JP2003330217A - Toner, developing cartridge and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress generation of image failure such as development stripes or the like particularly in a high temperature and high humidity environment and to form a preferable image in the method for forming an image by using a contact single component developing method with a rotary structure in which a developing roller and a photoreceptor touch and separate from each other. <P>SOLUTION: The toner shows ≥40°C tangential separation temperature in the endothermic peak by differential thermal analysis measurement and has 4 to 10 μm weight average particle size and properties that: (i) when a dispersion liquid prepared by dispersing 5 mg of the toner in 10 ml of water with 0.1 mg of a nonion surfactant dissolved is irradiated with ultrasonic waves at 20 kHz with 50 W/10 cm<SP>3</SP>energy density for five minutes, the proportion C1 of particles having 0.6 to 2.0 μm particle size measured by a flow type particle image analyzer is 3 to 65% on the number basis; (ii) when the above dispersion liquid is irradiated with ultrasonic waves at 20 kHz with 50 W/10 cm<SP>3</SP>energy density for one minute, the proportion C2 of particles having 0.6 to 2.0 μm particle size is 2 to 62% on the number basis; and (iii) a value C defined by C=(C1/C2)×100 ranges 102 to 150. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner, a developing cartridge, and a full-color image forming method used in a recording method using electrophotography or the like. More specifically, the present invention relates to a toner, a developing cartridge, and an image forming method used for contact one-component development having a rotary structure.

[0002]

2. Description of the Related Art Conventionally, a large number of electrophotographic methods are known as described in US Pat. No. 2,297,691. Generally, a photoconductive substance is used to form an electrical latent image on a photoconductor, the latent image is then developed with toner, and the toner image is transferred to a transfer material such as paper, if necessary. A copy is obtained by fixing with heat, pressure, heat and pressure, or solvent vapor. The toner remaining on the photoconductor without being transferred is cleaned by various methods, and the above steps are repeated.

Such a copying apparatus has begun to be used in the field of not only a general-purpose copying machine for copying original documents but also a printer as an output of a computer or a personal copy for individuals.

In recent years, the popularity of color printers has increased,
Among them, high image quality, space saving, maintainability,
From the viewpoint of low cost and material compatibility, Japanese Patent Laid-Open No. 2000-3
Attention has been paid to contact one-component development as described in the specification of JP-A 15020.

An example of a conventional color image forming apparatus (copier or laser beam printer) using an electrophotographic process will be briefly described with reference to FIG.

Reference numeral 1 denotes a drum-shaped photosensitive member as a first image bearing member, which is rotationally driven at a predetermined peripheral speed (process speed) in the direction of an arrow in the drawing. The photosensitive member 1 is uniformly charged to a predetermined polarity and potential by the primary charger 2 during the rotation process, and then exposed by the image exposing means (not shown) 3
Receive. In this way, an electrostatic latent image corresponding to the first color component image (for example, a yellow toner image) of the target color image is formed, and then the first developing device (yellow toner developing device 41) develops the first color image. It is developed into a certain yellow toner image.

The yellow toner image formed on the photoconductor 1 is sequentially transferred to the outer peripheral surface of the intermediate transfer belt 20. The surface of the photoconductor 1 that has transferred the yellow toner image of the first color corresponding to the intermediate transfer belt 20 is cleaned by the cleaning device 13.

Thereafter, the developing unit 40 rotates in the direction of the arrow in the drawing, and the second to fourth developing devices are sequentially moved to positions facing the photoconductor 1, whereby the second color image is formed in the same manner as the yellow toner image. The magenta toner image, the third color cyan toner image, and the fourth color black toner image are sequentially transferred onto the intermediate transfer belt 20 in an overlapping manner to form a full-color toner image corresponding to the target color image. Then, the color toner image is transferred and fixed on the transfer material P by a known process.

After the transfer of the image to the transfer material P is completed, the toner remaining on the intermediate transfer belt (transfer residual toner) is scraped off by the cleaning blade 50 and conveyed to the waste toner box.

As described above, in the case of a color printer using a developing method of a rotary structure in which toner images of respective colors are sequentially formed on the photoconductor 1, it is possible to form an image with only one photoconductor drum. Therefore, it is excellent in low cost. However, on the other hand, when printing a large number of sheets in a high temperature and high humidity environment, the temperature inside the machine tends to rise due to the drive motor. The toner that receives frictional force between the developing roller, which is the toner carrier, and the developing blade that regulates the amount of toner on the developing roller, is further damaged by the temperature rise in this machine and grows into blade fusion, The problem is that it causes development streaks. Further, in the case of the contact developing method in which the developing roller and the photoconductor contact and separate, the damage to the toner increases as continuous printing is performed.

From the above, there is a strong demand for thermal characteristics as the physical properties required for toner mounted on a rotary machine. A typical item of thermal characteristics of toner is a softening temperature by a flow tester. In the image forming method by the contact one-component development of the rotary constitution, as the prior art in which the toner flow tester measurement value is described, there are JP-A-2000-003072 and JP-A-200200.
There is, for example, JP-A 1-228652.

Further, if the toner particle size distribution is wide, selective development occurs, and when the number of printed sheets increases and the toner filling amount in the developing cartridge decreases, it becomes impossible to coat the toner carrier uniformly with a thin layer. Generation of development streaks is promoted. Therefore, controlling the toner particle size and toner sphericity in contact development is one of the key technologies. The above-mentioned JP 2000-003072 A and JP 2001-2
In Japanese Patent No. 28652, the shape of these toners is also described as an average circularity.

However, Japanese Patent Application Laid-Open No. 2000-003072 and Japanese Patent Application Laid-Open No. 200 which seem to be most similar to the present invention.
The evaluation of JP-A 1-228652 has not been discussed in a more severe environment of high temperature and high humidity. Further, the relationship between the temperature rise and the thermal characteristics of the toner is not clarified.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is possible to obtain a good image without developing streaks even when a large number of sheets are continuously printed in a high temperature and high humidity environment. An object of the present invention is to provide a toner, a developing cartridge, and an image forming method that can be used.

Further, the present invention is a toner capable of forming a good image without generation of fog on a transfer material or fusion on a photoconductor in a high temperature and high humidity environment, and white spots on an image. An object is to provide a developing cartridge and an image forming method.

[0016]

As a result of earnest studies, the inventors of the present invention have focused their attention on the tangential desorption temperature of the endothermic peak in the differential thermal analysis (DSC) of the toner, the weight average particle diameter, and the particle size distribution. It was found that by setting the ratio to be within a specific range, it is possible to prevent image defects such as development streaks even under a high temperature and high humidity environment and form a good image, and completed the present invention.

That is, the present invention is as follows.

The toner of the present invention is a toner for visualizing an electrostatic latent image carried on a photoconductor, and is an image forming method for forming a color image using two or more toners having different colors. And (I) a charging step of charging the surface of the photoconductor, and (II) a latent image forming step of sequentially forming electrostatic latent images corresponding to the respective colors on the charged photoconductor.
I) a developing step of visualizing the electrostatic latent image formed on the photoreceptor with toner of a corresponding color to form a toner image; and (IV) a toner image of each color visualized in the developing step. The image forming method includes a transfer step of sequentially superimposing and transferring the image on a transfer material, and the developing step uses a developing cartridge having a plurality of developing devices having a developing roller carrying a toner according to each color toner. , A developing roller of each developing device is sequentially brought into contact with the photosensitive member to sequentially form a toner image of each color, and when the formation of the toner image is completed, the developing roller is separated from the photosensitive member. It is a one-component development process,
The toner has a tangential desorption temperature of an endothermic peak in differential thermal analysis (DSC) of 40 ° C. or higher and a weight average particle diameter of 4 to 10 μm obtained by a Coulter counter method.
m, and (i) the dispersion liquid obtained by dispersing 5 mg of the toner in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. When the particle size is 0.6 to 2.0 μm, the ratio C1 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer is 3 to 65% by number, and (ii) the dispersion liquid contains 2
The ratio C2 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when irradiated with ultrasonic waves of 0 kHz and 50 W / 10 cm ³ for 1 minute is 2 to 62% by number, (Iii) The value of C represented by the following formula (1) is 1
It is characterized by being 02-150.

[0019]

[Equation 4] C = (C1 / C2) × 100 (1)

The developing cartridge of the present invention is a developing cartridge for visualizing an electrostatic latent image carried on a photoconductor, and forms a color image by using two or more toners having different colors. An image forming method, (I)
A charging step of charging the surface of the photoconductor, (II) a latent image forming step of sequentially forming an electrostatic latent image corresponding to each color on the charged photoconductor, and (III) forming on the photoconductor The developing step of visualizing the formed electrostatic latent image with the toner of the corresponding color to form a toner image, and (IV) transferring the toner images of the respective colors visualized in the developing step to the transfer material in sequence. And a plurality of developing devices each having a developing roller carrying a toner according to the toner of each color, and the developing roller of each developing device is sequentially brought into contact with the photoconductor. Thus, the toner image of each color is sequentially formed, and when the formation of the toner image is completed, the developing roller is separated from the photoconductor, and is a developing cartridge using the contact one-component developing method of the rotary structure, and the toner is The tangential desorption temperature of the endothermic peak in differential thermal analysis (DSC) is 40 ° C. or higher, and the weight average particle diameter obtained by the Coulter counter method is 4
10 μm, and (i) nonionic surfactant 0.1
In a dispersion liquid obtained by dispersing 5 mg of the toner in 10 ml of water in which 20 mg is dissolved, 20 kHz, 50 W / 10c
The ratio C1 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when irradiated with m ³ ultrasonic waves for 5 minutes is ³ to 65% by number, and (ii) the above When the dispersion is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 1 minute, the ratio C2 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer is 2 to 2.
62% by number, and (iii) C represented by the above formula (1)
Is 102 to 150.

Further, the image forming method of the present invention is an image forming method for forming a color image by using two or more toners having different colors, and includes (I) a charging step of charging the surface of the photoconductor and (II) ) A latent image step of sequentially forming electrostatic latent images corresponding to the respective colors on the charged photoconductor, and (III) electrostatic latent images formed on the photoconductor by toner of corresponding colors. A developing step of visualizing and forming a toner image;
(IV) a transfer step of sequentially superimposing and transferring the toner images of the respective colors visualized in the developing step onto a transfer material, and the developing step includes a developing device having a developing roller carrying toner for each color. A plurality of developing cartridges corresponding to the toner are used, and the developing roller of each developing device is sequentially brought into contact with the photoconductor to sequentially form toner images of respective colors. When the formation of the toner image is completed, the developing roller is Contact 1 in a rotary configuration separated from the photoreceptor
In the component developing step, the toner has a tangential desorption temperature of an endothermic peak in differential thermal analysis (DSC) of 40 ° C.
Above, the weight average particle diameter obtained by the Coulter counter method is 4 to 10 μm, and (i) 5 mg of the toner is dispersed in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved. In the dispersion liquid, 20 kHz,
The particle size measured by a flow-type particle image analyzer when irradiated with ultrasonic waves of 50 W / 10 cm ³ for 5 minutes is 0.6 to
The ratio C1 of 2.0 μm particles is 3 to 65% by number,
(Ii) 20 kHz, 50 W / 10 cm ^{3 in the} dispersion liquid
The ratio C2 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when the ultrasonic wave is irradiated for 1 minute is 2 to 62% by number, and (iii) the above formula ( The value of C represented by 1) is 102 to 150.

In the present invention, it is preferable that the tangential desorption temperature of the endothermic peak is 50 ° C. or higher.

In the present invention, the melt index value of the toner is preferably 1 to 50, more preferably 2 to 30.

In the present invention, the glass transition temperature of the toner is preferably 45 to 85 ° C, more preferably 50 to 70 ° C.

In the present invention, the average circularity in the number-based circle equivalent diameter-circularity scattergram measured with a toner flow type particle image measuring device is 0.950 to 0.9.
It is preferably 99, and more preferably 0.965 to 0.999.

In the present invention, the half width at the endothermic peak of the toner is preferably 10 ° C. or less, and 5
More preferably, the temperature is not higher than ° C.

In the present invention, it is preferable that the number of rotations of the developing roller is 100 to 500 rotations / minute.

In the present invention, the C1 is preferably 3 to 50% by number, the C2 is 2 to 40% by number, and the C is preferably 105 to 140.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention uses a developing cartridge having a plurality of developing devices each having a developing roller carrying the toner in accordance with the toner of each color, and the developing rollers of each developing device are sequentially applied to the photoconductor. The toner image of each color is sequentially formed by bringing them into contact with each other, and the developing roller is separated from the photoconductor when the formation of the toner image is completed, which is used in an image forming method using a rotary one-component contact developing method. Such a toner of the present invention has a tangential desorption temperature of an endothermic peak of 40 ° C. in differential thermal analysis (DSC).
The above is the feature that the weight average particle diameter obtained by the Coulter counter method is 4 to 10 μm. Further, the toner of the present invention is (i) 5 m of the toner in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved.
In a dispersion liquid obtained by dispersing g, 20 kHz, 50 W /
The particle size measured by a flow-type particle image analyzer when irradiated with 10 cm ³ of ultrasonic waves for 5 minutes is 0.6 to 2.0 μm.
The proportion C1 of the particles of m is 3 to 65% by number, and (ii) the particles measured by a flow-type particle image analyzer when the dispersion is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 1 minute. Ratio C2 of particles having a diameter of 0.6 to 2.0 μm
Is 2 to 62% by number, and (iii) the value of C represented by the following formula (1) is 102 to 150.

[0030]

[Equation 5] C = (C1 / C2) × 100 (1)

First, consideration will be given to the occurrence of development streaks, fog, fusion, and white spots during continuous printing of a large number of sheets under high temperature and high humidity, which is the subject of the present invention. Regarding the mechanism of development streak and streak-like fogging under high temperature and high humidity environment,
The present inventors consider as follows.

First, substances existing on the surface of the toner, such as external additives and ultrafine particles (fine particles in the submicron size) produced at the time of production, are released from the toner during continuous printing and abut on the developing blade and the developing roller. It adheres to parts or is slightly clogged. When continuous printing is further repeated, toner is accumulated on the adhered portion, and toner fusion occurs at the contact portion. Since the temperature in the vicinity of the abutting portion also rises as the frictional force and the pressing force of the abutting portion and the temperature inside the machine due to continuous printing rise, the fusion of the toner is promoted. As a result, the coated state of the toner layer on the developing roller becomes non-uniform, and finally development streaks occur. When the developing roller and the photoconductor perform the contacting / separating operation, it is considered that the above-mentioned frictional force and pressing force have an adverse effect, and the development streak is more likely to occur. This problem becomes more remarkable when an image is formed in a high temperature and high humidity environment and the temperature inside the machine rises significantly.

Further, it is considered that the streak-like fog occurs when the developing streak is generated and the toner on the developing roller is subjected to uneven triboelectric charging.

Further, the inventors of the present invention consider the mechanism of the generation of fused substances on the photosensitive member and the white spots in the formed image under the high temperature and high humidity environment as follows. First, at the contact portion between the developing blade and the developing roller during continuous printing,
The external additive adhering to the toner surface is released to form an aggregate. Next, this aggregate jumps and adheres to the photoconductor by the driving force in the rotation direction of the developing roller. The agglomerates adhering to the photoconductor are scraped off by a transfer member or a cleaning member in the initial stage, but as the number of continuous prints increases, the agglomerates that cannot be scraped off are fixed on the photoconductor. It is considered that this becomes a nucleus, attracts new external additives and agglomerates existing in the contact portion, and grows into a fused material on the photoconductor. In the case of the contact developing method in which the developing roller and the photoconductor perform the contact / separation operation, it is considered that the pressure applied to the photoconductor is further increased and the growth of the fused material is promoted.

When the size of the fused substance on the photoconductor is small, the influence on the image is small, but when it is large, the surface potential on the photoconductor is adversely affected, and white spots are generated on the image. This tends to occur particularly in a high temperature and high humidity environment where the adhesion strength between the colored particles contained in the toner particles constituting the toner and the external additive is considered to be weakened.

Therefore, the present inventors have found that the tangential departure temperature of the endothermic peak in the differential thermal analysis measurement (DSC) of the toner,
Weight average particle diameter obtained by the Coulter counter method,
C1 and C obtained by the above flow type particle image analyzer
An image forming system in which the developing step uses a contact one-component developing method having a rotary structure by limiting 2 and C within a specific range, and the developing roller and the photoconductor perform a contact / separation operation. In the above, even when a large number of sheets are continuously printed under high temperature and high humidity, it is possible to prevent the external additive and the toner particles from adhering to the vicinity of the contact portion between the developing blade and the developing roller, and to perform good image formation. Found.

The features of the present invention will be described below. In the toner of the present invention, the specified physical properties are roughly divided into two, one is the thermal characteristics of the toner and the other is the shape characteristics. The thermal characteristics of the toner here mean
It is the tangent departure temperature of the endothermic peak, the half width of the endothermic peak, the melt index value and the glass transition temperature. The shape characteristics of the toner are the weight average particle diameter, C1 value, C2 value, C value and average circularity obtained by the above measurement.

The toner of the present invention has a differential thermal analysis measurement (DS
The tangential departure temperature of the endothermic peak in C) is 40 ° C. or higher. The tangential desorption temperature is preferably 50 ° C. or higher, more preferably 52 ° C. or higher.

In a developing system in which a developing roller and a photosensitive member are brought into contact with and separated from each other by using a contact one-component developing method having a rotary structure, the endothermic in differential thermal analysis (DSC) is one of the thermal characteristics of the toner. Setting the peak tangential line detachment temperature within the above range has the effect of suppressing the growth of the fused material generated at the contact portion between the developing blade and the developing roller in the description of the mechanism of the development streak generation. The high temperature and high humidity environment referred to in the present invention is 30 ° C./80% RH.
(Relative humidity), and when the temperature rise in the machine in continuous printing is added thereto, the substantial temperature on the developing blade reaches 40 ° C. At this time, when the tangential line desorption temperature of the toner is less than 40 ° C., the tangential line desorption temperature of the release agent is substantially less than 40 ° C., so that the toner may be exuded by the release agent on the toner surface. The fluidity is lowered, and as a result, the adhesion to the developing blade is accelerated. Adjusting the melt index value, the glass transition temperature, and the full width at half maximum of the differential thermal analysis (DSC) of the toner within the ranges described below is also effective for preventing development streaks for the same reason.

Among the thermal characteristics of the toner, the physical properties of the endothermic peak tangential desorption temperature, the half-value width of the endothermic peak, the melt index value and the glass transition temperature listed in the present invention are as follows:
There is a close relationship from the viewpoint of exudation of the release agent contained in the toner, and ideally all of the above physical properties are desired to be within the ranges described in this specification. Among them, the inventors have found that the tangential line detachment temperature contributes most to the prevention of development streaks due to the fused material at the contact portion between the developing blade and the developing roller.

For the above-mentioned reason, the half value width at the endothermic peak of the differential thermal analysis (DSC) of the toner is 10 ° C.
The temperature is preferably below, more preferably below 5 ° C.,
More preferably, it is 3 ° C. or lower.

The melt index value of the toner of the present invention is preferably 1 to 50, more preferably 2 to 30, and further preferably 3 to 20.

The glass transition temperature of the toner of the present invention is 45 to
The temperature is preferably 85 ° C, more preferably 50 to 70 ° C.

When the tangential desorption temperature of the endothermic peak in the differential thermal analysis measurement of the toner is less than 40 ° C., the glass transition temperature is less than 45 ° C., or the melt index value is more than 50, the above-described developing stripes are used. As described in the mechanism of generation, the thermal characteristics of the toner during continuous printing are weak, and a fused substance is likely to be generated on the key parts that impart triboelectric charge to the toner.

On the other hand, the fact that the full width at half maximum at the endothermic peak of the toner exceeds 10 ° C. means that the full width at half maximum of the release agent contained in the toner is more than 10 ° C. measured by DSC. Such a release agent has a relatively low purity, and it may be difficult to set the tangential line release temperature within the above range.

If the glass transition temperature of the toner exceeds 85 ° C. or if the melt index value is less than 1, the low temperature fixability and OHT transparency are significantly deteriorated.

Further, the toner of the present invention is characterized in that the weight average particle diameter obtained by the Coulter counter method is 4 to 10 μm. The toner has a weight average particle diameter of preferably 5 to 9.5 μm, more preferably 6 to 9.0 μm.

When the dispersion liquid obtained by dispersing 5 mg of the toner of the present invention in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. The ratio C1 of particles having a particle size of 0.6 to 2.0 μm measured by the flow particle image analyzer of No. 3 is 3 to 65% by number. This C1 is preferably 3 to 50% by number, more preferably 5 to 35% by number.

In the toner of the present invention, the particle size measured by a flow type particle image analyzer is 0.6 to 2.0 μm when the dispersion liquid is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 1 minute. The proportion C2 of the particles is 2 to 62
It is characterized by the number%. This C2 is preferably 2 to 40% by number, more preferably 3 to 25% by number.
Is.

Further, the toner of the present invention has the following formula (1).
The value of C represented by is 102 to 150. This C is preferably 105 to 140, and more preferably 110 to 140.

[0051]

[Equation 6] C = (C1 / C2) × 100 (1)

The average circularity in the number-based circle equivalent diameter-circularity scattergram measured by the toner flow type particle image analyzer of the present invention is 0.950-0.
999 is preferable, and 0.965 to 0.999.
Is more preferable, and 0.970 to 0.990 is still more preferable.

Among the shape characteristics of the toner, the weight average particle diameter, C1 obtained by the above flow type particle image analyzer,
Setting C2 and C within the above range suppresses the release of the ultrafine particles (fine particles in the submicron size) and external additives, which have been described in the mechanism of development streak generation, during the toner production, and prevents the external additives from being transferred to the developing blade. It has the effect of suppressing adhesion and clogging. Furthermore, specify the average circularity of the toner,
By increasing the spheroidization, the adhesion strength of the external additive to the toner surface becomes stronger, and by suppressing the release of the external additive, it becomes possible to suppress the development streaks. To suppress the liberation of the external additive, in the image forming method of the present invention, because it leads to the suppression of the free external additive generation in the mechanism of fusion of the external additive and the like to the photoreceptor and the white spot of the formed image, It is also effective in preventing the formation of fused substances on the photoconductor and the prevention of white spots in the formed image.

When the weight average particle diameter of the toner is less than 4 μm, C1 exceeds 65% by number, C2 exceeds 62% by number, or C exceeds 150, the above-described developing stripes are present. As explained in the mechanism of generation, ultra-fine particles (fine particles in the sub-micron size) generated during the production of external additives and toner during continuous printing.
And the like are likely to be released from the toner surface, and it is easy to induce development streaks and the generation of fused substances on the photoconductor.

When the average circularity of the toner is less than 0.950, the adhesion strength of the external additive to the surface of the toner particles is weakened due to the irregular shape of the toner, and the toner transfer efficiency at the time of continuous printing. And the fused substance is easily attached to the photoreceptor.

On the other hand, the toner has a weight average particle diameter of 10 μm.
When it exceeds m, the non-uniform charging area becomes large when toner is clogged in the contact portion between the developing roller and the developing blade, and streaky fog is likely to occur.

When C1 is less than 3% by number, or C
When 2 is less than 2% by number, or when C is less than 102, or when the average circularity exceeds 0.999,
The reproducibility and yield of the toner in terms of manufacturing deteriorates significantly,
This will lead to higher costs.

The values of C1, C2 and C in the toner of the present invention can be adjusted to a desired range by appropriately changing the manufacturing conditions and classification conditions for the colored particles in the toner manufacturing process. Specifically, a method of adjusting the values of C1, C2, and C by classifying with a multi-division air classifier and a classifying system utilizing the Coanda effect in the classifying step in the production of toner is given as an example. However, the present invention is not limited to this method.

The rotation number of the developing roller used in the image forming method of the present invention is preferably 100 to 500 rotations / minute, more preferably 100 to 300 rotations / minute.

When the number of rotations of the developing roller is less than 100 rotations / minute, the toner is not uniformly charged, and fogging easily occurs in a high temperature and high humidity environment. When the number of revolutions exceeds 500 revolutions / minute, the rubbing force between the developing roller and the developing blade is large, and a fused substance is likely to be generated at the abutting portion.

Specific methods for measuring the physical properties of the toner of the present invention will be described below.

The endothermic peak value in the DSC endothermic curve of the release agent of the present invention is measured according to ASTM D3418-8.
It is measured according to 2. From this peak, the tangential departure temperature and the half-width are calculated. The tangential departure temperature of the DSC endothermic curve here means the temperature at which the endothermic curve departs from the baseline. In addition, the half width at the endothermic peak is the height of the peak from the baseline in the endothermic chart, which is 2
It is the temperature width of the endothermic peak at one-half the height.

As the apparatus for measuring the toner particles and the weight average particle diameter of the toner by the Coulter counter method in the present invention, for example, Coulter counter TA-II or Coulter Multisizer II (manufactured by Coulter Co.) is used. The electrolyte is approximately 1% using first-grade sodium chloride.
An aqueous NaCl solution is prepared. For example, ISOTON-II
(Manufactured by Coulter) can be used. As a measuring method,
0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of the electrolytic aqueous solution, and a measurement sample is further added to 2 to 20 m.
Add g. Use an ultrasonic disperser to disperse the electrolyte in which the sample is suspended
The dispersion treatment is performed for up to 3 minutes, and the volume and number of the toner particles or the toner are measured by the measuring device using a 100 μm aperture as the aperture to calculate the volume distribution and the number distribution. Then, the weight average particle diameter (D4) based on the toner particles or the toner mass is obtained.

As a channel, 2.00 to 2.52
Less than μm; 2.52 to less than 3.17 μm; 3.17 to
4. 4.0 μm or less; 4.00 to 5.04 μm or less;
04 to less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to 1
Less than 2.70 μm; 12.70 to less than 16.00 μm;
16.00 to less than 20.20 μm; 20.20 to 25.
Less than 40 μm; 25.40 to less than 32.00 μm; 3
13 channels of 2.00 to less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

C1 and C2 of the toner of the present invention are flow type particle image analyzer (Flow Particle Image).
Ge Analyzer) and the following measuring method.

The above-mentioned toner flow type particle image analyzer is used.
For example, flow-type particles manufactured by Toa Medical Electronics Co., Ltd.
Measuring with Child Image Analyzer FPIA-1000
You can Use a filter to remove fine dust.
Removed, resulting in 10 ^-3cm³Measuring range in water
(For example, a circle equivalent diameter of 0.60 μm or more and 159.21 μm
(Less than) particles in 20 ml or less of water
Nion-based surfactant (preferably contamination by Wako Pure Chemical Industries, Ltd.
Add a few drops of non-N). Furthermore, add 5 mg of measurement sample,
Ultrasonic disperser STM UH-50, 20 kHz, 50
W / 10 cm³Disperse for 1 minute under the conditions
Perform the dispersion treatment for a total of 5 minutes, and the particle concentration of the measurement sample is
4000-8000 pieces / 10^-3cm³(Measurement circle equivalent diameter range
A sample dispersion (for the surrounding particles) is obtained. This sample
For the dispersion, use the above flow-type particle image analyzer
Equivalent diameter of 0.60 μm or more and less than 159.21 μm
The particle size distribution of the particles having is measured.

The outline of the measurement is as follows: Catalog of FPIA-1000 issued by Toa Medical Electronics Co., Ltd. (June 1995 version), operation manual of measuring device, and JP-A-8-136.
It is described in Japanese Patent No. 439, but is as follows.

The sample dispersion is passed through a flat and flat transparent flow cell (thickness of about 200 μm) (spreading along the flow direction). A strobe and a CCD camera are mounted on opposite sides of the flow cell to form an optical path that passes across the thickness of the flow cell. While the sample dispersion is flowing, stroboscopic light is emitted at 1/30 second intervals to obtain an image of particles flowing in the flow cell. As a result, each particle has a certain range parallel to the flow cell.
It is taken as a three-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.

The equivalent circle diameter of 1200 or more particles can be measured in about 1 minute, and the number based on the equivalent circle diameter distribution and the proportion (number%) of particles having a prescribed equivalent circle diameter can be measured. . As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In the actual measurement, the equivalent circle diameter is 0.
Particles are measured in the range of 60 μm or more and less than 159.21 μm.

[0070]

[Table 1]

The circularity of the toner in the present invention is used as a simple method for quantitatively expressing the shape of toner particles. In the present invention, the flow type particle image measuring apparatus FPI is used.
The measurement was performed using A-1000 type (manufactured by Toa Medical Electronics Co., Ltd.) and calculated using the following formula.

[0072]

[Equation 7]

Here, the "particle projection area" is the area of the binarized toner particle image, and the "perimeter of the particle projection image".
Is defined as the length of the contour line obtained by connecting the edge points of the toner particle image.

The circularity in the present invention is an index showing the degree of unevenness of the toner particles, and shows 1.000 when the toner particles are perfectly spherical, and the more complicated the surface shape, the more
The circularity has a small value. Further, the average circularity Cm, which means the average value of the circularity frequency distribution, is calculated from the following equation, where the circularity (center value) at the dividing point i of the particle size distribution is ci and the frequency is fci.

[0075]

[Equation 8]

In the present invention, the melt index (M
I) is measured by the manual cutting method under the following measurement conditions using the device described in JIS K7210. At this time,
The measured value is converted into a 10-minute value. In other words, how many g in 10 minutes
It is a value indicating whether or not it has been cut off. -Measurement temperature: 135 ° C-Load: 2.2 kg-Sample filling amount: 5-10 g

The glass transition point of the toner of the present invention is determined by differential thermal analysis (DSC) measurement. In DSC measurement,
From the measurement principle, it is preferable to measure with a highly accurate differential scanning calorimeter of the internal heat type input compensation type. For example, DSC-7 manufactured by Perkin Elmer can be used. The measuring method is AS
Performed according to TM D3418-82. For the measurement, the temperature was measured once after raising and lowering the temperature once and taking the previous history.
In n, a DSC curve measured when the temperature is raised is used.
The glass transition point is a value using the midpoint method.

Next, the toner of the present invention will be described in detail.

The toner of the present invention has toner particles containing a binder resin, a release agent and a colorant, and if necessary, external additives added to the toner particles. The binder resin of the toner used when the toner of the present invention is manufactured by a pulverizing method is polystyrene; poly-p-chlorostyrene,
Styrene-substituted homopolymers such as polyvinyltoluene;
Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-
Chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer,
Styrene-based copolymers such as styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers; acrylic resins; methacrylic resins; polyvinyl acetate; silicone Resin; Polyester resin;
Polyamide resin; furan resin; epoxy resin; xylene resin and the like. These resins are used alone or as a mixture.

Comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodite acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. Acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, monocarboxylic acid having a double bond such as acrylamide or a substitution product thereof; maleic acid,
Dicarboxylic acids having a double bond such as butyl maleate, methyl maleate and dimethyl maleate and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene such as ethylene, propylene and butylene. Examples include olefins; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

It is preferable that the styrene copolymer is crosslinked with a crosslinking agent such as divinylbenzene in order to widen the fixing temperature range of the toner and improve the offset resistance.

As the polymerizable monomer used when the toner of the present invention is produced by a polymerization method, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. As the monofunctional polymerizable monomer, styrene; α-methylstyrene, β
-Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn Styrene derivatives such as octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, te
rt-butyl acrylate, n-amyl acrylate,
n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate,
Acrylic polymerizable monomers such as diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-
Amyl methacrylate, n-hexyl methacrylate,
Methacrylic polymerizable monomers such as 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl acetate, vinyl propionate Vinyl esters such as vinyl butyrate, vinyl benzoate and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane Tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,
2'-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.

In the present invention, the above monofunctional polymerizable monomers may be used alone or in combination of two or more kinds, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers may be combined. To use. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

An oil-soluble initiator and / or a water-soluble initiator is used as a polymerization initiator used in the polymerization of the above-mentioned polymerizable monomer. For example, as the oil-soluble initiator, 2,2'-azobisisobutyronitrile, 2,2'-
Azobis-2,4-dimethylvaleronitrile, 1,1 '
-Azobis (cyclohexane-1-carbonitrile),
Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide. , Acetyl peroxide,
t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide,
Examples thereof include peroxide-based initiators such as t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and the like.

As the water-soluble initiator, ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodino) is used. Propane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, known chain transfer agents, polymerization inhibitors and the like may be further added and used.

As the crosslinking agent used in the toner of the present invention, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinylaniline; Divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

When the molecular weight of the toner of the present invention is less than 10000, the external additive on the surface of the toner particles is more likely to be buried during continuous sheet feeding, as compared with the toner having the molecular weight within the optimum range, resulting in deterioration of transferability. It is easy and the adhered substances are easily fused on the photoconductor. Also, the high temperature offset property is poor. When the mass average molecular weight exceeds 1500000, the low temperature offset is weak, and the fixability of the secondary color of the thick paper is particularly weak.

The molecular weight and molecular weight distribution of the toner of the present invention are measured by the following method using GPC (gel permeation chromatography). The column is stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent is flowed through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko Corporation is used, and it is appropriate to use a standard polystyrene sample of at least about 10 points. is there.

An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, shodex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P combination and TOSgel G1000H (H manufactured by Tosoh Corporation
XL), G2000H (HXL), G3000H (HX
L), G4000H (HXL), G5000H (HX
L), G6000H (HXL), G7000H (HX
L) and a combination of TSKguardcolumn.

The sample is manufactured as follows. Put the sample in tetrahydrofuran (THF), leave it for several hours, shake it well, mix well with THF (until the coalescence of the sample disappears), and leave it still for 12 hours or more. At this time, the leaving time in THF should be 24 hours or more. Then, a sample processing filter (pore size 0.
45-0.5 μm, for example, Mysholydisc H-
25-5 manufactured by Tosoh Corporation, Excicro Disc 25CR Gelman Science Japan, etc. can be used)
What passed is used as a sample of GPC. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

As the release agent used in the toner of the present invention, candelilla wax, carnauba wax, rice wax, wood wax, plant wax such as jojoba oil,
Animal waxes such as beeswax, lanolin and whale wax, mineral waxes such as montan wax, ozokerite and ceresin, paraffin wax, microcrystalline wax, petroleum waxes such as petrolactam, polyolefin wax, synthetic carbonization such as Fischer-Tropish wax. Hydrogen; amide wax; ketone wax; ester wax; higher fatty acid; higher fatty acid metal salt; long-chain alkyl alcohol. These may be grafted, blocked, distilled or the like, if necessary.

In order to bring out the effect of the present invention more,
Among the above releasing agents, carnauba wax, rice wax, montan wax, paraffin wax, microcrystalline wax, polyolefin wax, Fischer-Tropsch wax, ester wax, amide wax and ketone wax are preferable. More preferred are carnauba wax, rice wax, paraffin wax, polyolefin wax, Fischer-Tropsch wax, ester wax, amide wax, and ketone wax.

Examples of ester wax, amide wax, and ketone wax are shown below, but other waxes may be used.

Examples of ester waxes include those represented by the following general formula.

[0097]

[Chemical 1] (In the formula, a and b are integers of 0 to 4 and a + b is 4. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms,
The carbon number difference between R ₁ and R ₂ is 3 or more. m and n are 0
It is an integer of 40, and m and n cannot be 0 at the same time. )

[0098]

[Chemical 2] (In the formula, a and b are integers of 0 to 3, and a + b is 1 to
It is 3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. R ₃ is a hydrogen atom or an organic group having 1 or more carbon atoms. k is an integer of 1 to 3, and a + b + k = 4.
m and n are integers of 0 to 40, and m and n cannot be 0 at the same time. )

[0099]

[Chemical 3] (In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms,
R ₁ and R ₃ may be the same or different. R
₂ represents an organic group having 1 to 40 carbon atoms. )

[0100]

[Chemical 4] (In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms,
R ₁ and R ₃ may be the same or different. R
₂ represents an organic group having 1 to 40 carbon atoms. )

[0101]

[Chemical 5] (In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. M and n are 0 to 0. It is an integer of 40, and m and n cannot be 0 at the same time).

As the amide wax, those comprising a compound represented by the following formula (VI) are preferable.

[0103]

[Chemical 6] (In the formula, R ₁ and R ₂ are an organic group having 1 to 45 carbon atoms, and
₁ and R ₂ may be the same or different, and R ₁ and R ₂ may have an unsaturated group. ) As the ketone wax, one composed of a compound represented by the following formula (VII) is preferable.

[0104]

[Chemical 7] (In the formula, R ₁ and R ₂ represent an organic group having 1 to 40 carbon atoms.)

The endothermic peak value in the DSC endothermic curve of the release agent used in the present invention is measured according to ASTM D3418-82. The endothermic peak value of the release agent used in the present invention is preferably 50 to 100 ° C.

If the endothermic peak value is less than 50 ° C., the self-aggregating force of the release agent is weak, so that it is difficult to form the inside or center of the toner particles, and the release agent is not formed on the surface of the toner particles during the production of the toner. If the amount exceeds the necessary amount, the charging roller and the photoconductor are easily contaminated in the contact one-component developing system used in the present invention. Also, since the blocking property is poor, toner packing easily occurs in the developing machine during continuous paper feeding.

On the other hand, when the endothermic peak exceeds 120 ° C.,
It is difficult for the release agent to ooze out instantly during fixing, and the secondary colors (red, green,
Blue) will deteriorate the fixability.

The release agent preferably has a mass average molecular weight (Mw) of 300 to 1,500.

When the mass average molecular weight is less than 300, the release agent is liable to be exposed on the surface of the toner particles, and in the contact one-component developing system used in the present invention, the developing property is deteriorated, and the releasing agent is exposed to high temperature and high humidity environment. The fog becomes worse. Further, the contamination of the photoconductor is remarkable. The mass average molecular weight is 1500.
If it exceeds, the low temperature fixability is deteriorated, and when outputting a full-color image, OHT transparency and haze are deteriorated. The mass average molecular weight of the release agent is 400 to 1,250.
Is particularly preferable.

The molecular weight of the release agent is measured by GPC under the following conditions. (GPC measurement conditions) Device: GPC-150C (manufactured by Waters) Column: GMH-MT 30 cm 2 stations (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min sample: A 0.15% sample is measured under the condition of 0.4 ml injection or more, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Further, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

The penetration of the release agent used in the present invention is JI.
It is measured according to SK2235. Measurement temperature is 25
℃. The penetration of the release agent is preferably 15 degrees or less, and more preferably 8 degrees or less. More preferably, it is 4 degrees or less. When it exceeds 15 degrees, in the contact one-component developing system used in the present invention, the contamination of each functional member is promoted and the developing characteristics are deteriorated.

The acid value and hydroxyl value of the release agent are measured by a method according to the wax analysis method described in the standard oil and fat analysis method.

The acid value is preferably 40 or less, more preferably 20 or less, still more preferably 10 or less. Also,
The hydroxyl value is preferably 50 or less, more preferably 30 or less, still more preferably 15 or less.

When the acid value exceeds 40 or the hydroxyl value exceeds 50, the charging characteristics in a high temperature and high humidity environment deteriorate, and fog and scattering in the machine deteriorate.

When the toner particles are produced by the melt-kneading and pulverization method, 1 part of the releasing agent is added to 100 parts by mass of the binder resin.
It is preferable to use 10 to 10 parts by mass. When the polymerizable monomer composition is used to directly produce the toner particles in an aqueous medium, the amount of the monomer is 5 per 100 parts by weight of the polymerizable monomer.
To 40 parts by mass, more preferably 5 to 30 parts by mass, and as a result, 5 to 40 parts by mass, and more preferably 5 to 5 parts by mass of the releasing agent per 100 parts by mass of the binder resin produced from the polymerizable monomer. It is preferable that 30 parts by mass of toner particles are contained.

Compared to the dry toner manufacturing method by the melt-kneading and pulverization method, in the toner manufacturing method by the polymerization method, since a large amount of the release agent is easily encapsulated in the toner particles by the polar resin,
Generally, a large amount of release agent can be used, which is particularly effective for the offset prevention effect at the time of fixing.

Examples of the colorant that can be contained in the toner of the present invention are shown below, but other colorants may be used.

As the black colorant, carbon black,
A magnetic material, which is toned in black with the following yellow / magenta / cyan colorant, is used.

As the yellow colorant, the following pigments and / or dyes can be preferably used. As the pigment, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yell
ow 3.7.10.12.13.14.15.17.12
3.24.60.62.74.75.83.93.9
4.95.9.100.101.104.108.1
09.110.111.117.123.128.12.
9.138.139.147.148.150.16
6.168.169.177.179.180.18
1.183.185.191: 1.191.192.1.
93.199 etc. are used suitably.

Examples of the dye include C.I. I. solve
ent Yellow 33.56.798.82.93.
112.162.163, C.I. I. disperse
Yellow 42.64.201.211 and the like.

As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8; 2, 48; 3, 48; 4, 57; 1, 81; 1, 1
22, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254, C.I.
I. Pigment Violet 19 is particularly preferable.

As the cyan colorant, phthalocyanine compounds and their derivatives, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 1
5: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used.

These colorants can be used alone or in combination, and can be used in the form of solid solution. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is 1 to 2 with respect to 100 parts by mass of the binder resin.
0 parts by weight are used.

The toner of the present invention may be used together with a charge control agent. The following substances control the toner to be negatively charged. One example is given, but other than these may be used.

For example, organic metal compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid type metal compounds. In addition, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples include esters and phenol derivatives such as bisphenol.

Further, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, 4
Examples include primary ammonium salts, calixarene, and resin-based charge control agents.

There are the following substances for controlling the toner to be positively charged. One example is given, but other than these may be used.

Nigrosine modified products of nigrosine and fatty acid metal salts, quaternary ammonium salts such as guanidine compounds, imidazole compounds, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
Onium salts such as phosphonium salts and their lake pigments which are analogs thereof; triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids;
Dibutyltin oxide, dioctyltin oxide,
Diorganotin oxides such as dicyclohexyltin oxide; diorganotinborates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate; and resin-based charge control agents.
These may be used alone or in combination of two or more.

The charge control agent is 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the binder resin.
Good to use parts by weight.

A condensation resin may be added when the toner of the present invention is produced by a polymerization method. One example is given, but other than these may be used.

The condensation resin used in the present invention is, for example,
Examples thereof include polyester, polycarbonate, phenol resin, epoxy resin, polyamide and cellulose. More preferably, polyester is desired due to the variety of materials. It is preferable to use 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, of the above condensation-based resin per 100 parts by mass of the binder resin.

The toner of the present invention contains an external additive externally added (externally added) after the production of toner particles in order to improve various properties such as fluidity, like other general toners. May be. In the present invention, the external additive is toner particles 100.
It is preferable to use 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, with respect to parts by mass of toner particles.

When the amount of the external additive added is less than 0.01 parts by mass, the fluidity imparting ability to the toner particles is insufficient, and when it exceeds 5 parts by mass, the external additive liberated from the toner particles is used. May contaminate the developing blade, the developing roller and the photoconductor, resulting in image defects. Further, the fixability at a low temperature, particularly the fixability in the halftone may be significantly deteriorated.

The external additive that can be contained in the toner of the present invention is
Metal oxide compounds such as titanium oxide (anatase type, rutile type, amorphous), aluminum oxide, strontium titanate, cerium oxide, magnesium oxide; nitrides such as silicon nitride; carbides such as silicon carbide; calcium sulfate, barium sulfate , Metal salts such as calcium carbonate; carbon fluoride, silicon compound fine powder (silica fine powder, silicone resin fine powder) and the like. Titanium oxide (anatase type, rutile type, non-crystalline), aluminum oxide, silicon compound fine powder, more preferably titanium oxide (anatase type, rutile type, non-crystalline), silicon compound fine powder is there.

The above external additives may or may not be hydrophobized. When performing the hydrophobic treatment, either a wet method or a dry method may be used.

As the hydrophobizing agent, a silane coupling agent,
Examples thereof include titanium-based coupling agents, aluminate-based coupling agents, zirco-aluminum-based coupling agents, and silicone oil.

In the toner of the present invention, in addition to the above-mentioned external additives, it is also preferable to use other known powders together for the purpose of improving charge stability, developing property, fluidity and continuous printability. It is desired that the powder used in this case more preferably has a particle diameter of 1/2 or less of the volume average diameter of the toner particles. The particle size here means the number average particle size obtained by observing the surface of the toner particles using an electron microscope.

An example of the method for producing the toner of the present invention will be shown below.

When the toner of the present invention is manufactured by a pulverization method, at least a binder resin and a colorant are kneaded and uniformly dispersed by using a pressure kneader, an extruder, a media disperser or the like, The particles are mechanically or in a jet stream made to collide with a target to be finely pulverized to a desired toner particle size, and after a classification step, mechanical particles are used to obtain toner particles having a desired particle size and particle size distribution. Alternatively, a method in which a wet or dry thermal spheroidizing treatment is performed after the above pulverization is mentioned.

When the toner of the present invention is produced by a polymerization method, it is not particularly limited, but is disclosed in Japanese Patent Publication No.
-10231, JP-A-59-53856,
A method of directly producing toner particles by using a suspension polymerization method described in JP-A-59-61842; a toner which is soluble in a monomer and is directly polymerized in the presence of a water-soluble polymerization initiator. The production of toner particles by an emulsion polymerization method typified by a soap-free polymerization method for producing particles can be mentioned. Also,
Interfacial polymerization method such as microcapsule manufacturing method, in-si
Production by a te polymerization method, a coacervation method or the like can also be mentioned. Further, an interface association method for obtaining at least a desired particle size by aggregating at least one kind of fine particles, as disclosed in JP-A-62-106473 and JP-A-63-186253, may be mentioned. To be

Among the above-mentioned polymerization methods, the suspension polymerization method is particularly preferable because it allows toner particles having a small particle diameter to be easily obtained. Furthermore, after further adsorbing the monomer to the obtained polymer particles,
A seed polymerization method in which a polymerization initiator is used for polymerization can also be preferably used in the present invention. At this time, it is also possible to disperse or dissolve the polar compound in the adsorbed monomer before use. In addition, there is also a method in which a toner binder, a colorant and the like are dissolved in an organic solvent, particles are formed in an aqueous solution to which a dispersion stabilizer is added, and then the solvent is evaporated.

When suspension polymerization is carried out, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer composition. As the dispersant used, for example, as an inorganic oxide, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate,
Examples thereof include calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and sodium dodecyl sulfate. As the organic compound, for example, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like are used. It is preferable to use 0.1 to 5.0 parts by mass of these dispersants with respect to 100 parts by mass of the polymerizable monomer. 0.001 to make these dispersants finer
You may use 0.1 mass% of surfactant together. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate,
Sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.

When a toner is produced by either a pulverization method or a polymerization method, an external additive and other powders are mixed (externally added) with the obtained toner particles, if necessary. The toner of the invention can be obtained.

The image forming method of the present invention will be described below with reference to FIG.

The image forming method of the present invention forms a color image by using two or more toners of the present invention having different colors. (I) a charging step of subjecting the surface of the photoreceptor to a charging treatment, and (II) A latent image step of sequentially forming electrostatic latent images corresponding to respective colors on the charged photoreceptor, (II
I) a developing step of visualizing the electrostatic latent image formed on the photoreceptor with toner of a corresponding color to form a toner image; and (IV) a toner image of each color visualized in the developing step. A transfer step of sequentially superimposing and transferring on a transfer material.

In the image forming method of the present invention as described above, in the developing step, a developing cartridge having a plurality of developing devices each having a developing roller carrying toner is used in accordance with each color toner, and the developing roller of each developing device is used. This is a contact one-component developing process of a rotary structure in which toner images of respective colors are sequentially formed by sequentially contacting the photoconductor, and the developing roller of the developing device that is not used to form the toner image is separated from the photoconductor. It is characterized by

An example of a color image forming apparatus (copier or laser beam printer) in which the image forming method of the present invention is preferably used will be described with reference to FIG.

Reference numeral 1 denotes a drum-shaped photosensitive member as a first image bearing member, which is rotationally driven at a predetermined peripheral speed (process speed) in the direction of the arrow in the figure. In the course of rotation, the photoconductor 1 is uniformly charged to a predetermined polarity and potential by the primary charger 2 (charging step), and then subjected to exposure 3 by an unillustrated image exposing means (latent image forming step). In this way, an electrostatic latent image corresponding to the first color component image (for example, yellow toner image) of the target color image is formed.

Next, the electrostatic latent image is developed into a yellow toner image of the first color by the first developing device (yellow toner developing device 41) (developing step). At this time 2nd-4th
The developing devices of the above, that is, the magenta toner developing device 42, the cyan toner developing device 43, and the black toner developing device 44 do not operate and do not act on the photoconductor 1.
The color yellow toner image is not affected by the second to fourth developing devices. That is, in the developing process used in the image forming method of the present invention, the developing roller of each developing device is sequentially brought into contact with the photoconductor to sequentially form toner images of respective colors, and when the toner image formation is completed, the developing roller is released. It is a contact one-component developing process of a rotary structure, which is separated from the photoconductor.

Each of the developing devices 41 to 41 used in the above developing process
Reference numeral 44 has a developing roller that carries toner and conveys the toner to a portion of the surface of the photosensitive member 1 where development is to be performed, and a developing blade that regulates the amount of toner on the developing roller and at the same time charges the toner. ing.

The developing roller in the present invention may be any conventionally known one as long as it has an elastic layer, and is not particularly limited. Further, as described above, the rotation number of the developing roller is preferably 100 to 500 rotations / minute.

The toner image formed on the photoconductor in the developing step is subjected to the transfer step. The transfer step used in the image forming method of the present invention is a color toner image to be formed on the transfer material by sequentially superposing and transferring the toner images of the respective colors formed on the photoconductor onto the intermediate transfer body. Primary transfer step of forming the color toner image on the intermediate transfer body, and transferring the color toner image formed on the intermediate transfer body onto the transfer material 2
It may consist of a next transfer step.

In FIG. 1, the intermediate transfer belt 20 as an intermediate transfer member is rotationally driven in the direction of the arrow at the same peripheral speed as the photosensitive member 1. In the process in which the yellow toner image of the first color formed on the photoconductor 1 passes through the contact portion between the photoconductor 1 and the intermediate transfer belt 20, from the bias power supply 29 via the roller 62, the intermediate transfer belt 20 is passed. An electric field formed by a bias applied to the intermediate transfer belt 20 causes the intermediate transfer belt 20 to be sequentially transferred to the outer peripheral surface thereof. This process is called primary transfer, the roller 62 is called a primary transfer roller, and the applied bias is called a primary transfer bias. The surface of the photoconductor 1 that has transferred the yellow toner image of the first color corresponding to the intermediate transfer belt 20 is cleaned by the cleaning device 13.

Thereafter, the developing unit 40 rotates in the direction of the arrow in the drawing, and the second to fourth developing devices are sequentially moved to the positions facing the photoconductor 1, so that the second color image is formed in the same manner as the yellow toner image. The magenta toner image, the third color cyan toner image, and the fourth color black toner image are sequentially transferred onto the intermediate transfer belt 20 in an overlapping manner to form a full-color toner image corresponding to the target color image.

Next, the color toner image is transferred onto the transfer material, and this step is called secondary transfer. Reference numeral 63 denotes a secondary transfer roller, which corresponds to the secondary transfer counter roller 64 and is supported in parallel with the lower surface portion of the intermediate transfer belt 20 so as to be separated therefrom.

The primary transfer bias for transferring the toner image from the photoconductor 1 to the intermediate transfer belt 20 is applied from the bias power source 29 with the polarity opposite to that of the toner. The applied voltage is, for example, in the range of + 100V to + 2kV.

First transfer from photoreceptor 1 to intermediate transfer belt 20
In the primary transfer process of the toner image of the third color, the secondary transfer roller 63 can be separated from the intermediate transfer belt 20. The secondary transfer roller 63 is the intermediate transfer belt 20.
And the transfer material P is fed from the paper feed roller 11 to the contact portion between the intermediate transfer belt 20 and the secondary transfer roller 63 at a predetermined timing. At this time, the secondary transfer bias is applied from the bias power supply 28 to the secondary transfer roller 63, so that the full-color image transferred onto the intermediate transfer belt 20 is secondarily transferred onto the transfer material P. The transfer material P on which the toner image has been transferred is introduced into the fixing device 15 and heat-fixed.

After the image transfer onto the transfer material P is completed, the toner remaining on the intermediate transfer belt (transfer residual toner) is scraped off by the cleaning blade 50 and carried to the waste toner box.

As described above, particularly in the image forming method having the developing process of the rotary structure in which the developing device of each color is integrally provided like the developing unit 40 and the toner image of each color is sequentially formed on the photoconductor 1. The toner may be damaged due to the increase of the temperature inside the machine under the high temperature and high humidity environment, and the toner may be fused to the developing blade to cause an image defect. However, in the image forming method of the present invention, since the toner of the present invention having the specific physical properties as described above is used, even when a large number of sheets are continuously printed under high temperature and high humidity, the contact portion between the developing blade and the developing roller is Since it is possible to prevent the generation of the fused substance in the above, it is possible to maintain good image formation.

[0160]

EXAMPLES The present invention will be explained more concretely by showing examples below, but this does not limit the present invention in any way.

Example 1 Magenta Toner No. 0.1 M to 1000 parts by mass of ion-exchanged water in the production reaction vessel
10 parts by mass of -Na ₃ PO ₄ aqueous solution and 9 parts by mass of 1M-HCl aqueous solution were charged, and the mixture was purged with N ₂ at 60 ° C at 60 ° C.
I kept warm for a minute. Using a TK homomixer (made by Tokushu Kika Kogyo), stirring at 12000 rpm, 1.0
Add 7 parts by mass of M-CaCl ₂ aqueous solution all at once, PH ≒
An aqueous medium containing 6.0 calcium phosphate salt was prepared.

On the other hand, the dispersoid system includes: styrene monomer 80 parts by mass, 2-ethylhexyl acrylate monomer 20 parts by mass, quinacridone pigment 10 parts by mass, aluminum benzylate compound 1.0 part by mass, saturated polyester resin 10 Parts by mass (polycondensation product of propylene oxide-modified bisphenol A and phthalic acid) -divinylbenzene 0.25 parts by mass After the above mixture is dispersed for 5 hours using a media-type disperser, a releasing agent (ester wax, tangential desorption temperature) 50 ℃,
20 parts by mass of full width at half maximum (4 ° C.) was added, the internal temperature was raised to 60 ° C., and the temperature was kept for 30 minutes. Then, the polymerization initiator 2,2 '
-Adding 3 parts by mass of azobis (2,4-dimethylvaleronitrile) to the above dispersion medium, 1200
Granulation was carried out for 5 minutes while maintaining 0 rpm. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was carried out at 150 rpm for 12 hours. After the polymerization is completed, the slurry is cooled,
After washing with water and drying to obtain magenta particles, C1 and C2 values were adjusted by classification with a multi-divided air classifier and classification system utilizing the Coanda effect.

To 100 parts by mass of the obtained magenta particles, 1.0 part by mass of fine silica powder having a hydrophobicity of 99% was added and uniformly fixed by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to prepare magenta toner No. Got 1. The obtained magenta toner No. The physical properties of No. 1 are shown in Table 2.

Example 2 Magenta Toner No. 2 in Production Example 1 except that the release agent was changed to an ester wax having a tangential desorption temperature of the DSC curve of 48 ° C. and a half width of 5 ° C., and the amount of the crosslinking agent (divinylbenzene) was 0.18.
Magenta Toner No. 1 was manufactured by the same method as in Example 1 except that the parts were changed to parts by mass. Got 2. The obtained magenta toner No. Table 2 shows the physical properties of No. 2.

Example 3 Magenta Toner No. 3 in Production Example 1 except that the compounding ratio of styrene and 2-ethylhexyl acrylate was changed from 80:20 to 76:24,
Further, magenta toner No. 1 was used in the same manner as in Example 1 except that the releasing agent was changed to ester wax having a tangential desorption temperature of DSC curve of 48 ° C. and a half width of 5 ° C. Three
Got The obtained magenta toner No. Table 2 shows the physical properties of 3.
Shown in.

Example 4 Magenta Toner No. 4 Production Example 1 was performed using the same method as in Example 3 above, except that when the conversion during the polymerization reaction reached 70%, the stirring conditions were changed to 10 minutes at 12000 rpm. Magenta toner No. Got 4. The obtained magenta toner N
o. The physical properties of No. 4 are shown in Table 2.

Example 5 Magenta Toner No. In Production Example 1 of Example 5, the release agent was changed to paraffin wax having a tangential line detachment temperature of 42 ° C. and a half width of 7 ° C., and the amount of the crosslinking agent (divinylbenzene) was changed to 0.1 part by mass. Except for the above, the same method as in Example 1 is used and the magenta toner No. Got 5. The obtained magenta toner No. 1
The physical properties of are shown in Table 2.

Example 6 Magenta Toner No. Production of 6 ・ Unsaturated polyester resin 100 parts by mass (polycondensation product of propylene oxide-modified bisphenol A and phthalic acid) ・ Quinacridone pigment 10 parts by mass ・ Aluminum benzylate compound 4 parts by mass ・ Ester wax 5 parts by mass (DSC curve (Tangential departure temperature 50 ° C, half-width 4 ° C) These are sufficiently premixed by a Henschel mixer, melt-kneaded by a twin-screw extruder, cooled, and roughly crushed to about 1 to 2 mm using a hammer mill. Magenta particles were obtained by classifying with a multi-division wind classifier and a classifying system using the Coanda effect and adjusting the C1 value and the C2 value. In the same manner as in Example 1, 1.0 part by mass of silica fine powder was added to the obtained magenta particles, and magenta toner No. 6
Got The obtained magenta toner No. Table 2 shows the physical properties of 6
Shown in.

<Comparative Production Example 1 of Toner> Magenta Toner No. Magenta Toner No. 7 was used in the same manner as in Production Example 1 except that the release agent was changed to ester wax having a tangential line desorption temperature of 35 ° C. and a half width of 8 ° C.
Got 7. The obtained magenta toner No. The physical properties of No. 7 are shown in Table 2.

<Comparative Production Example 2 of Toner> Magenta Toner No. No. 8 in the same manner as in the above-described Example 1 except that the 1M-HCl aqueous solution was not added. 8
Got The obtained magenta toner No. Table 2 shows the physical properties of 8.
Shown in.

<Comparative Production Example 3 of Toner> Magenta Toner No. 9 in Production Example 1 except that the release agent was changed to an ester wax having a tangential desorption temperature of 35 ° C. and a half width of 8 ° C.
Example 1 above, except that no aqueous HCl solution was added.
Magenta Toner No. Got 9.
The obtained magenta toner No. The physical properties of 9 are shown in Table 2.

Example 7 Yellow Toner No. Yellow toner No. 1 was manufactured in the same manner as in Production Example 1 except that the colorant was changed from a quinacridone pigment to a condensed azo pigment. Got 1. The obtained yellow toner No. The physical properties of No. 1 are shown in Table 2.

<Embodiment 8> Yellow toner No. No. 2 in the same manner as in the above-mentioned Example 5 except that the quinacridone pigment was changed to the condensed azo pigment in Production Example 5 of Preparation No. Got 2. The obtained yellow toner No. Table 2 shows the physical properties of No. 2.

Example 9 Yellow Toner No. Yellow toner No. 1 was manufactured in the same manner as in Example 6 except that the quinacridone pigment was changed to a condensed azo pigment in Production Example 6 of Production Example 3. Got 3. The obtained yellow toner No. The physical properties of No. 3 are shown in Table 2.

<Comparative Production Example 4 of Toner> Yellow toner No. No. 4 of the yellow toner was prepared by the same method as in Comparative Preparation Example 3 except that the colorant was changed from the quinacridone pigment to the condensed azo pigment in Comparative Preparation Example 3 of the manufactured toner of Example 4. Got 4. The obtained yellow toner No. The physical properties of No. 4 are shown in Table 2.

Example 10 Cyan Toner No. Cyan Toner No. 1 was used in the same manner as in Production Example 1, except that the colorant was changed from a quinacridone pigment to a copper phthalocyanine pigment. Got 1. The obtained cyan toner No. The physical properties of No. 1 are shown in Table 2.

<Embodiment 11> Cyan toner No. Cyan Toner No. 2 using the same method as in Example 5 except that the colorant was changed from a quinacridone pigment to a copper phthalocyanine pigment in Production Example 5 of Example 2. Got 2. The obtained cyan toner No. Table 2 shows the physical properties of No. 2.

Example 12 Cyan Toner No. Cyan Toner No. 3 was used in the same manner as in Production Example 6 except that the colorant was changed from a quinacridone pigment to a copper phthalocyanine pigment. Got 3. The obtained cyan toner No. The physical properties of No. 3 are shown in Table 2.

<Comparative Production Example 5 of Toner> Cyan Toner N
o. Cyan Toner No. 4 using the same method as in Comparative Production Example 3 above, except that the colorant was changed from the quinacridone pigment to the copper phthalocyanine pigment in Comparative Production Example 3 of Production Toner of Example 4.
Got 4. The obtained cyan toner No. Table 2 shows the physical properties of 4
Shown in.

Example 13 Black Toner No. Black toner No. 1 was manufactured using the same method as in Example 1 except that the colorant was changed from a quinacridone pigment to a carbon black pigment. Got 1. The obtained black toner No. The physical properties of No. 1 are shown in Table 2.

Example 14 Black Toner No. Black toner No. 2 was produced by the same method as in Example 5 except that the colorant was changed from a quinacridone pigment to a carbon black pigment in Production Example 5 of Example 2. Got 2. The obtained black toner No. Table 2 shows the physical properties of No. 2.

<Example 15> Black toner No. Black toner No. 1 was manufactured by the same method as in Example 6 except that the colorant was changed from the quinacridone pigment to the carbon black pigment in Production Example 6 of Preparation No. 3. Got 3. The obtained black toner No. The physical properties of No. 3 are shown in Table 2.

<Toner Comparative Production Example 6> Black Toner No. Black toner N was produced in the same manner as in Comparative Production Example 3 except that the colorant was changed from a quinacridone pigment to a carbon black pigment in Comparative Production Example 3 of Production Toner of Example 4.
o. Got 4. The obtained black toner No. The physical properties of No. 4 are shown in Table 2.

[0184]

[Table 2]

Sixteenth Embodiment Using the image forming apparatus of the contact one-component developing system of the rotary construction using the intermediate transfer belt shown in FIG. 1, magenta toner No. 1 in the high temperature and high humidity environment (30 ° C / 8
(5% RH), full-color mode, printing ratio 4%, continuous paper feeding. The sampling timing was set to the 100th sheet, the 2000th sheet, and the 4000th sheet, and development streaks of halftone images and fogging on paper were evaluated. The evaluation method is shown below. The rotation number of the developing roller at this time was 150 rpm.

In this embodiment, the full solid image is an image having a toner application amount of 0.55 to 0.75 mg / cm ² , and the halftone image is a toner application amount of 0.20 to 0.
An image of 40 mg / cm ² is shown.

(Development streak) The development streak was evaluated according to the following criteria from the halftone image obtained after continuous printing in the high temperature and high humidity environment. A: Vertical streaks in the paper discharge direction, which are considered to be development streaks, are not seen on the developing roller or on the image in the halftone portion, and there is no problem in practical use. B: Although there are 1 to 5 thin streaks in the circumferential direction at both ends of the developing roller, vertical streaks in the paper discharge direction, which are considered to be development streaks, are not seen on the image in the halftone portion, which is at a practically no problem level. C: There are several thin streaks in the circumferential direction on both ends of the developing roller, and several fine streaks are also seen on the image in the halftone portion. However, there is no practical problem at the level that can be erased by image processing. D: Many main development streaks are seen both on the developing roller and on the image in the halftone portion and cannot be erased even by image processing. There is a problem in practical use.

(Fog) Fog was judged from the white solid image obtained after the continuous printing in the high temperature and high humidity environment. The measurement of fog is made by REFLECTOMETER M
It measured using ODEL TC-6DS (made by Tokyo Denshoku Co., Ltd.). The black / magenta toner image was calculated using the green filter, the yellow toner image was calculated using the blue filter, and the cyan toner image was calculated using the amber filter. The smaller the fog value, the better.

[0189]

Fog (reflectance;%) = (reflectance of standard paper;
%)-(Reflectance of sample;%) A: Fog is 1.5% or less, and there is no problem in practical use. B: Fog is more than 1.5% and 2.0% or less, and there is no problem in practical use. C: Fog is more than 2.0% and 3.0% or less, and there is no problem in practical use. D: Fog exceeds 3.0%. There is a problem in practical use.

<Examples 17 to 30> In Example 16, magenta toner No. Evaluation was performed in the same manner as in Example 16 except that each toner shown in Table 3 was used instead of 1.

Comparative Examples 1 to 6 In Example 16, magenta toner No. Evaluation was performed in the same manner as in Example 16 except that each toner shown in Table 3 was used instead of 1.

Table 3 shows the evaluation results of Examples 16 to 30 and Comparative Examples 1 to 6.

[0193]

[Table 3]

<Embodiment 31> The image forming apparatus of the contact one-component developing system of the rotary construction using the intermediate transfer belt shown in FIG. 1, yellow toner No. 1, cyan toner No. 1. Black toner No. 1 1 set, full color mode under high temperature and high humidity environment (30 ° C / 85% RH),
Continuous printing was performed at a printing ratio of 4%. The sampling timing was set to the 100th sheet, the 2000th sheet, and the 4000th sheet, and the occurrence of fused substances on the photoconductor and the white spots in the halftone / full solid image were evaluated. The evaluation method is shown below.
The rotation number of the developing roller at this time was 150 rpm.
The definitions of all solid images and halftone images in this embodiment are the same as in the 16th embodiment.

(Generation of Fused Material on Photoreceptor) The occurrence of fused material on the photoconductor was evaluated according to the following criteria by observing the surface of the photoreceptor after continuous printing in the high temperature and high humidity environment. A: The surface of the photoconductor is clean without any fused substance and is at a level where there is no problem in practical use. B: A small fused substance is present on the surface of the photoconductor, but it can be easily removed with a slight force, and there is no problem in practical use. C: There is a small fused substance on the surface of the photoconductor, and it cannot be removed with a slight force, but there is no problem in practical use. D: There is a large melt deposit on the surface of the photoreceptor. There is a problem in practical use.

(Image Whiteout) Image whiteout was evaluated according to the following criteria from the halftone images and all solid images obtained after the continuous printing under the high temperature and high humidity environment. A: No white spots were found on the image of the entire solid area even in the halftone portion, and there was no problem in practical use. B: No white spots are found on the image of the halftone portion, but some small white spots are found on the image of the entire solid portion. However, there is no problem in practical use. C: White spots can be seen in the image of all solid portions even in the halftone portion, but there is no problem in practical use. D: White spots are also seen on the image of all solid areas even in the halftone area. There is a problem in practical use.

<Examples 32 and 33> Evaluations were made in the same manner as in Example 31 except that the toners shown in Table 4 were used instead of the toners used in Example 31.

Comparative Example 7 The same as Example 31 except that the toners shown in Table 4 were used instead of the toners used in Example 31, and the number of rotations of the developing roller was changed to 300 rpm. Evaluation was carried out using the method.

Table 4 shows the evaluation results of Examples 31 to 33 and Comparative Example 7.

[0200]

[Table 4]

[0201]

According to the present invention, in the developing method in which the developing roller and the photosensitive member are brought into contact with each other and separated from each other by using the developing process of the contact one-component developing system having the rotary structure, particularly in a high temperature and high humidity environment. By preventing the generation of a fused substance in the vicinity of the contact portion between the developing roller and the developing blade,
A good image can be formed by suppressing the occurrence of image defects such as fogging on the transfer material, fusing on the photosensitive member, and white spots in the halftone portion / full solid portion image.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of an image forming apparatus in which a toner and an image forming method of the present invention can be preferably used.

[Explanation of symbols]

1 photoconductor 2 Primary charger 3 exposure 11 Paper feed roller 13 Cleaning device 20 Intermediate transfer belt 40 development unit 41, 42, 43, 44 Developing device 50 cleaning blade 63 Secondary transfer roller 64 Secondary transfer counter roller P transfer material

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/08 501 501 G03G 15/08 503C 503 9/08 361 (72) Inventor Kenichi Nakayama 3-30 Shimomaruko, Ota-ku, Tokyo No. 2 in Canon Co., Ltd. F-term (reference) 2H005 AA06 AA15 AA21 CA13 CA14 EA03 EA05 EA10 2H077 AD02 AD06 AD13 AE03 AE04 BA09 EA11 EA15 GA13 2H300 EA06 EB02 EB08 EB08 EB08 EJ08 EJ08 EJ08EJ05 EJ08 EJ08EJ09 EF08 EF08 EF08 EF08 EF14 EF14 MM11 MM16 MM30

Claims (36)

[Claims] 1. An image forming method, comprising: a toner for visualizing an electrostatic latent image carried on a photoconductor, wherein a color image is formed by using two or more toners having different colors. ) A charging step of charging the surface of the photosensitive member, (II) a latent image forming step of sequentially forming electrostatic latent images corresponding to the respective colors on the charged photosensitive member, and (III) forming a latent image on the photosensitive member. A developing step of visualizing the formed electrostatic latent image with toner of a corresponding color to form a toner image, and (IV) sequentially superimposing the toner images of the respective colors visualized in the developing step on a transfer material. The image forming method includes a transfer step of transferring, and the developing step uses a developing cartridge having a plurality of developing devices each having a developing roller carrying a toner according to each color toner, and the developing roller of each developing device. To the photoreceptor This is a contact one-component developing process of a rotary configuration in which toner images of respective colors are sequentially formed by sequentially contacting each other, and when the formation of the toner image is completed, the developing roller is separated from the photoconductor. The tangential desorption temperature of the endothermic peak in thermal analysis measurement (DSC) is 40 ° C. or higher, and the weight average particle diameter obtained by the Coulter counter method is 4 to 10 μm.
m, and (i) the dispersion liquid obtained by dispersing 5 mg of the toner in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. When the particle size is 0.6 to 2.0 μm, the ratio C1 of the particles measured by the flow-type particle image analyzer is 3 to
65% by number, (ii) In the dispersion liquid, 20 kHz, 50 W / 10 cm ³
The ratio C2 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when the ultrasonic wave is irradiated for 1 minute is 2 to 62% by number, and (iii) the following formula ( The value of C represented by 1) is 102 to 15
A toner having a value of 0. ## EQU1 ## C = (C1 / C2) × 100 (1) 2. The tangential departure temperature of the endothermic peak is 50 ° C.
The toner according to claim 1, characterized in that the above is satisfied. 3. The toner according to claim 1, which has a melt index value of 1 to 50. 4. The toner according to claim 1, which has a melt index value of 2 to 30. 5. The toner according to any one of claims 1 to 4, which has a glass transition temperature of 45 to 85 ° C. 6. The toner according to claim 1, wherein the toner has a glass transition temperature of 50 to 70 ° C. 7. The average circularity in a number-based circle-equivalent diameter-circularity scattergram measured by a flow type particle image measuring device is 0.950 to 0.999. The toner according to any one of 1. 8. The average circularity in a number-based circle equivalent diameter-circularity scattergram measured by a flow type particle image measuring device is 0.965 to 0.999, wherein the average circularity is 0.965 to 0.999. The toner according to any one of 1. 9. The half width at the endothermic peak is 10 ° C.
The toner according to any one of claims 1 to 8, wherein: 10. The half width at the endothermic peak is 5 ° C.
The toner according to any one of claims 1 to 8, wherein: 11. The number of rotations of the developing roller is 100 to 5
The toner according to any one of claims 1 to 10, which has a rotation speed of 00 rpm. 12. The C1 is 3 to 50% by number, the C2 is 2 to 40% by number, and the C is 105 to 14%.
The toner according to claim 1, wherein the toner is 0. 13. A developing cartridge for visualizing an electrostatic latent image carried on a photoconductor, which is an image forming method for forming a color image using two or more toners of different colors. I) a charging step of charging the surface of the photosensitive member; (II) a latent image forming step of sequentially forming electrostatic latent images corresponding to the respective colors on the charged photosensitive member; and (III) the photosensitive member. A developing step of visualizing the electrostatic latent image formed on the toner with a toner of a corresponding color to form a toner image; and (IV) sequentially superimposing the toner images of the respective colors visualized in the developing step on a transfer material. And a plurality of developing devices each having a developing roller carrying a toner corresponding to each color toner, and the developing roller of each developing device is sequentially applied to the photoconductor. Each color by touching Are sequentially formed, and when the formation of the toner image is completed, the developing roller is separated from the photoconductor, and is a developing cartridge using a contact one-component developing method of a rotary structure, and the toner is a differential thermal analysis. The tangential desorption temperature of the endothermic peak in the measurement (DSC) is 40 ° C. or higher, and the weight average particle diameter obtained by the Coulter counter method is 4 to 10 μm.
m, and (i) the dispersion liquid obtained by dispersing 5 mg of the toner in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. When the particle size is 0.6 to 2.0 μm, the ratio C1 of the particles measured by the flow-type particle image analyzer is 3 to
65% by number, (ii) In the dispersion liquid, 20 kHz, 50 W / 10 cm ³
The ratio C2 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when the ultrasonic wave is irradiated for 1 minute is 2 to 62% by number, and (iii) the following formula ( The value of C represented by 1) is 102 to 15
A toner having a value of 0. ## EQU2 ## C = (C1 / C2) × 100 (1) 14. The tangential desorption temperature at the endothermic peak of the toner is 50 ° C. or higher.
3. The developing cartridge according to item 3. 15. The toner according to claim 13, wherein the melt index value of the toner is 1 to 50.
The developing cartridge described in. 16. The toner according to claim 13, wherein a melt index value of the toner is 2 to 30.
The developing cartridge described in. 17. The glass transition temperature of the toner is 45 to 50.
The developing cartridge according to any one of claims 13 to 16, which has a temperature of 85 ° C. 18. The glass transition temperature of the toner is 50 to 50.
The developing cartridge according to any one of claims 13 to 16, which has a temperature of 70 ° C. 19. The average circularity in a number-based circle equivalent diameter-circularity scattergram measured by the toner flow type particle image measuring device is 0.950 to 0.999. The developing cartridge according to any one of 13 to 18. 20. The average circularity in a number-based circle equivalent diameter-circularity scattergram measured by a toner flow type particle image measuring device is 0.965 to 0.999. The developing cartridge according to any one of 13 to 18. 21. The full width at half maximum at the endothermic peak of the toner is 10 ° C. or less.
The developing cartridge according to any one of 0. 22. The full width at half maximum at the endothermic peak of the toner is 5 ° C. or less.
The developing cartridge according to any one of 1. 23. The rotation number of the developing roller is 100 to 5
23 rotations / minute.
The developing cartridge according to any one of 1. 24. The C1 of the toner is 3 to 50% by number, the C2 is 2 to 40% by number, and the C is 10%.
The developing cartridge according to any one of claims 13 to 23, which is 5 to 140. 25. An image forming method for forming a color image using two or more toners of different colors, comprising: (I) a charging step of charging the surface of the photosensitive member; and (II) the photosensitive member subjected to the charging processing. A latent image forming step of sequentially forming electrostatic latent images corresponding to respective colors on the upper surface, and (III) visualizing the electrostatic latent images formed on the photoconductor with toner of corresponding colors to form a toner image. And (IV) a transfer step of sequentially superimposing and transferring the toner images of the respective colors visualized in the developing step on a transfer material, wherein the developing step includes a developing roller carrying a toner. A developing cartridge having a plurality of developing devices corresponding to the toners of the respective colors is used, and the developing roller of each developing device is sequentially brought into contact with the photoconductor to sequentially form the toner images of the respective colors, and the formation of the toner image is completed. Then development Is a rotary one-component contact developing step in which the toner is separated from the photoreceptor, and the toner has a tangential desorption temperature of an endothermic peak of 40 ° C. or more in a differential thermal analysis (DSC), and is measured by a Coulter counter method. The obtained weight average particle diameter is 4 to 10 μm.
m, and (i) the dispersion liquid obtained by dispersing 5 mg of the toner in 10 ml of water in which 0.1 mg of the nonionic surfactant is dissolved is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. When the particle size is 0.6 to 2.0 μm, the ratio C1 of the particles measured by the flow-type particle image analyzer is 3 to
65% by number, (ii) In the dispersion liquid, 20 kHz, 50 W / 10 cm ³
The ratio C2 of particles having a particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when the ultrasonic wave is irradiated for 1 minute is 2 to 62% by number, and (iii) the following formula ( The value of C represented by 1) is 102 to 15
An image forming method characterized by being 0. ## EQU3 ## C = (C1 / C2) × 100 (1) 26. The tangential departure temperature at the endothermic peak of the toner is 50 ° C. or higher.
5. The image forming method described in 5. 27. The melt index value of the toner is 1 to 50.
The image forming method described. 28. The melt index value of the toner is from 2 to 30.
The image forming method described. 29. The glass transition temperature of the toner is 45 to 45.
It is 85 degreeC, The image forming method as described in any one of Claims 25-28 characterized by the above-mentioned. 30. The glass transition temperature of the toner is 50 to 50.
The image forming method according to claim 25, wherein the temperature is 70 ° C. 31. The average circularity in a number-based circle equivalent diameter-circularity scattergram measured by a toner flow type particle image measuring device is 0.950 to 0.999. 31. The image forming method according to any one of 25 to 30. 32. The average circularity in a number-based circle equivalent diameter-circularity scattergram measured by a toner flow type particle image measuring device is 0.965 to 0.999. 31. The image forming method according to any one of 25 to 30. 33. The full width at half maximum at the endothermic peak of the toner is 10 ° C. or less.
2. The image forming method according to any one of 2. 34. The half value width at the endothermic peak of the toner is 5 ° C. or less.
The image forming method according to any one of 1. 35. The rotation number of the developing roller is 100 to 5
35 rotations / minute.
The image forming method according to any one of 1. 36. The C1 of the toner is 3 to 50% by number, the C2 is 2 to 40% by number, and the C is 10%.
The image forming method according to any one of claims 25 to 35, wherein the image forming method is 5 to 140.