is
primarily transferred to the intermediate transferring member, and
subsequently the visible image is secondarily transferred to the recording
medium. A more preferable aspect comprises, with a toner with two or
more colors or preferably a full-color toner as the toner,. a primary
transferring process where a complex transfer image is formed by
transferring the visible image onto the intermediate transferring
member and a secondary transferring process where the complex
transfer image is transferred onto the recording medium.
The transfer can be performed by charging the visible image
formed on the latent image bearing member (photoconductor) using a
transferring and charging section, and it can be performed by the
transferring unit. Regarding the transferring unit, the aspect having the
primary transferring unit where the complex transfer image is formed by
transferring the visible image onto the intermediate transferring
member and the secondary transferring unit where the complex transfer
image is transferred onto the recording medium is preferable.
The intermediate transfer member is not particularly limited,
and it can'be optionally selected from heretofore known transferring
members depending on the. purpose. It favorably includes, for example, a
transfer belt.
It is preferable that the transferring unit (the primary
transferring unit and the secondary transferring unit) comprises a
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WO 2006/075534 PCT/JP2005/024210
transferring section which releases and charges the visible image formed,
on the latent image bearing member onto the recording medium. The
transferring unit may be one, or it may be two or more.
Examples of the transferring section include a corona
transferring section by corona discharge, a transfer belt, a transfer roller,
pressure transfer roller and a tacky transferring section.
The recording medium is typified by plain paper, but it is not
particularly limited as long as an unfixed image after the development
can be transferred. It can be optionally selected depending on the
purpose, and a PET base for OHPs and the lite can be used.
-Fixing process and fixing unit-
The fixing process is a process of fixing the visible image
transferred onto the recording medium using a fixing apparatus. It may
be performed at every transfer of each color toner onto the recording
medium, or it may be performed all together simultaneously for
respective color toners in a laminated state.
The fixing apparatus is not particularly limited, and it can be
optionally selected depending on the purpose. A heating and
pressurizing unit heretofore known is preferable. The heating and
pressurizing unit includes a combination of a heating roller and a
pressurizing roller, and a combination of the heating roller, the
pressurizing roller and an endless belt.
A typical heating temperature in the heating and pressurizing
unit is preferably 80 °C to 200 °C.
In the present invention, depending on the purpose, a heretofore
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WO 2006/075534 PCT/JP2005/024210
known optical fixing section may be used along with or in place of the
fixing process
The neutralizing process is a process of applying a neutralization
bias to the latent image bearing member to neutralize, and it can be
suitably performed by the neutralizing unit.
The neutralizing unit is not particularly limited as long as the
neutralization bias can be applied to the latent image bearing member,
and it can be optionally selected from publicly known neutralizing
sections. Suitable examples include a neutralizing lamp.
The cleaning process is a process of removing the electrographic
toner left on the latent image bearing member, and it can be suitably
performed by the cleaning unit.
The cleaning unit is not particularly limited as long as the
electrographic toner left on the latent image bearing member can be
removed, and it can be optionally selected from heretofore known
cleaners. Suitable examples include magnetic cleaners, electrostatic
brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners
and web cleaners.
The recycling process is a process of recycling the toner for the
electrograph removed in the cleaning process to the developing unit, and
it can be suitably performed by the recycling unit.
The recycling unit is not particularly limited, and examples
include heretofore known feeding units.
The controlling unit is a process of controlling the above
respective steps, and it can be suitably performed by the controlling unit.
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The controlling unit is not particularly limited as long as the
movement of each unit can be controlled, and it can be optionally selected
depending on the purpose. Examples include instruments such as
sequencers and computers.
Subsequently, one aspect where the image forming method of the
present invention is carried out using the image forming apparatus of the
present invention is described with reference to Fig. 2. . The image
forming apparatus 100 comprises a photoconductor drum 10 (hereinafter
referred to as a 'photoconductor 10') as the latent image bearing member,
a charging roller 20 as the charging unit, an exposure apparatus 30 as
the exposing unit, a developing section 40 as the developing unit, an
intermediate transfer member 50, a cleaning apparatus 60 as the
cleaning unit having a cleaning blade, and a neutralizing lamp 70 as the
neutralizing unit.
The intermediate transfer member 50 is an endless belt, and it is
designed such that it moves in the arrow direction by three rollers 51
which are disposed inside the belt and extend the belt. A part of the
three rollers 51 works as a transfer bias roller capable of applying a
given transfer bias (primary transfer bias) to the intermediate transfer
member 50. A cleaning apparatus 90 having a cleaning blade is disposed
in the vicinity of the intermediate transfer member 50, and a transfer
roller 80 as the transferring unit capable of applying the transfer bias for
transferring (secondary transfer) the developed image (toner image) to
transfer paper 95 as the final recording medium is disposed in opposition
to the intermediate transfer member 50. Around the intermediate
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transfer member 50A, corona charging section 58 for electrically charging
the toner image on the intermediate transfer member 50 is disposed in
the rotating direction of the intermediate transfer member 50, between a
contact portion of the photoco'nductor 10 with the intermediate transfer
member 50 and a contact portion of the intermediate transfer member 50
with the transfer paper 95.
A developing section 40 is composed of a developing belt 41 as the
developer bearing member, and a black development unit 45K, a yellow
development unit 45Y, a magenta development unit 45 M and a cyan
development unit 45C installed side by side in the periphery of the
developing belt 41. The black development unit 45K comprises a
developer container 42K; a developer supply roller 43K and a developing
roller 44K. The yellow development unit 45Y comprises a developer
container 42Y, a developer supply roller 43Y and a developing roller 44Y.
The magenta development unit 45M comprises a developer container
42M, a developer supply roller 43M and a developing roller 44M. The
cyan development unit 45C comprises a developer container 42C, a
developer supply roller 43C and a developing roller 44C. The developing
belt 41 is the endless belt, ant it is rotatably extended over multiple belt
rollers. Apart thereof is contacted with the photoconductor 10.
In the image forming apparatus shown in Fig. 2, for example, the
charging roller 20 uniformly charges the photoconductor drum 10. The
exposing apparatus 30 exposes the photoconductor drum 10 according to
the image to form the latent electrostatic image. The latent electrostatic
image formed on the photoconductor drum 10 is developed using the
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WO 2006/075534 PCT/JP2005/024210
toner supplied from the developing section 40 to form a toner image. The
toner image is transferred (primary transfer) onto the intermediate
transfer member 50 and further transferred (secondary transfer) onto the
transfer paper 95 by the voltage applied by the rollers 51. As a result, a
transfer image is formed on the transfer paper 95. The toner left on the
photoconductor 10 is removed by the cleaning apparatus 60, and the
charge on the photoconductor 10 is once removed by the neutralizing
lamp 70.
Another aspect where the image forming method of the present
invention is carried out by the image forming apparatus of the present
invention is described with reference to Fig. 3. The image forming
apparatus 100 shown in Fig. 3 has the same constitution and the same
action effects as the image forming apparatus 100 shown in Fig. 2, except
that the developing belt 41 is not comprised and that the black
development unit 45K, the yellow development unit 45Y, the magenta .
development unit 45M and the cyan development unit 45C are disposed
directly opposite to the photoconductor 10 in the periphery thereof. The
parts in Fig. 3 which is equivalent to those in Fig. 3 are identified by the
same symbols.
Another aspect where the image forming method of the present
invention is carried out by the image forming apparatus of the present
invention is described with reference to Fig. 4. A tandem image forming
apparatus 100 shown in Fig. 4 is a tandem color image forming
apparatus. The tandem image forming apparatus 120 comprises a main
body 150 of the copying apparatus, a paper supply table 200, a scanner
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WO 2006/075534 PCT/JP2005/024210
300 and an automatic document feeder (ADF) 400.
The intermediate transfer member 50 in the form of an endless
belt is provided at the center of the main body 150. The intermediate
transfer member 50 is extended over support rollers 14, 15 and 16, and it
can be rotated clockwise in Fig. 4. An intermediate transferring member
cleaning apparatus 17 for removing the toner left on the intermediate
transferring member 50 is disposed in the vicinity of the support roller
15. A tandem developing section 120 where four image forming units 18
of yellow, cyan, magenta and black are arranged side by side at an
opposite side to the intermediate transferring member 50 is disposed
along the feeding direction of the intermediate transferring member 50
extended by the support rollers 14 and 15. The exposure apparatus 21 is
disposed in the vicinity of the tandem developing section 120. A
secondary transferring apparatus 22 is disposed on the opposite side of
the tandem developing section 120. In the secondary transferring
apparatus 22, a secondary transfer belt 24, an endless belt, extended
over a pair of rollers 23, and the transfer paper fed on the secondary
transfer belt 24 and the intermediate transferring member 50 can be
contacted one another. A fixing apparatus 25 is disposed in the vicinity of
the secondary transferring apparatus 22.
In the tandem image forming apparatus 100, a sheet reversing
apparatus 28 for reversing a transfer paper in order to forming images
on both sides of the transfer paper is disposed in the vicinity of the
secondary transferring apparatus 22 and the fixing apparatus 25.
Subsequently, the formation of a full-color image (color copy)
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using the tandem developing section 120 is described. First, a document
is set on a document table 130 in the automatic document feeder (ADF)
400, or the automatic document feeder 400 is opened. A document is set
on a contact glass 32 of the scanner 300, and, the automatic document
feeder 400 is closed.
When a start button (not shown in the figure) is pressed, the
scanner 300 drives, and a first carriage 33 and a second carriage 34 run
after the document is fed and moved onto the contact glass 32 in the case
the document has been set in the automatic document feeder 400, or
immediately in the case the document has been set on the contact glass
32. Here, a light is applied from a light source through the first carriage
33, and simultaneously the light reflected from the document surface is
reflected by a mirror in the second carriage 34. A color document (color
image) is read out from the light received in a reading sensor 36 through
an image forming lens 35 to produce image information of black, yellow,
magenta and cyan.
Each image information of black, yellow, magenta and cyan is
communicated to each image forming unit 18 (image forming unit for
black, image forming unit for yellow, image forming unit for magenta and
image forming unit for cyan) in the tandem developing section 120, and
in each image forming unit, each of toner images of black, yellow,
magenta and cyan is formed. That is, each image forming unit 18 (image
forming unit for black, image forming unit for yellow, image forming unit
for magenta and image forming unit for cyan) in the tandem developing
section 120 comprises the following" the photoconductor 10
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(photoconductor for black 10K, photoconductor for yellow 10Y,
photoconductor for magenta 10M and photoconductor for cyan IOC); the
charging section 60 which uniformly charges the photoconductor! the
exposing section which exposes (L in Fig. 5) the photoconductor according
to the image corresponding to each color image based on each color image
information and forms a latent electrostatic image corresponding to each
color image on the photoconductor; the developing section 61 which
develops the latent electrostatic image using each color toner (black toner,
yellow toner, magenta toner and cyan toner) to form a toner image by
each color toner; the transferring and charging section 62 for
transferring the toner image onto the intermediate transferring member
50; the photoconductor cleaning apparatus 63; and the neutralizing '
section 64. Each image forming unit 18 can form an image of each single
color (black image, yellow image, magenta image and cyan image) based
on each color image information. The black image, the yellow image, the
magenta image and the cyan image formed in this way are delivered to
the intermediate transferring member 50 rotated by the support rollers
14, 15 and 16, and the black image formed on the photoconductor for
black 10K, the yellow image formed on the photoconductor for yellow 10Y,
the magenta image formed on the photoconductor for magenta 10M and
the cyan image formed on the photoconductor for cyan 10C are
sequentially transferred onto the intermediate transferring member 50
(primary transfer). Then, a composite color image (color transfer image)
is formed on the intermediate transferring member 50 by superimposing
the black image, the yellow image, the magenta image and the cyan
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WO 2006/075534 PCT/JP2005/024210
image.
Meanwhile, in the paper supply table 200, one of paper supply-
rollers 142 is selectively rotated to supply a sheet (recording paper) from
one of multiple paper supply cassettes 144 provided in a paper bank 143.
The sheet is separated by a separation roller 145 and fed to a paper
supply path 146. It is then delivered by a feeding roller 147 to a paper
supply path 148 in the main body 150 and stopped by hitting a resist
roller 49. Alternatively, the sheet (recording paper) on a manual paper
feeding tray 54 is supplied by rotating the paper supply roller 142, is
separated by one by a separation roller 52 to place in a manual paper
feeding paper supply path 53 and is also stopped by hitting the resist
roller 49. The resist roller 49 is generally used grounded, but it may be
used in a bias-applied state for removing paper powder on the sheet.
Then, a color image is transferred and formed on the sheet (recording
paper) by rotating the resist roller 49 at the same timing as the.
composite color image made on the intermediate transferring member 50,
which sends out the sheet between the intermediate transferring
member 50 and the secondary transferring apparatus 22 and transfers
the composite color image (color transfer image) onto the sheet (recording
paper) by the secondary transferring apparatus 22. The toner left on the
intermediate transferring member 50 after transferring the image is
cleaned by an intermediate transferring member cleaning apparatus 17.
The sheet (recording paper) on which the color image has been
transferred and formed is delivered by the secondary transferring
apparatus 22 and sent to the fixing apparatus 25, and the composite
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WO 2006/075534 PCT/JP2005/024210
color image (color transfer image) is fixed on the sheet (recording paper)
with heat and pressure in the fixing apparatus 25. Subsequently, the
sheet (recording paper) is switched by a switch blade 55, discharged by a
discharging roller 56 and stacked on a catch tray 57. Alternatively, the
sheet is switched at a switch blade 55 and reversed by a reversing
apparatus 28 to lead again to a transfer position, and an image is also
recorded on a backside. Then, the sheet is discharged by the discharging
roller 56 and stacked on the catch tray 57
Fig. 11 is a schematic diagram showing one example of the image
forming apparatus according to the present invention. The image
forming apparatus 500 comprises a document reading part 520, an image
forming part 530 and a paper supply part 540. In the image forming part
530, a photoconductor 501 which is the latent image bearing member, a
charging unit 502, an. exposing unit 503, a developing unit 504, a
transferring unit 506, a fixing unit 507 and a cleaning unit 508 in the.
periphery of the photoconductor 501 are disposed. The surface of the
photoconductor 501 is uniformly charged by the charging unit 502, and
then the latent electrostatic image is formed on the charged surface by
exposure light of the exposing unit 503. The developer comprising the
toner having the same polarity as the polarity of the formed latent image
is supplied by the developing unit 504 to develop the latent image, which
is then transferred to a delivered recording member such as paper by the
transferring unit 506. The recording member is subsequently delivered
to the fixing unit 507, and the toner is fixed on the recording member
with hest and pressure. Meanwhile, the toner left on the photoconductor
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WO 2006/075534 PCT/JP2005/024210
501 after transferring is removed, by the cleaning unit 508.
The developer comprising the toner is used for the developing
unit 504. In the developing unit 504, a developer bearing member 504a
bears and delivers the developer, and the latent image on the
photoconductor 501 is developed by applying the alternating electric field
at an opposite position to the photoconductor 501. By applying the
alternating electric field, it is possible to activate the developer, to
narrow the charge distribution of the toner and to enhance the
developing property.
In accordance with the present invention, by finely controlling
the surface characteristics of the toner base particles, it is possible to
provide a toner and a developer which form a high quality image,
simultaneously satisfying the discharging property, the developing
property and the transfer property even when the toner which is
excellent in dot reproducibility is minimized in particle size and made .
spherical. In addition, a high-quality image with favorable cleaning
stability over time, charge stability, developing property and transfer
property as well as excellent reproducibility of fine dots may be provided
by employing the.image forming apparatus comprising the developer
with the toner of the present invention.
The present invention will be further described with reference to
the following examples, but these are not to be construed the present
invention. Hereinafter, 'part' and '%' represent part by mass and % by
mass, respectively..
For a magnetic carrier used for a two-component developer, the
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followings were used, which were common to respective Examples.

Cu-Zn ferrite particles as a core material with a weight average
diameter of 35 mm ' 5,000 parts
-Coating materials-
Toluene 450 parts
Silicone resin SR2400 (manufactured by Dow Corning Toray Co.,
Ltd. with non-volatile content of 50 %) 450 parts
Aminosilane SH6020 (manufactured by Dow Corning Toray Co.,
Ltd.) 10 parts
Carbon black 10 parts
The above coating materials were dispersed with a stirrer for 10
minutes to prepare a coating solution, and this coating solution and the
core material were placed in a coating apparatus in which a rotary base-
plate disc and mixing blades had been provided in a fluidized bed. The
coating was performed by generating a spiral flow to apply the coating
solution on the core material. The resulting coated material was calcined
in an electric furnace at 250 °C for two hours to obtain a carrier coated
with the silicone resin having an average thickness of 0.5 mm.
-Production of two-component developer-
The developer was produced by uniformly mixing seven parts of
each color toner shown in the following Examples to 100 parts of the
carrier using a tumbler mixer in which the stirring was performed by
rolling a container, followed by charging.
(Example l)
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-Synthesis of organic particulate emulsion-
In a reaction vessel equipped with a stirring bar and a
thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic
acid ethylene oxide adduct sulfate ester (Eleminol RS-30, manufactured
by Sanyo Chemical Industries Ltd.), 83 parts of styrene, 83 parts of
methacrylic acid, 110 parts of butyl acrylate and two parts of ammonium
persulfate were placed, and the mixture was stirred at 4,200 rpm for 60
minutes to obtain a white emulsion. This was heated until the
temperature in the system was 75 °C and reacted for four hours. Further,
30 parts of an aqueous solution of 1 % ammonium persulfate was added,
and the mixture was aged at 75 °C for six hours to yield an aqueous
emulsion (particulate emulsion, l) of a vinyl based resin (copolymer of
styrene-methacrylic acid-butyl acrylate-sodium salt of methacrylic acid
ethylene oxide adduct sulfate ester).
The volume average particle diameter of the resulting particulate .
emulsion 1, measured with a laser diffraction/scattering particle size
distribution measurement apparatus (LA-920, manufactured by Horiba
Seisakusho), was 50 run. A resin content was isolated by drying a part of
the particulate emulsion 1. The glass transition temperature (Tg) and
the weight average molecular weight of the resin content were 51 °C and
110,000, respectively.
-Preparation of aqueous phase -
A creamy white liquid was obtained by mixing and stirring 990
parts of water, 83 parts of particulate emulsion 1, 37 parts of an aqueous
solution of 48.3 % of sodium dodecyldiphenyletherdisulfonate (Eleminol
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WO 2006/075534 PCT/JP2005/024210
MON-7, manufactured by Sanyo Chemical Industries Ltd.) and 90 parts
of ethyl acetate. This is rendered an aqueous phase 1.
-Synthesis of low molecular polyester-
In a reaction vessel equipped with a cooling tube, a stirrer and a
nitrogen introducing tube, 724 parts of bisphenol Aethylene oxide 2 mole
adduct and 276 parts of terephthalic acid were placed for
polycondensation at 230 °C under normal pressure for seven hours and
further reacted under reduced pressure of 10 mmHg to 15 mmHg for five
hours to yield a lowmolecular polyester 1. The resulting lowmolecular
polyester 1 exhibited a number average molecular weight of 2,300, the
weight average molecular weight of 6,700, a peak molecular weight of
3,800, a glass transition temperature (Tg) of 43 °C and an acid value of
four.
-Synthesis of intermediate polyester (prepolymer)-
In a reaction vessel equipped with a cooling tube, a stirrer and a.
nitrogen introducing tube, 682 parts of bisphenol A ethylene oxide 2 mole
adduct, 81 parts of bisphenol A propylene oxide 2 mole adduct, 283 parts
of terephthalic acid, 22 parts of trimellitic acid anhydrate and two parts
of dibutyltin oxide were added, reacted at 230 °C under normal pressure
for seven hours and further reacted under reduced pressure of 10 mmHg
to 15 mmHg for five hours to yield an intermediate polyester 1.
The resulting intermediate polyester 1 exhibited a number
average molecular weight of 2,200, a weight average molecular weight of
9,700, a peak molecular weight of 3,000, a glass transition temperature
(Tg) of 54 °C, an acid value of 0.5 and a hydroxyl value of 52.
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Subsequently, in a reaction vessel equipped with a cooling tube, a
stirrer and a nitrogen introducing tube, 410 parts of the intermediate
polyester 1, 89 parts of isophorone diisocyanate and 500 parts of ethyl
acetate were placed and reacted at 100 °C for five hours to yield a
prepolymer 1. The mass fraction of the free isocyanate was 1.53 % by
mass in the prepolymer 1.
Synthesis of ketimine -
In a reaction vessel equipped with a stirring bar and a
thermometer, 170 parts of isophorone diamine and 75 parts of methyl
ethyl ketone were added and reacted at 50 °C for 4.5 hours to yield a
ketimine compound 1. An amine value of the ketimine compound 1 was
417.
Synthesis of master hatch-
A master batch 1 was obtained by mixing 1,200 parts of water, .
540 parts of carbon black (Printex 35, manufactured by Degussa AG with .
DBP oil absorption amount of 42 mL/100 mg and pH of 9.5) and 1,200
parts of a polyester resin with a Henschel mixer (Mitsui Mining Co.,
Ltd.). The mixture was kneaded using two rolls at 130 °C for one hour,
which was then rolled, cooled and pulverized in a pulverizer.
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 100 parts of
carnauba wax and 947 parts of ethyl acetate were placed. The vessel was
heated to 80 °C with stirring, which was maintained at 80 °C for five
hours. The vessel was subsequently cooled to 30°C over one hour. Then,
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500 parts of the master batch 1 and 500 parts of ethyl acetate were
added to the vessel, and it was mixed for one hour to yield a raw material
solution 1.
Subsequently, 1,324 parts of the raw material solution 1 was
transferred into a vessel, and carbon black and wax were dispersed using
a bead mill (Ultraviscomill, manufactured by IMEX Corporation) under a
condition with a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads packed at 80 % by volume and three
passes. Then, 1,324 parts of an ethyl acetate solution of 65 % low
molecular polyester 1 was added, and two passes by the bead mill under
the above condition was given thereto to yield a pigment/wax dispersion
1. The concentration of the solid content of the pigment/wax dispersion 1
was 50 %.
A composition obtained by adding 20 parts of inorganic
particulates (Organosilica sol MEK-ST-UP with an ER of 20 %, .
manufactured by Nissan Chemical Industries, Ltd.) to 100 parts of the
above pigment/wax dispersion 1 and mixing by the TK homomixer with a
rotational frequency of 7,000 rpm and a temperature of 25 °G for 10
minutes to give a pigment/wax/inorganic particulate dispersion 1. It is
preferable to use the dispersion for emulsification within eight weeks
from the preparation thereof. After this period, the inorganic
particulates are aggregated again to make the shape control impossible.
-Emulsification to desolvation-
In a vessel, 749 parts of the pigment/wax/inorganic particulate
dispersion 1, 115 parts of the prepolymer 1 and 2.9 parts of the ketimine
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compound 1 were placed and mixed using a TK homomixer
(manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for two
minutes. Subsequently, 1,200 parts of the aqueous phase 1 was added to
the vessel and mixed using the TK homomixer at a rotational frequency
of 13,000 rpm for 25 minutes to yield an emulsified slurry 1
In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 1 was added for desolvation at 30 °C for seven hours.
The vessel was aged at 45 °C for seven hours to yield a dispersed slurry
1.
Washing to drying-
After 100 parts of the dispersed slurry 1 was filtrated under
reduced pressure, the nitrate was washed as follows:
(i) One hundred (100) parts of ion-exchange water was added to
the filter cake, mixed using the TK homomixer at a rotational frequency
of 12,000 rpm for 10 minutes and subsequently filtered.
(ii) One hundred (100) parts of an aqueous solution of 10 %
sodium hydroxide was added to the filter cake of (i), mixed using the TK
homomixer at a rotational frequency of 12,000 rpm for 10 minutes and
subsequently filtered under reduced pressure.
(iii) One hundred (100) parts of 10 % hydrochloric acid was added
to the filter cake of (ii), mixed using the TK homomixer at a rotational
frequency of 12,000 rpm for 10 minutes and subsequently filtered.
(iv) Three hundred (300) parts of ion-exchange water was added
to the filter cake of (iii), mixed using the TK homomixer at a rotational
frequency of 12,000 rpm for 10 minutes and subsequently filtered. These
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WO 2006/075534 PCT/JP2005/024210
operations were repeated once to yield a filter cake 1.
The resulting filter cake 1 was dried in a circular wind dryer at
45 °C for 48 hours, and sieved with a mesh having 75 urn openings to
yield toner base particles 1. Subsequently, one part of hydrophobic silica
and one part of hydrophobic titanium oxide were mixed with 100 parts of
the toner base particles 1 using the Henschel mixer to yield a toner.
(Example 2)
A toner was obtained in the same manner as Example 1 except
that the conditions in Example 1 were changed as follows
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 100 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated to 80 °C
with stirring, maintained at 80 °C for five hours and subsequently cooled
to 30 °C over one hour. Then, 500 parts of the master batch 1 and 500 .
parts of ethyl acetate were added to the vessel and mixed for one hour to
yield the raw material solution 1.
Subsequently, 1,324 parts of the raw material solution 1 was
transferred into a vessel, and carbon black and wax were dispersed using
the bead mill (Ultraviscomill, manufactured by IMEX Corporation) under
the condition of a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads packed at 80 % by volume and three
passes. Then, 1,324 parts of an ethyl acetate solution of 65 % low
molecular polyester 1 was added and two passes by the bead mill under
the above condition was given thereto to yield a pigment/wax dispersion
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2. A solid content concentration of the pigment/wax dispersion 1 was
50%.
A composition obtained by adding 30 parts of inorganic
participates (Organosilica sol MEK-STUP with an ER of 20 %,
manufactured by Nissan Chemical Industries, Ltd.) to 100 parts of the
above pigment/wax dispersion 2 and mixing with the TK homomixer with
a rotational frequency of 7,000 rpm and a temperature of 25 °C for 13
minutes was rendered a pigment/wax/inorganic particulate dispersion 2.
It is desirable to use the dispersion for emulsification within eight weeks
from the preparation thereof. After this period, the inorganic
particulates are aggregated again to make the shape control impossible.
(Example 3)
A toner was obtained in the same manner as Example 1 except
that the conditions in Example 1 were changed as follows-"
-Emulsification to desolvation-
In a vessel, 749 parts of the pigment/wax/inorganic particulate
emulsion 1, 115 parts of the prepolymer 1 and 2.9 parts of the ketimine
compound 1 were placed and mixed using a TK homomixer
(manufactured by.Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for two
minutes. Subsequently, 1,200 parts of the aqueous phase 1 was added to
the vessel and mixed using the TK homomixer at a rotational frequency
of 10,000 rpm for 10 minutes to yield an emulsified slurry 2.
In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 2 was added for desolvation at 30 °C for six hours
which was aged at 45 °C for five hours to yield a dispersed slurry 2.
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WO 2006/075534 PCT/JP2005/024210
(Example 4)
A toner was obtained in the same manner as Example 1 except
that the process of emulsification to desolvation was changed as follows.
-Emulsification to desolvation-
In a vessel, 749 parts of the pigment/wax/inorganic particulate
emulsion 1, 115 parts of the prepolymer 1 and 2.9 parts of the ketimine
compound 1 were placed and mixed using a TK. homomixer
(manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for two
minutes. Subsequently, 1,200 parts of the aqueous phase 1 was added to
the vessel and mixed using the TK homomixer at a rotational frequency
of 10,000 rpm for 40 minutes to yield an emulsified slurry 3.
In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 3 was added for desolvation at a temperature of 30 °C
for eight hours, which was aged at 45 °C for five hours to yield a
dispersed slurry 3
(Example 5)
A toner was obtained in the same manner as Example 1, except
that the conditions were changed as follows. Physical properties and
evaluation results of the resulting toner 5 are shown in Table 1 and Table
2, respectively.
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 130 parts of
carnauba wax/rice wax (mass ratio of 5/5) and 947 parts of ethyl acetate
were placed and heated to 80 °C with stirring, maintained at 80 °C for
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WO 2006/075534 PCT/JP2005/024210
four hours and subsequently cooled to 30 °C over one hour. Then, 500
parts of the master batch 1 and 500 parts of ethyl acetate were added to
the vessel and mixed for two hours to yield a raw material solution 2.
Subsequently, 1,324 parts of the raw material solution 2 was
transferred into a vessel, and carbon black and wax were dispersed using
the bead mill (Ultraviscomill, manufactured by IMEX Corporation) under
the condition of a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads filled at 80 % by volume and 10 passes.
Then, 1,324 parts of an ethyl acetate solution of 65 % low molecular
polyester 1 was added, and 6 passes by the bead mill under the above
condition was given thereto to yield a pigment/wax dispersion 3. A solid
content concentration of the pigment/wax dispersion 3 was 50 %.
A composition obtained by adding 20 parts of inorganic
particulates (Organosilica sol MEK-ST-UP with an ER of 20 %,
manufactured by Nissan Chemical Industries, Ltd.) to 100 parts of the
above pigment/wax dispersion 3 and mixing by a TK homomixer with a
rotational frequency of 7,000 rpm and a temperature of 25 °C for 10
minutes was rendered a pigment/wax/inorganic particulate emulsion 3.
It is desirable to use the dispersion for emulsification within eight weeks
from the preparation thereof. After this period, the inorganic
particulates are aggregated again to make the shape control impossible.
(Example 6)
A toner was obtained in the same manner as Example 1, except
that the conditions were changed as follows.
-Production of oil phase-
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WO 2006/075534 PCT/JP2005/024210
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 100 parts of
carnauba wax/rice wax (mass ratio of 3/7) and 947 parts of ethyl acetate
were placed and heated to 80 °C with stirring, maintained at 80 °C for
four hours and subsequently cooled to 30 °C over one hour. Then, 500
parts of the master batch 1 and 500 parts of ethyl acetate were added to
the vessel and mixed for 0.8 hours to yield a raw material solution 3.
Subsequently, 1,324 parts of the raw material solution 3 was
transferred to a vessel, and carbon black and waxes were dispersed using
the bead mill (Ultraviscomill, manufactured by IMEX Corporation) under
the condition of a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads packed at 80 % by volume and five
passes. Then, 1,324 parts of an ethyl acetate solution of 65 % low
molecular polyester 1 was added and three passes by the bead mill under
the above condition was given thereto to yield a pigment/wax dispersion .
4. The concentration of the solid content of the pigment/wax dispersion 4
was 50 %.
The composition obtained by adding 20 parts of inorganic
particulates (Organosilica sol MEK-ST-UP with an ER of 20 %,
manufactured by Nissan Chemical Industries, Ltd.) to 100 parts of the
above pigment/wax dispersion 4 and mixing by the TK homomixer at a
rotational frequency of 7,000 rpm and a temperature of 25 °C for 10
minutes was rendered a pigment/wax/inorganic particulate dispersion 4.
It is desirable to use the dispersion for emulsification within eight weeks
from the preparation thereof. After this period, the inorganic
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particulates are aggregated again to make the shape control impossible.
(Example 7)
A toner was obtained in the same manner as Example 1 except
that the conditions were changed as follows-
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 380 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated to 80 °C
with stirring, maintained at 80 °C for four hours, and subsequently
cooled to 30 °C over one hour. Then, 500 parts of the master batch 1 and
500 parts of ethyl acetate were added to the vessel and mixed for two
hours to yield a raw material solution 5.
Subsequently, 1,324 parts of the raw material solution 5 was
transferred to a vessel, and carbon black and waxes were dispersed using
the bead mill (Ultraviscomill, manufactured by IMEX Corporation) under .
the condition of a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads packed at 80 % by volume and seven
passes. Then, 1,324 parts of an ethyl acetate solution of 65 % low
molecular polyester 1 was added and four passes by the bead mill under
the above condition was given thereto to yield a pigment/wax dispersion
5. A solid content concentration of the pigment/wax dispersion 5 was
50 %.
The composition obtained by adding 20 parts of inorganic
particulates (Organosilica sol MEK-ST-UP with an ER of 20 %,
manufactured by Nissan Chemical Industries, Ltd.) to 100 parts of the
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above pigment/wax dispersion 5 and mixing by tbe TK bomomixer at a
rotational frequency of 7,000 rpm and a temperature of 25 °C for 10
minutes was rendered a pigment/wax/inorganic participate dispersion 5.
It is desirable to use the dispersion for emulsification within eight weeks
from the preparation thereof. After this period, the inorganic
particulates are aggregated again to make the shape control impossible.
(Comparative Example l)
A toner was obtained in the same manner as Example 1 except
that the conditions were changed as follows
Production of oil phase-
In a reaction vessel equipped with, a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 100 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated to 80 °C
with stirring, maintained at 80°C for five hours and subsequently cooled
to 30 °C over one hour. Then, 500 parts of the master batch 1 and 500
parts of ethyl acetate were added to the vessel and mixed for one hours to
yield the raw material solution 1.
Subsequently, 1,324 parts of the raw material solution 1 was
transferred to a vessel, and carbon black and waxes were dispersed using
the bead mill (Ultraviscomill, manufactured by IMEX Corporation) under
the condition of a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads packed at 80 % by volume and one
pass. Then, 1,324 parts of an ethyl acetate solution of 65 % low
molecular polyester 1 was added, and three passes by the bead mill
under the above condition were given thereto to yield a pigment/wax
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WO 2006/075534 PCT/JP2005/024210
dispersion 6. A solid content concentration of the pigment/wax dispersion
6 was 50 %.
(Comparative Example 2)
A toner was obtained in the same manner as Example 1 except
that the conditions were changed as follows
Organic resin particulates on the toner surface were dissolved
and removed as well as smoothed by inserting a process of an alkali
(sodium hydroxide) treatment at a pH of 11 between the emulsifLcation
and the desolvation processes.
(Comparative Example 3)
-Synthesis of organic particulate emulsion-
In a reaction vessel equipped with a stirring bar and a
thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic
acid ethylene oxide adduct sulfate ester (Eleminol RS-30, manufactured
by Sanyo Chemical Industries Ltd.), 83 parts of styrene, 83 parts of.
methacrylic acid, 110 parts of butyl acrylate and one part of ammonium
persulfate were placed and stirred at 3,800 rpm for 30 minutes to obtain
a creamy white emulsion. This was heated to 75 °C and reacted for four
hours. Further, 30 parts of an aqueous solution of 1 % ammonium
persulfate was added, and the mixture was aged at 75 °C for six hours to
yield an aqueous dispersion, particulate emulsion 2, of a vinyl based
resin (copolymer of styrene-methacrylic acid-butyl acrylate-sodium salt of
methacrylic acid ethylene oxide adduct sulfate ester). The particulate
emulsion 2 was measured using a laser diffraction/scattering particle size
distribution measurement apparatus (LA-920, manufactured by Horiba
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WO 2006/075534 PCT/JP2005/024210
Seisakusho) to find that the volume average particle diameter was 110
nm. A resin content was isolated by drying a part of the p articulate
emulsion 2. The Tg and weight average molecular weight of the resin
content were 58 °C and 130,000, respectively.
Preparation of aqueous phase-
A creamy white liquid was obtained by mixing and stirring 990
parts of water, 83 parts of particulate emulsion 2, 37 parts of an aqueous
solution of 48.3% of sodium dodecyldiphenyletherdisulfonate (Eleminol
MON-7, manufactured by Sanyo Chemical Industries Ltd.) and 90 parts
of ethyl acetate. This is rendered the aqueous phase 1.
-Synthesis of low molecular polyester-
In a reaction vessel equipped with a cooling tube, a stirrer and a
nitrogen introducing tube, 724 parts of bisphenol Aethylene oxide 2 mole
adduct and 276 parts of terephthalic acid were placed, for
polycondensation at 230 °C under normal pressure for seven hours and
further reacted under reduced pressure of 10 mmHg to 15 mmHg for five
hours to yield the low molecular polyester 1. The low molecular polyester
1 exhibited a number average molecular weight of 2,300, a weight
average molecular weight of 6,700, a peak molecular weight of 3,800, a
glass transition temperature (Tg) of 43 °C and an acid value of four.
Synthesis of intermediate polyester-
In a reaction vessel equipped with a cooling tube, a stirrer and a
nitrogen introducing tube, 682 parts of bisphenol A ethylene oxide 2 mole
adduct, 81 parts of bisphenol A propylene oxide 2 mole adduct, 283 parts
of terephthalic acid, 22 parts of trimellitic acid anhydrate and 2 parts of
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dibutyltin oxide were placed, reacted at 230 °C under normal pressure
for seven hours and further reacted under reduced pressure of 10 mmHg
to 15 mmHg for five hours to yield an intermediate polyester 1.
The intermediate polyester 1 exhibited a number average
molecular weight of 2,200, a weight average molecular weight of 9,700, a
peak molecular weight of 3,000, a Tg of 54 °C, an acid value of 0.5 and a
hydroxyl value of 52.
Subsequently, in a reaction vessel equipped with a cooling tube, a
stirrer and a nitrogen introducing tube, 410 parts of the intermediate
polyester 1, 89 parts of isophorone diisocyanate and 500 parts of ethyl
acetate were placed and reacted at 100 °C for five hours to yield a
prepolymer 1. The mass fraction of the free isocyanate comprises in the
prepolymer 1 was 1.53 % by mass.
-Synthesis of ketimine -
In a reaction vessel equipped with a stirring bar and a
thermometer, 170 parts of isophorone diamine and 75 parts of methyl
ethyl ketone were placed and reacted at 50 °C for 4.5 hours to yield the
ketimine compound 1. The amine value of the ketimine compound 1 was
417.
-Synthesis of master batch-
A master batch 1 was obtained by placing 1,200 parts of water,
540 parts of carbon black (Printex 35, manufactured by Degussa AG with
DBP oil absorption amount of 42 mL/100 mg and pH of 9.5) and 1,200
parts of a polyester resin, mixing using a Henschel mixer (Mitsui Mining
Co., Ltd.). The mixture was kneaded using two rolls at 130 °C for one
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WO 2006/075534 PCT/JP2005/024210
hour, which was then rolled, cooled and pulverized in a pulverizer.
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 100 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated to 80 °C
with stirring, maintained at 80°C for five hours, and subsequently cooled
to 30 °C over one hour. Then, 500 parts of the master batch 1 and 500
parts of ethyl acetate were added into the vessel and mixed for one hour
to yield the raw material solution 1.
Subsequently, 1,324 parts of the raw material solution 1 was
transferred to a vessel, and carbon black and wax were dispersed using
the bead mill (Ultraviscomill, manufactured by IMEX Corporation) under
the condition of a solution sending rate of 1 kg/hr, a disc peripheral speed
of 6 m/sec, 0.5-mm zirconia beads packed at 80 % by volume and three
passes. Then, 1,324 parts of an ethyl acetate solution of 65 % low
molecular polyester 1 was added and two passes by the bead mill under
the above condition were given thereto to yield a pigment/wax dispersion
1. A solid content concentration of the pigment/wax dispersion 1 was
50 %.
-Emulsification to desolvation-
In a vessel, 749 parts of the pigment/wax/inorganic particulate
emulsion 1, 115 parts of the prepolymer 1 and 2.9 parts of the ketimine
compound 1 were placed and mixed using a TK homomixer
(manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for two
minutes Subsequently 1,200 parts of the aqueous phase 1 was added to
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the vessel and mixed using TK mixer at a rotational frequency of 13,000
rpm for 25 minutes to yield an emulsified slurry 1.
In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 1 was placed for desolvation at 30 °C for seven hours,
which was aged at 45 °C for seven hours to yield a dispersed slurry 1.
-Washing to drying-
After 100 parts of the dispersed slurry 1 was filtrated under
reduced pressure, the filtrate was washed as follows.
(i) One hundred (100) parts of ion-exchange water was added to
the filter cake, mixed using the TK homomixer at a rotational frequency
of 12,000 rpm for 10 minutes and subsequently filtered.
(ii) One hundred (100) parts of an aqueous solution of 10 %
sodium hydroxide was added to the filter cake of (i), mixed using the TK
homomixer at a rotational frequency of 12,000 rpm for 10 minutes and
subsequently filtered under reduced pressure.
(in) One hundred (100) parts of 10 % hydrochloric acid was added
to the filter cake of (ii), mixed using the TK homomixer at a rotational
frequency of 12,000 rpm for 10 minutes and subsequently filtered.
(iv) Three hundred (300) parts of ion-exchange water was added
to the filter cake of (iii), mixed using the TK homomixer at a rotational
frequency of 12,000 rpm for 10 minutes and subsequently filtered. These
operations were repeated once to yield a filter cake 1.
The filter cake 1 was dried in a circular wind dryer at 45 °C for 48
hours and sieved with a mesh having 75 mm openings to yield toner base
particles. Subsequently, one part of hydrophobic silica and one part of
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hydrophobic titanium oxide were mixed with 100 parts of the toner base
particles 1 using the Henschel mixer to yield a toner.
(Comparative Example 4)
A toner was obtained in the same manner as Comparative
Example 3 except that the conditions were changed as follows:
-Synthesis of organic particulate emulsion-
In a reaction vessel equipped with a stirring bar and a
thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic
acid ethylene oxide adduct sulfate ester (Eleminol RS-30, manufactured
by Sanyo Chemical Industries Ltd.), 83 parts of styrene, 83 parts of
methacrylic acid, 110 parts of butyl acrylate and one part of ammonium
persulfate were placed and stirred at 3,800 rpm for 30 minutes to obtain,
a creamy white emulsion. This was heated to 75 °C and reacted for one
hour. Further, 30 parts of an aqueous solution of 1 % ammonium
persulfate was added, and the mixture was aged at 75 °C for six hours to
yield an aqueous dispersion (particulate emulsion 3) of a vinyl based
resin (copolymer of styrene-methacrylic acid-butyl acrylate-sodium salt of
methacrylic acid ethylene oxide adduct sulfate ester). The particulate
emulsion 3 was measured using a particle size distribution measurement
apparatus (LA-920, manufactured by Sysmex Corporation) to find that
the volume average particle diameter was 40 nm, A resin content was
isolated by drying a part of the particulate emulsion 3. The Tg and the
weight average molecular weight of the resin content were 56 °C and
120,000, respectively.
(Comparative Example 5)
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A toner was obtained in the same manner as Comparative
Example 3 except that the conditions were changed as follows-
Emulsification to desolvation-
In a vessel, 749 parts' of the pigment/wax/inorganic particulate
dispersion 1, 115 parts of the prepolymer 1 and 2.9 parts of the ketimine
compound 1 were placed and mixed using a TK homomixer
(manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for two
minutes. Subsequently, 1,200 parts of the aqueous phase 1 was added to
the vessel and mixed using the TK homomixer at a rotational frequency
of 13,000 rpm for 10 minutes to yield an emulsified slurry 2.
In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 2 was added for desolvation at 30 °C for six hours,
which was aged at 45 °C for five hours to yield a dispersed slurry 2.
(Comparative Example 6)
A toner was obtained in the same manner as Comparative
Example 3 except that the conditions in the process of emulsification to
desolvation were changed to the following:
Emulsification to desolvation
In a vessel 749 parts of the pigment/wax/inorganic particulate
dispersion 1, 115 parts of the prepolymer 1 and 2.9 parts of the ketimine
compound 1 were placed and mixed using a TK homomixer
(manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for two
minutes. Subsequently, 1,200 parts of the aqueous phase 1 was added to
the vessel and mixed using the TK homomixer at a rotational frequency
of 13,000 rpm for 40 minutes to yield an emulsified slurry 3.
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In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 3 was added for desolvation at 30 °C for eight hours,
which was aged at 45 °C for five hours to yield a dispersed slurry 3.
(Comparative Example 7)
A toner was obtained in the same manner as Comparative
Example 3 except that the conditions were changed as follows
-Production of oil phase -
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 130 parts of
carnauba wax/rice wax (mass ratio of 5/5) and 947 parts of ethyl acetate
were placed, heated to 80 °C with stirring maintained at 80 °C for four
hours and subsequently cooled to 30 °C over one hour. Then, 500 parts of
the master batch 1 and 500 parts of ethyl acetate were added to the
vessel and mixed for two hours to yield a raw material solution 2.
Subsequently, 1,324 parts of the raw material solution 2 was
transferred to a vessel, and carbon black and wax were dispersed using a
bead mill (Ultraviscomill, manufactured by IMEX Corporation) under the
condition of a solution sending rate of 1 kg/hr, a disc peripheral speed of 6
m/sec, 0.5-mm zirconia beads packed at 80 % by volume and 10 passes.
Then, 1,324 parts of an ethyl acetate solution of 65 % low molecular
polyester 1 was added and five passes by the bead mill under the above
condition were given thereto to yield a pigment/wax dispersion 2. The
concentration of the solid content of the pigment/wax dispersion 2 was
50 %.
(Comparative Example 8)
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A toner was obtained in the same manner as Comparative
Example 3 except that the conditions were changed as follows.
-Production of oil phase -
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 100 parts of
caraauba wax/rice wax (mass ratio of 3/7) and 947 parts of ethyl acetate
were placed, heated to 80 °C with stirring, maintained at 80°C for four
hours and subsequently cooled to 30 °C over one hour. Then, 500 parts of
the master batch 1 and 500 parts of ethyl acetate were added to the
vessel and mixed for 0.8 hours to yield a raw material solution 3.
Subsequently, 1,324 parts of the raw material solution 3 was
transferred to a vessel, and carbon black and wax were dispersed using a
bead mill (Ultraviscomill, manufactured by IMEX Corporation) under the
condition of a solution sending rate of 1 kg/hr, a disc peripheral speed of 6
m/sec, 0.5-m.m zirconia beads packed at 80 % by volume and five passes..
Then, 1,324 parts of an ethyl acetate solution of 65 % low molecular
polyester 1 was added, and three passes by the bead mill under the above
condition was given thereto to yield a pigment/wax dispersion 3. The
concentration of the solid content of the pigment/wax dispersion 3 was
50 %.
(Comparative Example 9)
A toner was obtained in the same manner as Comparative
Example 3 except that the conditions for the processes from the low
molecular polyester, the emulsification to the desolvation were changed
to the following.
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-Synthesis of low molecular polyester-
In a reaction vessel equipped with a cooling tube, a stirrer and a
nitrogen introducing tube, 229 parts of bisphenol Aethylene oxide 2 mole
adduct, 529 parts of bisphenol A propylene oxide 3 mole adduct, 208
parts of terephthalic acid, 46 parts of adipic acid and two parts of
dibutyltin oxide were placed, reacted at 230 °C under normal pressure
for seven hours, and further reacted under reduced pressure of 10 mmHg
to 15 mmHg for five hours. Subsequently, 44 parts of trimellitic acid
anhydrate was added to the vessel, and reacted at 180 °C under normal
pressure for three hours to yield a low molecular polyester 2. The low
molecular polyester 2 exhibited a number average molecular weight of
2,300, a weight average molecular weight of 6,700, a peak molecular
weight of 3,100, a Tg of 43 °C and an acid value of 25.
Production of oil phase-
In a reaction vessel equipped with a stirring bar and a.
thermometer, 378 parts of the low molecular polyester 2, 100 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated to 80 °C
with stirring, maintained at 80 °C for five hours and subsequently cooled
to 30 °C over one hour. Then, 500 parts of the master batch 1 and 500
parts of ethyl acetate were added to the vessel and mixed for one hour to
yield a raw material solution 4.
Subsequently, 1,324 parts of the raw material solution 4 was
transferred to a vessel, and carbon black and wax were dispersed using a
bead mill (Ultraviscomill, manufactured by IMEX Corporation) under the
condition of a solution sending rate of 1 kg/hr, a disc peripheral speed of 6
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WO 2006/075534 PCT/JP2005/024210
m/sec, 0.5-mm zirconia beads packed at 80 % by volume and three passes.
Then, 1,324 parts of an ethyl acetate solution of 65 % low molecular
polyester 2 was added, and three passes by the bead mill under the above
condition was given thereto to yield a pigment/wax dispersion 4. The
concentration of the solid content of the pigment/wax dispersion 4 was
50 %.
-Emulsification to desolvation-
In a vessel, 749 parts of the pigment/wax dispersion 4, 115 parts
of the prepolymer 1 and 2.9 parts of the ketimine compound 1 were
added and mixed using a TK homomixer (manufactured by Tokushu Kika
Kogyo Co., Ltd.) at 5,000 rpm for two minutes. Subsequently, 1,200 parts
of the aqueous phase 1 was added to the vessel and mixed using the TK
homomixer at a rotational frequency of 13,000 rpm for 40 minutes to
yield an emulsified slurry 4. In a vessel equipped with a stirrer and a
thermometer, the emulsified slurry 4 was added for desolvation at 30 °C
for eight hours, which was aged at 45 °C for five hours to yield a
dispersed slurry 4.
(Comparative Example 10)
A toner was obtained in the same manner as Comparative
Example 3 except that the conditions were changes as follows.
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 1, 380 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated to 80 °C
with stirring, maintained at 80 °C for four hours and subsequently cooled
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to 30 °C over one hour. Then, 500 parts of the master batch 1 and 500
parts of ethyl acetate were added to the vessel and mixed for two hours
to yield a raw material solution 5.
Subsequently, 1,324 parts of the raw material solution 5 was
transferred to a vessel, and carbon black and wax were dispersed using a
bead mill (Ultraviscomill, manufactured by IMEX Corporation) under the
condition of a solution sending rate of 1 kg/hr, a disc peripheral speed of 6
m/sec, 0.5-mm zirconia beads packed at 80 % by volume and seven passes.
Then, 1,324 parts of an ethyl acetate solution of 65 % low molecular
polyester 1 was added, and four passes by the bead mill under the above
condition was given thereto to yield a pigment/wax dispersion 5. The
concentration of the solid content of the pigment/wax dispersion 5 was
50 %.
(Comparative Example 11)
A toner was obtained in the same manner as Comparative
Example 3 except that the conditions were changed as follows.
Organic resin particulates on the toner surface were dissolved by
inserting a process of an alkali (sodium hydroxide) treatment at a pH of
11 between the emulsification and the desolvation processes.
(Comparative Example 12)
A toner was obtained in the same manner as Comparative
Example 3 except that the.conditions were changed as follows.
-Synthesis of low molecular polyester-
In a reaction vessel equipped with a cooling tube, a stirrer and a
nitrogen introducing tube, 229 parts of bisphenol A ethylene oxide 2 mole
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adduct, 529 parts of bisphenol A propylene oxide 3 mole adduct, 208
parts of terephthalic acid, 46 parts of adipic acid and two parts of
dibutyltin oxide were placed, reacted at 230 °C under normal pressure
for seven hours and further reacted under reduced pressure of 10 mmHg
to 15 mmHg for five hours. Subsequently, 44 parts of trimellitic acid
anhydrate was added to the vessel and reacted at 180 °C under normal
pressure for three hours to yield a low molecular polyester- 2. The low
molecular polyester 2 exhibited a number average molecular weight of
2,300, a weight average molecular weight of 6,700, a peak molecular
weight of 3,100, a Tg of 43 °C and an acid value of 25.
-Production of oil phase-
In a reaction vessel equipped with a stirring bar and a
thermometer, 378 parts of the low molecular polyester 2, 100 parts of
carnauba wax and 947 parts of ethyl acetate were placed, heated at 80 °C
with stirring, maintained at 80 °C for five hours and subsequently cooled.
to 30 °C over one hour. Then, 500 parts of the master batch 1 and 500
parts of ethyl acetate were added to the vessel and mixed for one hour to
yield a raw material solution 4.
Subsequently, 1,324 parts of the raw material solution 4 was
transferred to a vessel, and carbon black and wax were dispersed using a
bead mill (Ultraviscomill, manufactured by IMEX Corporation) under the
condition of a solution sending rate of 1 kg/hr, a disc peripheral speed of 6
m/sec, 0.5-mm zirconia beads packed at 80 % by volume and three passes.
Then, 1,324 parts of an ethyl acetate solution of 65 % low molecular
polyester 2 was added, and two passes by the bead mill under the above
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condition was given thereto to yield a pigment/wax dispersion 4. The
concentration of the solid content of the pigment/wax dispersion 4 was
50 %.
-Emulsification to desolvation"-

In a vessel, 749 parts of the pigment/wax dispersion 4, 115 parts
of the prepolymer 1 and 2.9 parts of the ketimine compound 1 were
placed and mixed using a TK homomixer (manufactured by Tokushu
Kika Kogyo Co., Ltd.) at 5,000 rpm for two minutes. Subsequently, 1,200
parts of the aqueous phase 1 was added to the vessel and left stand for
one hour to yield an emulsified slurry 5.
In a vessel equipped with a stirrer and a thermometer, the
emulsified slurry 5 was added for desolvation at 30 °C for eight hours to
yield a dispersed slurry 5.
(Comparative Example 13)

-Preparation of emulsion (l)-
Styrene 370 g
n-Butyl acrylate 30 g
Acrylic acid 8 g
Dodecane thiol 24 g
Carbon tetrabromide 4 g
The above were mixed and dissolved. This was then dispersed
and emulsified in a flask with 550 g of ion-exchange water in which 6 g of
a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical
Industries Ltd.) and 10 g of an anionic surfactant (Neogen SC,
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WO 2006/075534 PCT/JP2005/024210
manufactured by Darichi Kogyo Seiyaku Co., Ltd.) had been dissolved.
With slowly mixing for 10 minutes, 50 g of ion-exchange water in which 4
g of ammonium persulfate had been dissolved was added thereto. After
nitrogen substitution, the content in the flask was heated to 70 °C in an
oil bath with stirring, and emulsification polymerization was continued
without any change for five hours. As a result, an emulsion (l) in which
resin particles having an average particle diameter of 155 nm, a Tg of 59
°C and a weight average molecular weight of 12,000 were dispersed was
prepared.
-Preparation of emulsion (2)-
Styrene 280 g
n-Butyl acrylate 120 g
Acrylic acid 8 g
The above had been mixed and dissolved. This was then
dispersed and emulsified In a flask with 550 g of ion-exchange water in
which 6 g of a nonionic surfactant (Nonipol 400, manufactured by Sanyo
Chemical Industries Ltd.) and 12 g of an anionic surfactant (Neogen SC,
manufactured by Darichi Kogyo Seiyaku Co., Ltd.) had been dissolved.
With slowly mixing for 10 minutes, 50 g of ion-exchange water in which 3
g of ammonium persulfate had been dissolved was added thereto. After
nitrogen substitution, the content in the flask was heated to 70 °C in an
oil bath with stirring, and emulsification polymerization was continued
without any change for five hours to prepare an emulsion (2) in which
resin particles having an average particle diameter of 105 nm, a Tg of 53
°C and a weight average molecular weight of 550,000 were dispersed.
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-Preparation of colorant dispersion (l)-
Carbon black (Morgal L, manufactured, by Cabot Corporation)
50 g
Nonionic surfactant "(Nonipol 400 manufactured by Sanyo
Chemical Industries Ltd.) 5 g
Ion-exchange water 200 g
The above were mixed, dissolved and then dispersed for 10
minutes using a homogenizer (Ultratalax T50, manufactured by IKA) to
prepare a colorant dispersion (l) in which a colorant (carbon black)
having the average particle diameter of 250 nm was dispersed.
Preparation of releasing agent dispersion (l)-
Paraffin wax (HNPO 190, melting point 85 °C, manufactured by
Nippon Seiro Co., Ltd.) 50 g
Cationic surfactant (Sanisol B50 manufactured by Kao
Corporation) 7 g
Ion-exchange water 200 g
The above were heated to 95 °C, dispersed using a homogenizer
(Ultratalax T50, manufactured by IKA) and subsequently dispersed
using a pressure discharge homogenizer to prepare a releasing agent
dispersion (l) in which a releasing agent having the average particle
diameter of 550 nm was dispersed.
-Preparation of agglomerated particles
Emulsion (l) 120 g
Emulsion (2) " 80 g
Colorant dispersion (l) 30 g
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Releasing agent dispersion (l) 40 g
Cationic surfactant (Sanisol B50, manufactured by Kao
Corporation) 1.5 g
The above were mixed and dispersed in a round bottom flask
made of stainless steel using a homogenizer (Ultratalax T50,
manufactured by IKA), which, was then heated to 48 °C in an oil bath for
heating with stirring inside the flask. After maintaining at 48 °C for 30
minutes, it was confirmed that agglomerated particles with a volume of
95 cm3 having an average particle diameter of about 5 mm had been
formed when observed by optical microscope.

-Preparation of adhering particles-
Thereto, 60 g of the emulsion (l) as a resin containing participate
emulsion was mildly added. The volume of the resin particles contained
in the emulsion (l) was 25 cm3. The temperature of the oil bath for
heating was raised to 50 °C and maintained for one hour.

Subsequently, 3 g of an anionic surfactant (Neogen SC,
manufactured by Darichi Kogyo Seiyaku Co., Ltd.) was added thereto.
The stainless steal flask was sealed, heated to 105 °C with continuous
stirring using a magnetic seal and maintained for three hours. A toner
base was obtained by cooling, subsequently filtrating the reaction
product, which was thoroughly washed with water and dried. Then, one
part of hydrophobic silica and one part of hydrophobic titanium oxide
were mixed with 100 parts of the toner base particles using the Henschel
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mixer to yield a toner.
(Comparative Example 14)
In a reactor equipped with a cooling tube, a stirrer and a nitrogen
introducing tube, 724 parts of bisphenol A ethylene oxide 2 mole adduct,
276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed,
reacted at 230 °C under normal pressure for eight hours, further reacted
under reduced pressure of 10 mmHg to 15 mmHg for five hours and
cooled to 160 °C. Thereto, 32 parts of phthalic acid anhydrate was added
and reacted for two hours. Next, this was cooled to 80 °C and reacted
with 188 parts of isophorone diisocyanate in ethyl acetate for two hours
to yield an isocyanate containing prepolymer 2. Then, 267 parts of the
prepolymer 2 was reacted with 14 parts of isophorone diamine at 50 °C
for two hours to yield an urea-modified polyester 1 having a weight
average molecular weight of 64,000.
Similarly to the above, 724 parts of bisphenol A ethylene oxide 2.
mole adduct, 138 parts of terephthalic acid and 138 parts of isophthalic
acid were subjected to polycondensation at 230 °C under normal pressure
for six hours and then reacted under reduced pressure of 10 mmHg to 15
mmHg for five hours to yield an unmodified polyester (a) having a peak
molecular weight of 2,300, a hydroxyl value of 55 and an acid value of
one.
Subsequently, 200.parts of the urea-modified polyester 1 and 800
parts of the unmodified polyester (a) were dissolved and mixed in 1,000
parts of a mixed solvent of ethyl acetate/MEK (l/l) to yield an ethyl
acetate/MEK solution of a toner binder. In a reactor equipped with a
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cooling tube, a stixrer and a nitrogen introducing tube, 942 parts of water
and 58 parts of 10 % hydroxyapatite suspension (Supertite 10,
manufactured by Nippon Chemical Industrial Co., Ltd.) was placed, and
1,000 parts of the ethyl acetate/MEK solution of the toner binder was
added thereto and dispersed. The organic solvents were distilled off by
raising the temperature to 98 °C followed by cooling. The product was
separated from water by filtration, washed and dried to yield a toner
binder 1. The toner binder 1 had a Tg of 52 °C , Tq of 123 °C and TG' of
132 °C.
Then, 100 parts of the toner binder 1, seven parts of glycerin
tribehenate and four parts of cyanine blue (manufactured by Sanyo Color
Works Ltd.) were incorporated into the toner by the following method.
First, they were preliminarily mixed using a Henschel mixer (FM10B,
manufactured by Mitsui Miike Kako K.K.) and subsequently kneaded by
a biaxial kneader (PCM-30, manufactured by Ikegai Corporation). Then,.
they were finely pulverized using a supersonic jet pulverizer lab jet
(manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and classified by an
airflow classifier (MDS-I, manufactured by Nippon Pneumatic Mfg. Co.,
Ltd.) to yield toner base particles. Subsequently, one part of hydrophobic
silica and one part of hydrophobic titanium oxide were mixed with 100
parts of the toner base particles using the Henschel mixer to yield the
toner.
(Comparative Example 15)
-Production of prepolymer-
In a reactor equipped with a cooling tube, a stirrer and a nitrogen
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introducing tube, 724 parts of bisphenol A ethylene oxide 2 mole adduct,
276 parts of isophthalic acid and two parts of dibutyltin oxide were
placed, reacted at 230 °C under normal pressure for eight hours, further
reacted under reduced pressure of 10 mmHg to 15 mmHg for five hours
with dehydrating and subsequently cooled to 160 °C. Next, 74 parts of
phthalic acid anhydrate was added thereto and reacted for two hours.
Then,this was cooled to 80 °C and reacted with 174 parts of ethylene
glycol diglycidyl ether in toluene for two hours to yield an epoxy group
comprising prepolymer 3 having a weight average molecular weight of
13,000.
-Synthesis of ketimine compound-
In a reactor equipped with a stirring bar and a thermometer, 30
parts of isophorone diamine and 70 parts of MEK were added and
reacted at 50 °C for five hours to yield a ketimine compound 2.
(Production of dead polymer)
Similarly to the above, 654 parts of bisphenol A ethylene oxide 2
mole adduct and 516 parts of terephthalate dimethyl ester were
subjected to polycondensation at 230 °C under normal pressure for six
hours and then reacted under reduced pressure of 10 mmHg to 15 mmHg
for five hours with dehydration to yield a dead polymer 1 having a peak
molecular weight of 2,400 and the hydroxyl value of two.
-Production of toner-
In a beaker, 15.4 parts of the prepolymer 3, 64 parts of the dead
polymer 1 and 78.6 parts of ethyl acetate were placed, stirred and
dissolved. Then, 20 parts of pentaerythritol tetrabehenate and four parts
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WO 2006/075534 PCT/JP2005/024210
of cyanine blue KRO (manufactured by Sanyo Color Works Ltd.) were
added thereto and stirred at 60 °C using the TK type homogenizer ,at
12,000 rpm for uniform dissolution and dispersion. Finally, 2.7 parts of
the ketimine compound 2 was added and dissolved. This is rendered a
toner material solution (l).
In a beaker, 706 parts of ion-exchange water, 294 parts of 10 %
hydroxyapatite suspension (Supertite 10, manufactured by Nippon
Chemical Industrial Co., Ltd.) and 0.2 parts of sodium
dodecylbenzenesulfonate were added and uniformly dissolved. Then, the
temperature was raised to 60 °C with stirring using the TK type
homomixer at 12,000 rpm. The above toner material solution (l) was
added thereto and stirred for 10 minutes. Then, this mixed solution was
transferred to a kolven equipped with a stirring bar and a thermometer,
and heated to 98 °C to remove the solvent via urea formation reaction.
After filtrating, washing and drying, wind force classi&caion was
performed to yield toner base particles. Subsequently, one part of
hydrophobic silica and one part of hydrophobic titanium oxide were
mixed with 100 parts of the toner base particles using the Henschel
mixer to yield a toner. The toner binder component had a weight average
molecular weight of 14,000, a number average molecular weight of 2,000
and a Tg of 52°C.
(Comparative Example 16)
-Method for producing A polymer-
In a flask equipped with a stirrer, a condenser, a thermometer
and a nitrogen introducing tube, 300 g of methanol, 100 g of toluene, 570
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g of styrene, 30 g of 2-acrylairdde-2-methylpropanesulfonic acid and 12 g
of lauroyl peroxide were placed, which was subjected to solution-
polymerization with stirring and under nitrogen introduction at 65 °C for
10 hours. The content was removed from the flask, dried under reduced
pressure and subsequently pulverized by a jet mill to produce an A
polymer having a weight average molecular weight of 3,000.
-Production of toner-
Styrene 183 parts
2-Ethylhexyl acrylate 17 parts
The above A polymer 0.1 parts
C.I. Pigment yellow 17 7 parts
Paraffin, wax (with a melting point of 155 °F, manufactured by
Taisei Kosan K.K.) 32 parts
Initiator (V-601, manufactured by Wako Pure Chemical
Industries Ltd.) 10 parts
The above formulation was warmed up to 65 °C and uniformly
dissolved or dispersed to make a monomer composition. Separately, 0.3 g
of a silane coupling agent (KBE903, manufactured by ShhvEtsu Silicone)
was uniformly dispersed in 1,200 mL of ion-exchange water, and 6 g of
colloidal silica (Aerosil #200, manufactured by Nippon Aerosil Co., Ltd.)
was added thereto and further uniformly dispersed. The pH of this
dispersion was adjusted to six with hydrochloric acid to prepare a
disperse medium system. The above monomer composition was added to
this dispersing medium system and stirred at 70 °C under a nitrogen
atmosphere using the TK homomixer at 6,500 rpm for 60 minutes to
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granulate the monomer composition. Subsequently, the granules were
polymerized. at 75 °C for eight hours with stirring by paddle stirring
wings.
After the completion of the polymerization, a reaction product
was cooled, treated with alkali overnight by adding 42 g of an aqueous
solution of 20 % sodium hydroxide. The dispersant was dissolved,
filtrated, washed with water and dried to yield a toner.
The physical properties of the toner were evaluated as follows.

ERA-8800FE, manufactured by Elionix Co., Ltd., was used as a
field emission electron beam three dimensional roughness analyzer. The
toner was measured with an acceleration voltage of 5 kV and no
evaporation, and its surface characteristics were analyzed using an
accessory software of the analyzer.
Platinum (Pt) and the like are evaporated in general for
measurement in order to prevent charge-up due to electron beams when
an organic substance is measured by an FE-SEM. However, there is a
possibility that the original surface characteristics may not be observed
because of the platinum evaporation. Therefore, the measurement was
conducted without the evaporation for prevention of charge-up. The low
acceleration voltage at 5 kV as well as a short duration of the electron-
beam irradiation successfully prevented the charge-up.
A relationship of the surface roughness (Ra) with its standard
deviation (RMS) obtained in Examples and Comparative Examples is
shown in Fig. 6. From this result, it is found that the standard deviation
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RMS is extremely small even when the surface roughness (Ra) is large in
the toner of the present invention.
Fig. 7 show an SEM photograph of the toner base particle of the
toner in Example 1. Figs. 8 and 9 show the surface concavoconvex by 3D-
SEM of the toner base particles of the toner in Example 1. Fig. 10 shows
the quantitative results of the above roughness analysis for such toner
base particles. From these figures, it is understood that the toner
surface is remarkably concavo-convex because the toner is produced by
dissolution/dispersion of the toner material comprising an inorganic
particulate using the organic solvent and granulation in the aqueous
medium followed by desolvation.

The measurement was performed using a flow type particle
image analyzer (FPIA-2000, manufactured by Sysmex Corporation). In a
given vessel, 100 mL to 150 mL of water in which solid impurities had
been previously removed was placed, 0.1 mL to 0.5 mL of a surfactant
was added as a dispersant, and further about 0.1 g to 9.5 g of a sample to
be measured was added. A suspension in which the sample had been
dispersed was dispersed for about one minute to three minutes using an
ultrasonic distributor to make a dispersion concentration 3,000
particles/uL to 10,000 particles/mL, and the shape and the distribution of
the toner were measured
A photograph of the toner was taken using a scanning electron
microscope (S-4200, manufactured by Hitachi, Ltd.) and analyzed by an
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image analyzer (Luzex AP, manufactured by Nireco Corporation) for
calculation. .

A number distribution and a volume distribution were measured
using Coulter Counter TA-II type (manufactured by Coulter), which was
connected with an interface (manufactured by The Institute of Japanese
Union of Scientists & Engineers) and PC9801 personal computer
(manufactured by NEC Corporation) for output.
The toner was evaluated as follows.

Using an evaluation machine obtained by rebuilding an image
forming apparatus (IPSiO Color 8100, manufactured by Eicoh Company,
Ltd.) to an oilless fixing mode and tuning, the stability of cleaning blades
was examined after outputting 10,000 sheets of a chart with an image
area fraction of 95 %. The transferred toner left on the photoconductor
which had passed the cleaning process was sampled on a white paper
using a scotch tape (manufactured by Sumitomo Three M Co., Ltd.) and
was measured using a Macbeth reflection densitometer, RD 514. The
results were rated as follows:
A: discrepancy from a blank of less than 0.005
B: discrepancy of 0.005 to 0.010
C: discrepancy of 0.011 to 0.02
D"- discrepancy of greater than 0.2

Using the evaluation machine obtained by rebuilding the image
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WO 2006/075534 PCT/JP2005/024210
forming apparatus (IPSiO Color 8100, manufactured by Ricoh Company,
Ltd.) to the oilless fixing method and tuning, the transferred toner left,on
the photoconductor after a chart with an image area rate of 20 % had
been transferred onto a paper and just before the cleaning step was
sampled onto a white paper using a scotch tape (manufactured by
Sumitomo Three M Co., Ltd.) and was measured using a Macbeth
reflection densitometer, RD 514. The results were rated as follows:
A: discrepancy from a blank of less than 0.005
B: discrepancy of 0.005 to 0.010
C: discrepancy of 0.011 to 0.02
D: discrepancy of greater than 0.2

Using the evaluation machine obtained by rebuilding the image
forming apparatus (IPSiO Color 8100, manufactured by Ricoh Company,
Ltd.) to the oilless fixing method and tuning, an endurance test in which
100,000 sheets of a chart with an image area fraction of 5 % were
continuously output using each toner was carried out, and the change of
charging amounts at that time was evaluated. Namely, 1 g of the
developer was weighed, and the change of charge amounts was obtained
by a blow off method. The results w.ere rated as follows:
A: the change in the charge of 5 p.c or less
B: the change of 10 uc or less
B: the change of 15 uc or less
C: the change of greater than 15 mC

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WO 2006/075534 PCT/JP2005/024210
Using the evaluation machine obtained by rebuilding the image
forming apparatus (IPSiO Color 8100 manufactured by Ricoh Company,
Ltd.) to the oilless fixing method and tuning, a solid image having an
adhered amount of 0.4 ±0.1 mg/cm2 was output onto a transfer paper of a
plain paper (Type 6200, manufactured by Ricoh Company, Ltd.), and
subsequently the image density was measured by X-Rite (manufactured
by X-Rite). The image densities of 1.4 or more was marked as 'OK,' 'NG',
otherwise.

Using the evaluation machine obtained by rebuilding the image
forming apparatus (IPSiO Color 8100, manufactured by Ricoh Company,
Ltd.) to the oilless fixing method and tuning, a photograph image with
single color was output, and levels of graininess and sharpness were
visually evaluated. They were evaluated as A, B, C and D sequentially
from the excellent level as follows^
A offset printing level
B: slightly inferior to the offset printing level
C: considerably inferior to the offset printing level
D: conventional electrographic level and very inferior

In an environment with a temperature of 10 °C and a relative
humidity of 15 %, using the evaluation machine obtained by rebuilding
the image forming apparatus (IPSiO Color 8100, manufactured by Ricoh
Company, Ltd.) to the oilless fixing method and tuning, an endurance
test in which 100,000 sheets of a chart with an image area rate of 5 %
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WO 2006/075534 PCT/JP2005/024210
were continuously output was carried out using each toner, and
subsequently a stain level with the toner on the surface of the transfer
paper was visually (loupe) evaluated. They were evaluated as A, B, C
and D sequentially from the excellent level as follows:
A excellent with no toner stain observed
B: favorable with little toner stain observed
C: fair with some toner stain observed
D: poor with severe toner stain, not acceptable

In an environment with a temperature of 40 °C and a relative
humidity of 90 %, using the evaluation machine obtained by rebuilding
the image forming apparatus (IPSiO Color 8100, manufactured by Ricoh
Company, Ltd.) to the oilless fixing method and tuning, an endurance
test in which 100,000 sheets of the chart with an image area rate of 5 %
were continuously output using each toner and was carried out, and
subsequently a contaminated state with the toner in the copying machine
was visually evaluated as follows-
A: excellent with no toner stain observed
B: favorable with little toner stain observed
C: fair with some toner stain observed
D: poor with severe toner stain, not acceptable
Environmental storage stability (blocking resistance)>
A penetration was measured by a penetrometer after 10 g of the
toner was weighed, placed in a 20 mL glass vessel, which was then
tapped 100 times and subsequently left stand in an incubator set at
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WO 2006/075534 PCT/JP2005/024210
temperature of 55 °C and a relative humidity of 80 % for 24 hours. The
penetration was also evaluated for the toner stored at a low temperature
of 10 °C and a low relative humidity 15 %. In either environment with
high temperature and high humidity or with low temperature and low
humidity, a lower value of the penetration was accepted and evaluated as
follows from the superior:
A: 20 mm or more
B: 15 mm or more and less than 20 mm
C: 10 mm or more and less than 15 mm
D: less than 10 mm.
The physical properties and evaluation results of the toners
obtained in the above Examples and Comparative Examples are shown
in Table 1 and 2, respectively.
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WO 2006/075534 PCT/JP2005/024210


WO 2006/075534 PCT/JP2005/024210
Tables 1 and 2 indicate that a toner having the surface
characteristics defined in the present invention has excellent charge
property, developing property and transfer property. It is also possible to
make the toner superior in terms of cleaning stability over time and
environmental storage stability without fog and toner scattering by
controlling the circularity, the shape coefficient and the particle diameter.
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WO 2006/075534 PCT/JP2005/024210
CLAIMS
1. A toner comprising toner base particles, which comprise a
binder resin and a colorant
wherein the toner base particles have a surface roughness (Ra) of
18 nm to 50 nm and a standard deviation (RMS) of the surface roughness
of 0.5 nm to 9.9 nm
2. The toner according to claim 1, wherein the - surface
roughness (Rz) of the toner base particles is 30 nm to 200 nm.
3. The toner according to any one of claims 1 to 2, wherein
inorganic particulates are comprised inside of the toner base particles.
4. The toner according to any one of claims 1 to 3, wherein
the average circularity of the toner base particles is 0.93 to 1.00.
5. The toner according to any one of claims 1 to 4, wherein
the volume average particle diameter (Dv) of the toner base particles is
2.0 urn to 6.0 um, and the ratio of the volume average particle diameter
(Dv) to the number average particle diameter (Dn), i.e. Dv/Dn, is 1.00 to
1.40.
6. The toner according to any one of claims 1 to 5, wherein
the ratio of the surface roughness (Ra) to the volume average particle
diameter (Dv), Ra (nm)/Dv (mm), is 0.3 to 17.0.
7. The toner according to any one of claims 1 to 6, wherein
the toner base particle has a shape coefficient SF-2 represented by the
Formula III below of 100 to 140 and the ratio of the surface roughness
(Ra) to the shape coefficient (SF-2), i.e. Ra/SF-2, of 0.008 to 0.500:
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WO 2006/075534 PCT/JP2005/024210

wherein PERI represents the peripheral length of the shape obtained by-
projecting the toner base particle to a two dimensional plane, and AREA
represents the area of the shape obtained by projecting the toner base
particle to the two dimensional plane.
8. The toner according to any one of claims 1 to 7, wherein
the toner base particles comprise a resin which is different from the
binder resin on the surface of the toner base particles.
9. The toner according to any one of claims 1 to 8, wherein
the toner base particles comprising a releasing agent in the toner base
particles.
10. The toner according to any one of claims 1 to 9, wherein
the toner is obtained by granulation in a liquid medium.
11. The toner according to any one of claims 1 to 10, wherein
the toner is obtained by granulation of a solution or a dispersion in which
a toner material comprising inorganic particulates is dissolved or
dispersed in an organic solvent in an aqueous medium followed by
removal of the organic solvent.
12. The toner according, to any one of claims 10 to 11, wherein
the toner is obtained by dissolution or dispersion of a toner material
which comprises a polyester prepolymer with a functional group
comprising a nitrogen atom, a polyester resin, a colorant and a releasing
agent in an organic solvent, followed by dispersion of the solution or the
dispersion in an aqueous medium for any one of a crosslinking reaction
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WO 2006/075534 PCT/JP2005/024210
and an extending reaction.
13. A developer which comprises the toner according to any
one of claims 1 to 12.
14. The developer according to claim 13, wherein the
developer is any one of a one-component developer and a two-component
developer.
15. A developing apparatus, wherein a developer is borne and
delivered by a latent image bearing member, and an alternating electric
field is applied at a position opposite to the latent image bearing member
to develop a latent electrostatic image on the latent image bearing
member,
wherein the developer is the developer according to any one of
claims 13 to 14.
16. A process cartridge, which comprises a latent image
bearing member and a developing unit in which a latent electrostatic
image formed on the latent image bearing member is developed using the
developer according to any one of claims 13 to 14 to form a visible image.
17. An image forming apparatus which comprises: a latent
image bearing member; a latent electrostatic image forming unit wherein
a latent electrostatic image is formed on the latent image bearing
member; a developing unit in which the latent electrostatic image is
developed using the developer according to any of claims 13 to 14 to form
a visible image; a transferring unit in which the visible image is
transferred to a recording medium; and a fixing unit in which a transfer
image transferred to the recording medium is fixed.
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WO 2006/075534 PCT/JP2005/024210
18. An image forming apparatus which comprises: a latent
image bearing member,' a latent electrostatic image forming unit wherein
a latent electrostatic image is formed on the latent image bearing
member? a developing unit in which the latent electrostatic image is
developed using the developer to form a visible image; a transferring unit
in which the visible image is transferred to a recording medium,' and a
fixing unit in which a transfer image transferred onto the recording
medium is fixed
wherein the developing unit is the developing apparatus
according to claim 15.
19. An image forming method which comprises: a latent
electrostatic image forming process wherein a latent electrostatic image
is formed on a latent image bearing member: a developing process
wherein the latent electrostatic image is developed using the developer
according to any one of claims 13 to 14 to form a visible image,' a
transferring process wherein the visible image is transferred to a
recording medium; and a fixing process wherein a transfer image
transferred to the recording medium is fixed.
116

The present invention provides the following: a toner which comprises toner base particles comprising a binder resin
and a colorant where the toner base particles have a surface roughness (Ra) of 18 nm to 50 nm and a standard deviation (RMS) of
the surface roughness of 0.5 nm to 9.9 nm; a developer comprising the toner; a developing apparatus; a process cartridge; an image
forming apparatus; and an image forming method using the developer.

Documents:

02650-kolnp-2007-abstract.pdf

02650-kolnp-2007-claims.pdf

02650-kolnp-2007-correspondence others.pdf

02650-kolnp-2007-description complete.pdf

02650-kolnp-2007-drawings.pdf

02650-kolnp-2007-form 1.pdf

02650-kolnp-2007-form 3.pdf

02650-kolnp-2007-form 5.pdf

02650-kolnp-2007-international publication.pdf

02650-kolnp-2007-international search report.pdf

02650-kolnp-2007-pct request form.pdf

02650-kolnp-2007-priority document.pdf

2650-KOLNP-2007-(05-05-2014)-ANNEXURE TO FORM 3.pdf

2650-KOLNP-2007-(05-05-2014)-CORRESPONDENCE.pdf

2650-KOLNP-2007-(05-05-2014)-OTHERS.pdf

2650-KOLNP-2007-(18-04-2013)-CORRESPONDENCE.pdf

2650-KOLNP-2007-(18-04-2013)-FORM 3.pdf

2650-KOLNP-2007-(29-01-2014)-ABSTRACT.pdf

2650-KOLNP-2007-(29-01-2014)-ANNEXURE TO FORM 3.pdf

2650-KOLNP-2007-(29-01-2014)-CLAIMS.pdf

2650-KOLNP-2007-(29-01-2014)-CORRESPONDENCE.pdf

2650-KOLNP-2007-(29-01-2014)-DRAWINGS.pdf

2650-KOLNP-2007-(29-01-2014)-FORM-2.pdf

2650-KOLNP-2007-(29-01-2014)-PA.pdf

2650-KOLNP-2007-(29-01-2014)-PETITION UNDER RULE 137.pdf

2650-KOLNP-2007-(30-01-2014)-CORRESPONDENCE.pdf

2650-KOLNP-2007-ASSIGNMENT.pdf

2650-KOLNP-2007-CORRESPONDENCE 1.1.pdf

2650-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

2650-KOLNP-2007-FORM 3-1.1.pdf

2650-kolnp-2007-form-18.pdf

2650-KOLNP-2007-PA.pdf


Patent Number 263570
Indian Patent Application Number 2650/KOLNP/2007
PG Journal Number 45/2014
Publication Date 07-Nov-2014
Grant Date 31-Oct-2014
Date of Filing 16-Jul-2007
Name of Patentee RICOH COMPANY LTD.
Applicant Address 3-6 NAKAMAGOME 1-CHOME, OHTA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 SUGIURA, HIDEKI 837-16, MIYAJIMA, FUJI-SHI, SHIZUOKA 416-0945
2 NAKAYAMA, SHINYA SHIMOKANUKI, NUMAZU-SHI, SHIZUOKA 410-0822
PCT International Classification Number G03G 9/08, G03G 9/10
PCT International Application Number PCT/JP2005/024210
PCT International Filing date 2005-12-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2005-004533 2005-01-11 Japan