JP2000221783A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method in which good low-temperature fixability is exhibited, an image faithful to a latent image is continuously obtained over a long period of time and image running is not caused even at high temperature and high humidity. SOLUTION: An electrostatic charge image formed on an electrostatic charge image carrier 1 is developed with a toner 13 to form a toner image, this toner image is transferred from the electrostatic charge image carrier to a transfer material P optionally through an interim transfer body and the remaining toner on the electrostatic charge image carrier is removed using a cleaning blade 8. The toner has toner particles containing at least a bonding resin, a wax and a colorant and an inorganic fine powder. The bonding resin contains a vinyl resin, a polyester resin and a hybrid resin component having vinyl polymer units and polyester units and also contains a certain amount of a component having composition selectively soluble in specified plural solvents and molecular weights. The toner and the cleaning blade have specified viscoelastic characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic latent image
Forming method and image forming using toner for making
Related to the device. [0002] 2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
No. 7,691 and Japanese Patent Publication No. 42-23910
And Japanese Patent Publication No. 43-24748.
Numerous methods are known. Generally, photoconductive materials are used.
To form an electrostatic charge image on the photoreceptor by various means,
Next, the electrostatic image is developed using toner, and if necessary,
After transferring the toner image to a transfer material such as paper, heat and pressure
Fixing to transfer material by force, heat and pressure or solvent vapor
To obtain a ner image. [0003] In the above-mentioned final step, a toner image is transferred to a transfer material.
Various methods and equipment are used for the process of fixing to a sheet as
Has been developed. Currently the most common method is a heat roller
-Or pressure bonding with a fixed heating heater via a heat-resistant film
It is a heating method. [0004] The compression heating method using a heating roller is a toner heating method.
The surface of the heat roller and the sheet to be fixed
Sheet to be fixed while the toner image surface of
Fix the toner image by passing
It is. This method uses the surface of the heat roller and the sheet to be fixed.
Because the upper toner image contacts under pressure, the toner image
Has very good thermal efficiency when fusing
Yes, it can fix quickly. [0005] The surface of the heating roller and the toner image are in a molten state.
Part of the toner image is fixed
Is transferred to the next sheet to be fixed
The so-called offset current that retransfers and stains the sheet to be fixed
The elephant is greatly affected by the fixing speed and the fixing temperature. General
If the fixing speed is low, the surface temperature of the heating roller
If the setting is relatively low and the fixing speed is high,
The surface temperature is set relatively high. This is the toner
Of heat applied to toner from heated roller to fix toner
Is made substantially constant regardless of the fixing speed. The toner image on the sheet to be fixed has several layers.
Because the toner layer is formed, the fixing speed is particularly fast,
In systems where the surface temperature of the roller is high, use a heating roller.
The toner layer in contact with
The temperature difference from the lower toner layer becomes large. Therefore,
If the surface temperature of the heating roller is high,
Is a high-temperature offset that causes the transfer to the heating roller.
If the surface temperature of the heating roller is low due to
In this case, the toner in the lowermost layer does not melt
The phenomenon of low-temperature offset due to toner not fixing on the sheet
Easy to come. In order to solve this problem, the fixing speed is increased.
The fixing pressure, raise the toner
Anchoring is usually done.
With this method, the heating roller temperature can be reduced to some extent.
To prevent high temperature offset phenomenon of the uppermost toner layer
Becomes possible. However, the shearing force on the toner is very
The sheet to be fixed wraps around the fixing roller
So-called winding offset phenomenon
Used to separate the sheet to be fixed from the fixing roller.
After separation of the used separation nail, it is easy to appear on the fixed image. Sa
Because of the high pressure, the line image
The toner image may be crushed,
Image quality is likely to deteriorate. [0008] Conventionally, as binder resin for toner,
Vinyl copolymers such as tere resin and styrene resin
Mainly used. Polyester resin has excellent low-temperature fixability
Although it has the function, the offset phenomenon at high temperature is
It has a problem that it easily occurs. This problem
To compensate, increase the molecular weight of the polyester resin
Attempts have been made to improve the
There is a problem that the thermal fixability is impaired.
The pulverizability at the time of manufacturing is also deteriorated, and fine particles of toner
The binder resin becomes unsuitable for densification. [0010] Vinyl copolymers such as styrene resins
Has excellent pulverizability during toner production,
Therefore, it has excellent hot offset resistance, but low temperature fixability.
Low molecular weight or glass transition temperature to improve
Lowering the blocking resistance and developability deteriorate.
There was a problem that. Utilizing the advantages of these two resins effectively
Mix these resins to make up for the shortcomings
Several methods are being considered. For example, Japanese Patent Application Laid-Open No. 54-114245
Now, we mixed the polyester resin and vinyl copolymer
A toner containing a resin is disclosed. However
Et al., Polyester resin and vinyl copolymer are chemically
Poor compatibility due to greatly different structure, low-temperature fixability,
Satisfies all high-temperature offset resistance and blocking resistance
It is difficult to do. Further, various toners added at the time of toner production are
It is difficult to uniformly disperse additives, especially wax, and
Not only fixing performance, but also developability tends to cause problems.
In particular, this is particularly true for toners that have become finer in recent years.
The problem becomes noticeable. JP-A-56-116043 and JP-A-56-16043
JP-A-58-159546 discloses a polyester resin.
Contains a polymer obtained by polymerizing a monomer in the presence of
Are disclosed. JP-A-58-102246 and JP-A-58-102246
JP-A-1-156759 discloses an unsaturated polyester compound.
Polymer obtained by polymerizing a vinyl copolymer in the presence of
There is disclosed a toner characterized by having. In Japanese Patent Publication No. Hei 8-16796, a specific
Polyester resin with acid value and specific acid value and molecular weight
Copolymerization of esterified styrene resin
Discloses a toner characterized by containing a body
You. In Japanese Patent Application Laid-Open No. Hei 8-54553, a binding tree
The fat consists of polycondensation resin and vinyl resin,
Has peaks in roloform insolubles and specific molecular weight range
There is disclosed a toner characterized by the following. In the above-mentioned binder resin, the condensation polymerization resin is added
It can maintain a stable phase separation state with the polymer resin.
Wear. However, toners using these binder resins are resistant to
High-temperature offset properties are improved to some extent, but low toner
Thermal fixability is still insufficient, toner contains wax
It is difficult to control the dispersion of wax
It is difficult. In the case of toner, not only low-temperature fixability
And still have issues to be improved in developability.
You. JP-A-62-195681 and JP-A-62-195681
JP-A-62-195682 discloses that a vinyl-based resin is
Vinyl resin contained in specific amount relative to steal resin
Related to electrophotographic developer compositions composed of polyester resin
It has been described. However, these electrophotographic developers
The binder resin used in the composition is a polyester resin.
A mixture of vinyl resin dispersed and mixed with
Satisfies low-temperature fixability and high-temperature offset resistance
It is difficult. In recent years, digital copying machines
Multi-function copiers and cores
There is a demand for high-quality p-images. But fine particles
Colorant relatively contained in the toner
(Magnetic material) to maintain low-temperature fixability of toner
Is difficult, and the strictness of the developing property is more severe than before.
Will receive about. Further, as an approach to environmental issues,
For high-speed machines, heat-resistant filters that require little residual heat or heat storage
To reduce power consumption by a crimping heating method using
In high-speed copying machines,
Roller wattage down to reduce power consumption
It is also important to design the main unit from the viewpoint of energy saving.
Is coming. The low-temperature fixability of the toner is reduced by
This is particularly noticeable in the connection part. This is a halftone picture
The amount of toner that forms an image on the sheet to be fixed is a solid image
Less for that of the department. In other words, in a solid image
Is not only the adhesion between toner and the sheet to be fixed, but also toner
ー Adhesion between each other acts as a synergistic effect,
Even if the toner can maintain the adhesion,
Low-temperature fixability for halftone images where
Is difficult to maintain. Use a heat-resistant film.
The pressure bonding heating method used for
In order to maintain the fixing performance, it is necessary to
It is necessary for low-temperature fixability in halftone images
Will be severe. As a countermeasure, the amount of heat supplied to the heater is reduced.
Raise the temperature rise problem in the non-paper passing area
Occurs. This is when A4 paper is fed vertically continuously.
When the paper passes continuously on the fixing member, heat is taken away
Therefore, to maintain the temperature required for fixing, the fixing heater
Becomes ON state. However, in the non-paper passing area, paper
Temperature rises due to heat storage. this
As a countermeasure, the body design that does not cause heater cracking etc.
Therefore, a toner that is resistant to high-temperature offset is required. Further, during the step of obtaining a toner image,
When the toner image is transferred to the transfer material,
Transfer residual toner exists. Prompt continuous copying
To remove the residual toner on the photoconductor,
I need to do it. If this cleaning is not enough
In this case, it causes various image defects. This cleanin
Magnetic brush cleaning, blade cleaning
Training or the like is used. In the cleaning method described above, the magnetic brush
In the brush cleaning method, the toner remaining on the photoreceptor
Is electrostatically adsorbed and collected on the cleaning material carrier.
Things. However, this method does not
Magnetic brush generated when the charge amount of the carrier
Problems such as toner scattering from the printer and poor cleaning
I have. As a method for solving these problems,
JP-A-5-88595 discloses that the cleaning material is charged.
How to change the rotation speed of the cleaning roller itself
A method for preventing toner scattering by a method has been proposed. Only
However, in this method, paper generated or adhered on the photoreceptor
Powder, ozone deposits and the like cannot be completely removed. Also, a cleaning method using a blade
In this method, the residual toner is scraped directly from the photoconductor surface.
For this reason, various types of filming, toner fusion,
There is a problem. Further, an organic photoreceptor and an amorphous silicon
The photoreceptor can be used in a high-temperature, high-humidity environment,
Image flow due to paper dust and ozone deposits
This phenomenon occurs. The solution to these problems is
JP-A-2-110475 discloses a metal-crosslinked steel.
Two types of inorganic fine powder
Paper powder that is generated or adhered to the photoreceptor
Removal of zonal adducts and toner scattering and image under high temperature and high humidity
A method for improving image deletion and image density reduction has been disclosed.
You. However, this method also removes the photoconductor itself.
Therefore, there is a problem in image stability during continuous copying. In recent years, digital copiers
Multi-function copiers and cores
To improve the quality of P-images and to address environmental issues
Photoconductor as a measure against high temperature and high humidity from the viewpoint of energy saving
It is desired to eliminate the heater (drum heater). Further, the copying speed is increased, and the material of the transfer paper is increased.
Removal of residual toner on photoconductor and generation on photoconductor, depending on quality
Or a method to remove adhering paper dust, ozone adducts, etc.
Further improvement is required. In JP-A-9-190125,
Use blade with rebound resilience at room temperature of 35-60%
Inorganic particles are contained on the surface of the organic photoreceptor,
Cleaning with a surface roughness Rz of 0.05 to 1.0 μm
Bring the blade into contact with the photoconductor against the counter
Vibrating the cleaning blade to 10-200 μm
A cleaning method is disclosed. This method
To improve the cleaning performance under normal temperature and normal humidity
Is possible, but prevents image deletion under high temperature and high humidity
There is a problem in balancing shaving. That is, the problems as described above, especially
Good low-temperature fixability and strong against high-temperature offset
And the wax dispersion in the toner is uniform, causing image defects.
Cleans under high temperature and high humidity
Image that does not cause printing defects, toner fusion, and image deletion
At present, no forming method or apparatus has been realized. [0033] SUMMARY OF THE INVENTION The object of the present invention is to
Image forming method and image forming apparatus solving the above problems
To provide a location. It is an object of the present invention that the wax is contained in the binder resin.
Image forming method and toner using uniformly dispersed toner
An object of the present invention is to provide a forming apparatus. An object of the present invention is to provide a colorant (particularly a magnetic substance).
High image quality and high quality even with fine particle toner with increased content
An image forming method and an image forming apparatus capable of obtaining an image density are provided.
To provide. An object of the present invention is to provide a colorant (particularly a magnetic substance).
Even in a fine particle toner with an increased content,
Image forming method capable of obtaining good low-temperature fixability in an image
An object of the present invention is to provide an image forming apparatus. It is an object of the present invention to use a hot roll fuser.
High-speed machine and fixed heating heater via heat-resistant film
Good even with medium to low speed machines
Demonstrates low-temperature fixability and high-temperature offset
Forming method and image forming showing no wide fixing temperature range
It is to provide a device. The object of the present invention is to determine the type and amount of wax added.
Adversely affect the fixability and developability of the toner
Forming method and image forming controlled in dispersed state
It is to provide a device. An object of the present invention is to provide a latent image that is faithful to long-term durability.
FORMING METHOD AND IMAGE FORM CAPABLE OF CONTINUOUSLY OBTAINING IMAGE
An object of the present invention is to provide a synthesizing apparatus. An object of the present invention is to remove an image even under high temperature and high humidity.
To provide an image forming method and an image forming apparatus which do not cause a problem
And there. An object of the present invention is to provide an image processing apparatus used in a high-speed copying machine.
Even in the case, photoreceptor shaving does not occur and excellent durability for many sheets
To provide an image forming method and an image forming apparatus
is there. [0042] SUMMARY OF THE INVENTION The present invention provides an electrostatic image bearing device.
The electrostatic charge image formed on the body is developed using toner and
Forming a toner image, and carrying the formed toner image as an electrostatic image.
Transfer from body to transfer material with or without intermediate transfer body
Cleaning the transfer residual toner on the electrostatic image carrier.
Image type having a step of cleaning using a blade
In the forming method, the toner contains at least a binder resin and a wax.
Toner particles containing fine particles and colorant and inorganic fine powder.
And the binder resin is (1) a vinyl resin
Fat, polyester resin, and vinyl polymer unit
And hybrid resin having polyester unit
And (2) tetrahydrofuran (THF)
Soxhlet extraction for 10 hours as a medium, THF soluble
Content of 50 to 85% by weight (W1) and insoluble in THF
15 to 50% by weight (W2).
Soxhlet extraction for 10 hours using chill
Containing 40 to 98% by weight (W3) of an ethyl-soluble component;
Contains 2-60% by weight (W4) of ethyl acetate insoluble component
(4) 10-hour sock using chloroform as a solvent
55-90 layers of chloroform soluble components by sley extraction
% (W5), and chloroform-insoluble components from 10 to
45% by weight (W6), and (5) the value of W4 / W6 is
1.1 to 4.0, and the toner has a temperature of 50 to 75.
In ° C., (a) storage elastic modulus (G′T) and loss elastic modulus
There is a temperature (TT.C) at which (G "T) is equal to
(B) Temperature at which the loss tangent (tan δTP) is maximized
(TT.P) is present and the cleaning blade is
(C) Storage elastic modulus (G′B) at a temperature of 40 to 80 ° C.
But 5 × 10^Five~ 1 × 10⁷Pa, and (d) temperature 4
At 0 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10^Three
~ 1 × 10⁶Pa, (e) temperature of 40 to 80 ° C.
And the temperature (T) at which the loss tangent (tan δBP) is minimized.
T. B) is present, and (f) loss occurs at a temperature of 70 to 130 ° C.
The temperature (TB.) At which the tangent (tan δBP) becomes a maximum.
P) is present and the toner and the cleaning blade
In loss tangent, (g) difference (TT.P-TB.P)
-40 to 20 ° C., and (h) temperature (TT.C)
And the temperature (T)
T. Loss modulus of the cleaning blade in C)
The ratio (G "T) / (G" BC) to (G "BC) is
5 × 10^Two~ 5 × 10^FourAn image shape characterized by being
The method of formation. Further, according to the present invention, there is provided an image forming apparatus for an electrostatic image carrier.
Developed electrostatic image using toner to form toner image
Developing means for developing the toner image thus formed,
Transfer material from carrier to intermediate material with or without intermediate
Transfer means for transferring, transfer residue on the electrostatic image carrier
Clean the toner with a cleaning blade.
Formation having at least cleaning means for cleaning
In the apparatus, the toner is at least a binder resin and a wax.
Containing toner particles containing fine particles and colorant and inorganic fine powder.
And the binder resin is (1) a vinyl resin
Fat, polyester resin, and vinyl polymer unit
And hybrid resin having polyester unit
And (2) tetrahydrofuran (THF)
Soxhlet extraction for 10 hours as a medium, THF soluble
Content of 50 to 85% by weight (W1) and insoluble in THF
15 to 50% by weight (W2).
Soxhlet extraction for 10 hours using chill
Containing 40 to 98% by weight (W3) of an ethyl-soluble component;
Contains 2-60% by weight (W4) of ethyl acetate insoluble component
(4) 10-hour sock using chloroform as a solvent
55-90 layers of chloroform soluble components by sley extraction
% (W5), and chloroform-insoluble components from 10 to
45% by weight (W6), and (5) the value of W4 / W6 is
1.1 to 4.0, and the toner has a temperature of 50 to 75.
In ° C., (a) storage elastic modulus (G′T) and loss elastic modulus
There is a temperature (TT.C) at which (G "T) is equal to
(B) Temperature at which the loss tangent (tan δTP) is maximized
(TT.P) is present and the cleaning blade is
(C) Storage elastic modulus (G′B) at a temperature of 40 to 80 ° C.
But 5 × 10^Five~ 1 × 10⁷Pa, and (d) temperature 4
At 0 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10^Three
~ 1 × 10⁶Pa, (e) temperature of 40 to 80 ° C.
And the temperature (T) at which the loss tangent (tan δBP) is minimized.
T. B) is present, and (f) loss occurs at a temperature of 70 to 130 ° C.
The temperature (TB.) At which the tangent (tan δBP) becomes a maximum.
P) is present and the toner and the cleaning blade
In loss tangent, (g) difference (TT.P-TB.P)
-40 to 20 ° C., and (h) temperature (TT.C)
And the temperature (T)
T. Loss modulus of the cleaning blade in C)
The ratio (G "T) / (G" BC) to (G "BC) is
5 × 10^Two~ 5 × 10^FourAn image shape characterized by being
Related to forming equipment. [0044] BEST MODE FOR CARRYING OUT THE INVENTION According to the study of the present inventors, a colorant
Small particle size toner with increased content of (especially magnetic substance)
Even if the halftone image is
Good low-temperature fixability on images, and high-temperature offset
In order to obtain a toner that is high in temperature and difficult to offset,
The binder resin of the toner selectively dissolves in multiple specific solvents
It is important to contain a certain amount of components having different composition and molecular weight.
It is important. Conventionally, the text contained in the binder resin of the toner has
Trihydrofuran, chloroform or ethyl acetate
Quantifies resin components insoluble in any one of the solvents
And the temperature at which high temperature offset occurs
Can take measures, but not only the fixability of the toner
And may greatly affect the developability of the toner.
To evaluate the dispersion state of wax contained in toner
It is not a point evaluation. According to the study of the present inventors, tetrahydroph
Run (THF) is a binder resin contained in the toner of the present invention.
Good solvent for vinyl polymer units
However, it is not always
Not a medium. Quantifying the components insoluble in THF is difficult
Components with extremely high molecular weight in the ester resin
Or highly crosslinked components and hybrid resin components
Defined as a component with a relatively high percentage of polyester units
Is to weigh. The component insoluble in THF is the toner
Can be evaluated for low-temperature fixability. Further better
In order to achieve an excellent low-temperature fixability, a component soluble in THF is required.
It is important to have specific molecular weights and molecular weight components
You. Ethyl acetate is contained in the toner of the present invention.
Good solvent for polyester unit of binder resin
However, for vinyl polymer units, it is not necessarily
Not a good solvent. Quantify components insoluble in ethyl acetate
Has a very high molecular weight in the vinyl resin
Or highly cross-linked components and hybrid resins
The proportion of vinyl polymer units in the components is relatively high
And quantification of the components. In ethyl acetate insoluble components
Is soluble in chloroform and insoluble in chloroform
Components. Not only the fixability of toner
Stable developability for toner (eg, image density, fog, etc.)
That have a significant effect on the
The dispersion state of the mix can be evaluated. Chloroform is contained in the toner of the present invention.
Vinyl polymer unit of binder resin and polyester
A good solvent for any of these units. Black
Quantifying components insoluble in roform
Components with very high molecular weight or highly cross-linked
Components and extremely large molecules in the polyester resin
With high or high cross-linked components
Component having an extremely high molecular weight in the pad resin component or
Is to quantify the highly crosslinked components. this
Very high molecular weight in hybrid resin components
Components or crosslinked components are
It is closely related to the temperature at which the gas is generated. Therefore, the vinegar contained in the binder resin of the toner
The ratio of ethyl acetate insoluble to chloroform insoluble is simple
Shows the balance between wax dispersion and hot offset resistance.
Not only does the toner cause image defects
It is an index for showing stable developing property. In the present invention, the binder resin is insoluble in THF.
Content (W2) of 15 to 50% by weight.
, Preferably 20 to 45% by weight, more preferably 2 to 45% by weight.
The content is preferably 5 to 40% by weight. THF insoluble matter
If the content is less than 15% by weight, the toner
Offset generation temperature is lowered, resulting in hot offset resistance
Not only causes problems but also deteriorates the shelf life of the toner
In some cases, this is not preferable. The content of THF insolubles is 50
If the content is more than 10% by weight, the low-temperature fixability of the toner deteriorates.
May not be preferable. In the present invention, the binder resin is ethyl acetate
2 to 60% by weight of insoluble matter (W4)
Good, preferably 5 to 50% by weight, more preferably 1 to 50% by weight.
The content is preferably 0 to 40% by weight. Ethyl acetate insoluble
Content is less than 2% by weight, the toner
A problem occurs in the hot offset property, which is contained in the toner
It becomes difficult to control the dispersion state of the wax,
The image density may further decrease, which is not preferable. Acetic acid
When the content of the ethyl-insoluble component exceeds 60% by weight,
A problem occurs in the low-temperature fixability of the toner.
The degree may be high, which is not preferable. In the present invention, the binder resin is chloroform.
10 to 45% by weight of insoluble matter (W6)
Good, preferably 15 to 40% by weight, more preferably
The content is preferably 17 to 37% by weight. Chloroform
If the insoluble content is less than 10% by weight,
Not only has a problem with the offset
The phenomenon that the toner fuses on the photoconductor may occur
There is not preferred. Chloroform insoluble content is 45
If the amount is more than 10% by weight, there is a problem in the low-temperature fixability of the toner.
Not only occurs, but also the toner on the photoconductor is
Leaning may be difficult, which is not preferable. Ethyl acetate insoluble matter (W4) and chloroform
The value of the ratio (W4 / W6) to the insoluble matter (W6) is 1.1
It is preferably from 4.0 to 4.0, preferably from 1.2 to 3.0.
5, more preferably 1.3 to 3.0
No. When the ratio (W4 / W6) is less than 1.1 or more than 4.0
In any case, image density decreases due to durability
I do. Further, in the present invention, the binder resin is
(I) contains THF-insoluble matter (W2) and is
The soluble matter (W2) is further chloroform-insoluble (W6A)
A weight% (based on the weight of the binder resin)
(Ii) vinegar containing ethyl acetate insoluble matter (W4)
Ethyl acid insolubles (W4) are further chloroform insolubles
(W6B) B weight% (based on the weight of the binder resin)
ing. This THF-insoluble component (W2) contains
Of chloroform-insoluble component (W6A) and ethyl acetate
Chloroform-insoluble component contained in water-insoluble component (W4)
Content (W6B) may satisfy the following conditions:
Preferably 3% by weight ≦ W6A ≦ 25% by weight 7% by weight ≦ W6B ≦ 30% by weight 10% by weight ≦ W6A + W6B ≦ 45% by weight W6A: W6B = 1: 1 to 3 More preferably, the following conditions should be satisfied. 5% by weight ≦ W6A ≦ 20% by weight 10% by weight ≦ W6B ≦ 25% by weight 15% by weight ≦ W6A + W6B ≦ 40% by weight W6A: W6B = 1: 1.5-2.5 The THF-insoluble matter (W2) is insoluble in chloroform
(W6A) less than 3% by weight,
Not only is the hot offset resistance of the toner impaired,
The image density may decrease due to the durability of the toner.
Not good. The THF-insoluble matter (W2) is chloroform-insoluble
Min (W6A) more than 25% by weight
Is preferable because the low-temperature fixability of the toner may be impaired.
I don't. Ethyl acetate insoluble matter (W4) is chloroform
When the content of insoluble matter (W6B) is less than 7% by weight
Can only impair the high-temperature offset resistance of the toner.
And the blocking resistance of the toner may be impaired.
Is not preferred. Ethyl acetate insoluble matter (W4) is chloroform
When the content of insoluble matter (W6B) is more than 30% by weight
In this case, the low-temperature fixability of the toner may be impaired,
Not good. Chromium contained in THF-insoluble matter (W2)
Content of roform insoluble matter (W6A) and ethyl acetate insoluble matter
Chloroform insolubles contained in (W4) (W6B)
And the total amount (W6A + W6B) of the binder resin
It is equivalent to the content of chloroform-insoluble matter (W6)
Yes, so from the upper and lower limits of the total amount (W6A + W6B)
If it deviates, the above-mentioned chloroform-insoluble matter (W6)
Is similar to the case where the content falls outside the upper and lower limits. Further, a THF insoluble matter (W2) is contained.
Of chloroform-insoluble matter (W6A) and ethyl acetate
Chloroform insolubles (W4) contained in insolubles (W4)
When the ratio to the content of 6B) is less than 1: 1
Not only impairs the hot offset resistance of the
Blocker may impair the blocking resistance of the toner.
I don't. When the ratio exceeds 1: 3, the low-temperature fixing property of the toner
Not only damage, but also image density
It is not preferable because it may cause The soluble matter in THF was determined by gel permeation
Molecular weight fraction measured by chromatography (GPC)
In the cloth, the main peak has a molecular weight of 4000 to 900.
0, and preferably has a molecular weight of 5,000
In the region of up to 8500, more preferably a molecule
It is good to have it in the area of 4500 to 8000
No. Having a main peak in a region having a molecular weight of less than 4000
In some cases, the hot offset resistance of the toner may deteriorate.
And the main peak is located in the region where the molecular weight exceeds 9000.
The toner, the low-temperature fixability of the toner may be impaired.
Is not preferred. Components in the region having a molecular weight of 500 to less than 10,000
(A1) should be contained at 35.0 to 65.0%.
And preferably 37.0 to 60.0%, more preferably
More preferably, the content is 40.0 to 55.0%.
good. Content of components in the molecular weight range of 500 to less than 10,000
Is less than 35.0%, the low-temperature fixability of the toner
May worsen, and if it exceeds 65.0%,
This is not preferred because the shelf life of the toner may deteriorate. Components in the region having a molecular weight of 10,000 to less than 100,000
(A2) should be contained at 25.0 to 45.0%.
And preferably 27.0 to 42.0%, more preferably
Preferably 30.0 to 40.0%
good. Content of components in the molecular weight range of 10,000 to less than 100,000
Is less than 25.0%, the toner
Fsetability may be deteriorated, and may exceed 45.0%
In this case, the low-temperature fixability of the toner may be deteriorated.
Not good. Component (A3) in a region having a molecular weight of 100,000 or more
Is preferably contained in the range of 10.0 to 30.0%.
, Preferably 12.0 to 25.0%, more preferably
Is preferably contained at 15.0 to 22.0%.
The content of components in the region having a molecular weight of 100,000 or more is 10.0%
When the value is less than the above, the hot offset resistance of the toner is poor.
If it exceeds 30.0%, the toner
Is not preferred because the low-temperature fixability of the toner may deteriorate. The value of the ratio (A1 / A2) is from 1.05 to 2.
00, preferably 1.10 to 1.9.
0, more preferably 1.15 to 1.80
good. If the ratio (A1 / A2) is less than 1.05
The low-temperature fixability of the toner may be deteriorated, and may exceed 2.00.
When this happens, the hot offset resistance of the toner deteriorates.
May not be preferable. In the present invention, when synthesizing a binder resin,
Monomers and binders for synthesizing the polyester resin used
Synthesizes polyester resin with the charge ratio to phenyl-based monomer
100 parts by weight of the monomer
Nomer 10 to 100 parts by weight, preferably 15 to 80 parts
Parts by weight, more preferably 20 to 70 parts by weight.
And good. The binder resin contained in the toner of the present invention
The “hybrid resin component” is a vinyl polymer
Unit and polyester unit are chemically bonded
Means resin. Specifically, the polyester unit and
Carboxylic esters such as (meth) acrylic esters
-Based polymer unit obtained by polymerizing a monomer having a hydroxyl group
Is formed by a transesterification reaction,
Preferably, a vinyl polymer is used as a trunk polymer or a polyester polymer.
Graft copolymer (or block) using knit as a branch polymer
Rock copolymer). Accordingly, in the present invention, the hybrid tree
Vinyl polymer unit and polyester unit of fat component
Is [0072] Embedded image Are connected via The binder resin contained in the toner of the present invention is:
Of all carboxylic acid esters in the vinyl polymer unit
Reaction rate with ester unit, ie, grafting rate
(Meth) acrylic acid S contained in a vinyl polymer
Preferably 10 to 60 mol%, based on ter
More preferably 15 to 55 mol%, more preferably 20
To 50 mol%. Graft ratio is 1
If the amount is less than 0 mol%, the vinyl polymer unit
The compatibility of the polyester unit deteriorates and the wax
The dispersibility may be deteriorated, which is not preferable.
, Components with relatively high molecular weight increase
As a result, the low-temperature fixability of the toner may be deteriorated.
Absent. The component (W4) insoluble in ethyl acetate was prepared
An ester resin component (Gp) containing 40 to 98% by weight.
And preferably 50 to 95% by weight,
Preferably contains 60 to 90% by weight.
No. Polyester resin component (Gp) content is 40% by weight
If the value is less than, the fixability of the toner may be deteriorated.
If the content exceeds 98% by weight, charcoal
Good compatibility with hydride wax
Absent. The component (W3) dissolved in ethyl acetate is
Contains 20 to 90% by weight of ester resin component (Sp)
And preferably 25 to 85% by weight,
More preferably, the content is 30 to 80% by weight.
good. The content of the polyester resin component (Sp) is 20
If the amount is less than%, the hydrocarbon wax
To be evenly dispersed throughout the binder resin contained in
If the adhesion is not improved and exceeds 90% by weight,
Compatibility with hydrogen-based wax tends to worsen and localization occurs
And hot offset is not easily generated. The ratio (Sp / Gp) is 0.50 to 1.0
0, preferably 0.60 to 0.9.
5, more preferably 0.65 to 0.90
good. When the ratio (Sp / Gp) is less than 0.5; and
If the ratio (Sp / Gp) exceeds 1.00,
The components insoluble and soluble in ethyl acetate are evenly mixed.
Is not acceptable, and the developability of the toner may deteriorate.
I don't. In the present invention, the entire binder resin of the toner is used.
Acid value (AV1) is 7 to 40 mgKOH / g
Good, but preferably 10-37 mgKOH / g, more preferably
Preferably 15 to 35 mg KOH / g, more preferably
The content is preferably 17 to 30 mgKOH / g. Further, the ethyl acetate-soluble matter (W
The acid value (AV2) of 3) is 10 to 45 mgKOH / g.
But preferably 15 to 45 mg KOH / g,
More preferably 17 to 40 mgKOH / g, even more preferably
Preferably, it is 20 to 35 mgKOH / g. The acid value (AV) of the entire binder resin of this toner
1) and the acid value (AV) of the ethyl acetate-soluble component (W3) of the toner
2) is preferably 0.7 to 0.7.
2.0, more preferably 0.9-1.7, even more preferred
More preferably, it is 1.0 to 1.5. The acid value (AV1) of the whole binder resin of the toner is
If less than 7 mg KOH / g and 40 mg KOH / g
If both values are exceeded, the image density may decrease due to durability.
In some cases, it is not preferable. Acid Value of Ethyl Acetate Soluble (W3) in Toner
When (AV2) is less than 10 mgKOH / g,
The hot offset resistance may be impaired.
If it exceeds 45 mgKOH / g,
Low-temperature fixability may be impaired, which is not preferable. When the value of AV1 / AV2 is less than 0.7
Is not preferable because image density may decrease due to durability.
If it exceeds 2.0, the high temperature offset resistance of the toner
The properties may be impaired, which is not preferred. In the toner of the present invention, the polyester resin
The knit can preferably be represented by equations (1) to (4)
Divalent carboxylic acid, monovalent carboxylic acid represented by formula (5)
Or at least the monohydric alcohol represented by the formula (6)
Also contains one or more kinds. [0084] Embedded image [Wherein, R₁Is a straight, branched or cyclic C14 or more
Represents an alkyl group or an alkenyl group of_Three, R_Four, R_Five
And R₆Is a hydrogen atom, a straight chain having 3 or more carbon atoms, a branched or
Represents a cyclic alkyl or alkenyl group, and has the same substitution
It may be a group, but it cannot be a hydrogen atom at the same time.
K, R₇And R₈Is a straight-chain, branched or ring having 12 or more carbon atoms
Represents an alkyl or alkenyl group in the form of
Represents an integer of 40. ] As the compound represented by the formula (1), for example,
Examples thereof include the following compounds (1-1) to (1-6). [0086] Embedded image As the compound represented by the formula (2), for example,
Examples thereof include the following compounds (2-1) to (2-4). [0088] Embedded image As the compound represented by the formula (3), for example,
Examples include the following compounds (3-1) to (3-3). [0090] Embedded image As the compound represented by the formula (4), for example,
Examples thereof include the following compounds (4-1) to (4-2). [0092] Embedded imageAs the compound represented by the formula (5), for example,
Examples thereof include the following compounds (5-1) to (5-5). [0094] Embedded image As the compound represented by the formula (6), for example,
Examples thereof include the following compounds (6-1) to (6-5). [0096] Embedded image Further, the present inventors have found that under high temperature and high humidity conditions,
Check for poor cleaning, toner fusion and image deletion.
He continued the discussion and found the following: Residual toner on the photoreceptor and formation or adhesion
As a method of cleaning paper dust and ozone adducts
Is the electrostatic attraction method using a magnetic brush,
A method of scraping by ceding is considered. However, in the magnetic brush method, the residual
Is effective for cleaning the toner,
Cleaning paper dust and ozone adducts generated or adhered to
There is a problem with how to do this. Also, the cleaning
In the scraping method using a blade, the
Can be obtained by the material of the cable and the method of contact with the photoconductor.
The effect is different. The hard blade is brought into contact with the photoconductor,
Above residual toner and generated or adhered paper powder, ozone added
When cleaning an object, etc.,
Adhesion is difficult to obtain, and cleaning
Good is easy to occur. In order to avoid this phenomenon,
If the contact pressure on the photoconductor is increased, the photoconductor
Problems such as fusion of the toner on the optical body occur. On the contrary, a soft blade is brought into contact with the photoreceptor.
, Residual toner on the photoreceptor and generated or adhered paper dust,
When cleaning ozone adducts, etc.
Adhesion with the blade increases, but the blade is turned up or the photoconductor rotates.
Cleanin generated from chatter etc. due to the effect of rotating vibration
Failure occurs. In order to avoid this phenomenon,
If the contact pressure on the light body is reduced,
Residual toner on the photoreceptor
A problem arises in cleaning the zon additive and the like. Furthermore, the cleaning property and the polishing property are both compatible.
Cleaning blade and magnetic brush together.
There are other methods that can be considered, but the light weight of the copier itself and the
Points that cannot be reduced and the degree of freedom in setting is reduced
There are problems such as points. Further, the material of the above-mentioned blade is always
Defining rebound resilience at temperature and humidity and organic photoreceptor
The surface layer contains inorganic fine powder to regulate the surface roughness,
Hold the blade against the body at the counter and shake
A method of cleaning by vibrating the card itself is also considered.
Cleaning the residual toner on the photoconductor
Even if effective, formed or adhered under high temperature and high humidity
Problems when cleaning paper powder, ozone adducts, etc.
There is. Further, the polishing effect is used as a cleaning aid.
In the method of adding the third component to the toner,
Of paper dust and ozone adducts etc.
Has the effect of cleaning,
It is not something that satisfies all the characteristics. Therefore, the present inventors, particularly under high temperature and high humidity
Consider the toner developability and cleaning
After examining the issues in leaning in detail,
Viscoelastic properties of cleaning blades in high-speed copying machines
That there is a close relationship between the viscoelastic properties of
I found it. In addition, blades and toners that meet this condition
The composite oxide is used as the inorganic fine powder in the toner.
It has been found that the above effect further enhances this effect. Cleaning blade in contact with photoreceptor
During continuous copying, the temperature rises due to friction with the photoreceptor. this
The phenomenon is more pronounced depending on the environment in which the copier is installed.
You. In other words, the temperature rise under high temperature and high humidity is extremely severe.
In high-speed copying machines, the
The lading temperature can be as high as 40-70 ° C. Therefore, the present inventors have proposed various toners and toners.
Measurement of viscoelastic properties as a temperature-dependent property of the lade
And development under high temperature and high humidity in these combinations
The focus was on the characteristics, image deletion, and scraping of the photoreceptor.
I found the following. The developer is an inorganic fine powder represented by the following formula (1):
By having the composite oxide (A) particles as a body,
Abrasiveness against paper dust and ozone adduct from optical body is good
Up. [0109] [M₁]_a[M_Two]_bO_c                (1) (Where M₁Are Sr, Mg, Zn, Co, Mn, Ca and
Indicates a metal element selected from the group consisting of
Then M_TwoIndicates a metal element selected from Ti or Si
A represents an integer of 1 to 9; b represents an integer of 1 to 9
And c represents an integer of 3 to 9. ) In addition, blocking of the toner in the developing device,
Regarding fusion to an optical body, etc.
It can be prevented by setting the characteristics in the following range
You. When the temperature of the toner is 50 to 75 ° C., a) The storage modulus (G'T) and the loss modulus (G "T) are
There is an equal temperature (TT.C), b) The temperature (T) at which the loss tangent (tan δTP) is maximized
T. P) is present and the cleaning blade is c) At a temperature of 40 to 80 ° C., the storage elastic modulus (G′B) is
5 × 10^Five~ 1 × 10⁷Pa, d) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is
5 × 10^Three~ 1 × 10⁶Pa, e) loss tangent (tan δB.
P) has a minimum temperature (TT.B), f) Loss tangent (tan δB.
P) is at a maximum temperature (TB.P), and the toner
And in the loss tangent of the cleaning blade, g) The difference (TT.P-TB.P) is -40 to 20 ° C.
Yes, h) cleaning blade at temperature (TT.C)
Loss modulus (G "BC) ratio (G" T / G "BC)
Is 5 × 10^Two~ 5 × 10^FourIt is. Note that 1 Pa = 10 dyn / cm^TwoIn
You. From the above, especially using a high-speed copying machine
Even when performing continuous copying in a high-temperature, high-humidity environment,
Quality, high image density, residual toner on the photoreceptor
Removal of paper dust and ozone adducts generated or adhered to the light body
To prevent poor cleaning, image deletion, etc.
The viscoelastic properties of the toner and the blade.
It is important that the binder resin
Vibration between toner and blade by incorporating hybrid resin
The above formula (1) is used for the toner having the specified characteristics.
It is important to use the composite oxide that is used. The toner of the present invention has a temperature of 50 to 7
Storage elastic modulus (G'T) and loss elastic modulus (G ') at 5 ° C
Temperature (T. TC), and the loss tangent (tan)
δT. P) has a maximum temperature (T.TP)
However, preferably, the T.C. T
C and T.C. When TP is present, more preferably
T. to 55-70 ° C. TC and T.C. TP exists
Is the case. If the temperature is lower than 50.degree. TC and T.C.
In the presence of TP, the viscoelastic properties of the cleaning blade
Regardless of quality, toner is removed on electrophotographic photoreceptor during cleaning
A phenomenon called drum fusion that sticks to the
Is not preferred. T. When the temperature exceeds 75 ° C. TC and T.C. TP
Is present in the viscoelastic properties of the cleaning blade
Regardless of the toner on the surface of the electrophotographic photosensitive member during cleaning
It is not preferable because a large scratch may be formed. In the present invention, the cleaning blade is
At a temperature of 40 to 80 ° C., the storage modulus (G′B) is 5 × 1.
0^Five~ 1 × 10⁷Pa may be used, but preferably 7 ×
10^Five~ 7 × 10⁶It is when it becomes Pa, more preferred
1x10⁶~ 5 × 10⁶This is the case when it becomes Pa. Also
And G'B is 5 × 10^FiveIf less than Pa,
Electrophotographic feeling during cleaning regardless of the viscoelastic properties of
Cleaner not completely cleaning toner on optical body
May cause a phenomenon called
No. G'B is 1 × 10⁷If the pressure exceeds Pa, electronic
It is called drum abrasion where the surface of the true photoreceptor wears significantly.
A phenomenon may occur, which is not preferable. In the present invention, the cleaning blade is
At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 1
0^Three~ 1 × 10⁶Pa, but preferably 7 × 1
0^Three~ 7 × 10^FivePa, more preferably
Is 1 × 10^Four~ 5 × 10^FiveThis is the case when it becomes Pa. Also
And G ″ B is 5 × 10^ThreeIf less than Pa,
Drum fusion during cleaning regardless of viscoelastic properties
A phenomenon may occur, which is not preferable. G ″ B is 1 × 1
0⁶If it exceeds Pa, it is called cleaning failure.
Phenomenon may occur, which is not preferable. In the present invention, the cleaning blade is
At a temperature of 40 to 80 ° C., the loss tangent (tan δB.P) is
It is sufficient that a minimum temperature (TT.B) exists, but it is preferable.
Or loss tangent (tan δB.
P) is at a minimum (TT.B)
Loss tangent (t) at a temperature of 45 to 70 ° C.
anδB. P) has a minimum temperature (TT.B)
Is the case. If the temperature at which (tan δBP) is minimized,
Degree TT. If B is less than 40 ° C., the toner
Drum fusing occurs during cleaning regardless of sexual properties
In some cases, this is not preferable. (TanδB.P) is minimal
Temperature TT. If B exceeds 80 ° C,
This may occur, which is not preferable. In the present invention, the cleaning blade is
Loss tangent (tan δ BP) at a temperature of 70 to 130 ° C
It is sufficient that there is a temperature (TB.P) at which
Preferably TB. In the case where P becomes a temperature of 75 to 120 ° C.
And more preferably TB. P is 80-110 ° C
This is the case. If the temperature TB. P is less than 70 ° C and temperature
TB. If P exceeds 130 ° C., cleaning is not possible.
Good may occur, which is not preferable. In the present invention, the difference (TT.P-TB.
P) may be −40 to 20 ° C., preferably −
30 to 10 ° C., and more preferably −2.
This is the case when the temperature is 0 to 5 ° C. If the difference (TT.P-TB.P) is -40
° C and the difference (TT.P-TBB.P) exceeds 20 ° C
In this case, sufficient removal effect from the drum cannot be obtained,
Drum fusing, poor cleaning, etc. may occur.
Not good. In the present invention, the temperature (TT.C)
Ratio (G ″) of the loss elastic modulus of the toner and the cleaning blade.
T / G "BC" is 5 × 10^Two~ 5 × 10^FourBe Pa
It is good, but preferably 7 × 10^Two~ 3 × 10^FourPa
And more preferably 1 × 10^Three~ 1 × 10^Four
This is the case when it becomes Pa. If the ratio (G "T / G" BC) is 5 × 1
0^TwoIf it is less than this, drum scraping may occur.
And the ratio (G "T / G" BC) is 5 × 10
^FourIf it is too high, drum fusion may occur, which is
Not good. Further, in the present invention, more preferable toner
Will be described in detail below. The polyester resin used in the present invention
Nomers include the following. As the alcohol component, ethylene glycol
, Propylene glycol, 1,3-butanediol
1,4-butanediol, 2,3-butanediol
, Diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol
, Neopentyl glycol, 2-ethyl 1,3-hex
Sundiol, hydrogenated bisphenol A, the following (7-
1) The bisphenol derivative represented by the formula and the following (7)
-2) Diols represented by the formula. [0129] Embedded image [0130] Embedded image Examples of the acidic component include phthalic acid and isophthalic acid.
And aromatic dicarboxylic acids such as terephthalic acid or
Anhydrides; succinic, adipic, sebacic and azera
Alkyl dicarboxylic acids such as formic acid or anhydrides thereof;
Succinic acid substituted with an alkyl group having 6 to 12 carbon atoms
Or its anhydride; fumaric acid, maleic acid and citracone
Unsaturated dicarboxylic acids such as acids or anhydrides thereof;
Can be A vinyl-based resin for producing a vinyl-based resin
Nomers include the following. Styrene; o-methylstyrene, m-methyl
Styrene, p-methylstyrene, p-phenylstyrene
, P-ethylstyrene, 2,4-dimethylstyrene,
pn-butylstyrene, p-tert-butylstyrene
, Pn-hexylstyrene, pn-octylstyne
Len, pn-nonylstyrene, pn-decylstyrene
, P-n-dodecylstyrene, p-methoxystyrene
, P-chlorostyrene, 3,4-dichlorostyrene,
m-nitrostyrene, o-nitrostyrene, p-nitro
Styrene such as styrene and its derivatives;
Unsaturated styrene such as propylene, butylene, and isobutylene
Mono-olefins such as butadiene and isoprene
Saturated polyenes; vinyl chloride, vinyldene chloride, vinyl bromide
Vinyl halides such as vinyl and vinyl fluoride;
Vinyl, vinyl propionate, vinyl benzoate
Nyl esters; methyl methacrylate, methacrylic acid
Chill, propyl methacrylate, n-butyl methacrylate
, Isobutyl methacrylate, n-octyl methacrylate
Dodecyl methacrylate, 2-ethyl methacrylate
Xyl, stearyl methacrylate, phenyl methacrylate
Dimethylaminoethyl methacrylate, methacrylic acid
Α-methylene aliphatic monoca such as diethylaminoethyl
Rubonates: methyl acrylate, acrylic acid
Chill, propyl acrylate, n-butyl acrylate,
Isobutyl acrylate, n-octyl acrylate, acrylic
Dodecyl luate, 2-ethylhexyl acrylate, acrylic
Stearyl luate, 2-chloroethyl acrylate, acrylic
Acrylic esters such as phenyl luate; vinyl methyl
Ether, vinyl ethyl ether, vinyl isobutyl
Vinyl ethers such as ether; vinyl methyl keto
, Vinylhexyl ketone, methyl isopropenyl keto
Vinyl ketones such as N-vinyl pyrrole, N-bi
Nilcarbazole, N-vinylindole, N-vinyl
N-vinyl compounds such as pyrrolidone; vinylnaphthalene
And acrylonitrile, methacrylonitrile, acrylic
Acrylic or methacrylic acid derivatives such as amide
Is mentioned. Further, maleic acid, citraconic acid,
Of conic acid, alkenyl succinic acid, fumaric acid, mesaconic acid
Unsaturated dibasic acids such as maleic anhydride, citraconic acid
Anhydride, itaconic anhydride, alkenyl succinic anhydride
Unsaturated dibasic acid anhydrides such as methyl maleate maleate
Ester, ethyl maleate half ester, maleic
Acid butyl half ester, methyl citraconic acid half ester
Stele, ethyl citraconic acid half ester, citraco
Butyl acid half-ester, methyl itaconate half-e
Stele, alkenyl succinic acid methyl half ester,
Methyl malate half ester, methyl mesaconate half
Half esters of unsaturated dibasic acids such as esters;
Unsaturated dibasic such as tilmaleic acid and dimethyl fumaric acid
Acid esters; acrylic acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
Anhydride of β-unsaturated acid and lower fatty acid; alkenyl malo
Acid, alkenyl glutaric acid, alkenyl adipic acid,
These acid anhydrides and their monoesters such as monoesters
Examples include a monomer having a boxyl group. Further, 2-hydroxyethyl acrylate
G, 2-hydroxyethyl methacrylate, 2-hydro
Acrylic acid such as xypropyl methacrylate or
Tacrylic esters; 4- (1-hydroxy-1-me)
Butyl) styrene, 4- (1-hydroxy-1-me)
Molybdenum having a hydroxy group such as tylhexyl) styrene
Nomers. In the toner of the present invention, the binder resin
The ester unit is a trivalent or higher polycarboxylic acid or
Cross-linked with the anhydride or tri- or higher polyhydric alcohol
It has a crosslinked structure. Trivalent or higher
Examples of the divalent carboxylic acid or its anhydride include 1,1,
2,4-benzenetricarboxylic acid, 1,2,4-sic
Rohexanetricarboxylic acid, 1,2,4-naphthalene
Licarboxylic acid, pyromellitic acid and their acid anhydrides
Or lower alkyl esters, etc.
Examples of the dihydric alcohol include 1,2,3-propane
Triol, trimethylolpropane, hexane trio
And pentaerythritol, but are preferred.
1,2,4-benzenetricarboxylic acid and its acid-free
It is a marine product. In the toner of the present invention, the binder resin
Polymer units are crosslinked with two or more vinyl groups
May have a cross-linked structure cross-linked with an agent,
The crosslinking agent used in this case is an aromatic divinyl compound.
Examples include divinylbenzene and divinylnaphthalene.
Diacrylate compounds linked by alkyl chains;
And, for example, ethylene glycol diacrylate, 1,
3-butylene glycol diacrylate, 1,4-buta
Diol diacrylate, 1,5-pentanediol
Diacrylate, 1,6 hexanediol diacrylate
G, neopentyl glycol diacrylate and above
Compounds obtained by replacing acrylate with methacrylate
Di-linked by alkyl chains containing ether linkages
As acrylate compounds, for example, diethylene glycol
Recall diacrylate, triethylene glycol dia
Acrylate, tetraethylene glycol diaclair
G, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, dip
Propylene glycol diacrylate and the above compounds
Examples include methacrylate instead of acrylate.
A chain connected by a chain containing an aromatic group and an ether bond
As acrylate compounds, for example, polyoxyethylene
(2) -2,2-bis (4-hydroxyphenyl) pro
Pan diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacry
Acrylates and acrylates of the above compounds
Polyester type diacryle
For example, brands such as MANDA (Nippon Kayaku)
No. As the polyfunctional crosslinking agent, pentaerythri
Tall triacrylate, trimethylolethanetria
Acrylate, trimethylolpropane triacrylate
G, tetramethylolmethanetetraacrylate,
Acrylate of goester acrylate and the above compounds
Methacrylate instead of triaryl cyanurate
And triallyl trimellitate. [0139] These cross-linking agents may be used in combination with other monomer components 10
0.01 to 10 parts by weight relative to 0 parts by weight (more preferably
Or 0.03 to 5 parts by weight). Of these crosslinkable monomers, toner
Suitable for fixing to resin and offset resistance
As aromatic divinyl compounds (particularly divinyl
), Connected by a chain containing an aromatic group and an ether bond.
Diacrylate compounds. In the present invention, the vinyl copolymer component and / or
Can react with both resin components in the polyester resin component
It is preferable to include a monomer component. Polyester resin
Reacts with vinyl copolymer among the constituent monomers
Examples of what can be made include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid;
Is an anhydride thereof. Vinyl copolymer component
Reacts with the polyester resin component of the monomers composing
A carboxyl group or a hydroxy group
Having acrylic acid or methacrylic acid
Ters. Reaction product between vinyl resin and polyester resin
As a method for obtaining the product, the vinyl resins mentioned above and
Monomer components that can react with each of the polyester resins
Where the polymer containing
Or by polymerizing both resins
The method is preferred. When producing the vinyl copolymer of the present invention
Examples of the polymerization initiator used for 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (-2,4-dimethylvaleronitrile
), 2,2'-azobis (-2methylbutyronitrile
), Dimethyl-2,2'-azobisisobutyrate,
1,1'-azobis (1-cyclohexanecarbonitrile
), 2- (carbamoylazo) -isobutyronitrile
, 2,2'-azobis (2,4,4-trimethylpen
Tan), 2-phenylazo-2,4-dimethyl-4-meth
Toxivaleronitrile, 2,2'-azobis (2-methyl
Le-propane), methyl ethyl ketone peroxide,
Acetylacetone peroxide, cyclohexanone
2,2-ketone peroxides such as oxides
Bis (t-butylperoxy) butane, t-butyl high
Dropper oxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxy
Side, di-t-butyl peroxide, t-butyl chloride
Mil peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxyisopropyl) ben
Zen, isobutyl peroxide, octanoyl peroxide
Oxide, decanoyl peroxide, lauroyl par
Oxide, 3,5,5-trimethylhexanoyl par
Oxide, benzoyl peroxide, m-trioy
Luper oxide, di-isopropyl peroxy dicar
Bonate, di-2-ethylhexylperoxydicarbo
, Di-n-propylperoxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxy isopropyl peroxy dicarbonate, di
(3-methyl-3-methoxybutyl) peroxycarb
Nitrate, acetylcyclohexylsulfonylperoxa
Id, t-butyl peroxyacetate, t-butyl
-Oxyisobutyrate, t-butylperoxyneode
Canoate, t-butylperoxy 2-ethylhexano
Eight, t-butyl peroxylaurate, t-butyl
Peroxybenzoate, t-butyl peroxyisop
Ropyl carbonate, di-t-butylperoxyisoph
Tartrate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
Di-t-butyl peroxyazelate. The binder resin used in the toner of the present invention was prepared.
As a production method that can be produced, for example, the following (1) to
The manufacturing method shown in (6) can be mentioned. (1) Vinyl resins, polyester resins and
And hybrid resin components are blended after each
Blending is performed using an organic solvent (for example,
Organic solvent is distilled off after dissolution and swelling in
Preferably, wax is added during this blending step.
Manufactured. The hybrid resin component is a vinyl resin
After separately producing the polymer and polyester resin,
Dissolve and swell in solvent, esterification catalyst and alcohol
Is added and heated to carry out the transesterification reaction.
Can be used. (2) After the production of the vinyl polymer unit,
Polyester units and hybrids in the presence of this
This is a method for producing a resin component. Hybrid resin component
Is a vinyl polymer unit (if necessary,
And polyester monomer (Alcohol)
Carboxylic acid) and / or polyester
Manufactured. Also in this case, use an organic solvent as appropriate.
be able to. Preferably, add wax in this step
I do. (3) After manufacturing the polyester unit,
Polymer units and hybrids in the presence of
This is a method for producing a resin component. Hybrid resin component
Is a polyester unit (if necessary,
And a vinyl monomer and / or
It is produced by a reaction with a vinyl polymer unit. Good
Preferably, a wax is added in this step. (4) Vinyl polymer unit and polyether
After the production of steal units, the presence of these polymer units
Under vinyl monomer and / or polyester monomer
-(Alcohol, carboxylic acid)
The hybrid resin component is manufactured. Also in this case,
Solvent can be used. Preferably, this step
Add wax. (5) After producing the hybrid resin component,
Nyl-based monomers and / or polyester monomers (A
Alcohol, carboxylic acid) and / or addition polymerization and / or
By conducting the polycondensation reaction, the vinyl polymer unit and
And polyester units are manufactured. In this case, high
The brid resin component is used in the production method of (2) to (4) above.
More manufactured ones can be used, if necessary
Using products manufactured by known manufacturing methods
Can also. Furthermore, it is possible to use an organic solvent as appropriate.
Wear. Preferably, a wax is added in this step. (6) Vinyl monomers and polyesters
Mix and add monomers (alcohol, carboxylic acid, etc.)
By conducting polymerization and polycondensation reactions continuously, vinyl
Polymer unit, polyester unit and hybrid unit
A resin component is produced. In addition, use organic solvents as appropriate.
Can be used. Preferably, the wax in this step
Is added. In the manufacturing method of the above (1) to (5),
And a vinyl polymer unit and / or polyester
Units are polymers with different molecular weights and degrees of crosslinking
Units can be used. In the above production methods (1) to (6),
Especially, the production method of (3) is a method wherein the vinyl polymer unit is used.
Easy to control the molecular weight of
Can control the composition and add wax
Is preferable in that the dispersion state can be controlled. Toner containing wax and toner of the present invention
In a DSC curve measured by a differential scanning calorimeter,
Preferably at a temperature of 70 to 160 ° C, more preferably at a temperature
70 to 140 ° C, more preferably 75 to 140
° C, most preferably in the range of 80 to 135 ° C.
Low peak fixability and off-resistance of toner
Good in setability. More preferably, wax containing wax is used.
Is the difference between the DSC curve measured with a differential scanning calorimeter.
At a temperature of 80 to 155 ° C, preferably 90 to 130 ° C.
The endothermic main peak and endothermic subpeak or endothermic
Low temperature fixability and offset resistance
It is preferable from the viewpoints of properties and blocking resistance. In the DSC curve of the toner, a temperature of 70 ° C.
To form a clear endothermic peak in the region from
Is limited in the wax used. Differential scanning heat described later
Wax in the temperature range of 30 to 200 ° C by a meter
Temperature corresponding to the maximum endothermic peak in the DSC curve of
Is defined as the melting point of wax.
The point is preferably 70 to 160 ° C, more preferably 75 to 160 ° C.
160 ° C, more preferably 75 to 140 ° C, most preferably
Alternatively, a material having a temperature of 80 to 135 ° C. is used. As such a wax, for example,
Molecular polyethylene, low molecular polypropylene, micro
Fats such as Listerin wax and Paraffin wax
Aromatic hydrocarbon wax; such as oxidized polyethylene wax
Oxides of aliphatic hydrocarbon waxes;
Block copolymer of hydride wax; Carnaubawack
, Sasol wax and montanic acid ester wax
Waxes based on fatty acid esters such as
Some or some fatty acid esters such as carnauba wax
The thing which deoxidized all is mentioned. Furthermore, palmich
Acid, stearic acid, montanic acid, or even longer chain
Saturation such as long-chain alkylcarboxylic acids having an alkyl group
Japanese straight-chain fatty acids; brandinic acid, eleostearic acid,
Unsaturated fatty acids such as vinaric acid; stearic alcohol
Alcohol, aralkyl alcohol, behenyl alcohol,
Lunavivir alcohol, seryl alcohol, melisylua
Alcohol, or long chains with longer alkyl groups
Saturated alcohols such as alkyl alcohols; Sorbi
Polyhydric alcohols such as tall; Calcium stearate
Mu, calcium laurate, zinc stearate, steer
Metal salts of fatty acids such as magnesium phosphate (generally
What is called ken); aliphatic hydrocarbon wax
Using vinyl monomers such as styrene and acrylic acid
-Grafted waxes; behenic acid monoglyceride
Partial esterification of fatty acids such as lido with polyhydric alcohols
Products; hydroxy obtained by hydrogenation of vegetable fats and oils
And a methyl ester compound having a methyl group. Low melting point preferably used in the present invention
As the wax component, use a long-chain alkyl group with few branches.
Consisting of hydrocarbons, specifically, for example, alkylene
Radical polymerization under high pressure or Ziegler touch under low pressure
Low molecular weight alkylene polymer polymerized with a medium, high molecular weight
Alkylene obtained by thermally decomposing an alkylene polymer of
Polymer, synthesis gas composed of carbon monoxide and hydrogen
From the distillation residue of hydrocarbons obtained by the
Washing such as synthetic hydrocarbons obtained by hydrogenating these
Is good. In addition, press sweating method, solvent method, vacuum distillation
Separation of hydrocarbon wax by use and separation crystallization method
Those that have become more preferred are used. Charcoal as a mother
Hydrogen is a metal oxide catalyst (mostly two or more
Synthesized by the reaction of carbon monoxide and hydrogen
Such as the Zintol method and the Hydrochol method (flow
Using a catalytic bed) or waxy hydrocarbons
Obtained by the Age method (using a fixed catalyst bed)
You. High melting point preferably used in the present invention
As the wax component, use a long-chain alkyl group with few branches.
Consisting of hydrocarbons, specifically, for example, alkylene
Radical polymerization under high pressure or Ziegler touch under low pressure
Low molecular weight alkylene polymer polymerized with a medium, high molecular weight
Alkylene obtained by thermally decomposing an alkylene polymer of
Polymer, synthesis gas composed of carbon monoxide and hydrogen
From the distillation residue of hydrocarbons obtained by the
Washing such as synthetic hydrocarbons obtained by hydrogenating these
Is good. Other preferred waxes
Equipment with a substitution machine for hydroxyl groups, carboxyl groups, etc.
There is a substituted alkyl wax. Hydrocarbons preferably used in the present invention
Specific examples of the raw wax include ethylene and
Radical polymerization of alkylene such as pyrene under high pressure
Is a low molecular weight alkylated polymerized with Ziegler catalyst under low pressure
Thermal decomposition of ren polymer and high molecular weight alkylene polymer
Alkylene polymer, carbon monoxide and hydrogen obtained by
Obtained from the synthesis gas consisting of arsenic by the Age method
From the distillation residue of
Wax such as synthetic hydrocarbons. In addition,
Less sweating, solvent method, use of vacuum distillation and fractional crystallization
Those that have been further separated are more preferably used. As petroleum waxes, paraffin wax
Box, microcrystalline wax, petrolactam
A wax separated from petroleum is used. In the present invention, the hydrocarbon wax, petroleum-based
Wax has substantially no functional groups. "Substantial"
Means that the number of functional groups is 0.1 or less per molecule
Point to. The hydrocarbon wax used in the present invention
Wax or petroleum-based wax
In a DSC curve measured by a differential scanning calorimeter,
Has an endothermic main peak in the temperature range of 70 to 140 ° C
In terms of low-temperature fixability and offset resistance of the toner.
preferable. More preferably, a hydrocarbon wax or
Is a differential scanning calorimeter for toner containing petroleum wax
In the DSC curve measured at 80-135 ° C
It is preferable that the region has an endothermic main peak. Further
Preferably, the toner containing the wax is a differential scanning
In the DSC curve measured by the calorimeter, the temperature is 90 to 1
The endothermic main peak and endothermic subpeak or
Has an endothermic shoulder to ensure low-temperature fixability and
It is preferable in terms of the fset property and the blocking resistance. Content of wax used in the present invention
The amount is 0.1 to 30 weight per 100 weight parts of binder resin
Parts, preferably 0.5 to 20 parts by weight. As the composite oxide (A), M₁As a ma
Gnesium, zinc, cobalt, manganese, strontium
Calcium, cerium. M_TwoAs
Are titanium and silica. Especially the effect of the present invention
Strontium silicate [Sr]
_a[Si]_bO_cAnd strontium titanate [Sr]
_a[Ti]_bO_cIs preferred. More specifically, SrSi
O_Three, Sr_ThreeSiO_Five, Sr_TwoSiO_Four, SrSiO_Five, Sr
_ThreeSi_TwoO₇And SrTiO_Three, Sr_TwoTiO_Four, Sr_ThreeTi_Two
O₇And among them, SrSiO_ThreeAnd SrTiO_ThreeBut
preferable. Particles having a composite oxide used in the present invention
Generated by, for example, a sintering method,
It is good to classify by force and use the one with the desired particle size distribution.
No. The composite oxide according to the present invention comprises toner particles
Fine particles containing the composite oxide (A) per 100 parts by weight
0.10 to 10 parts by weight, preferably 0.2 to 5.0 parts
It is good to use parts by weight. Particles containing composite oxides are
Average particle size is 0.1 to 5.0 μm, preferably 0.3 to
3.0 μm, more preferably 0.5 to 2.5 μm
You. Use of the toner of the present invention as a magnetic toner
In this case, the magnetic material contained in the magnetic toner
Iron oxides such as tight, maghemite, ferrite, and
Iron oxide containing other metal oxides; like Fe, Co, Ni
Metals, or these metals and Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
with metals such as d, Ca, Mn, Se, Ti, W, V
Alloys, and mixtures thereof. Specifically, as the magnetic material,
Iron (Fe_ThreeO_Four), Iron sesquioxide (γ-Fe_TwoO_Three),iron oxide
Zinc (ZnFe_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_Five
O₁₂), Cadmium iron oxide (CdFe_TwoO_Four), Iron oxide gas
Dolinium (Gd_ThreeFe_Five-O₁₂), Copper iron oxide (CuFe
_TwoO_Four), Lead iron oxide (PbFe₁₂-O₁₉), Iron oxide nickel
(NiFe_TwoO_Four), Iron neodymium oxide (NdFe
_TwoO_Three), Barium iron oxide (BaFe)₁₂O₁₉), Iron oxide
Gnesium (MgFe_TwoO_Four), Iron manganese oxide (MnF)
e_TwoO_Four), Iron oxide lanthanum (LaFeO)_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
I can do it. The above magnetic materials can be used alone or in combination of two or more.
Use in combination. A particularly preferred magnetic material is ferric oxide
Or a fine powder of γ-iron sesquioxide. These ferromagnetic materials have an average particle size of 0.05 to
2μm, 795.8kA / m applied magnetic properties coercive
Force 1.6-12.0kA / m, saturation magnetization 50-200A
m^Two/ Kg (preferably 50-100 Am^Two/ Kg), remaining
2 to 20 Am^Two/ Kg is preferred. The magnetic substance 1 was added to 100 parts by weight of the binder resin.
0 to 200 parts by weight, preferably 20 to 150 parts by weight
Good to do. Non-magnetic coloring usable in the toner of the present invention
Agents include any suitable pigments or dyes.
For example, pigments such as carbon black and aniline black
K, acetylene black, naphthol yellow, Hansa
Yellow, rhodamine rake, alizarin rake, ben
Gala, phthalocyanine blue, indanthrene blue, etc.
There is. These are 0.1 to 100 parts by weight of the binder resin.
20 parts by weight, preferably 1 to 10 parts by weight
No. Similarly, dyes are used, for example,
There are non dyes, xanthene dyes, methine dyes,
0.1 to 20 parts by weight, preferably 100 parts by weight of binder resin
More preferably, the addition amount is 0.3 to 10 parts by weight. The toner of the present invention further reduces the chargeability.
It is possible to use a charge control agent as needed to stabilize
No. The charge control agent is preferably used per 100 parts by weight of the binder resin.
Is 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight
It is preferable to use parts. Examples of the charge control agent include the following.
It is. For example, organometallic complexes, chelate compounds,
Metal salts. Specifically, a monoazo metal complex
Body: aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid
Metal complexes or metal salts of the compounds are mentioned. In addition,
Aromatic hydroxycarboxylic acid, aromatic mono and polycar
Boric acid and its anhydrides and esters; bisphenol
Phenol derivatives. A flowability improver is added to the toner of the present invention.
Is also good. The fluidity improver is externally added to the toner particles.
More fluidity can be increased before and after addition
is there. For example, vinylidene fluoride fine powder, polytetraf
Fluorine resin powder such as fluoroethylene fine powder; wet type
Fine silica, fine powder, such as process silica and dry process silica
Titanium oxide, fine powder alumina, silane coupling
Coupling agent, titanium coupling agent, silicone oil
Surface-treated silica. Preferred examples of the fluidity improver include silicon
Is a fine powder produced by the vapor phase oxidation of
Is called dry silica or fumed silica.
It is what is done. For example, oxyhydrogen flame of silicon tetrachloride gas
It utilizes the thermal decomposition oxidation reaction in
The reaction equation is as follows. [0178] SiCl_Two+ 2H_Two+ O_Two→ SiO_Two+4 HCl In this manufacturing process, aluminum chloride
Or other metal halides such as titanium chloride
Silane and other gold
It is also possible to obtain composite fine powders of oxides of the
As well as those. The particle size is the average primary particle
The diameter is preferably in the range of 0.001 to 2 μm.
Particularly preferably, the thickness is in the range of 0.002 to 0.2 μm.
It is preferable to use the silica fine powder in the box. By the vapor phase oxidation of silicon halides
As the commercially available silica fine powder produced, for example, the following
Some are marketed under various trade names. [0181]   AEROSIL (Nippon Aerosil) 130                                                       200                                                       300                                                       380                                                       TT600                                                       MOX170                                                       MOX80                                                       COK84   Ca-O-SiL (CABOT Co.) M-5                                                       MS-7                                                       MS-75                                                       HS-5                                                       EH-5   Wacker HDK N 20 V15     (WACKER-CHEMIE GMBH) N20E                                                       T30                                                       T40   DC Fine Silica (Dow Corning Co.)   Fransol (Fransil) Furthermore, the gas phase of the silicon halide compound
Hydrophobizing silica fine powder generated by oxidation
Fine silica powder is more preferred. The treated silica fine powder
The hydrophobicity measured by the methanol titration test
Silica fine powder so that the degree shows a value in the range of 30 to 80
Treated ones are particularly preferred. As a method for hydrophobizing, a reaction with fine silica powder is performed.
Alternatively, it is chemically treated with an organosilicon compound that physically adsorbs.
Is given by processing. The preferred method
Is produced by the vapor phase oxidation of silicon halides
The silica fine powder is treated with an organosilicon compound. As the organosilicon compound, hexamethyl
Disilazane, trimethylsilane, trimethylchlorosila
, Trimethylethoxysilane, dimethyldichlorosila
, Methyltrichlorosilane, allyldimethylchlorosi
Orchid, allylphenyldichlorosilane, benzyldimethy
Chlorosilane, bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyl
Trichlorosilane, chloromethyldimethylchlorosila
, Triorganosilyl mercaptan, trimethylsilyl
Rumercaptan, triorganosilyl acrylate,
Nyldimethylacetoxysilane, dimethylethoxysila
Dimethyldimethoxysilane, diphenyldiethoxy
Silane, hexamethyldisiloxane, 1,3-divinyl
Tetramethyldisiloxane, 1,3-diphenyltetra
Methyldisiloxane and 2 to 12 silicones per molecule
One for each of the units located at the end with siloxane units
Hydroxyl-containing dimethylpolysilo bonded to Si
There is a xan and the like. In addition, dimethyl silicone oil
Such silicone oils are exemplified. These are one kind
Or a mixture of two or more. The fluidity improver is nitrogen as measured by the BET method.
Specific surface area by adsorption is 30m^Two/ G or more, preferably 5
0m^Two/ G gives good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used. To prepare the toner of the present invention, a binder tree
Fat, colorant and / or magnetic substance, charge control agent or other
Additives such as Henschel mixer and ball mill
Mix well with the kneading machine, kneader, extruder
Melt and knead using a heat kneading machine such as
Melt, crush the solidified material after cooling and solidifying the melt-kneaded material,
The toner of the present invention can be obtained by classifying the pulverized product. [0187] Toner particles are used in terms of image density and resolution.
The weight average particle size is preferably 3 to 12 μm, more preferably
The thickness is preferably 3 to 9 μm. Further, the fluidity improver and the toner particles are
Mix well with a mixer such as
Toner having a fluidity improver on the surface of the toner
You. Next, the image forming method of the present invention will be described.
You. Referring to FIG. 8 and FIG.
An example of an image forming apparatus capable of performing an image forming method will be described.
I will tell. 1 electrostatic charge image carrier (photoconductor) by primary charger 2
Charge the surface to negative or positive polarity,
An electrostatic charge image (for example, an image
Digital latent image is formed by canning, and magnetic
And the magnetic pole N₁, N_Two, S₁And S_TwoMagnet 23 having
Of the developing device 9 having the developing sleeve 4 including
The electrostatic charge image is formed by reversal development or regular development with the magnetic toner 13.
And develop. In the developing section, the conductive substrate 16 of the photoconductor 1
Between the developing sleeve 4 and the bias applying means 12.
Alternate bias, pulse bias and / or DC via
Is applied. The magnetic toner image passes through the intermediate transfer member.
The image is transferred to the transfer material with or without intervention. Transfer paper P
When the sheet is conveyed and reaches the transfer section, the transfer paper 3
Positive or negative from the back of P (opposite to photoconductor)
Charge on the photoreceptor surface
When the toner image or the positively charged magnetic toner image is
Electrotransferred. After static elimination by the static elimination means 22,
The separated transfer paper P is heated by the heating paper containing the heater 21.
The toner image on the transfer paper P is added by the pressure roller fixing device 7 to the toner image.
It is fixed by heat and pressure. Magnetic toner remaining on photoconductor 1 after transfer process
Is a cleaning hand having a cleaning blade 8
Removed in the step. The photoconductor 1 after cleaning is erased.
And the charge is removed by the primary charger 2 again.
The process starting from the electrical process is repeated. Next, various physical properties measured in the following Examples
The method for measuring data will be described below. (1) Tetrahydrofuran (TH)
F) Quantification of ethyl acetate and chloroform insoluble components 2 g of the toner is precisely weighed (TW1), and the filter paper (for example, East
No. manufactured by Yoroishi 86R) soxhlet extractor
And use 200 ml of THF. Temperature to about 120 ° C
Reflux for 10 hours using the adjusted oil bath. TH
The component (W1) soluble in F is obtained by concentrating and drying THF.
It can be quantified by vacuum drying at 60 ° C. for 24 hours.
When quantifying the THF insoluble component (W2) of the toner,
THF-insoluble components other than the binder resin such as colorant (magnetic material) (T
W2) is calculated from the following equation. [0194] (Equation 1) Similarly, the solvent was changed to ethyl acetate and chloro
By changing to Holm, for each solvent
Quantify the soluble and insoluble components of the binder resin
You. FIG. 7 shows an example of a Soxhlet extraction apparatus.
You. The THF 52 contained in the container 51 is
Is heated and vaporized by the heater 53, and the vaporized THF passes through a pipe 54.
To the cooler 55. The cooler 55 includes a cooling water 56
It is always cooled. Cooled by the cooler 55 and liquefied
The collected THF is stored in a storage section 58 having a cylindrical filter paper 57.
When the liquid level of THF becomes higher than the middle pipe 59, the storage unit
Is discharged to the container 51 from the. Enter cylindrical filter paper 57
The toner or resin is removed by circulating THF.
It is extracted. (2)¹H-NMR and¹³C-NMR measurement
Of insoluble and soluble components in ethyl acetate
Determination of ester resin¹ H-NMR and¹³Each monomer composition using C-NMR
Calculate the abundance ratio by mole ratio, and calculate each monomer at this mole ratio.
-Use the molecular weight of each monomer from the composition
Neglecting the amount of dehydration associated with
The weight is calculated in% by weight. (¹H-NMR (nuclear magnetic resonance) spectrum
Measurement) Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL) Measurement frequency: 400MHz Pulse condition: 5.0 μs Data points: 32768 Frequency range: 10500Hz Number of accumulation: 10000 times Measurement temperature: 60 ° C Sample: 50 mg of a measurement sample was
And put CDCl as solvent_ThreeAnd add this
It is prepared by dissolving in a 60 ° C. thermostat. (¹³C-NMR (nuclear magnetic resonance) spectrum
Measurement) Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL) Measurement frequency: 400MHz Pulse condition: 5.0 μs Data points: 32768 Delay time: 25 sec. Frequency range: 10500Hz Number of accumulations: 16 times Measurement temperature: 40 ° C Specimen: 200mg of measurement sample with 5mm diameter
Put in a tube and use CDCl as solvent_Three(TMS0.0
5%) and dissolve this in a 40 ° C.
Prepare. [0201]¹H-NMR and¹³By C-NMR measurement
Polyes in components insoluble and soluble in ethyl acetate
FIGS. 3 and 4 to 6 show one specific example of the determination of the content of the tellurium resin.
Is described below using [0202]Alcohol component by ¹ H-NMR measurement
Of existence ratio (see FIGS. 4 and 5) Propoxylated bisphenol A (PO-BPA)
Existence ratio of toxinated bisphenol A (EO-BPA)
Is¹5.2 ppm in the H-NMR spectrum,
Water of propoxy group around 5.3ppm and 5.4ppm
Signal (corresponding to each 1H: see FIG. 6) and 4.3 ppm
And about 4.65 ppm of ethoxy group hydrogen (4H phase each)
It is determined from the intensity ratio with the signal of (2). [0203]Aromatic carboxylic acid by ¹ H-NMR measurement
Determination of the acid component abundance ratio (see FIGS. 4 and 5) The proportion of terephthalic acid and trimellitic acid is¹H-
Terephthalic acid around 8 ppm in NMR spectrum
Of hydrogen (corresponding to 4H) and 7.6 ppm 7.8 p
pm and hydrogen of trimellitic acid around 8.4 ppm (each
(Equivalent to 1H). [0204]Styrene abundance ratio by ¹ H NMR measurement
Determination of rate (see FIGS. 4 and 5) The content ratio of styrene is¹In the H-NMR spectrum
Signal strength of hydrogen (equivalent to 1H) around 6.6 ppm
Obtained from the ratio. [0205]Aliphatic carboxylic acid by ¹³ C-NMR measurement
Acid, (meth) acrylate and PO-BPA, E
O-BPA (meth) acrylate compound (vinyl
Product of the reaction between a polyester polymer and a polyester resin)
Determination of ratio (see Fig. 3) Aliphatic carboxylic acid, (meth) acrylic acid ester and bi
Of reaction products between phenyl-based polymers and polyester resins
The ratio is¹³173.5p in C-NMR spectrum
pm and carbohydrates of aliphatic carboxylic acids around 174 ppm
The signal of the carbon of the xyl group (corresponding to 1C each) and 176 pp
Carboxyl group of (meth) acrylic acid ester around m
Carbon (equivalent to 1C) signal and a new signal around 169 ppm
The peak of (meth) acrylic acid ester
Signal of carboxyl group carbon (corresponding to 1C) and intensity ratio
Ask from. [0206]Aliphatic carboxylic acid by ¹³ C-NMR measurement
Determination of the ratio of acid to aromatic carboxylic acid (see Fig. 3) The existence ratio of the aliphatic carboxylic acid and the aromatic carboxylic acid,¹³
In the C-NMR spectrum, the telescope around 165 ppm
Carboxyl carbon of phthalic acid and trimellitic acid
(Corresponding to 1C) and the above aliphatic carboxylic acid
Signal intensity of carboxyl group carbon (equivalent to 1C each)
Determined by comparing the ratios. [0207]Existence of styrene by ¹³ C-NMR measurement
Determination of ratio (see Fig. 3) The content ratio of styrene is¹³In C-NMR spectrum
Of the para-position carbon (1C equivalent) around 125 ppm
It is determined from the null intensity ratio. [0208]Insoluble and soluble components in ethyl acetate
Of the content of polyester resin component in water Above¹From the H-NMR spectrum, PO-B
PA, EO-BPA, terephthalic acid, trimellitic acid and
Calculate the molar ratio of each monomer composition in styrene and styrene
And further above¹³C-NMR spectrum
Et al., PO-BPA, EO-BPA (meth) acrylic acid
Ester compounds (vinyl polymer and polyester resin
Reaction products), aliphatic carboxylic acids, aromatic carboxylic acids
Calculate the molar ratio of each monomer composition of styrene and styrene
The composition ratio of all constituent monomers.
Calculate with the file ratio. The composition of each monomer at this molar ratio
Using the molecular weight of each monomer from the abundance ratio,
The amount of dehydration is ignored and the content of the polyester resin component is weighted.
Calculate in% by volume. (3) Measurement of melting point of wax Differential scanning calorimeter (DSC measurement device), DSC-7 (Part
ASTM D3418-8 using Kinelmer)
Measure according to 2. The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely. [0211] This is placed in an aluminum pan and
Using an empty aluminum pan as the measurement temperature range 30 to 20
Measured at room temperature and normal humidity at a heating rate of 10 ° C / min between 0 ° C
Perform settings. In this heating process, the temperature range of 30 to 200 ° C.
The endothermic peak of the main peak of the DSC curve
Can be The temperature of this endothermic main peak was
Melting point of (4) Measurement of DSC curve of toner In the same manner as the measurement of the melting point of the wax,
Measure the DSC curve in the process. (5) Glass transition temperature (Tg) of binder resin
Measurement Differential scanning calorimeter (DSC measurement device), DSC-7 (Part
ASTM D3418-8 using Kinelmer)
Measure according to 2. The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This was put in an aluminum pan and
Using an empty aluminum pan as the measurement temperature range 30 to 20
Measured at room temperature and normal humidity at a heating rate of 10 ° C / min between 0 ° C
Perform settings. In this heating process, the temperature range of 40 to 100 ° C.
The endothermic peak of the main peak in the box is obtained. At this time, before and after the endothermic peak appears.
The intersection of the line at the midpoint of the baseline and the differential thermal curve
The glass transition temperature in light is defined as Tg. (6) Measurement of molecular weight distribution of wax Gel permeation chromatography (GPC) measurement
Equipment: GPC-150C (Waters) Column: GMH-HT 30 cm 2 stations (Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (added with 0.1% ionol
Addition) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample is injected Measurement was performed under the above conditions, and the molecular weight of the sample was calculated.
In this case, it was made with a monodisperse polystyrene standard sample.
Use a molecular weight calibration curve. In addition, Mark-Hou
Polyethylene in conversion formula derived from wink viscosity formula
It is calculated by conversion. (7) Binder resin raw material or toner binder resin
Of molecular weight distribution of The molecular weight of the chromatogram by GPC is measured under the following conditions
Is done. The column was settled in a 40 ° C. heat chamber.
And the column at this temperature,
Flow lahydrofuran (THF) at a flow rate of 1 ml per minute.
If the sample is a binder resin material, roll the binder resin material
Used at 130 ° C for 15 minutes. Trial
When the toner is a toner, 0.2 μm after dissolving the toner in THF.
m, and the filtrate is used as a sample.
Resin adjusted to 0.05-0.6% by weight as sample concentration
Inject 50-200 μl of THF sample solution
You. When measuring the molecular weight of a sample,
Quantitative distributions were generated using several monodisperse polystyrene standards.
Calculated from the relationship between the logarithmic value of the manufactured calibration curve and the count number
I do. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0^Two, 2.1 × 10^Three, 4 × 10^Three, 1.75 × 1
0^Four, 5.1 × 10^Four, 1.1 × 10^Five, 3.9 × 10
^Five, 8.6 × 10^Five, 2 × 10⁶, 4.48 × 10⁶of
Use at least 10 points of standard polystyrene
It is appropriate to use a sample. The detector uses RI (refractive
Rate) using a detector. As the column, 10^Three~ 2 × 10⁶Minute
To accurately measure the molecular weight range, commercially available polystyrene
It is better to combine a plurality of gel columns, for example,
μ-styragel 500, 10 manufactured by rs^Three, 1
0^Four, 10^FiveCombinations and Shodex manufactured by Showa Denko
  KA-801, 802, 803, 804, 805, 8
06,807 are preferred. (8) The binder resin contained in the toner¹³C
-NMR measurement Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL) Measurement frequency: 100.40MHz Pulse condition: 5.0 μs (45 °) by DEPT method Data points: 32768 Delay time: 25 sec. Number of accumulation: 50,000 times Measurement temperature: 26 ° C Sample: 10 g of toner at room temperature in 100 ml of concentrated hydrochloric acid
(About 12M) and stir for about 70 hours.
Dissolve the magnetic material contained. Next, the filtrate is slightly acidic (about
Filter and wash until pH 5). Obtained resin composition
The sample is vacuum dried at 60 ° C. for about 20 hours to obtain a measurement sample.
About 1 g of this measurement sample is placed in a sample tube of φ10 mm.
And then use deuterated chloroform (CDCl_Three) 3ml
And adjusted by dissolving it in a 55 ° C constant temperature bath.
You. (9) Measurement of acid value According to the measurement method described in JIS K0070-1992
Do it. Measuring device: Automatic potentiometric titrator AT-400 (Kyoto
Electronic company) Calibration of equipment: toluene 120ml and ethanol 30ml
Is used. Measurement temperature: 25 ° C Sample preparation: 0.5 g of toner (for ethyl acetate-soluble components)
0.3 g) was added to 120 ml of toluene, and room temperature (about 2 g) was added.
(5 ° C.) for about 10 hours to dissolve. More ethanol
Add 30 ml to make a sample solution. (10) Measurement of OH value (hydroxyl value) 0.5 g of the sample is precisely weighed in a 100 ml volumetric flask, and
Add 5 ml of acetylating reagent correctly to this. Then 10
Heat by immersing in a bath at 0 ° C. ± 5 ° C. Hula after 1-2 hours
Take the scoop out of the bath, let it cool down, add water and shake it
Decomposes acetic anhydride. To complete the disassembly again,
Rasco is heated in a bath for at least 10 minutes and allowed to cool.
Wash the walls of the flask thoroughly. Use a glass electrode for this liquid
Potentiometric drop with N / 2 potassium hydroxide ethyl alcohol solution
To determine the OH value (JIS K0070-1966)
According to. ). [0228]   (11) Measurement of X-ray diffraction   Apparatus used: X-ray diffractometer CN2013 [Rigaku Denki Co., Ltd.]           : Powder sample molding machine PX-700 [manufactured by Thermonics Co., Ltd.] Using the above-mentioned molding apparatus, the measurement sample is compressed.
Press. The molded sample is set on the X-ray diffractometer,
Measure under the following conditions. Of the obtained X-ray diffraction pattern
The structure is determined from the peak strength and the 2θ angle. Target Filter Cu, Ni Voltage Current 32.5kV, 15mA Counter Se Time Constant 1 sec Divergence Slit 1 ° Receiving Slit 0.15mm Scatter Slit 1 ° Angle Range 60-20 ° [0230]   (12) Method for quantifying composite oxide in toner   Apparatus used: X-ray fluorescence analyzer 3080 (Rigaku Denki Co., Ltd.)           : Sample press molding machine MAEKAWA Testing               Machine (MFGCo., LTD) Preparation of calibration curve To the magnetic toner (X), a complex oxide for quantitative
Mix each in the following ratios (% by weight) using a hero mill,
Make a sample for the calibration curve. 0%, 0.5%, 1.0%, 2.0%, 3.0%, 5.
0%, 10.0% The above 7 samples were pressed using a sample press molding machine.
Shape. [M] Kα peak in composite oxide from 2θ table
The angle (a) is determined. Calibration curve into X-ray fluorescence analyzer
The sample is placed, and the sample chamber is evacuated and evacuated. Article below
Calculate the X-ray intensity of each sample and create a calibration curve
You. [Measurement conditions] Measurement potential, voltage 50kV-50mA 2θ angle a Crystal plate LiF Measurement time 60 seconds Determination of Complex Oxide in Toner After forming the sample in the same manner as above,
Calculate the amount of addition from the calibration curve based on the X-ray intensity
You. (13) Measurement of particle size distribution The particle size distribution can be measured by various methods
However, in the present invention, the multi-
This was performed using an Iser. As a measuring device, a Coulter counter was used.
Using Multisizer II (Coulter)
Interface to output distribution and volume distribution (Nikkaki
) And CX-1 personal computer (Canon
Made) and the electrolyte is special grade or first grade sodium chloride
To prepare a 1% aqueous solution of NaCl. As a measuring method
Is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution.
Surfactant (preferably alkylbenzene sulfonic acid
0.1 to 5 ml), and the measurement sample is further added to 2 to 20 ml.
Add mg. The electrolyte in which the sample is suspended is
Perform a dispersion treatment for 1 to 3 minutes.
By the Multisizer II of, as aperture
When measuring toner particle size, use 100μm aperture
Use 13μm aperture when measuring the particle size of inorganic fine powder
Measure using a char. Body of toner and inorganic fine powder
Measure product and number to calculate volume distribution and number distribution
Was. Then, the weight-based weight average diameter obtained from the volume distribution
Ask for. (14) Toner and cleaning blade
Measurement of viscoelastic properties of Viscoelasticity measuring device (rheometer) RDA-II (Rheome
(Manufactured by Trix Corporation). Measuring jig: Parallel plate with a diameter of 7.9 mm Measurement sample: toner is 8 mm in diameter and 2 in height after heating and melting
It is used by shaping into a disk-shaped sample of 5 to 5 mm. Measurement jig
Fixing is performed according to a conventional method. The cleaning blade has a thickness of 1 to 5 mm.
Punched into a disc with a diameter of about 8mm
Or cut out and use. Fixing to measuring jig is instantaneous
Adhesion and fixation are performed using an intervening adhesive. Measurement frequency: 6.28 radians / second Measurement temperature: from room temperature to 170 ° C at a rate of 1 ° C per minute
Warm up. [0238] Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. [0239]   Production Example I of Binder Resin:   (Resin Production Example I-1)   (Ia) Production of low cross-linking degree resin composition   (Production of resin composition containing substantially 0 to 10% by weight of chloroform-insoluble matter ) -Terephthalic acid: 5.0 mol ・ Succinic acid derivative represented by the formula (1-3): 1.0 mol -Trimellitic anhydride: 1.0 mol -PO-BPA: 7.0 mol -EO-BPA: 3.0 mol The above polyester monomer is esterified
Charged in an autoclave together with the medium, decompression device, water separation
Equipment, nitrogen gas introduction equipment, temperature measurement equipment and stirring equipment
Attach and mount under a nitrogen atmosphere while reducing the pressure according to a standard method.
By conducting the condensation polymerization reaction while heating to 0 ° C,
Low cross-linking degree polye containing about 3% by weight of roloform-insoluble matter
A steal resin was obtained. Next, 50 parts by weight of xylene was added to the obtained
80 parts by weight of polyester resin, 16 parts by weight of styrene
Parts by weight, 4 parts by weight of 2-ethylhexyl acrylate and S
0.3 parts by weight of dibutyltin oxide as a tellurization catalyst
And heated to 110 ° C. to dissolve and swell. Nitrification
Under a hydrogen atmosphere, t-butyl high as a radical polymerization initiator
Dissolve 1 part by weight of dropper oxide in 10 parts by weight of xylene
The solution was dropped over about 30 minutes. At that temperature further
The radical polymerization reaction was completed by holding for 10 hours. More
Reduce the degree of cross-linking by depressurizing while heating and removing the solvent.
Polyester resin, vinyl polymer and polyester resin
Hybrid having knit and vinyl polymer unit
Approximately 7 weight percent of chloroform-insoluble components
% Low-crosslinking resin composition (a-1) was obtained. [0242]   (Ib) Production of high cross-linking degree resin composition   (Production of a resin composition containing 15 to 70% by weight of a chloroform-insoluble content) -Terephthalic acid: 2.0 mol -Succinic acid derivative represented by the formula (1-3): 4.0 mol -Trimellitic anhydride: 4.0 mol ・ PO-BPA: 10.0mol -EO-BPA: 4.0 mol The above polyester monomer is esterified
Charged in an autoclave together with the medium, decompression device, water separation
Equipment, nitrogen gas introduction equipment, temperature measurement equipment and stirring equipment
Attach and mount under a nitrogen atmosphere while reducing the pressure according to a standard method.
By conducting the condensation polymerization reaction while heating to 0 ° C,
Highly crosslinked poly containing about 25% by weight of roloform insolubles
An ester resin was obtained. Next, 50 parts by weight of xylene was obtained here.
80 parts by weight of polyester resin, 10 parts by weight of styrene
Parts, 2-ethylhexyl acrylate 10 parts by weight,
Nylbenzene 0.01 parts by weight and as an esterification catalyst
0.3 parts by weight of dibutyltin oxide was added, and
It was heated to 0 ° C. to dissolve and swell. Radiation under nitrogen atmosphere
T-butyl hydroperoxide as a cal polymerization initiator
1 part by weight of xylene dissolved in 10 parts by weight of xylene
It was added dropwise over 0 minutes. Hold at that temperature for another 10 hours
The radical polymerization reaction was completed. Reduce the pressure while heating
By removing the solvent
Fat, vinyl polymer and polyester unit and vinyl
Hybrid resin component having a polymer unit
Containing about 33% by weight of chloroform-insoluble matter.
Thus, a resin composition (b-1) having a degree of crosslinking was obtained. (Ic) Production of Binder Resin 100 parts by weight of xylene and low crosslinking degree resin composition (a-1)
60 parts by weight, 30 parts by weight of the highly crosslinked resin composition (b-1)
Parts, styrene 5 parts by weight, 2-ethylhexyl acrylate
5 parts by weight and divinylbenzene 0.01 parts by weight
And heated to 110 ° C. to swell and dissolve. Nitrogen atmosphere
Below, t-butyl hydropar as a radical polymerization initiator
1 part by weight of oxide dissolved in 10 parts by weight of xylene
Was dropped over about 30 minutes. 10 hours at that temperature
The radical polymerization reaction was terminated by holding. Further heating
The pressure is reduced and the solvent is removed.
Tell resin, high cross-linking degree polyester resin, vinyl polymer
And a polyester unit and a vinyl polymer unit.
Consisting of a hybrid resin component
Resin (C-1) containing about 28% by weight of
Obtained. (Resin Production Example I-2) Resin production example I-1
In producing the resin composition (b-1) having a high degree of crosslinking,
16.6 parts by weight based on 80 parts by weight of the polyester resin
Parts of hydrocarbon wax (melting point 100 ° C, weight average molecule
1800) with styrene and 2-ethylhexylacrylic acid.
With wax, containing wax and chloro
Highly crosslinked resin composition containing 37% by weight of form-insoluble matter
(B-2) was obtained. High crosslinking degree resin composition (b-2) 35
Except for using 5 parts by weight (including 5 parts by weight of wax)
In the same manner as in Preparation Example I-1, a low-crosslinking degree polyester resin,
Highly crosslinked polyester resin, vinyl polymer and polyether
Has a steal unit and a vinyl polymer unit
Consists of a hybrid resin component to remove chloroform-insoluble
A binder resin (C-2) containing about 30% by weight was obtained. (Resin Production Examples I-3 to I-5)
By changing the type and composition ratio,
The binder resins (C-3) to (C-5) were obtained. (Resin Production Example I-1) Resin Production Example I-
In Example 1, instead of the succinic acid derivative (1-3),
Tables 1 to 3 show the same procedures except that phthalic acid was used.
Thus, a comparative binder resin (C-1) was obtained. (Resin Production Example I-2) Resin Production Example I-
In Example 1, instead of the succinic acid derivative (1-3),
Using phthalic acid and increasing the amount of trimellitic anhydride
In the same manner except that a bridge resin composition was used, Tables 1 to
Thus, a comparative binder resin (C-2) shown in Fig. 3 was obtained. [0250] [Table 1] [0251] [Table 2][0252] [Table 3] (Production Example 1 of Composite Oxide: Strontium Silicate)
A) Strontium carbonate 1500g and silicon oxide 600
g in a ball mill for 8 hours, followed by filtration and drying.
Then, this mixture is 5 kg / cm^TwoMolded under pressure of 13
Calcination was performed at 00 ° C. for 8 hours. This is mechanically crushed and
Strontium silicate fine powder having an average diameter of 2.0 μm (M-
1) was obtained. Further, X obtained with respect to the obtained (M-1)
X-ray diffraction was performed, and it was manufactured from the peak pattern of FIG.
The composite oxide is SrSiO_Three(A = 1, b =
1, c = 3) and Sr_TwoSiO_Four(A = 2, b in equation (1)
= 1, c = 4). (Production Example 2 of Composite Oxide: Titanate oxide
600 g of strontium carbonate and titanium oxide 3
20 g was wet mixed in a ball mill for 8 hours and then filtered.
Dry and mix this mixture to 5 kg / cm^TwoMolding with the pressure of
Calcination was performed at 1100 ° C. for 8 hours. This is mechanically crushed,
Fine powder of strontium titanate having a weight average diameter of 1.7 μm
(M-2) was obtained. (Production Example 3 of Composite Oxide: Cerium Oxide)
(Comparative) In the presence of 1500 g of cerium carbonate and oxygen
Burned at 1300 ° C. for 10 hours. This is mechanically crushed
Cerium oxide fine powder having a weight average diameter of 2.0 μm (M-
3) was obtained. (Test blade) Blade A shown in Table 4
To K were prepared as blades for this study. The break
All dimensions are 331.5 ± 1.0mm in length and 20 ± width.
The thickness was 0.2 mm and the thickness was 3 ± 0.1 mm. The viscoelasticity data of blade B (data:
1) is attached as FIG. [0258] [Table 4] [0259]   (Example of toner production) ・ 100 parts by weight of binder resin (C-1) ・ 90 parts by weight of magnetic iron oxide   (Average particle size 0.15 μm, Hc 9.2 kA / m (120 Oersted), σs     = 83 Am^Two/ Kg (83 emu / g), σr = 11.5 Am^Two/ Kg     (11.5 emu / g)) ・ Azo-based iron complex compound (negative charge control agent) 2 parts by weight ・ 5 parts by weight of low molecular weight polyethylene wax   (Melting point 110 ° C, weight average molecular weight 1880) The above materials were mixed with a Henschel mixer
After that, melt kneading was performed at 130 ° C by a twin screw kneading extruder.
After cooling the mixture, coarsely pulverizing it with a cutter mill,
Pulverized using a fine pulverizer using a jet stream
Classify using a classifier and load with a weight average diameter of 6.3 μm.
As a result, conductive magnetic toner particles (P) were obtained. By using the toner (P), a binder resin
Tetrahydrofuran (THF), ethyl acetate and
Soxhlet extraction of soluble and insoluble components of
Quantitative analysis revealed that mixed wax was excluded.
The resin composition has a THF insoluble content (W2) of 31% by weight.
And the ethyl acetate insoluble matter (W4) was 34% by weight.
The content of roloform insoluble matter (W6) was 15% by weight, and the ratio (W
4 / W6) is 2.7, and the content of THF-insoluble matter (W2)
Chloroform-insoluble matter (W6A) is 6.7% by weight;
Chloroform insolubles (W4) in ethyl acetate insolubles (W4)
6B) was 8.3% by weight. Of the soluble component (W1) of tetrahydrofuran
When the molecular weight was measured by GPC, the main peak was
Having a molecular weight of 4400, a molecular weight of 500 or more and less than 10,000
The component (A1) in the region is 48.9% and the molecular weight is 10,000 or more and 10
26.7% of component (A2) in a region of less than 10,000 and a molecular weight of 10
The component (A3) in the area of 10,000 or more is 24.4%,
(A1 / A2) was 1.83. Binder Resin for Toner and Ethyl Acetate for Toner
The acid value of the soluble component (W3) of
The acid value (AV1) of the contained binder resin is 26.7 m
gKOH / g, the acid of the ethyl acetate-soluble component of the toner
The value (AV2) is 21.6 mg KOH / g and the ratio (A
V1 / AV2) was 1.2. [0264]¹H-NMR and¹³By C-NMR,
Vinyl copolymer, polyester resin and poly
Has an ester unit and a vinyl polymer unit
Make sure that the hybrid resin component
Was. In the toner, a polyester unit and
Hybrid resin having vinyl polymer unit
The ingredients are¹³Ester bond newly formed by C-NMR
Can be verified by detecting the signal
You. In general, acrylic acid copolymerized with styrene
Of the ester group of the ester¹³Measured by C-NMR
The signal is that of the acrylate homopolymer.
Higher magnetic field side by several ppm due to the effect of styrene ring of styrene
Is known. This is acrylic acid
The alcohol component of the ester is the alcohol of the polyester
Hybrid resin obtained by transesterification with components
The same is true for the components, which are introduced by transesterification.
Of benzene ring in polyester unit
The signal is also affected by the signal of the vinyl polymer unit.
Detected as a signal on the higher magnetic field side than acrylate
Will be issued. The low crosslinking degree polyester¹³C-NMR measurement
The results are shown in FIG. 1, where styrene-2-ethylhexyl acryl
FIG. 2 shows the measurement results of the toner copolymer.
FIG. 3 shows the measurement results of the binder resin (C-1). As a result
Approximately 22 mol% of acrylic acid ester
As a hybrid resin component esterified with
It was found to exist. Each of the¹³Table 5 shows the C-NMR measurement results.
You. [0269] [Table 5] Further, by NMR, a bond insoluble in ethyl acetate was obtained.
Binder resin component (W4) and soluble binder resin component (W3)
Polyester resin components (Gp) and (S) contained in
When p) was quantified, Gp = about 83% by weight and Sp = about
77% by weight, and the ratio (Sp / Gp) = 0.93
The amount of the succinic acid derivative represented by the formula (1-3)
As a result of the quantification, the total amount of ingredients insoluble in ethyl acetate
Of about 74% by weight. Ingredient contained in the component (W4) insoluble in ethyl acetate
The amount of wax to be dissolved is measured by DSC
From the toner, and as a result,
It was found that about 61% by weight of the catalyst was present. The results of the toner analysis are shown in Tables 6 and 7.
Was. In 100 parts by weight of the magnetic toner particles (P),
On the other hand, hydrophobic silica (specific surface area: 200 m^Two/ G) 1.
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1)
Externally mixed with a gel mixer, the magnetic toner for evaluation (P-
1). <Evaluation-1> Density as an evaluation of toner fixability
The temperature reduction rate and high temperature offset are based on the following evaluation methods.
It was carried out. Regarding low-temperature fixability, 3% density reduction rate
And good results.
Did not. The evaluation results are shown in Table 8. [0275]Low temperature fixability test: Canon digital copy
GP215 remodeling machine (developing, drum, optical, paper transport system, etc.)
Was adjusted to increase the copying speed by 20%. ) Low
Install in a warm and low humidity room (temperature: 5 ° C, humidity: 5%). The magnetic toner for evaluation (P-1)
Using a tone image as an original, output 100 continuous papers
And sample the 100th image,
4900N / m^Two(50g / cm^Two)
Rubbing with a thin thin paper, image density difference before and after
(Image density reduction rate (%)). (Low-temperature fixability evaluation level) A: Concentration reduction rate is less than 5% B: Density reduction rate is 5% or more and less than 10% C: Concentration reduction rate is 10% or more and less than 15% D: Density reduction rate is 15% or more and less than 25% E: Density reduction rate is 25% or more [0278]High temperature offset test: Canon copier N
Remove the fixing unit of P6085, external drive and temperature control
Install the equipment. Evaluation was performed using a Canon copier NP6085.
Unfixed image using magnetic toner (P-1)
The fixing temperature of the fixing device is changed to
Check whether the set has occurred on the fixing roller and on the fixed image.
Judgment and evaluation by visually confirming toner adhesion to
Was. (Evaluation level for high-temperature offset resistance) A: No offset at 250 ° C B: Minor offset generation at 250 ° C C: slight offset generation at 230 ° C to 240 ° C D: Offset occurs at 220 to 230 ° C E: Offset occurs below 210 ° C <Evaluation-2> The binder resin in the toner material was
In (a-2), the negative charge control agent was changed to an Al complex compound.
Except that the weight average diameter
As a result, 7.0 μm magnetic toner particles (Q) were obtained. To 100 parts by weight of the magnetic toner particles (Q)
On the other hand, hydrophobic silica (specific surface area: 200 m^Two/ G) 1.
0 parts by weight and 4.0 parts by weight of the composite oxide (M-2)
Externally mixed with a gel mixer, the magnetic toner for evaluation (Q-
1). Using this toner, evaluation similar to that of evaluation-1 was made.
Value. Low-temperature fixability and high-temperature offset resistance
Was a good result. Table 8 shows the evaluation results. <Evaluation-3 to 5> Binder Resin in Toner Material
Except that was changed to (a-3), (a-4), and (a-5)
In the same manner as in Evaluation-1, each had a weight average diameter of 6.4 μm,
6.8 μm, 6.6 μm magnetic toner particles (R),
(S) and (T) were obtained. Each of the magnetic toner particles (R)
(S), (T) 100 parts by weight of hydrophobic silica
(Specific surface area 200m^Two/ G) 1.0 part by weight and composite oxide
(M-2) 4.0 parts by weight externally added with a Henschel mixer
The magnetic toners for evaluation (R-1), (S-1),
(T-1). Using this toner, evaluation similar to that of evaluation-1 was made.
Value. Low-temperature fixability and high-temperature offset resistance
Was a good result. Table 8 shows the evaluation results. <Evaluation-6 to 7: Comparative Example>
Except that the binder resin was changed to (A-1) and (A-2)
In the same manner as in the toner production example, the weight average diameter was 6.4 μm.
m and 6.8 μm magnetic toner particles (S) and (S)
Obtained. The magnetic toner particles (sa) and
(S) 100 parts by weight of hydrophobic silica (specific surface area)
200m^Two/ G) 1.0 part by weight and composite oxide (M-2)
4.0 parts by weight were externally added and mixed with a Henschel mixer,
Comparative evaluation magnetic toners (S-1) and (S-1). Using this toner, evaluation similar to that of evaluation-1 was made.
Value. Regarding (sa-1), high-temperature offset resistance
In addition, with respect to (C-1), there was a problem in the low-temperature fixability.
Table 8 shows the evaluation results. <Evaluation-8> The above toner (Q),
(R), (S), (T), (sa) and (si)
The same analysis as for toner (P) was performed, and the results in Tables 6 and 7 were obtained.
I got <Evaluation-9> Canon copier NP608
5 remodeling machines (adjust all development, drum, optics, paper transport system, etc.)
The copying speed was increased by 20%. ) The high temperature and high humidity room
(Temperature: 32.5 ° C., humidity: 85%). this
At the time, B in Table 4
Then, they were brought into contact at a total pressure of 680 g. Using the magnetic toner for evaluation (P-1),
Continuous 300,000 image output, image density, fog, image flow
And the amount of drum scraping was evaluated. The result is from the beginning of endurance
Image density is stable up to the last 300,000 sheets.
High image quality without fog was obtained. Also, image deletion occurs
Did not. Furthermore, the drum film thickness was measured before and after endurance.
However, the shaving amount was 10 °. Detailed results are shown in Table 9.
Indicated. The image density evaluation level is the maximum
Density-Judgment was made based on the image density at the end of 300,000 copies. The evaluation level of fog is 300,000
Judgment was made based on fog in the solid white image at the time. The fog measurement was performed by using a reflection measurement device R for fog measurement.
At EFLECTMETER (Tokyo Denshoku Co., Ltd.)
Measure the reflectance of the solid white image and the unused paper of
The difference is assumed to be fog. Unused paper reflectance-solid white reflectance = power
Yellowtail The evaluation of the image deletion was made on the image during the running.
When injuries occurred, evaluation was made based on this maximum missing image area. [0297] The evaluation of the drum scraping amount was made by comparing the drum before the endurance with the endurance.
Determined by the difference in film thickness with the drum after the
Refused. [0298]   (Image density evaluation level) A: Maximum image density-image density at end of durability less than 0.05 B: Maximum image density-End of endurance image density 0.05 or more and less than 0.10 C: maximum image density-image density at end of durability 0.10 or more and less than 0.15 D: maximum image density-end-of-life image density 0.15 or more and less than 0.25 E: Maximum image density-end of endurance image density 0.25 or more (Fog evaluation level) A: Fog less than 0.1% B: Fog 0.1 or more and less than 0.5% C: Fog 0.5 or more and less than 1.0% D: Fog 1.0 or more and less than 1.5% E: fog 1.5 or more (Image deletion evaluation level) A: No missing image area B: missing image area 0.15cm^TwoLess than C: Missing image area 0.15 or more and 5.0 cm^TwoLess than D: Area of missing image 5.0 to 10.0 cm^TwoLess than E: missing image area 10.0cm^Twothat's all (Drum scraping amount evaluation level) A: Less than 10.0mm B: Shaving amount 10.0 or more and less than 25.0% C: Shaving amount 25.0 or more and less than 50.0% D: Shaving amount 50.0 or more and less than 150.0 mm E: Shaving amount 150.0 mm or more <Evaluation-10 to 14> Cleaning Bray
Was changed to C, D, F, G, H, and the same as in Evaluation -9.
An evaluation was performed. Image density is high, stable and fog
High image quality without resolution was obtained. In addition, image flow
It was an untitled level. Detailed results are shown in Table 9. <Evaluation-15 to 19: Comparative Example> Cleanin
Change blades to A, E, I, J, K and evaluate -9
The same evaluation was performed. Image density is high and stable
Image quality with high resolution without fog
Was done. Furthermore, the image flow was at a level without any problem,
For A, E, I, and K, cleaning is not possible during
OK, drum fusion occurred during J
Was. Detailed results are shown in Table 9. <Evaluation-20 to 23>
(Q-1), (R-1), (S-1), (T-1)
Furthermore, the same evaluation as the evaluation -9 was performed. High image density
High resolution, stable and fog free
High image quality was obtained. In addition, the image flow is
It was. Detailed results are shown in Table 9. <Evaluation-24 to 25: Comparative Example> Magnetism for evaluation
Change the toner to (c-1) and (c-1) and evaluate
The same evaluation as in No. 9 was performed. The image density of each toner is
There was a tendency to decrease, and an image quality with poor fog suppression was obtained. Change
In the meantime, the image flow was at a level without any problem.
In 1), the cleaning failure is related to (sa-1).
Drum fusion occurred. Detailed results are shown in Table 9.
Was. <Evaluation -26 to 29: Comparative Example>
Magnetic toner particles (Q), (R), (S), (S) 100
To the parts by weight, hydrophobic silica (specific surface area 200 m^Two/
g) 1.0 part by weight and 4.0 parts by weight of the composite oxide (M-3)
Is externally added and mixed with a Henschel mixer, and is used for comparative evaluation.
Toners (Q-2), (R-2), (c-2) and (c)
2). Using this toner, evaluation similar to that of evaluation -9 was made.
Value. Both toners have the durability and drum
Image density tends to decrease and fog
Poorly controlled image quality was obtained. However, image flow is a problem
There was no level. Detailed results are shown in Table 9. <Evaluation-30: Comparative Example> Magnetic toner particles
(Q) 100 parts by weight of hydrophobic silica (specific surface area)
200m^Two/ G) 1.0 part by weight to Henschel mixer
And externally mixed to obtain a magnetic toner (Q-3) for comparative evaluation.
Was. Using this toner, evaluation similar to that of evaluation -9 was made.
Value. The result is that the image density tends to decrease due to durability.
Yes, image quality with poor fog suppression was obtained. Furthermore, the image flow
This occurred from the beginning of endurance. Also, drum scraping is a problem
Although there was no level, drum fusion began to occur.
Detailed results are shown in Table 9. [0310] [Table 6] [0311] [Table 7][0312] [Table 8] [0313] [Table 9] (Visco-elastic properties of toner and blade)
Gnar (P), (Q), (R), (S), (T), (sa)
The viscoelasticity was measured for (A) and (B). Table 10 shows the results.
It became. FIG. 11 shows the viscoelasticity measurement chart of (P).
Attach. Further, Table 11 shows the toners used in this study.
(P) shows the viscoelastic properties of the blade. [0316] [Table 10] [0317] [Table 11] [0318] According to the present invention, the method for use as described above is used.
Improvement of cleaning tool and cleaning blade
High image quality and high image density even under high temperature and high humidity.
Cleaning failure, toner fusion and image deletion
Provided is an image forming method and an image forming apparatus that do not generate an image.
can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 ¹³ C-NM of low cross-linking degree polyester resin composition
2 shows an R spectrum. FIG. 2 shows a ¹³ C-NMR spectrum of a styrene / 2-ethylhexyl acrylate copolymer. FIG. 3 shows ¹³ C-NM of the binder resin (C-1) according to the present invention.
2 shows an R spectrum. FIG. 4 shows a ¹ H-NMR spectrum of a component soluble in ethyl acetate of the binder resin (C-1) according to the present invention. FIG. 5 shows a ¹ H-NMR spectrum of an ethyl acetate-insoluble component of the binder resin (C-1) according to the present invention. FIG. 6 is an explanatory diagram showing assignment of ¹ H-NMR signals of PO groups of PO-BPA. FIG. 7 is a schematic diagram showing a specific example of a Soxhlet extraction device used for Soxhlet extraction. FIG. 8 is an explanatory diagram illustrating an example of an image forming apparatus that can execute the image forming method of the present invention. FIG. 9 is an enlarged view of a developing unit of the image forming apparatus shown in FIG. FIG. 10 is a graph showing viscoelastic data of blade B. FIG. 11 is a graph showing viscoelasticity data of the toner (P). FIG. 12 is a graph showing an X-ray diffraction peak pattern of the composite oxide of Production Example 1. [Description of Signs] 1 electrostatic latent image holding member (photoconductor) 4 toner carrier (developing sleeve) 7 fixing device 8 cleaning blade 9 developing device 11 magnetic blade 13 toner P recording material (transfer material)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 21/00 318 (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasuko Shibayama 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term within Canon Inc. (Reference) 2H005 AA01 AA02 AA06 AA08 AB02 AB03 CA02 CA08 CA13 CA14 CA17 CA18 CB07 CB13 DA06 DA07 DA10 EA03 EA06 EA07 EA10 FA06 2H034 AA02 AA06 BF02 2H077 AD06 AD32 AD35 AD37 EA13

Claims (1)

Claims: 1. An electrostatic image formed on an electrostatic image carrier.
Is developed with toner to form a toner image,
The obtained toner image is transferred from the electrostatic image carrier through an intermediate transfer member.
Transfer to a transfer material without or with intermediary
Transfer residual toner using a cleaning blade.
An image forming method having a step of polishing, wherein the toner comprises at least a binder resin, a wax and a colorant.
Containing toner particles and inorganic fine powder.
The binder resin includes (1) a vinyl resin, a polyester resin, and a vinyl resin.
Has a polymer unit and a polyester unit
Contains a hybrid resin component, and (2) 10 using tetrahydrofuran (THF) as a solvent
The soxhlet extraction of the time, the THF soluble component from 50 to
85% by weight (W1), and a THF-insoluble component of 15 to
(3) Soxhlet for 10 hours using ethyl acetate as a solvent
In the extraction, the ethyl acetate-soluble component was reduced to 40 to 98% by weight (W
3) Contains 2 to 60% by weight of ethyl acetate insoluble component
(W4), (4) Soxhlet for 10 hours using chloroform as a solvent
-55-90% by weight of chloroform-soluble components by extraction
(W5) containing 10 to 45 chloroform-insoluble components.
(5) The value of W4 / W6 is from 1.1 to 4.0, and when the toner is at a temperature of 50 to 75 ° C., (a) storage elastic modulus (G′T) and loss Elastic modulus (G "T)
(B) a temperature at which the loss tangent (tanδTP) is at a maximum.
(TT.P), and the cleaning blade: (c) at a temperature of 40 to 80 ° C., at a storage elastic modulus (G′B)
But 5 × 10 ^Five ~ 1 × 10 ⁷ (D) Loss modulus (G ″ B) at a temperature of 40 to 80 ° C.
But 5 × 10 ^Three ~ 1 × 10 ⁶ (E) At a temperature of 40 to 80 ° C., a loss tangent (tan δB.
P) has a minimum temperature (TT.B), and (f) a loss tangent (tan δ) at a temperature of 70 to 130 ° C.
B. P) has a temperature (TB.P) at which the toner and the cleaning blade have a loss tangent.
(G) the difference (TT.P-TB.P) is -40 to 20 ° C.
(H) loss elastic modulus of the toner at a temperature (TT.C)
(G "T) and cleaning at temperature (TT.C)
Ratio (G "T) to loss elastic modulus (G" BC) of blade
/ (G ″ BC) is 5 × 10 ^Two ~ 5 × 10 ^Four Is
And an image forming method. 2. The binder resin is a gel-soluble THF-soluble component.
-Measurement by chromatography (GPC)
In a molecular weight distribution of 4000 to 9000,
It has a main peak in the region and has a molecular weight of 500 to less than 10,000
Is 35.0 to 65.0% (A1).
The components in the region having a molecular weight of 10,000 to less than 100,000 are 25.0.
From 45.0% (A2), and a molecular weight of 100,000 or more.
Is 10.0 to 30.0% (A3), and A1 / A
2 is 1.05 to 2.00.
The image forming method according to claim 1. 3. The polyester resin of a binder resin and the polyester resin.
The ester unit is a trivalent or higher polycarboxylic acid or
Is an anhydride or a trihydric or higher alcohol.
Claims characterized by having a bridged crosslinked structure
3. The image forming method according to 1 or 2. 4. The vinyl resin as a binder resin and the vinyl
The polymer unit is a crosslinking agent having two or more vinyl groups.
Characterized by having a cross-linked structure cross-linked by
An image forming method according to any one of claims 1 to 3. 5. The binder resin is a THF-insoluble component (W2).
20 to 45% by weight.
5. The image forming method according to any one of 1 to 4. 6. The binder resin is a THF-insoluble component (W2).
25 to 40% by weight.
5. The image forming method according to any one of 1 to 4. 7. The binder resin comprises an ethyl acetate-insoluble component (W
(4) is contained in an amount of 5 to 50% by weight.
Item 7. The image forming method according to any one of Items 1 to 6. 8. The binder resin comprises an ethyl acetate-insoluble component (W
(4) is contained in an amount of 10 to 40% by weight.
An image forming method according to any one of claims 1 to 6. 9. The binder resin comprises a chloroform-insoluble component.
(W6) is contained in an amount of 15 to 40% by weight.
An image forming method according to claim 1. 10. The binder resin is a chloroform-insoluble component.
(W6) is contained in an amount of 17 to 37% by weight.
An image forming method according to claim 1. 11. The binder resin comprises an ethyl acetate-insoluble component.
(W4) and chloroform-insoluble component (W6) (W4
/ W6) is 1.2 to 3.5.
The image forming method according to claim 1. 12. The binder resin comprises an ethyl acetate-insoluble component.
(W4) and chloroform-insoluble component (W6) (W4
/ W6) is 1.5 to 3.0.
The image forming method according to claim 1. 13. The composition containing the THF-insoluble component (W2).
Of the chloroform-insoluble component (W6A) and the acetic acid
Chloroform insoluble in ethyl-insoluble component (W4)
The content of the dissolved component (W6B) is determined by the following condition: 3% by weight ≦ W6A ≦ 25% by weight 7% by weight ≦ W6B ≦ 30% by weight 10% by weight ≦ W6A + W6B ≦ 45% by weight W6A: W6B = 1: 1 to 3% 13. The method according to claim 1, wherein the content is satisfied.
An image forming method according to any one of the above. 14. The composition containing the THF-insoluble component (W2).
Of the chloroform-insoluble component (W6A) and the acetic acid
Chloroform insoluble in ethyl-insoluble component (W4)
The content of the soluble component (W6B) is as follows: 5% by weight ≦ W6A ≦ 20% by weight 10% by weight ≦ W6B ≦ 25% by weight 15% by weight ≦ W6A + W6B ≦ 40% by weight W6A: W6B = 1: 1.5 to 13. The method according to claim 1, wherein the value of 2.5 is satisfied.
An image forming method according to any one of the above. 15. A vinyl polymerization of the hybrid resin component.
The body unit and the polyester unit are as follows: 2. The method according to claim 1, wherein the connection is made through
5. The image forming method according to any one of 4. 16. The hybrid resin component is a polyester resin.
Monomers having ter units and carboxylic acid ester groups
Transesterification with vinyl polymer unit by polymerization of
Characterized by a copolymer formed by reaction
The image forming method according to claim 1. 17. The method according to claim 17, wherein the hybrid resin component is a vinyl resin.
The polymer unit is the trunk polymer, and the polyester unit
Characterized in that it is a graft polymer with
An image forming method according to claim 1. 18. The binder resin has a content of 10 to 60 mol%.
2. The composition according to claim 1, wherein the composition has a grafting ratio.
8. The image forming method according to any one of 7. 19. The binder resin has a content of 15 to 55 mol%.
2. The composition according to claim 1, wherein the composition has a grafting ratio.
8. The image forming method according to any one of 7. 20. The binder resin comprises: (1) a component (W4) insoluble in ethyl acetate;
2 to 60% by weight based on 0 parts by weight, (2) Ethyl acetate-insoluble component (W4) is polyester
The resin component (Gp) contains 40 to 98% by weight, and (3) a component (W3) soluble in ethyl acetate is
(4) Polyethylene containing a component (W4) which is insoluble in ethyl acetate.
Ester resin component (Gp) content and dissolved in ethyl acetate
Resin component (S3) contained in component (W3)
The ratio (Sp / Gp) to the content of p) is from 0.50 to 1.
Wherein the wax comprises a hydrocarbon wax.
The image forming method according to claim 1, wherein 21. The component (W4) insoluble in ethyl acetate
Contains 55 to 95% by weight of a polyester resin component (Gp)
21. The image forming method according to claim 20, further comprising:
Law. 22. The component (W4) insoluble in ethyl acetate
Contains 60 to 90% by weight of polyester resin component (Gp)
21. The image forming method according to claim 20, further comprising:
Law. 23. A component (W3) soluble in said ethyl acetate
Is 25 to 85% by weight of the polyester resin component (Sp)
23. Any of claims 20 to 22, characterized by containing
An image forming method according to any one of the above. 24. A component (W3) soluble in said ethyl acetate
Is 30 to 80% by weight of the polyester resin component (Sp)
23. Any of claims 20 to 22, characterized by containing
An image forming method according to any one of the above. 25. The component (W4) insoluble in ethyl acetate
Polyester Resin Component (Gp) Content and Acetic Acid
Polyester containing component (W3) soluble in ethyl
The ratio (Sp / Gp) to the resin component (Sp) is from 0.60 to
25. The method according to claim 20, wherein the value is 0.95.
The image forming method according to any one of the above. 26. The component (W4) insoluble in said ethyl acetate
Polyester Resin Component (Gp) Content and Acetic Acid
Polyester containing component (W3) soluble in ethyl
The ratio (Sp / Gp) to the resin component (Sp) is from 0.65 to
25. The method according to claim 20, wherein the value is 0.90.
The image forming method according to any one of the above. 27. The total binder resin of the toner is 7 to 40.
It has an acid value (AV1) of mgKOH / g.
An image forming apparatus according to any one of claims 1 to 26, characterized in that:
Method. 28. The total binder resin of the toner is 10 to 3
Having an acid value (AV1) of 7 mg KOH / g
The image form according to any one of claims 1 to 26, characterized in that:
Method. 29. An ethyl acetate-soluble component (W) of the toner.
3) is an acid value of 10 to 45 mgKOH / g (AV2)
29. The method according to claim 1, wherein:
An image forming method according to any one of the preceding claims. 30. An ethyl acetate-soluble component (W) of the toner.
3) is an acid value of 15 to 45 mgKOH / g (AV2)
29. The method according to claim 1, wherein:
An image forming method according to any one of the preceding claims. 31. An acid value (AV) of all binder resins of the toner.
1) and the acid value of the ethyl acetate-soluble component (W3) of the toner
The ratio (AV1 / AV2) to (AV2) is 0.7 to
31. The method according to claim 1, wherein the value is 2.0.
An image forming method according to any one of the preceding claims. 32. An acid value (AV) of all binder resins of the toner.
1) and the acid value of the ethyl acetate-soluble component (W3) of the toner
The ratio (AV1 / AV2) to (AV2) is 1.0 to
31. The method according to claim 1, wherein the value is 1.5.
An image forming method according to any one of the preceding claims. 33. The wax may be a differential scanning calorimeter (D
SC) is determined by the endothermic peak temperature at the time of
A melting point of 70 to 140 ° C.
Item 33. The image forming method according to any one of Items 1 to 32. 34. The wax may be a differential scanning calorimeter (D
SC) is determined by the endothermic peak temperature at the time of
A melting point of 80 to 135 ° C.
Item 33. The image forming method according to any one of Items 1 to 32. 35. The wax may be a differential scanning calorimeter (D)
SC) is determined by the endothermic peak temperature at the time of
A melting point of 90 to 130 ° C.
Item 33. The image forming method according to any one of Items 1 to 32. 36. A method for producing a binder resin, comprising:
Bonding tree containing wax, produced in the presence of cousin
Fatty acid is contained.
The image forming method according to any one of the above. 37. The inorganic fine powder represented by the following formula (1):
A composite oxide (A) particle
An image forming method according to any one of claims 1 to 36. [M ₁ ] _a [M _Two ] _b O _c (1) (where M ₁ Are Sr, Mg, Zn, Co, Mn, Ca and
Indicates a metal element selected from the group consisting of
Then M _Two Indicates a metal element selected from Ti or Si
A represents an integer of 1 to 9; b represents an integer of 1 to 9
And c represents an integer of 3 to 9. 38. A method according to claim 38, wherein 100 parts by weight of the toner particles
0.10 to 10 parts by weight of the composite oxide (A) particles is externally added
38. The method according to claim 1, wherein
Image forming method described above. 39. 100 parts by weight of toner particles
0.20 to 5 parts by weight of the composite oxide (A) particles is externally added
The method according to any one of claims 1 to 37, wherein
Image forming method. (M) ₁ ) Is Sr.
The image forming method according to any one of claims 1 to 39. 41. (M _Two ) Is Ti
The image forming method according to any one of claims 1 to 40. 42. The composite oxide (A) is composed of stron titanate.
Titanium (SrTiO _Three )
42. The image forming method according to any one of 1 to 41. 43. (M _Two ) Is Si.
The image forming method according to any one of claims 1 to 40. 44. The composite oxide (A) is a strontium silicate
(SrSiO _Three 43. The method of claim 43, wherein
2. The image forming method according to 1., 45. The composite oxide (A) particles are formed by a sintering method.
5. A method according to claim 1, characterized in that it is generated.
5. The image forming method according to any one of 4. 46. The composite oxide (A) particles have a weight average diameter
Is 0.1 to 5.0 μm.
45. The image forming method according to any one of the above items. 47. The composite oxide (A) particles have a weight average diameter
Is 0.3 to 3.0 μm.
45. The image forming method according to any one of the above items. 48. The composite oxide (A) particles have a weight average diameter
Is 0.5 to 2.5 μm.
45. The image forming method according to any one of the above items. 49. The method according to claim 49, wherein the colorant is a magnetic material.
The image forming method according to any one of claims 1 to 48. 50. The toner particles are composite oxide (A) particles
Characterized by having a larger weight average diameter than
The image forming method according to any one of claims 1 to 49. 51. The toner particles have a weight average diameter of 3 to 12.
The image form according to claim 50, wherein the image form is μm.
Method. 52. The toner particles have a weight average diameter of 3 to 9 μm.
51. The image forming apparatus according to claim 50, wherein m is
Method. 53. A cleaning blade comprising: (a) a storage elastic modulus (G′B) at a temperature of 40 to 80 ° C.
1 × 10 ⁶ ~ 5 × 10 ⁶ (B) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is
1 × 10 ^Four ~ 5 × 10 ^Five Pa that is characterized by Pa
23. The image forming method according to any one of claims 1 to 22. 54. An electrostatic image formed on an electrostatic image carrier
Is developed using toner to form a toner image.
Image means for transferring the formed toner image from the electrostatic image carrier
To transfer to transfer material with or without intermediary transfer body
Transfer means, and cleans the transfer residual toner on the electrostatic image carrier.
Cleaning blade using a cleaning blade
Image forming apparatus having at least
The toner comprises at least a binder resin, a wax and a colorant.
Containing toner particles and inorganic fine powder.
The binder resin includes (1) a vinyl resin, a polyester resin, and a vinyl resin.
Has a polymer unit and a polyester unit
Contains a hybrid resin component, and (2) 10 using tetrahydrofuran (THF) as a solvent
The soxhlet extraction of the time, the THF soluble component from 50 to
85% by weight (W1), and a THF-insoluble component of 15 to
(3) Soxhlet for 10 hours using ethyl acetate as a solvent
In the extraction, the ethyl acetate-soluble component was reduced to 40 to 98% by weight (W
3) Contains 2 to 60% by weight of ethyl acetate insoluble component
(W4), (4) Soxhlet for 10 hours using chloroform as a solvent
-55-90% by weight of chloroform-soluble components by extraction
(W5) containing 10 to 45 chloroform-insoluble components.
(5) The value of W4 / W6 is from 1.1 to 4.0, and when the toner is at a temperature of 50 to 75 ° C., (a) storage elastic modulus (G′T) and loss Elastic modulus (G "T)
(B) a temperature at which the loss tangent (tanδTP) is at a maximum.
(TT.P), and the cleaning blade: (c) at a temperature of 40 to 80 ° C., at a storage elastic modulus (G′B)
But 5 × 10 ^Five ~ 1 × 10 ⁷ (D) Loss modulus (G ″ B) at a temperature of 40 to 80 ° C.
But 5 × 10 ^Three ~ 1 × 10 ⁶ (E) At a temperature of 40 to 80 ° C., a loss tangent (tan δB.
P) has a minimum temperature (TT.B), and (f) a loss tangent (tan δ) at a temperature of 70 to 130 ° C.
B. P) has a temperature (TB.P) at which the toner and the cleaning blade have a loss tangent.
(G) the difference (TT.P-TB.P) is -40 to 20 ° C.
(H) loss elastic modulus of the toner at a temperature (TT.C)
(G "T) and cleaning at temperature (TT.C)
Ratio (G "T) to loss elastic modulus (G" BC) of blade
/ (G ″ BC) is 5 × 10 ^Two ~ 5 × 10 ^Four Is
An image forming apparatus comprising: 55. The binder resin is a gel of a THF-soluble component.
For permeation chromatography (GPC) measurement
The molecular weight distribution is 4000 to 9000
Has a main peak in the region with a molecular weight of 500 to 10,000
The component of the full area is 35.0 to 65.0% (A1).
The components in the region having a molecular weight of 10,000 to less than 100,000 are 25.0.
From 45.0% (A2), and a molecular weight of 100,000 or more.
Is 10.0 to 30.0% (A3), and A1 / A
2 is 1.05 to 2.00.
The image forming apparatus according to claim 54. 56. The polyester resin as a binder resin and the polyester resin
Polyester units include tri- or higher polycarboxylic acids or
Or its anhydride or trihydric or higher polyhydric alcohol
Claims characterized by having a crosslinked structure
Item 54 or 55 is an image forming apparatus. 57. The vinyl resin as a binder resin and the vinyl resin.
Polymer units are crosslinked with two or more vinyl groups
Characterized by having a cross-linked structure cross-linked with an agent
The image forming apparatus according to any one of claims 54 to 56. 58. The binder resin comprises a THF-insoluble component (W
2) 20 to 45% by weight.
An image forming apparatus according to any one of claims 54 to 57. 59. The binder resin comprises a THF-insoluble component (W
2) 25 to 40% by weight.
An image forming apparatus according to any one of claims 54 to 57. 60. The binder resin comprises an ethyl acetate-insoluble component.
(W4) is contained in an amount of 5 to 50% by weight.
The image forming apparatus according to any one of claims 54 to 59. 61. The binder resin comprises an ethyl acetate-insoluble component.
(W4) is contained in an amount of 10 to 40% by weight.
The image forming apparatus according to any one of claims 54 to 59.
Place. 62. The binder resin is a chloroform-insoluble component.
(W6) is contained in an amount of 15 to 40% by weight.
The image forming apparatus according to any one of claims 54 to 61.
Place. 63. The binder resin is a chloroform-insoluble component.
(W6) is contained in an amount of 17 to 37% by weight.
The image forming apparatus according to any one of claims 54 to 61.
Place. 64. The binder resin comprises an ethyl acetate-insoluble component.
(W4) and chloroform-insoluble component (W6) (W4
/ W6) is 1.2 to 3.5.
The image forming apparatus according to any one of claims 54 to 63.
Place. 65. The binder resin is an ethyl acetate-insoluble component.
(W4) and chloroform-insoluble component (W6) (W4
/ W6) is 1.5 to 3.0.
The image forming apparatus according to any one of claims 54 to 63.
Place. 66. The composition containing the THF-insoluble component (W2).
Of the chloroform-insoluble component (W6A) and the acetic acid
Chloroform insoluble in ethyl-insoluble component (W4)
The content of the dissolved component (W6B) is determined by the following condition: 3% by weight ≦ W6A ≦ 25% by weight 7% by weight ≦ W6B ≦ 30% by weight 10% by weight ≦ W6A + W6B ≦ 45% by weight W6A: W6B = 1: 1 to 3% 66. The method according to claim 54, wherein the satisfaction is satisfied.
An image forming apparatus according to any one of the preceding claims. 67. The composition containing the THF-insoluble component (W2).
Of the chloroform-insoluble component (W6A) and the acetic acid
Chloroform insoluble in ethyl-insoluble component (W4)
The content of the soluble component (W6B) is as follows: 5% by weight ≦ W6A ≦ 20% by weight 10% by weight ≦ W6B ≦ 25% by weight 15% by weight ≦ W6A + W6B ≦ 40% by weight W6A: W6B = 1: 1.5 to 65. Any one of claims 54 to 65, wherein 2.5 is satisfied.
An image forming method according to any one of the preceding claims. 68. Vinyl polymerization of the hybrid resin component
The body unit and the polyester unit are as follows: 55 through 54.
The image forming apparatus according to any one of claims 67. 69. The hybrid resin component is a polyester resin.
Monomers having ter units and carboxylic acid ester groups
Transesterification with vinyl polymer unit by polymerization of
Characterized by a copolymer formed by reaction
The image forming apparatus according to any one of claims 54 to 68. 70. The hybrid resin component is a vinyl resin
The polymer unit is the trunk polymer, and the polyester unit
Characterized in that it is a graft polymer with
The image forming apparatus according to any one of claims 54 to 69.
Place. 71. The binder resin has a content of 10 to 60 mol%.
55. The composition having a grafting ratio.
70. The image forming apparatus according to any one of 70s. 72. The binder resin has a content of 15 to 55 mol%.
55. The composition having a grafting ratio.
70. The image forming apparatus according to any one of 70s. 73. The binder resin comprises: (1) a component (W4) insoluble in ethyl acetate;
2 to 60% by weight based on 0 parts by weight, (2) Ethyl acetate-insoluble component (W4) is polyester
The resin component (Gp) contains 40 to 98% by weight, and (3) a component (W3) soluble in ethyl acetate is
(4) Polyethylene containing a component (W4) which is insoluble in ethyl acetate.
Ester resin component (Gp) content and dissolved in ethyl acetate
Resin component (S3) contained in component (W3)
The ratio (Sp / Gp) to the content of p) is from 0.50 to 1.
Wherein the wax comprises a hydrocarbon wax.
The image forming apparatus according to claim 54, wherein 74. The component (W4) insoluble in ethyl acetate
Contains 55 to 95% by weight of a polyester resin component (Gp)
The image forming apparatus according to claim 73, further comprising:
Place. 75. The component (W4) insoluble in ethyl acetate
Contains 60 to 90% by weight of polyester resin component (Gp)
The image forming apparatus according to claim 73, further comprising:
Place. 76. A component (W3) soluble in said ethyl acetate
Is 25 to 85% by weight of the polyester resin component (Sp)
76. The composition according to claim 73, wherein
An image forming apparatus according to any one of the above. 77. A component (W3) soluble in said ethyl acetate
Is 30 to 80% by weight of the polyester resin component (Sp)
76. The composition according to claim 73, wherein
An image forming apparatus according to any one of the above. 78. The component (W4) insoluble in ethyl acetate
Polyester Resin Component (Gp) Content and Acetic Acid
Polyester containing component (W3) soluble in ethyl
The ratio (Sp / Gp) to the resin component (Sp) is from 0.60 to
78. The method according to claim 73, wherein the value is 0.95.
An image forming apparatus according to any one of the above. 79. The component (W4) insoluble in ethyl acetate
Polyester Resin Component (Gp) Content and Acetic Acid
Polyester containing component (W3) soluble in ethyl
The ratio (Sp / Gp) to the resin component (Sp) is from 0.65 to
90. The method of claim 73, wherein
An image forming apparatus according to any one of the above. 80. The total binder resin of the toner is 7 to 40.
It has an acid value (AV1) of mgKOH / g.
An image form according to any one of claims 54 to 79, wherein
Equipment. 81. The total binder resin of the toner is 10 to 3
Having an acid value (AV1) of 7 mg KOH / g
The image according to any one of claims 54 to 79, characterized in that:
Forming equipment. 82. An ethyl acetate-soluble component (W) of the toner.
3) is an acid value of 10 to 45 mgKOH / g (AV2)
82. The method according to claim 54, wherein
An image forming apparatus according to any of the preceding claims. 83. An ethyl acetate-soluble component (W) of the toner.
3) is an acid value of 15 to 45 mgKOH / g (AV2)
82. The method according to claim 54, wherein
An image forming apparatus according to any of the preceding claims. 84. An acid value (AV) of all binder resins of the toner.
1) and the acid value of the ethyl acetate-soluble component (W3) of the toner
The ratio (AV1 / AV2) to (AV2) is 0.7 to
84. The method according to claims 54 to 83, wherein the value is 2.0.
An image forming apparatus according to any of the preceding claims. 85. Acid value (AV1) of all binder resins of the toner
And the acid value (AV) of the ethyl acetate-soluble component (W3) of the toner.
The ratio (AV1 / AV2) to 2) is 1.0 to 1.5.
84. The method according to claim 54, wherein
The image forming apparatus as described in the above. 86. The wax may be a differential scanning calorimeter (D)
SC) is determined by the endothermic peak temperature at the time of
A melting point of 70 to 140 ° C.
Item 90. The image forming apparatus according to any one of Items 54 to 85. 87. The wax may be a differential scanning calorimeter (D)
SC) is determined by the endothermic peak temperature at the time of
A melting point of 80 to 135 ° C.
Item 90. The image forming apparatus according to any one of Items 54 to 85. 88. The wax may be a differential scanning calorimeter (D)
SC) is determined by the endothermic peak temperature at the time of
A melting point of 90 to 130 ° C.
Item 90. The image forming apparatus according to any one of Items 54 to 85. 89. A toner for producing a binder resin.
Bonding tree containing wax, produced in the presence of cousin
90. The composition according to claim 54, further comprising fat.
The image forming apparatus according to any one of the above. 90. The inorganic fine powder represented by the following formula (1):
A composite oxide (A) particle
The image forming apparatus according to any one of claims 54 to 89. [M ₁ ] _a [M _Two ] _b O _c (1) (where M ₁ Are Sr, Mg, Zn, Co, Mn, Ca and
Indicates a metal element selected from the group consisting of
Then M _Two Indicates a metal element selected from Ti or Si
A represents an integer of 1 to 9; b represents an integer of 1 to 9
And c represents an integer of 3 to 9. 91. A method according to claim 91, wherein 100 parts by weight of toner particles
0.10 to 10 parts by weight of the composite oxide (A) particles is externally added
90. The method according to claim 54, wherein
The image forming apparatus as described in the above. 92. A toner is used for 100 parts by weight of toner particles.
0.20 to 5 parts by weight of the composite oxide (A) particles is externally added
90. The method according to claim 54, wherein
Image forming apparatus. (M) ₁ ) Is Sr.
An image forming apparatus according to any one of claims 54 to 92.
Place. 94. (M _Two ) Is Ti
An image forming apparatus according to any one of claims 54 to 93.
Place. 95. The composite oxide (A) is a stron titanate
Titanium (SrTiO _Three )
95. The image forming apparatus according to any one of items 54 to 94. 96. (M _Two ) Is Si.
An image forming apparatus according to any one of claims 54 to 93.
Place. 97. The composite oxide (A) is a strontium silicate
(SrSiO _Three 97. The method of claim 96, wherein
An image forming apparatus according to claim 1. 98. The composite oxide (A) particles are formed by a sintering method.
55. The method according to claim 54, wherein the information is generated.
97. The image forming apparatus according to any one of claims 97. 99. The composite oxide (A) particles have a weight average diameter
Is 0.1 to 5.0 μm.
The image forming apparatus according to any one of Items 4 to 98. 100. The composite oxide (A) particles have a weight average
The diameter is 0.3-3.0 micrometers.
The image forming apparatus according to any one of claims 54 to 98. 101. The composite oxide (A) particles have a weight average
The diameter is 0.5 to 2.5 μm.
The image forming apparatus according to any one of claims 54 to 98. 102. The colorant is a magnetic substance.
The image forming method according to any one of claims 54 to 100.
apparatus. 103. The toner particles are composite oxide (A) particles.
Characterized by having a larger weight average diameter than the
An image forming apparatus according to any one of claims 54 to 102.
Place. 104. The toner particles have a weight average diameter of 3-1.
The image according to claim 103, wherein the thickness is 2 µm.
Image forming device. 105. The toner particles have a weight average particle diameter of 3 to 9.
104. The image of claim 103, wherein
Forming equipment. 106. A cleaning blade comprising: (a) at a temperature of 40 to 80 ° C., a storage elastic modulus (G′B)
1 × 10 ⁶ ~ 5 × 10 ⁶ (B) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is
1 × 10 ^Four ~ 5 × 10 ^Five Pa that is characterized by Pa
An image forming apparatus according to any one of claims 54 to 105.