U.S. patent application number 13/288653 was filed with the patent office on 2012-05-10 for toner.
This patent application is currently assigned to CANON KABUSHIKI KAISHA. Invention is credited to Naotaka Ikeda, Taiji Katsura, Yuhei Terui, Emi Watanabe.
Application Number | 20120115079 13/288653 |
Document ID | / |
Family ID | 46019951 |
Filed Date | 2012-05-10 |
United States Patent
Application |
20120115079 |
Kind Code |
A1 |
Ikeda; Naotaka ; et
al. |
May 10, 2012 |
TONER
Abstract
A toner containing toner particles, each of which contains a
binder resin and a colorant, and silica particles, wherein the
silica particles have a volume average particle diameter (Dv) of 70
nm or more and 500 nm or less, the variation coefficient of
diameters of the silica particles, based on volume distribution
thereof, is 23% or less, and wherein when the silica particles are
heated from 105.degree. C. to 200.degree. C., the ratio of mass
decrease is 0.60% or less.
Inventors: |
Ikeda; Naotaka;
(Kamakura-shi, JP) ; Watanabe; Emi; (Suntou-gun,
JP) ; Terui; Yuhei; (Numazu-shi, JP) ;
Katsura; Taiji; (Suntou-gun, JP) |
Assignee: |
CANON KABUSHIKI KAISHA
Tokyo
JP
|
Family ID: |
46019951 |
Appl. No.: |
13/288653 |
Filed: |
November 3, 2011 |
Current U.S.
Class: |
430/108.7 ;
977/773 |
Current CPC
Class: |
G03G 9/09725 20130101;
G03G 9/0812 20130101; B82Y 30/00 20130101; G03G 9/0819 20130101;
G03G 9/09716 20130101 |
Class at
Publication: |
430/108.7 ;
977/773 |
International
Class: |
G03G 9/08 20060101
G03G009/08 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 10, 2010 |
JP |
2010-251905 |
Claims
1. A toner comprising: toner particles, each of which contains a
binder resin and a colorant, and silica particles; wherein the
silica particles have a volume average particle diameter (Dv) of 70
nm or more and 500 nm or less, the variation coefficient of
diameters of the silica particles, based on volume distribution
thereof, is 23% or less, and wherein when heating the silica
particles to measure the mass variation, the ratio of mass decrease
of the silica particles at the temperature in the range of
105.degree. C. to 200.degree. C. is 0.60% or less.
2. The toner according to claim 1, wherein the silica particles are
produced by a sol-gel method.
3. The toner according to claim 1, wherein the silica particles are
treated with a hydrophobizing agent, and the fixing ratio of the
hydrophobizing agent to the silica particles is 90% or more.
4. The toner according to claim 3, wherein the silica particles
have the amount of carbon derived from the hydrophobizing agent of
0.01% by mass or more and 4.5% by mass or less.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a toner for developing an
electrostatic image used for image forming of an
electrophotographic system typified by a copying machine and a
printer.
[0003] 2. Description of the Related Art
[0004] Addition of an external additive having a large particle
diameter has been proposed as a technique to improve the
transferability of a toner (refer to Japanese Patent Laid-Open No.
2007-171666). This proposal is directed to improve the
transferability by adding silica particles having large particle
diameters to toner particles and reducing physical adhesion between
the toner and a photo conductor. However, the silica particles,
which are used in this proposal and which have large particle
diameters, are particles obtained by a deflagration method and,
therefore, have a wide particle size distribution. Consequently, in
the case where the toner is used over a long term, particles having
large particle diameters are eliminated from the toner easily, and
particles having small particle diameters are embedded in toner
particles easily. Furthermore, when silica particles move to
concave portions of toner particle surfaces, it is difficult to
give stable chargeability, fluidity, and transferability to the
toner.
[0005] As for a technique to improve this harmful effect, addition
of silica particles having large particle diameters with a narrow
particle size distribution to toner particles has been proposed
(refer to Japanese Patent Laid-Open No. 2007-322919). Japanese
Patent Laid-Open No. 2007-322919 discloses that silica particles
which have large particle diameters with a sharp particle size
distribution and which are produced by a sol-gel method are used,
so as to improve long-term stable chargeability and improve
transferability. However, silica particles, which have large
particle diameters and which are obtained by the sol-gel method, in
the related art are hydrophilic particles having silanol groups to
a large extent. Therefore, even when a hydrophobizing treatment is
performed, there are large amounts of remaining silanol groups.
Consequently, the property of the silica particles to give the
chargeability to the toner is influenced by the temperature and the
humidity easily, and it is difficult to give stable chargeability
to the toner. Meanwhile, in the case where large amounts of
hydrophobizing agent is used for silica particles in order to
improve this harmful effect, a property to give fluidity to the
toner is degraded. Consequently, in the case where a toner
including such silica particles is used and images are output over
a long term, it is difficult to maintain high image quality.
[0006] As for a technique to improve these harmful effects, use of
silica particles, which have silanol groups to a relatively small
extent and which have large particle diameters with a specific
particle size distribution, to a toner has been proposed (refer to
Japanese Patent Laid-Open No. 2008-262171). However, silica
particles, which have large particle diameters and which are used
in Japanese Patent Laid-Open No. 2008-262171, have a wide particle
size distribution and there are problems in properties to give the
fluidity and the chargeability to a toner.
[0007] As described above, it is difficult to obtain silica
particles which have large particle diameters and which can give
stable chargeability and fluidity to a toner regardless of
environment.
SUMMARY OF THE INVENTION
[0008] The present invention provides a toner having stable
chargeability and fluidity regardless of environment. Furthermore,
the present invention provides a toner which can produce a
high-definition high-quality image over a long term stably in the
case where the toner is used for image forming.
[0009] The present invention relates to a toner containing toner
particles, each of which contains a binder resin and a colorant,
and silica particles, wherein the above described silica particles
have a volume average particle diameter (Dv) of 70 nm or more and
500 nm or less, the variation coefficient of diameters of the
silica particles, based on volume distribution thereof, is 23% or
less, and wherein when heating the silica particles to measure the
mass variation, the ratio of mass decrease of the silica particles
at the temperature in the range of 105.degree. C. to 200.degree. C.
is 0.60% or less.
[0010] The toner according to the present invention has stable
chargeability and fluidity regardless of environment. Furthermore,
in the case where the toner according to the present invention is
used for image forming, a high-definition high-quality image can be
produced over a long term stably.
[0011] Further features of the present invention will become
apparent from the following description of exemplary
embodiments.
DESCRIPTION OF THE EMBODIMENTS
[0012] The present inventors performed intensive research on the
properties of silica particles having large particle diameters with
respect to a toner, to which silica particles having large particle
diameters are added externally. As a result, it was found that the
above described problems were able to be solved by adding the
silica particles, which have large particle diameters and having
the following properties, to the toner externally.
[0013] The silica particles used in the present invention are
silica particles having large particle diameters and having a
volume average particle diameter (Dv) of 70 nm or more and 500 nm
or less. In the case where the volume average particle diameter is
more than 500 nm, the fluidity of the toner is hindered and, in
addition, silica particles are eliminated from the toner surface
easily. Therefore, such silica particles cannot give long-term
stable chargeability and fluidity to the toner. Furthermore,
eliminated silica particles adhere to developing agent constituent
materials and image forming system members or contaminate them.
Consequently, degradation in charge characteristics and an
occurrence of toner scattering may be caused. On the other hand, in
the case where the volume average particle diameter of the silica
particles is less than 70 nm, a sufficient spacer effect of silica
particles having large particle diameters is not exerted.
Therefore, in the case where such silica particles are used for the
toner, degradation of the toner transferability and degradation of
the toner surface may occur. The volume average particle diameter
(Dv) of the silica particles is preferably 80 nm or more and 200 nm
or less.
[0014] The variation coefficient of diameters of the silica
particles, based on volume distribution thereof, is 23% or less. In
the case where the variation coefficient of diameters of the silica
particles, based on volume distribution thereof, is within the
above described range, the silica particles exert a spacer effect
on the toner surface more effectively. As a result, the toner
transferability is improved. Furthermore, a toner having long-term
stable chargeability and fluidity is obtained. In the case where
the variation coefficient of diameters of the silica particles is
more than 23%, there are large variations in volume distribution of
diameters of the silica particles. Consequently, even when the
volume average particle diameter (Dv) of the silica particles is
within the above described range, the proportion of particles which
do not function as spacer particles is large and the toner
transferability is not obtained sufficiently. Moreover, there are
differences in properties to give the chargeability and the
fluidity to a toner among individual silica particles.
Consequently, the charge distribution of the toner is extended, so
that in the case where such a toner is used for image forming,
fogging or the like occur easily. The variation coefficient of
diameters of the silica particles, based on volume distribution
thereof, is preferably 15% or less, and further preferably 10% or
less.
[0015] Measurements of volume average particle diameter (Dv) of
silica particles and variation coefficient of diameters of silica
particles, based on volume distribution thereof.
[0016] Measurements of the volume average particle diameter (Dv) of
silica particles and the variation coefficient of diameters of
silica particles, based on volume distribution thereof, are
performed by using Zetasizer Nano ZS (produced by SYSMEX
CORPORATION). The variation coefficient is determined in a manner
as described below. Initially, the volume distribution of the
particle size is measured, so as to determine the half-width of the
volume distribution thereof and the volume average particle
diameter (Dv). Subsequently, the ratio (%) of the half-width to the
volume average particle diameter is calculated and, thereby the
variation coefficient is determined.
[0017] Sample preparation and the measurement condition are as
described below. About 1 mg of silica particles are added to 20 ml
of pure water, and dispersion is performed for 3 minutes by using
Homogenizer (produced by SMT). In order to reduce an influence of
aggregation of silica particles, the volume average particle
diameter (Dv) and the variation coefficient are measured just after
the dispersion under the following condition.
[0018] Measurement Condition
[0019] Cell: DTS0012-Disposable sizing cuvette
[0020] Dispersant: Water
[0021] Refractive index: [0022] material: 1.460 [0023] dispersant:
1.330
[0024] Temperature: 25.degree. C.
[0025] Measurement duration: [0026] Number of runs: 5 [0027] Runs
duration (Seconds): 10
[0028] Result Calculation General Purpose
[0029] Regarding the silica particles used in the present
invention, when heating the silica particles to measure the mass
variation, the ratio of mass decrease at the temperature in the
range of 105.degree. C. to 200.degree. C. (hereafter may be simply
referred to as ratio of mass decrease) is 0.60% or less. The ratio
of mass decrease refers to the percentage of mass decrease of
silica particles in the range of 105.degree. C. to 200.degree. C.
when a thermogravimetric analyzer (TGA) is used and the silica
particles are heated from 50.degree. C. to 500.degree. C. at normal
pressure. When the silica particles are heated, silanol groups of
the silica particles are dehydrated and condensed at about
130.degree. C. and, thereby, the mass of silica particles
decreases. Meanwhile, water (not derived from the silanol group),
volatile substances, and the like adhering to the silica particles
are almost volatilized at normal pressure at about 105.degree. C.
Hexamethyldisilazane (HMDS), silicone oil, and the like, which are
used as agents for treating silica, begin to volatilize at normal
pressure at a temperature higher than 200.degree. C. (about
250.degree. C.). Consequently, the present inventors believe that
the amount of silanol groups included in the silica particles is
quantified by measuring the ratio of mass decrease of silica
particles in the range of 105.degree. C. to 200.degree. C.
[0030] The silanol groups of the silica particles are
water-adsorption sites and, therefore, the amount of silanol groups
in the silica particles exerts a large effect on the hygroscopicity
of the silica particles. Consequently, the amount of silanol groups
included in the silica particles exerts a large effect on the
properties to give the chargeability, the fluidity, and the
transferability to the toner. In the case where the ratio of mass
decrease of the silica particles is more than 0.60%, the amount of
silanol groups in the silica particles is large. As a result, in
particular under a high-humidity environment, silica particles
adsorb a large amount of water, so that the toner is not provided
with the chargeability and the fluidity sufficiently. The ratio of
mass decrease of the silica particles is preferably 0.10% or less,
and further preferably 0.02% or less.
[0031] Method for Measuring Ratio of Mass Decrease of Silica
Particles
[0032] The ratio of mass decrease of silica particles is measured
by using Hi-Res TGA 2950 Thermogravimetric Analyzer (produced by TA
Instrument). About 0.03 g of silica particles serving as a sample
are added to a pan for the above described analyzer, and the
resulting pan is set into the analyzer. At that time, in
consideration of the bulkiness of silica particles, the amount of
sample is adjusted appropriately. After an equilibrium state is
reached at normal pressure at 50.degree. C., that state is held for
10 minutes, and the mass of the silica particles is measured.
Subsequently, a nitrogen gas is supplied, the temperature is raised
to 500.degree. C. at 20.degree. C./min at normal pressure, and the
mass variation is measured. Then, the percentage of the amount of
mass decrease of the silica particles in the range from 105.degree.
C. to 200.degree. C. relative to the mass of the silica particles
after being held at 50.degree. C. for 10 minutes is taken as the
ratio of mass decrease.
[0033] The silica particles used in the present invention have a
small ratio of mass decrease of 0.60% or less and, therefore, the
hygroscopicity is very small as compared with that of the
large-diameter silica particles obtained by a sol-gel method in the
related art. Consequently, the surfaces thereof are not necessarily
subjected to a hydrophobizing treatment in contrast to the
large-diameter silica particles obtained by the sol-gel method in
the related art. However, in order to give long-term stable
chargeability, fluidity, and transferability to the toner, the
silica particles used in the present invention may be subjected to
the hydrophobizing treatment.
[0034] The method for subjecting the silica particles to the
hydrophobizing treatment is not specifically limited, and known
methods may be used. Examples of methods for subjecting the silica
particles to the hydrophobizing treatment include a method in which
the silica particles are treated with a hydrophobizing agent in a
dry condition and a method in which the silica particles are
treated with a hydrophobizing agent in a wet condition.
[0035] Most of all, the dry hydrophobizing treatment method can be
employed because the toner is provided with excellent fluidity
while aggregation of the silica particles is prevented. Examples of
dry hydrophobizing treatment methods include a method in which the
silica particles are treated by spraying of a hydrophobizing agent
under agitation and a method in which a vapor of hydrophobizing
agent is introduced to the silica particles in a fluidized bed or
under agitation.
[0036] Examples of hydrophobizing agents include the following:
chlorosilanes, e.g., methyltrichlorosilane, dimethyldichlorosilane,
trimethylchlorosilane, phenyltrichlorosilane,
diphenyldichlorosilane, t-butyldimethylchlorosilane, and
vinyltrichlorosilane; alkoxysilanes, e.g., tetramethoxysilane,
methyltrimethoxysilane, dimethyldimethoxysilane,
phenyltrimethoxysilane, diphenyldimethoxysilane,
o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane,
n-butyltrimethoxysilane, i-butyltrimethoxysilane,
hexyltrimethoxysilane, octyltrimethoxysilane,
decyltrimethoxysilane, dodecyltrimethoxysilane, tetraethoxysilane,
methyltriethoxysilane, dimethyldiethoxysilane,
phenyltriethoxysilane, diphenyldiethoxysilane,
i-butyltriethoxysilane, decyltriethoxysilane, vinyltriethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-chloropropyltrimethoxysilane,
.gamma.-aminopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane, and
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane; silazanes,
e.g., hexamethyldisilazane, hexaethyldisilazane,
hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane,
hexahexyldisilazane, hexacyclohexyldisilazane,
hexaphenyldisilazane, divinyltetramethyldisilazane, and
dimethyltetravinyldisilazane; silicone oils, e.g., dimethyl
silicone oil, methylhydrogen silicone oil, methylphenyl silicone
oil, alkyl-modified silicone oil, chloroalkyl-modified silicone
oil, chlorophenyl-modified silicone oil, fatty acid-modified
silicone oil, polyether-modified silicone oil, alkoxy-modified
silicone oil, carbinol-modified silicone oil, amino-modified
silicone oil, fluorine-modified silicone oil, and
terminally-reactive silicone oil; siloxanes, e.g.,
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, hexamethyldisiloxane, and
octamethyltrisiloxane; long chain fatty acids, e.g., undecylic
acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid,
palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid,
arachic acid, montanic acid, oleic acid, linoleic acid, and
arachidonic acid; and salts of the above described fatty acids and
metals, e.g., zinc, iron, magnesium, aluminum, calcium, sodium, and
lithium. Among them, alkoxysilanes, silazanes, and straight
silicone oils can be used because a hydrophobizing treatment is
performed easily. Such hydrophobizing agents may be used alone or
in combination. The above described hydrophobizing agents may be
used stepwise sequentially to surface-treat silica particles.
[0037] In the case where the silica particles used in the present
invention are subjected to the hydrophobizing treatment, the amount
of carbon derived from a hydrophobizing agent in the silica
particles is preferably 0.01% by mass or more and 4.5% by mass or
less. In the case where the above described amount of carbon is
within the above described range, the usage of the hydrophobizing
agent is appropriate and degradation in fluidity of the silica
particles is prevented. Meanwhile, as described above, the silica
particles before being subjected to the hydrophobizing treatment
have low hygroscopicity as compared with those in the related art.
Therefore, in order to exert this effect sufficiently, the usage of
the hydrophobizing agent is minimized. Consequently, good
chargeability and fluidity of the toner is enhanced. The above
described amount of carbon is further preferably 0.02% by mass or
more and 1.0% by mass or less, and particularly preferably 0.03% by
mass or more and 0.08% by mass or less.
[0038] Method for Measuring Amount of Carbon of Silica
Particles
[0039] The amount of carbon of the silica particles is measured by
using a carbon and sulfur analyzer (EMIA-320 produced by HORIBA,
Ltd.). About 0.3 g of sample is precisely weighed into a crucible
for the above described measurement apparatus, and 0.3 g.+-.0.05 g
of tin (Spare No. 9052012500) and 1.5 g.+-.0.1 g of tungsten (Spare
No. 9051104100) are added as fuel oil additives. Then, the silica
particles are heated to 1,100.degree. C. in an oxygen atmosphere
following the description of the instruction manual attached to the
measurement apparatus. Consequently, hydrophobic groups derived
from the hydrophobizing agent on the silica particle surfaces are
thermally decomposed to CO.sub.2. Thereafter, the amount of carbon
contained in the silica particles is determined from the amount of
the resulting CO.sub.2 and this is taken as the amount of carbon
derived from the hydrophobizing agent.
[0040] Regarding the silica particles used in the present
invention, the fixing ratio of the hydrophobizing agent to the
silica particles is preferably 90% or more. In the case where the
fixing ratio is within the above described range, the silica
particles give good chargeability, fluidity, and transferability to
the toner regardless of the environment.
[0041] Method for Measuring Fixing Ratio of Hydrophobizing Agent to
Silica Particles
[0042] The fixing ratio of the hydrophobizing agent to the silica
particles is measured by the following method. An Erlenmeyer flask
is charged with 0.50 g of silica fine particles and 40 ml of
chloroform and is covered with a lid, followed by agitation for 2
hours. Subsequently, agitation is stopped. Standing for 12 hours
and centrifugal separation are performed and a supernatant liquid
is removed completely. The centrifugal separation is performed with
Centrifuge H-9R (produced by KOKUSAN) by using Bn1 rotor and a
plastic centrifuge tube for Bn1 rotor under the condition of
20.degree. C., 10,000 rpm, and 5 minutes.
[0043] The centrifugally separated silica particles are put into
the Erlenmeyer flask again, 40 ml of chloroform is added, the lid
is set, and agitation is performed for 2 hours. Subsequently,
agitation is stopped. Standing for 12 hours and centrifugal
separation are performed and a supernatant liquid is removed
completely. This operation is further repeated two times. The
resulting sample is dried by using a constant temperature bath at
50.degree. C. for 2 hours. Furthermore, decompression to 0.07 MPa
is performed, followed by drying at 50.degree. C. for 24 hours, so
as to volatilize chloroform sufficiently.
[0044] The amount of carbon of the silica particles treated with
chloroform, as described above, and the amount of carbon of the
silica particles before the treatment with chloroform are measured
following the above described "Method for measuring amount of
carbon of silica particles". The fixing ratio is calculated by
using a formula described below.
fixing ratio of hydrophobizing agent to the silica particles
(%)=(amount of carbon of silica particles treated with
chloroform/amount of carbon of silica particles).times.100
[0045] The method for producing the silica particles used in the
present invention will be described below. The method for producing
the silica particles used in the present invention is not
specifically limited. Examples thereof include the following
methods: a combustion method in which silica particles are obtained
by combustion of a silane compound (that is, a method for producing
fumed silica); a deflagration method in which silica particles are
obtained by explosive combustion of a metal silicon powder; wet
methods in which silica particles are obtained by a neutralization
reaction between sodium silicate and a mineral acid (among them,
synthesis under an alkaline condition is referred to as a
sedimentation method, and synthesis under an acid condition is
referred to as a gel method); and a sol-gel method in which silica
particles are obtained by hydrolysis of alkoxysilanes, e.g.,
hydrocarbyloxysilane (a so-called Stoeber method). Among them, the
sol-gel method can be employed as a method for producing
large-diameter silica particles because a sharp particle size
distribution of the silica particles is obtained as compared with
the other methods.
[0046] The method for producing silica particles by the sol-gel
method will be described below. Initially, in an organic solvent in
which water is present, an alkoxysilane is subjected to hydrolysis
and condensation reactions in the presence of a catalyst, so as to
obtain a silica sol suspension liquid. The catalyst is removed from
the silica sol suspension liquid, and drying is performed, so that
silica particles are obtained. The silica particles obtained at
this stage have silanol groups to a large extent and are
hydrophilic. Therefore, the ratio of mass decrease takes on a value
larger than 2%. In order to make the ratio of mass decrease of the
silica particles obtained by the above described sol-gel method
fall within the range specified in the present invention, the
silica particles are heat-treated at 300.degree. C. to 500.degree.
C. Consequently, the silanol groups of the silica particles are
dehydrated and condensed, so that the amount of silanol groups is
reduced and it is possible to reduce the value of the ratio of mass
decrease of the silica particles.
[0047] In the case where the silica particles are treated with the
hydrophobizing agent, the timing of the heat treatment at
300.degree. C. to 500.degree. C. may be before, after, or at the
same time with the hydrophobizing treatment. However, in the case
where the heat treatment is performed after the hydrophobizing
treatment, the hydrophobizing agent is thermally decomposed, and
the above described fixing ratio of the hydrophobizing agent may
not be obtained. Therefore, the heat treatment can be performed
before the hydrophobizing treatment.
[0048] Moreover, in order that the silica particles become
monodisperse on the toner particle surface easily and a stable
spacer effect is exerted, the silica particles can be subjected to
a disintegration treatment after being heat-treated. Regarding the
timing of the disintegration treatment, the disintegration
treatment can be performed before the surface treatment is
performed with the hydrophobizing agent because the silica particle
surfaces can be uniformly treated with the hydrophobizing
agent.
[0049] The amount of addition (amount of external addition) of the
silica particles used in the present invention to the toner is
preferably 0.01 parts by mass or more and 2.50 parts by mass or
less relative to 100 parts by mass of the toner particles. In the
case where the amount of addition of the silica particles is within
the above described range, the above described effects of the
silica particles are exerted favorably. The amount of addition of
the silica particles to the toner is more preferably 0.10 parts by
mass or more and 2.00 parts by mass or less relative to 100 parts
by mass of toner particles.
[0050] The weight average particle diameter (D4) of the toner
according to the present invention is preferably 4.0 .mu.m or more
and 9.0 .mu.m or less, and more preferably 5.0 .mu.m or more and
7.5 .mu.m or less. In the case where the weight average particle
diameter (D4) of the toner is within the above described range, an
occurrence of charge up is suppressed and fogging, toner
scattering, and reduction in image density are prevented.
[0051] Method for Measuring Weight Average Particle Diameter (D4)
and Number Average Particle Diameter (D1)
[0052] The weight average particle diameter (D4) and the number
average particle diameter (D1) of the toner are calculated in a
manner described below. As for a measurement apparatus, a precise
particle size distribution measurement apparatus "Coulter Counter
Multisizer 3" (registered trademark, produced by Beckman Coulter,
Inc.) equipped with a 100 .mu.m aperture tube on the basis of a
pore electrical resistance method is used. Regarding setting of the
measurement conditions and analysis of the measurement data, an
attached dedicated software "Beckman Coulter Multisizer 3 Version
3.51" (produced by Beckman Coulter, Inc.) is used. In this regard,
the measurement is performed with the number of effective
measurement channels of 25,000 channels. As for the electrolytic
aqueous solution used for the measurement, a solution prepared by
dissolving special grade sodium chloride into ion-exchanged water
in such a way as to have a concentration of about 1% by mass, for
example, "ISOTON II" (produced by Beckman Coulter, Inc.), may be
used.
[0053] By the way, prior to the measurement and the analysis, the
above-described dedicated software is set as described below. In
the screen of "Modification of the standard operating method (SOM)"
of the above-described dedicated software, the total count number
in the control mode is set at 50,000 particles, the number of
measurements is set at 1 time, and the Kd value is set at a value
obtained by using "Standard particles 10.0 .mu.m" (produced by
Beckman Coulter, Inc.). The threshold value and the noise level are
automatically set by pressing "Threshold value/noise level
measurement button". In addition, the current is set at 1,600
.mu.A, the gain is set at 2, the electrolytic solution is set at
ISOTON II, and a check is entered in "Post-measurement aperture
tube flush". In the screen of "Setting of conversion from pulses to
particle diameter" of the above-described dedicated software, the
bin interval is set at logarithmic particle diameter, the particle
diameter bin is set at 256 particle diameter bins, and the particle
diameter range is set at 2 .mu.m to 60 .mu.m.
[0054] The specific measurement procedure is as described
below.
(1) A 250 ml round-bottom glass beaker dedicated to Multisizer 3 is
charged with about 200 ml of the above-described electrolytic
aqueous solution, the beaker is set in a sample stand, and
counterclockwise agitation is performed with a stirrer rod at 24
revolutions/sec. Then, contamination and air bubbles in the
aperture tube are removed by "Aperture flush" function of the
dedicated software. (2) A 100 ml flat-bottom glass beaker is
charged with about 30 ml of the above-described electrolytic
aqueous solution. A diluted solution is prepared by diluting
"Contaminon N" (a 10% by mass aqueous solution of neutral detergent
for washing a precision measuring device, including a nonionic
surfactant, an anionic surfactant, and an organic builder and
having a pH of 7, produced by Wako Pure Chemical Industries, Ltd.)
with ion-exchanged water by a factor of about 3 on a mass basis and
about 0.3 ml of the diluted solution serving as a dispersing agent
is added to the inside of the beaker. (3) An ultrasonic dispersing
machine "Ultrasonic Dispersion System Tetora 150" (produced by
Nikkaki Bios Co., Ltd.) is prepared, the system incorporating two
oscillators with an oscillatory frequency of 50 kHz in such a way
that the phases are displaced by 180 degrees and having an
electrical output of 120 W. Then, about 3.3 l of ion-exchanged
water is put into a water tank of the ultrasonic dispersion system,
and about 2 ml of Contaminon N is added to the inside of this water
tank. (4) The beaker in the above-described item (2) is set in a
beaker fixing hole of the above-described ultrasonic dispersion
system, and the ultrasonic dispersion system is actuated. The
height position of the beaker is adjusted in such a way that the
resonance state of the liquid surface of the electrolytic aqueous
solution in the beaker is maximized. (5) Ultrasonic waves are
applied to the electrolytic aqueous solution in the beaker of the
above-described item (4). In this state, about 10 mg of toner is
added to the above-described electrolytic aqueous solution little
by little and is dispersed. Subsequently, an ultrasonic dispersion
treatment is further continued for 60 seconds. In this regard, in
the ultrasonic dispersion, the water temperature of the water tank
is controlled at 10.degree. C. or higher and 40.degree. C. or lower
appropriately. (6) The electrolytic aqueous solution, in which the
toner is dispersed, of the above-described item (5) is dropped to
the round-bottom beaker of the above-described item (1) set in the
sample stand by using a pipette in such a way that the measurement
concentration is adjusted to become about 5%. Then, the measurement
is performed until the number of measured particles reaches 50,000.
(7) The measurement data are analyzed by the above-described
dedicated software attached to the apparatus, so that the weight
average particle diameter (D4) and the number average particle
diameter (D1) are calculated. In this regard, when Graph/% by
volume is set in the above-described dedicated software, "Average
diameter" on the screen of "Analysis/statistical value on volume
(arithmetic average)" is the weight average particle diameter (D4),
and when Graph/% by the number is set in the above-described
dedicated software, "Average diameter" on the screen of
"Analysis/statistical value on the number (arithmetic average)" is
the number average particle diameter (D1).
[0055] The toner according to the present invention can contain at
least one type of wax. The total amount of waxes contained in the
toner is preferably 2.5 parts by mass or more and 25.0 parts by
mass or less relative to 100 parts by mass of the toner particles.
The total amount of waxes contained in the toner particles is
preferably 4.0 parts by mass or more and 20 parts by mass or less,
and further preferably 6.0 parts by mass or more and 18.0 parts by
mass or less. In the case where the amount of wax is 2.5 parts by
mass or more and 25.0 parts by mass or less, an appropriate
bleeding property of wax is ensured during heating and pressurizing
of the toner, so that winding resistance is improved. Furthermore,
even when the toner undergoes a stress during development or
transfer, exposure of wax at the toner surface is at a low level
and individual toner particles obtain nearly uniform triboelectric
chargeability. Examples of waxes include the following: aliphatic
hydrocarbon based waxes, e.g., low-molecular weight polyethylene,
low-molecular weight polypropylene, microcrystalline waxes,
Fischer-Tropsch waxes, and paraffin waxes; oxides of aliphatic
hydrocarbon based waxes, e.g., oxidized polyethylene wax, or block
copolymers thereof; waxes containing a fatty acid ester as a
primary component, e.g., carnauba wax and montanic acid ester wax,
and waxes produced by partly or wholly deacidifying fatty acid
esters, e.g., deacidified carnauba wax; saturated straight chain
fatty acids, e.g., palmitic acid, stearic acid, and montanic acid;
unsaturated fatty acids, e.g., brassidic acid, eleostearic acid,
and parinaric acid; saturated alcohols, e.g., stearyl alcohol,
aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol,
and melissyl alcohol; polyhydric alcohols, e.g., sorbitol; fatty
acid amides, e.g., linolamide, oleamide, and lauramide; saturated
fatty acid bis-amides, e.g., methylene-bis-stearamide,
ethylene-bis-capramide, ethylene-bis-lauramide, and
hexamethylene-bis-stearamide; unsaturated fatty acid amides, e.g.,
ethylene-bis-oleamide, hexamethylene-bis-oleamide, N,N'-dioleyl
adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides, e.g.,
m-xylene-bis-stearamide, and N,N'-distearyl isophthalamide;
aliphatic metal salts (those generally referred to as metallic
soaps), e.g., calcium stearate, calcium laurate, zinc stearate, and
magnesium stearate; waxes which are aliphatic hydrocarbon based
waxes grafted by using vinyl based monomers, e.g., styrene and
acrylic acid; partly esterified products of fatty acids and
polyhydric alcohols, e.g., behenic monoglyceride; and methyl ester
compounds which are obtained by hydrogenation of vegetable oils and
fats and which have hydroxyl groups.
[0056] Examples of binder resins of the toner include the
following: polystyrenes; homopolymers of styrene substitution
products, e.g., poly-p-chlorostyrene and polyvinyltoluene; styrene
based copolymers, e.g., styrene-p-chlorostyrene copolymers,
styrene-vinyltoluene copolymers, styrene-vinylnaphthalene
copolymers, styrene-acrylic acid ester copolymers,
styrene-methacrylic acid ester copolymers, styrene-methyl
.alpha.-chloromethacrylate copolymers, styrene-acrylonitrile
copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl
ethyl ether copolymers, styrene-vinyl methyl ketone copolymers,
styrene-butadiene copolymers, styrene-isoprene copolymers, and
styrene-acrylonitrile-indene copolymers; acrylic resins;
methacrylic resins; polyvinyl acetate; silicone resins; polyester
resins; polyamide resins; furan resins; epoxy resins; and xylene
resins. These resins may be used alone or in combination.
[0057] The toner particles used in the present invention may be
produced by using a known pulverization method or polymerization
method. In particular, the polymerization method can be employed
because toner particles which are close to a sphere and which have
surfaces with a low level of unevenness are obtained as compared
with the pulverization method and, thereby the effect of giving the
transferability is exerted by the silica particles synergetically.
Among the polymerization methods, in particular, toner particles
can be obtained by a suspension polymerization method.
[0058] The method for producing toner particles by the suspension
polymerization method will be described below. A polymerizable
monomer composition containing a polymerizable monomer, a colorant,
a wax, other additives as necessary, and the like is dissolved or
dispersed with a dispersing machine, e.g., a homogenizer, a ball
mill, a colloid mill, or an ultrasonic dispersing machine, so as to
be suspended in an aqueous medium containing a dispersion
stabilizer. A polymerization initiator is used and the
polymerizable monomer in the polymerizable monomer composition is
polymerized, so as to produce toner particles. The polymerization
initiator may be added at the same time as addition of the other
additives to the polymerizable monomer, or be mixed just before the
polymerizable monomer composition is suspended in the aqueous
medium. Alternatively, the polymerization initiator dissolved into
the polymerizable monomer or the solvent may be added just after
granulation is completed and before the polymerization reaction is
initiated.
[0059] As for the polymerizable monomer, a vinyl based
polymerizable monomer capable of being radically polymerized is
used. As for the vinyl based polymerizable monomer, a
monofunctional monomer or a polyfunctional monomer may be used.
Examples of monofunctional polymerizable monomers include the
following: styrene; styrene derivatives, e.g., .alpha.-methyl
styrene, .beta.-methyl styrene, o-methyl styrene, m-methyl styrene,
p-methyl styrene, 2,4-dimethyl styrene, p-n-butyl styrene,
p-tert-butyl styrene, p-n-hexyl styrene, p-n-octyl styrene,
p-n-nonyl styrene, p-n-decyl styrene, p-n-dodecyl styrene,
p-methoxy styrene, and p-phenyl styrene; acrylic polymerizable
monomers, e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate,
iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate,
tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate,
cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl
acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl
acrylate, and 2-benzoyloxy ethyl acrylate; methacrylic
polymerizable monomers, e.g., methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, iso-propyl methacrylate,
n-butyl methacrylate, iso-butyl methacrylate, tert-butyl
methacrylate, n-amyl methacrylate, n-hexyl methacrylate,
2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl
methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl
phosphate ethyl methacrylate; methylene aliphatic monocarboxylic
acid ester; vinyl esters, e.g., vinyl acetate, vinyl propionate,
vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl ethers,
e.g., vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl
ether; and vinyl ketones, e.g., vinyl methyl ketone, vinyl hexyl
ketone, and vinyl isopropyl ketone.
[0060] Examples of polyfunctional polymerizable monomers include
the following: diethylene glycol diacrylate, triethylene glycol
diacrylate, tetraethylene glycol diacrylate, polyethylene glycol
diacrylate, 1,6-hexane diol diacrylate, neopentyl glycol
diacrylate, tripropylene glycol diacrylate, polypropylene glycol
diacrylate, 2,2'-bis(4-(acryloxy.cndot.diethoxy)phenyl)propane,
trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
triethylene glycol dimethacrylate, tetraethylene glycol
dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene
glycol dimethacrylate, 1,6-hexane diol dimethacrylate, neopentyl
glycol dimethacrylate, polypropylene glycol dimethacrylate,
2,2'-bis(4-(methacryloxy.cndot.diethoxy)phenyl)propane,
2,2'-bis(4-(methacryloxy.cndot.polyethoxy)phenyl)propane,
trimethylolpropane trimethacrylate, tetramethylolmethane
tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl
ether.
[0061] The monofunctional polymerizable monomers are used alone, in
combination of at least two types, or in combination with the
polyfunctional polymerizable monomers. The polyfunctional
polymerizable monomer may also be used as a cross-linking
agent.
[0062] As for the polymerization initiator used in polymerization
of the polymerizable monomer, oil-soluble initiators and/or
water-soluble initiators are used. Examples of oil-soluble
initiators include the following: azo compounds, e.g.,
2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile,
1,1'-azobis(cyclohexane-1-carbonitrile), and
2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; and peroxide based
initiators, e.g., acetylcyclohexylsulfonyl peroxide, diisopropyl
peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl
peroxide, propionyl peroxide, acetyl peroxide, t-butyl
peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl
peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone
peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl
peroxide, and cumene hydroperoxide. Examples of water-soluble
initiators include the following: ammonium persulfate, potassium
persulfate, 2,2'-azobis(N,N'-dimethylene isobutyl amidine)
hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride,
azobis(isobutyl amidine) hydrochloride, sodium
2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate, and
hydrogen peroxide. Furthermore, a chain transfer agent, a
polymerization inhibitor, and the like may be used in order to
control the degree of polymerization of the polymerizable
monomer.
[0063] As for the cross-linking agent, a compound having at least
two polymerizable double bonds is used. Specific examples thereof
include aromatic divinyl compounds; e.g., divinylbenzene and
divinylnaphthalene; carboxylic acid esters having two double bonds,
e.g., ethylene glycol diacrylate, ethylene glycol dimethacrylate,
and 1,3-butane diol dimethacrylate; divinyl compounds, e.g.,
divinylaniline, divinyl ether, divinyl sulfide, and divinyl
sulfone; and compounds having at least three vinyl groups. They are
used alone or as a mixture.
[0064] As for the colorant, black, yellow, magenta, and cyan
colorants, described below, may be used.
[0065] As for the black colorant, carbon black and magnetic
substances may be used. Furthermore, a color and a toner resistance
may be adjusted by mixing the following coloring materials.
[0066] As for pigment based yellow colorants, compounds typified by
condensed azo compounds, isoindolinone compounds, anthraquinone
compounds, azo metal complex methine compounds, and allylamide
compounds are used. Specific examples include C. I. Pigment Yellow
3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94,
95, 99, 100, 101, 104, 108, 109, 110, 111, 117, 123, 128, 129, 138,
139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183,
185, 191:1, 191, 192, 193, and 199. Examples of die based yellow
colorants include C. I. solvent Yellow 33, 56, 79, 82, 93, 112,
162, and 163, and C. I. disperse Yellow 42, 64, 201, and 211.
[0067] As for magenta colorants, condensed azo compounds,
diketopyrrolopyrrole compounds, anthraquinone, quinacridone
compounds, basic dye lake compounds, naphthol compounds,
benzimidazolone compounds, thioindigo compounds, and perylene
compounds are used. Specific examples include C. I. Pigment Red 2,
3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 146, 166, 169,
177, 184, 185, 202, 206, 220, 221, 238, 254, and 269 and C. I.
Pigment Violet 19.
[0068] As for cyan colorants, phthalocyanine compounds and
derivatives thereof, anthraquinone compounds, and basic dye lake
compounds are used. Specific examples include C. I. Pigment Blue 1,
7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.
[0069] These colorants may be used alone or in combination.
Furthermore, the colorant may be used in the state of solid
solution. The colorant is selected from the viewpoint of the hue
angle, the saturation, the brightness, the weather resistance, the
OHP transparency, and dispersibility into the toner. The amount of
addition of the colorant is preferably 1 part by mass or more and
20 parts by mass or less relative to 100 parts by mass of binder
resin.
[0070] In order to keep the stable chargeability of the toner, a
charge control agent can be applied to the toner. Examples of
negative charge control agents include the following: monoazo metal
compounds; acetylacetone metal compounds; aromatic oxycarboxylic
acids, aromatic dicarboxylic acids, oxycarboxylic acids,
dicarboxylic acids, and metal compounds, anhydrides, and ester
compounds of these acids; phenol derivatives, e.g., bisphenol; urea
derivatives; metal-containing salicylic acid based compounds;
metal-containing naphthoic acid based compounds; boron compounds;
quaternary ammonium salts; calixarenes; and resin based charge
control agents. Examples of positive charge control agents include
the following: nigrosine-modified compounds on the basis of
nigrosine, fatty acid metal salts, and the like; guanidine
compounds, imidazole compounds,
tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary
ammonium salts, e.g., tetrabutylammonium tetrafluoroborate, onium
salts which are analogues thereof, e.g., phosphonium salts, and
lake pigments thereof; triphenylmethane dyes and lake pigments
thereof (examples of laking agents include phosphotungstic acid,
phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid,
lauric acid, gallic acid, ferricyanides, and ferrocyanides); metal
salts of higher fatty acids; diorganotin oxides, e.g., dibutyltin
oxide, dioctyltin oxide, and dicyclohexyltin oxide; diorganotin
borates, e.g., dibutyltin borate, dioctyltin borate, and
dicyclohexyltin borate; and resin based charge control agents. They
may be used alone or in combination.
[0071] Most of all, salicylic acid based metal compounds can be
used as the charge control agent, and furthermore, aluminum or
zirconium can be employed as the metal thereof. In particular,
aluminum salicylate compounds can be used as the charge control
agent. The content of the charge control agent is preferably 0.01
parts by mass or more and 20.00 parts by mass or less relative to
100 parts by mass of binder resin, and more preferably 0.50 parts
by mass or more and 10.00 parts by mass or less.
[0072] Besides the above described silica particles, other
inorganic fine powders can be externally added in order to improve
the charge stability, developability, the fluidity, the
transferability, and the like. Examples of other fine particles
include metal oxides, e.g., silica, alumina, and titania, and
compound oxides thereof and fluorocarbon. At least two types of
them may be used in combination. In particular, silica, alumina,
titania, and compound oxides thereof can be used because the
fluidity and the chargeability of the toner are maintained
favorably and adsorption performance with respect to toner
particles is high.
[0073] The inorganic fine powder used besides the above described
silica particles has an average primary particle diameter of
preferably 5 nm or more and 70 nm or less. In the case where the
average primary particle diameter of the inorganic fine powder is
within the above described range, good fluidity and chargeability
of the toner can be maintained over a long term.
[0074] Method for Measuring Average Primary Particle Diameter of
Inorganic Fine Powder
[0075] Regarding the average primary particle diameter of the
inorganic fine powder, the inorganic fine powder is observed with a
transmission electron microscope, and in a field of view magnified
by 30,000 to 50,000 times, an average value of major axes of 300
primary particles having major axes of 1 nm or more is calculated.
In this regard, in the case where sampled particles are small in
such a way that the particle diameter cannot be measured under a
magnification of 50,000 times, the photograph is further magnified
in such a way that the primary diameters become 5 mm or more, and
the measurement is performed.
[0076] The inorganic fine powder can be subjected to a
hydrophobizing treatment. The hydrophobizing treatment method and
the hydrophobizing agent are the same as those in the case where
the above described silica particles are subjected to the
hydrophobizing treatment.
[0077] The total amount of the silica particles and the inorganic
fine powder added to the toner is preferably 0.5 parts by mass or
more and 4.5 parts by mass or less, and more preferably 0.8 parts
by mass or more and 3.5 parts by mass or less relative to 100 parts
by mass of toner particles. In the case where the total amount of
the silica particles and the inorganic fine powder is within the
above described range, the fluidity of the toner is obtained
sufficiently, degradation in fogging and toner scattering
associated with reduction in chargeability of the toner can be
prevented.
[0078] Known external additives, e.g., charge control particles, an
abrasive, and a caking inhibitor, may be used besides the inorganic
fine powder. Examples of charge control particles include metal
oxides (tin oxide, titania, zinc oxide, alumina, antimony oxide,
and the like) and carbon black. Examples of abrasives include metal
oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium
oxide, chromium oxide, and the like), nitrides (silicon nitride and
the like), carbides (silicon carbide and the like), and meal salts
(calcium sulfate, barium sulfate, calcium carbonate, and the
like).
[0079] Furthermore, a lubricant may also be used in order to reduce
contamination of the members. Examples of lubricants include
fluorine based resin powders (polyvinylidene fluoride,
polytetrafluoroethylene, and the like) and fatty acid metal salts
(zinc stearate, calcium stearate, and the like). Among those
described above, zinc stearate can be used. The amount of addition
of these charge control particles, abrasive, caking inhibitor, and
the like (excluding the silica particles and the above described
inorganic fine powder) is preferably 0.01 parts by mass or more and
2.50 parts by mass or less, and more preferably 0.10 parts by mass
or more and 2.00 parts by mass or less relative to 100 parts by
mass of toner particles.
[0080] The toner according to the present invention may be used for
any one of a high-speed system, oilless fixing, a cleaner-less
system, and a developing system in which carriers degraded through
a long term of use in a developing device are recovered
sequentially and fresh carriers are supplied. Moreover, the toner
can be applied to known image forming methods by using a
one-component developing system or a two-component developing
system. In particular, the toner according to the present invention
has very good transferability and, therefore, can be used in an
image forming method including an intermediate transfer body and an
image forming method including a cleaner-less system regardless of
the one-component developing system or the two-component developing
system.
[0081] The toner according to the present invention may be used as
a two-component system developing agent with respect to either full
color or monochrome.
EXAMPLES
Production Example of Silica Particles 1
[0082] A 3-liter glass reactor provided with an agitator, a
dropping funnel, and a thermometer was charged with 589.6 g of
methanol, 42.0 g of water, and 47.1 g of 28% by mass ammonia water,
followed by mixing. The resulting solution was adjusted to become
35.degree. C., and addition of 1,100.0 g (7.23 mol) of
tetramethoxysilane and 395.2 g of 5.4% by mass ammonia water was
started at the same time under agitation. Tetramethoxysilane was
dropped over 6 hours and ammonia water was dropped over 5 hours.
After the dropping was completed, agitation was continued for
further 0.5 hours to effect hydrolysis, so that a methanol-water
dispersion liquid of hydrophilic spherical sol-gel silica fine
particles was obtained. Subsequently, an ester adaptor and a
cooling tube were attached to the glass reactor and the above
described dispersion liquid was dried at 80.degree. C. under
reduced pressure sufficiently. The resulting silica particles were
heated in a constant temperature bath at 400.degree. C. for 10
minutes.
[0083] The above described step was performed several tens of
times, and the resulting silica particles were subjected to a
disintegration treatment with Pulverizer (produced by Hosokawa
Micron Corporation).
[0084] Thereafter, 500 g of silica particles were charged into a
polytetrafluoroethylene internal cylinder type stainless steel
autoclave having an internal volume of 1,000 ml. The inside of the
autoclave was substituted with nitrogen and, then, 0.5 g of
hexamethyldisilazane (HMDS) and 0.1 g of water made into a fog with
a two-fluid nozzle were blown on the silica particles uniformly
while an agitation blade attached to the autoclave was rotated at
400 rpm. After agitation was performed for 30 minutes, the
autoclave was sealed and heated at 200.degree. C. for 2 hours.
Subsequently, the inside of the system was decompressed while
heating was continued, so that a deammoniation treatment was
performed to obtain Silica particles 1. The properties of Silica
particles 1 are shown in Table 1.
Production Examples of Silica Particles 2 to 4
[0085] Regarding the production example of Silica particles 1, the
amount of methanol used at an initial stage was changed to 530.6 g,
634.0 g, and 737.3 g, respectively. Furthermore, the dropping time
of tetramethoxysilane was changed to 7 hours, 6 hours, and 5 hours,
respectively, and the dropping time of the 5.4% by mass ammonia
water was changed to 6 hours, 5 hours, and 4 hours, respectively.
The volume average particle diameter (Dv) of the silica particles
and the variation coefficient of diameters of the silica particles,
based on volume distribution thereof, were adjusted by the above
described operation. Moreover, in the surface treatment with HMDS,
the amounts of HMDS and water were adjusted in such a way that the
amount of carbon became the same as the amount of Silica particles
1 and, thereby, Silica particles 2 to 4 were obtained. The
properties of Silica particles 2 to 4 are shown in Table 1.
Production Examples of Silica Particles 5 to 7
[0086] Regarding the production example of Silica particles 1, the
amount of methanol used at an initial stage was changed to 491.3 g,
360.1 g, and 294.8 g, respectively. Furthermore, the dropping time
of tetramethoxysilane was changed to 7 hours, 5.5 hours, and 5
hours, respectively, and the dropping time of the 5.4% by mass
ammonia water was changed to 6 hours, 4.5 hours, and 4 hours,
respectively. The volume average particle diameter (Dv) of the
silica particles and the variation coefficient of diameters of the
silica particles, based on volume distribution thereof, were
adjusted by the above described operation. Moreover, in the surface
treatment with HMDS, the amounts of HMDS and water were adjusted in
such a way that the amount of carbon became the same as the amount
of Silica particles 1 and, thereby, Silica particles 5 to 7 were
obtained. The properties of Silica particles 5 to 7 are shown in
Table 1.
Production Examples of Silica Particles 8 to 11
[0087] Regarding the production example of Silica particles 1, the
dropping time of tetramethoxysilane was changed to 6 hours, 5
hours, 3.5 hours, and 2 hours, respectively, and the dropping time
of the 5.4% by mass ammonia water was changed to 5 hours, 4 hours,
3 hours, and 2 hours, respectively. The volume average particle
diameter (Dv) of the silica particles and the variation coefficient
of diameters of the silica particles, based on volume distribution
thereof, were adjusted by the above described operation. Moreover,
in the surface treatment with HMDS, the amounts of HMDS and water
were adjusted in such a way that the amount of carbon became the
same as the amount of Silica particles 1 and, thereby, Silica
particles 8 to 11 were obtained. The properties of Silica particles
8 to 11 are shown in Table 1.
Production Examples of Silica Particles 12 to 15
[0088] Regarding the production example of Silica particles 1, the
time of heating in the constant temperature bath at 400.degree. C.
was changed to 9 minutes, 8 minutes, 3.2 minutes, and 1.4 minutes,
respectively. The ratio of mass decrease when heating from
105.degree. C. to 200.degree. C. was performed was adjusted and,
thereby, Silica particles 12 to 15 were obtained. The properties of
Silica particles 12 to 15 are shown in Table 1.
Production Example of Silica Particles 16
[0089] Silica particles (fumed silica) having a volume average
particle diameter (Dv) of 92 nm were produced by a combustion
method. The variation coefficient of diameters of the silica
particles, based on volume distribution thereof, was 35%. The
particles were classified and, thereby, silica particles having a
volume average particle diameter (Dv) of 85 nm and a variation
coefficient of diameters of particles, based on volume distribution
thereof, of 21% were obtained. The particles were surface-treated
with HMDS in the same manner as that for Silica particles 1, so as
to obtain Silica particles 16. The properties of Silica particles
16 are shown in Table 1.
Production Example of Silica Particles 17
[0090] Silica particles having a volume average particle diameter
(Dv) of 150 nm ware produced from metal silicon serving as a raw
material through deflagration on the basis of the method described
in Japanese Patent Laid-Open No. 60-255602. The variation
coefficient of diameters of the silica particles, based on volume
distribution thereof, was 30%. The particles were classified and,
thereby, silica particles having a volume average particle diameter
(Dv) of 120 nm and a variation coefficient of diameters of
particles, based on volume distribution thereof, of 21% were
obtained. The particles were surface-treated with HMDS in the same
manner as that for Silica particles 1, so as to obtain Silica
particles 17. The properties of Silica particles 17 are shown in
Table 1.
Production Examples of Silica Particles 18 and 19
[0091] Regarding the production example of Silica particles 1, the
heating temperature in the surface treatment with HMDS was adjusted
in such a way that the fixing ratio became 90% and 86%,
respectively, so as to obtain Silica particles 18 and 19. The
properties of Silica particles 18 and 19 are shown in Table 1.
Production Example of Silica Particles 20
[0092] Regarding the production example of Silica particles 1, the
amounts of HMDS and water in the surface treatment with HMDS were
changed to 0.80 g and 0.15 g, respectively, so as to obtain Silica
particles 20. The properties of Silica particles 20 are shown in
Table 1.
Production Example of Silica Particles 21
[0093] Regarding the production example of Silica particles 1, the
amounts of HMDS and water in the surface treatment with HMDS were
changed to 10.00 g and 1.50 g, respectively, so as to obtain Silica
particles 21. The properties of Silica particles 21 are shown in
Table 1.
Production Example of Silica Particles 22
[0094] Regarding the production example of Silica particles 1, the
amounts of HMDS and water in the surface treatment with HMDS were
changed to 50.00 g and 7.50 g, respectively, so as to obtain Silica
particles 22. The properties of Silica particles 22 are shown in
Table 1.
Production Example of Silica Particles 23
[0095] Regarding the production example of Silica particles 1, the
amounts of HMDS and water in the surface treatment with HMDS were
changed to 65.00 g and 9.50 g, respectively, so as to obtain Silica
particles 23. The properties of Silica particles 23 are shown in
Table 1.
Production Example of Silica Particles 24
[0096] Regarding the production example of Silica particles 1, the
surface treatment with HMDS was not performed and the time of
heating in the constant temperature bath at 400.degree. C. was
changed to 15 minutes. Silica particles 24 were obtained as in the
production example of Silica particles 1 except those described
above. The properties of Silica particles 24 are shown in Table
1.
TABLE-US-00001 TABLE 1 Volume Variation coefficient of average
diameter of particles, Ratio of Fixing ratio of Amount of Silica
particle based on volume mass Production hydrophobizing carbon (%
particles diameter (nm) distribution (%) decrease (%) method agent
(%) by mass) Silica 100 9 0.01 sol-gel 95 0.05 particles 1 method
Silica 80 9 0.01 sol-gel 94 0.05 particles 2 method Silica 70 10
0.01 sol-gel 93 0.05 particles 3 method Silica 60 18 0.01 sol-gel
94 0.05 particles 4 method Silica 200 9 0.01 sol-gel 95 0.05
particles 5 method Silica 500 13 0.01 sol-gel 93 0.05 particles 6
method Silica 600 21 0.01 sol-gel 92 0.05 particles 7 method Silica
100 10 0.01 sol-gel 94 0.05 particles 8 method Silica 190 15 0.01
sol-gel 95 0.05 particles 9 method Silica 200 23 0.01 sol-gel 95
0.05 particles 10 method Silica 200 27 0.01 sol-gel 92 0.05
particles 11 method Silica 100 9 0.02 sol-gel 91 0.05 particles 12
method Silica 100 9 0.10 sol-gel 93 0.05 particles 13 method Silica
100 9 0.60 sol-gel 95 0.05 particles 14 method Silica 100 9 0.90
sol-gel 94 0.05 particles 15 method Silica 85 21 0.14 fuming 91
0.05 particles 16 method Silica 120 21 0.06 deflagration 91 0.05
particles 17 method Silica 100 9 0.01 sol-gel 90 0.05 particles 18
method Silica 100 9 0.01 sol-gel 86 0.05 particles 19 method Silica
100 9 0.01 sol-gel 93 0.08 particles 20 method Silica 100 9 0.01
sol-gel 91 1.0 particles 21 method Silica 100 9 0.01 sol-gel 91 4.5
particles 22 method Silica 100 9 0.01 sol-gel 90 6.2 particles 23
method Silica 100 9 0 sol-gel untreated -- particles 24 method
Production Example of Charge Control Resin 1
[0097] A pressurizable reaction container provided with a reflux
tube, an agitator, a thermometer, a nitrogen introduction tube, a
dropping device, and a decompression device is charged with 250
parts by mass of methanol, 150 parts by mass of 2-butanone, and 100
parts by mass of 2-propanol, which are solvents, and 77 parts by
mass of styrene, 15 parts by mass of 2-ethylhexyl acrylate, and 8
parts by mass of 2-acrylamide-2-methylpropane sulfonic acid, which
are monomers, and was heated to a reflux temperature under
agitation. A solution, in which 1 part by mass of
t-butylperoxy-2-ethylhexanoate serving as a polymerization
initiator was diluted with 20 parts by mass of 2-butanone, was
dropped over 30 minutes and agitation was continued for 5 hours.
Furthermore, the solution, in which 1 part by mass of
t-butylperoxy-2-ethylhexanoate was diluted with 20 parts by mass of
2-butanone, was dropped over 30 minutes, agitation was performed
for 5 hours, and polymerization was terminated. While the
temperature was maintained, 500 parts by mass of deionized water
was added, and agitation was performed at 80 to 100 revolutions per
minute for 2 hours in such a way that the interface between an
organic layer and a water layer was not disturbed. After the layers
were separated by being stood for 30 minutes, the water layer was
removed, and anhydrous sodium sulfate was added to the organic
layer, so as to dehydrate. Subsequently, the polymerization
solvents were removed through distillation under reduced pressure,
and the resulting polymer was coarsely pulverized into 100 .mu.m or
less by using a cutter mill equipped with a 150 mesh screen. The
resulting Charge control resin 1 containing a sulfur atom had Tg of
58.degree. C., Mp of 13,000, and Mw of 30,000.
Production Example of Toner Particles 1
[0098] With respect to 100 parts by mass of styrene monomer, 16.5
parts by mass of C. I. Pigment Blue 15:3 and 3.0 parts by mass of
aluminum compound of di-tert-butylsalicylic acid (Bontron E-88
produced by Orient Chemical Industries, Ltd.) were prepared. They
were introduced into an attritor (produced by MITSUI MINING
COMPANY, LIMITED), and agitation was performed at 25.degree. C. for
180 minutes by using zirconia beads having a radius of 1.25 mm (140
parts by mass) at 200 rpm, so that Master batch dispersion liquid 1
was prepared.
[0099] Meanwhile, 450 parts by mass of 0.1 M-Na.sub.3PO.sub.4
aqueous solution was put into 710 parts by mass of ion-exchanged
water, the temperature was raised to 60.degree. C., and 67.7 parts
by mass of 1.0 M-CaCl.sub.2 aqueous solution was added gradually,
so that an aqueous medium containing a calcium phosphate compound
was obtained.
TABLE-US-00002 Master batch dispersion liquid 1 40 parts by mass
Styrene monomer 28 parts by mass n-Butyl acrylate monomer 18 parts
by mass Low-molecular weight polystyrene 20 parts by mass (Mw =
3,000, Mn = 1,050, Tg = 55.degree. C.) Hydrocarbon based wax 9
parts by mass (Fischer-Tropsch wax, peak temperature of maximum
endothermic peak = 78.degree. C., Mw = 750) Charge control resin 1
0.3 parts by mass Polyester resin 5 parts by mass
[0100] (Polycondensate of terephthalic acid:isophthalic acid:
propylene oxide-modified bisphenol A (2 mol adduct):ethylene
oxide-modified bisphenol A (2 mol adduct)=30:30:30:10, acid value
11 mgKOH/g, Tg=74.degree. C., Mw=11,000, Mn=4,000)
[0101] The above described materials were heated to 65.degree. C.,
and were dissolved and dispersed homogeneously with TK type
Homomixer (produced by Tokushu Kika Kogyou Co., Ltd.) at 5,000 rpm.
A polymerizable monomer composition was prepared by dissolving 7.1
parts by mass of 70% toluene solution of
1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate serving as a
polymerization initiator into the dispersion liquid.
[0102] The above described polymerizable monomer composition was
put into the above described aqueous medium, and agitation was
performed at a temperature of 65.degree. C. for 10 minutes in a
N.sub.2 atmosphere with TK type Homomixer at 10,000 rpm, so as to
granulate the polymerizable monomer composition. Thereafter, the
temperature was raised to 67.degree. C. while agitation was
performed with a paddle agitation blade, and when the degree of
polymerization conversion of the polymerizable vinyl based monomer
reached 90%, 0.1 mol/l sodium hydroxide aqueous solution was added
to adjust the pH of the aqueous dispersion medium to 9.
Furthermore, the temperature was raised to 80.degree. C. at a
temperature increase rate of 40.degree. C./h and the reaction was
effected for 4 hours. After the polymerization was terminated,
remaining monomers of toner particles for supply were removed
through distillation under reduced pressure. The aqueous medium was
cooled and, subsequently, hydrochloric acid was added to adjust the
pH to 1.4, and calcium phosphate was dissolved by performing
agitation for 6 hours. Toner particles were separated through
filtration and were washed with water. Then, drying was performed
at a temperature of 40.degree. C. for 48 hours. Regarding the
resulting dried product, ultrafine powders and coarse powders were
precisely classified and removed with a multi-division classifier
(Elbow-Jet Classifier produced by Nittetsu Mining Co., Ltd.) at the
same time, so that cyan Toner particles 1 having a weight average
particle diameter (D4) of 6.3 .mu.m was obtained.
Example 1
[0103] Toner 1 was obtained by dry-mixing 1.5 parts by mass of
Silica particles 1 and 0.2 parts by mass of rutile-type titanium
dioxide fine powder surface-treated with dimethyl silicone oil
(average primary particle diameter: 30 nm) relative to 100 parts by
mass of Toner particles 1 for 5 minutes with Henschel mixer
(produced by MITSUI MINING COMPANY, LIMITED). Then, Toner 1 was
evaluated as described below. The evaluation results are shown in
Table 2.
[0104] Image Output Test
[0105] A printer LBP-7200C produced by CANON KABUSHIKI KAISHA was
used, and images were evaluated in various environments. In this
regard, LBP 7200C is a system which does not have a cleaning member
in an intermediate transfer unit portion and which recovers
remaining toners of primary and secondary transfer with a cleaning
member in a photo conductor unit. A cartridge filled with 70 g of
Toner 1 was mounted on the cyan station of the above described
printer, dummy cartridges were mounted on other stations, and an
image output test was performed.
[0106] Images were evaluated in each of environments of 15.degree.
C./10% Rh (low-temperature low-humidity environment) and
32.5.degree. C./90% Rh (high-temperature high-humidity
environment). In each environment, an operation to output an image
with a coverage of 1% was repeated, and every time the number of
the output sheets reached 200, standing was performed for a week in
each environment. Thereafter, the step to output 200 sheets in the
above described manner was repeated, and finally 4,600 sheets were
output. Then, an evaluation was performed by a method as described
below.
[0107] (1) Evaluation of Fogging
[0108] In the above described image output test, every time after
standing for a week, one sheet of image having a white background
portion was output. Subsequently, regarding every image having a
white background portion, the fogging concentration (%) (=Dr (%)-Ds
(%)) was calculated from the difference between the degree of
whiteness (reflectance Ds (%)) of the white background portion of
the image having a white background portion and the degree of
whiteness (average reflectance Dr (%)) of transfer paper. In this
regard, the degree of whiteness was measured with "REFLECTMETER
MODEL TC-6DS" (produced by Tokyo Denshoku Co., Ltd.). As for the
filter, the Amberlite filter was used. The fogging concentrations
were ranked as described below. A, B, and C are acceptable levels
in the present invention.
A: The fogging concentration is less than 0.3%. B: The fogging
concentration is 0.3% or more and less than 0.8%. C: The fogging
concentration is 0.8% or more and less than 1.3%. D: The fogging
concentration is 1.3% or more.
[0109] (2) Stability of Image Density
[0110] The image density was measured with a color reflection
densitometer (X-RITE 404 produced by X-Rite). In the above
described image output test, every time after standing for about
one week, one sheet of solid image was output, and the density of
each image was measured. Among the resulting image densities, the
difference between the maximum density and the minimum density was
determined and was evaluated on the basis of the criteria described
below.
A: The image density difference is 0.1 or less. B: The image
density difference is more than 0.1 and 0.3 or less. C: The image
density difference is more than 0.3 and 0.5 or less. D: The image
density difference is more than 0.5.
[0111] (3) Thin Line Reproducibility
[0112] The thin line reproducibility was evaluated from the
viewpoint of image quality. In the above described image output
test, after 4,600 sheets of images were output, an image in which a
lattice pattern with a line width of 3 pixels was drawn all over an
A4 paper (coverage of 4% on a volume basis) was printed, and the
thin line reproducibility was evaluated on the basis of the
criteria described below. The line width of 3 pixels are 127 .mu.m
theoretically. The line width of the image was measured with
Microscope VK-8500 (produced by KEYENCE CORPORATION). The line
widths at 5 points selected at random were measured, the maximum
value and the minimum value were excluded, and when an average
value of the remaining 3 points was represented by d (.mu.m), the
thin line reproducibility index L was defined as described
below.
L(.mu.m)=|127-d|
[0113] The thin line reproducibility index L is defined as the
difference between the theoretical line width of 127 .mu.m and the
line width d in the output image. The absolute value of the
difference is employed in the definition because d may be larger
than 127 or be smaller than 127. Smaller L indicates that the thin
line reproducibility is excellent.
A: L is 0 .mu.m or more and less than 5 .mu.m (thin line
reproducibility is excellent). B: L is 5 .mu.m or more and less
than 15 .mu.m, and slight variations in the width of thin line are
observed (thin line reproducibility is good). C: L is 15 .mu.m or
more and less than 30 .mu.m, and thinning and scattering of thin
line are conspicuous. D: L is 30 .mu.m or more and breakage or
thickening of thin line is observed in places (thin line
reproducibility is poor).
Examples 2 and 3, comparative Example 1
[0114] Toners 2 to 4 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 2 to 4,
respectively, in Example 1. Then, Toners 2 to 4 were evaluated as
in Example 1. The results of evaluation are shown in Table 2. As is
clear from the results, regarding Comparative example 1, the
stability of image density and the thin line reproducibility (image
quality) were degraded. The reason for this is estimated that the
volume average particle diameter (Dv) of the silica particles was
too small and, thereby, the silica particles were not able to exert
the effect as the spacer particles on the toner surfaces, so as to
degrade the transferability.
Examples 4 and 5, Comparative Example 2
[0115] Toners 5 to 7 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 5 to 7,
respectively, in Example 1. Then, Toners 5 to 7 were evaluated as
in Example 1. The results of evaluation are shown in Table 2. As is
clear from the results, regarding Comparative example 2, all items
were degraded in evaluation. The reason for this is estimated that
the volume average particle diameter (Dv) of the silica particles
was too large and, thereby, the silica particles were eliminated
from the toner particle surfaces easily in a long term of use, and
stable chargeability and fluidity were not given to the toner
continuously.
Examples 6 to 8, Comparative Example 3
[0116] Toners 8 to 11 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 8 to 11,
respectively, in Example 1. Then, Toners 8 to 11 were evaluated as
in Example 1. The results of evaluation are shown in Table 2. As is
clear from the results, regarding Comparative example 3, in
particular the thin line reproducibility (image quality) was
degraded. The reason for this is believed to be that there were
large variations in size of the silica particles, the individual
particles became difficult to function as spacer particles
efficiently and, thereby, the transferability was degraded.
Furthermore, the reason is estimated that differences among the
individual particles occurred in giving the chargeability and the
fluidity to the toner, distribution of charge was extended, so as
to degrade fogging and the like and, thereby stable chargeability,
fluidity, and transferability were not ensured over a long
term.
Examples 9 to 11, Comparative Example 4
[0117] Toners 12 to 15 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 12 to 15,
respectively, in Example 1. Then, Toners 12 to 15 were evaluated as
in Example 1. The results of evaluation are shown in Table 2. As is
clear from the results, regarding Comparative example 4, all items
were degraded in evaluation with respect to high-temperature and
high-humidity. The reason for this is estimated that the ratio of
mass decrease of Silica particles 15 was large and, thereby the
amount of silanol groups was large, a large amount of water was
adsorbed, the degrees of giving of the chargeability and the
fluidity to the toner were degraded significantly, and stable
developability and transferability were not obtained.
Examples 12 and 13
[0118] Toners 16 and 17 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 16 and 17,
respectively, in Example 1. Then, Toners 16 and 17 were evaluated
as in Example 1. The results of evaluation are shown in Table 2. As
is clear from the results, the thin line reproducibility (image
quality) was degraded slightly. The reason for this is believed to
be that the silica particles were obtained by a fuming method or a
deflagration method, the variation coefficient of diameters of the
silica particles, based on volume distribution thereof, is large as
compared with the silica particles obtained by a sol-gel method
and, thereby, the individual particles became difficult to function
as spacer particles efficiently and the transferability was
degraded slightly. Furthermore, the reason is estimated that
differences among the individual particles occurred slightly in
giving the chargeability and the fluidity to the toner and,
thereby, distribution of charge was extended, so as to degrade
fogging and the like slightly.
Examples 14 and 15
[0119] Toners 18 and 19 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 18 and 19,
respectively, in Example 1. Then, Toners 18 and 19 were evaluated
as in Example 1. The results of evaluation are shown in Table 2. As
is clear from the results, regarding Example 15, fogging and the
thin line reproducibility (image quality) were degraded slightly
with respect to high-temperature and high-humidity. The reason for
this is estimated that the fixing ratio of the hydrophobizing agent
of Silica particles 19 was low and, thereby, in a long term of use,
the hydrophobizing agent was isolated from the silica particles
because of the stress in the developing device, and stable
hydrophobicity and fluidity were not obtained.
Examples 16 to 19
[0120] Toners 20 to 23 were produced as in Example 1 except that
Silica particles 1 was changed to Silica particles 20 to 23,
respectively, in Example 1. Then, Toners 20 to 23 were evaluated as
in Example 1. The results of evaluation are shown in Table 2. As is
clear from the results, regarding Example 19, all items were
degraded in evaluation with respect to high-temperature and
high-humidity. The reason for this is estimated that the amount of
surface treatment of the silica particles with the hydrophobizing
agent was large, the degree of giving of the fluidity to the toner
was reduced slightly, the start-up of charging of the toner was
delayed slightly and, thereby, when the image was output after a
long term of standing, fogging and the transferability were
degraded slightly.
Example 20
[0121] Toner 24 was produced as in Example 1 except that Silica
particles 1 was changed to Silica particles 24 in Example 1. Then,
Toner 24 was evaluated as in Example 1. The results of evaluation
are shown in Table 2. As is clear from the results, good results
were obtained.
TABLE-US-00003 TABLE 2 Low-temperature low-humidity environment
High-temperature high-humidity environment Fogging Stability of
image Thin line Fogging Stability of image Thin line (measured
density (measured reproducibility (measured density (measured
reproducibility Toner Silica particles value) value) (measured
value) value) value) (measured value) Example 1 Toner 1 Silica
particles 1 A(0.1) A(0.1) A(3) A(0.1) A(0.1) A(3) Example 2 Toner 2
Silica particles 2 A(0.2) A(0.1) A(4) A(0.2) A(0.1) A(4) Example 3
Toner 3 Silica particles 3 B(0.5) B(0.2) C(18) B(0.4) B(0.2) C(17)
Comparative Toner 4 Silica particles 4 C(1.0) D(0.7) D(31) C(0.7)
D(0.5) D(30) example 1 Example 4 Toner 5 Silica particles 5 A(0.2)
A(0.1) A(4) A(0.2) A(0.1) A(4) Example 5 Toner 6 Silica particles 6
B(0.8) C(0.4) C(19) B(0.5) C(0.4) C(22) Comparative Toner 7 Silica
particles 7 D(1.8) D(0.6) D(30) D(1.5) D(0.5) D(32) example 2
Example 6 Toner 8 Silica particles 8 A(0.2) A(0.1) A(4) A(0.2)
A(0.1) A(4) Example 7 Toner 9 Silica particles 9 B(0.4) B(0.2) B(8)
B(0.5) B(0.2) B(9) Example 8 Toner 10 Silica particles 10 B(0.6)
B(0.3) C(16) C(1.0) B(0.3) C(18) Comparative Toner 11 Silica
particles 11 C(1.3) C(0.5) D(30) D(1.8) C(0.4) D(31) example 3
Example 9 Toner 12 Silica particles 12 A(0.2) A(0.1) A(4) A(0.2)
A(0.1) A(4) Example 10 Toner 13 Silica particles 13 B(0.3) B0.3)
B(5) B(0.4) B(0.2) B(7) Example 11 Toner 14 Silica particles 14
B(0.8) C(0.4) B(12) C(0.9) C(0.4) B(14) Comparative Toner 15 Silica
particles 15 C(1.2) D(0.7) C(29) D(1.6) D(0.6) D(33) example 4
Example 12 Toner 16 Silica particles 16 B(0.8) B(0.3) C(23) C(0.9)
B(0.3) C(27) Example 13 Toner 17 Silica particles 17 B(0.8) B(0.3)
C(22) C(0.9) B(0.3) C(24) Example 14 Toner 18 Silica particles 18
B(0.4) B(0.2) B(7) B(0.7) B(0.2) B(6) Example 15 Toner 19 Silica
particles 19 B(0.8) B(0.3) C(16) C(1.0) B(0.3) C(23) Example 16
Toner 20 Silica particles 20 A(0.2) A(0.1) A(4) A(0.2) A(0.1) A(4)
Example 17 Toner 21 Silica particles 21 B(0.3) B(0.2) B(6) B(0.3)
B(0.2) B(8) Example 18 Toner 22 Silica particles 22 B(0.5) C(0.4)
B(8) C(0.8) B(0.3) B(12) Example 19 Toner 23 Silica particles 23
B(0.7) C(0.4) B(12) C(1.1) C(0.4) C(17) Example 20 Toner 24 Silica
particles 24 A(0.2) A(0.1) B(5) A(0.2) A(0.1) B(5)
[0122] While the present invention has been described with
reference to exemplary embodiments, it is to be understood that the
invention is not limited to the disclosed exemplary embodiments.
The scope of the following claims is to be accorded the broadest
interpretation so as to encompass all such modifications and
equivalent structures and functions.
[0123] This application claims the benefit of Japanese Patent
Application No. 2010-251905 filed Nov. 10, 2010, which is hereby
incorporated by reference herein in its entirety.
* * * * *