Toner, Two-component Developer, Image Forming Method and Apparatus Unit

专利摘要:
SUMMARY OF THE INVENTION An object of the present invention is toner that does not deteriorate even after long-term use, has excellent image density stability and fine detail reproducibility, and is capable of obtaining an image free of fog, a two-component developer using the same, and an apparatus unit. To provide. In order to achieve the above object, the present invention In the particle size distribution according to the circular distribution and the diameter corresponding to the circular shape of the particles measured by the flow type particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and the diameter corresponding to the circular shape is 3.0 μm to Containing 8.0 to 30.0% by volume of particles having a diameter 0.60 μm to less than 2.0 μm, corresponding to a circle, having a maximum value Y in the area of 0.60 μm to 2.00 μm, corresponding to a maximum X in the region of 9.0 μm and a circle; The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And the number average length of at least 30-600 micrometers non-spherical inorganic fine powder (B) containing, A toner containing a binder resin and a colorant, and a toner containing an external additive fine powder are provided.
公开号:KR19990068188A
申请号:KR1019990002770
申请日:1999-01-28
公开日:1999-08-25
发明作者:유지 모리끼；겐지 오까도；히로아끼 가와까미；신야 야찌；미찌히사 마고메
申请人:미따라이 하지메；캐논 가부시끼가이샤；
IPC主号:

专利说明:

Toner, two-component developer, image forming method and apparatus unit {Toner, Two-component Developer, Image Forming Method and Apparatus Unit}
The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, or a toner-jet recording method. More specifically, the present invention uses toners used in copiers, printers and faxes, and toners, which first form a toner image on an electrostatic latent image bearing member, and then transfer the toner image onto a transfer member to form an image. A two-component developer, an image forming method, and an apparatus unit are described.
Conventionally, an electrostatic latent image is formed on a photosensitive member (drum) using an exposure optical system, and the electrostatic latent image thus formed is developed by a developing apparatus to form a toner image, and the formed toner image is transferred onto a recording sheet to fix the image formation. Devices are known.
The developer used in the developing apparatus includes a one-component developer and a two-component developer. In the one-component developer, the toner particles are charged by friction between the toner particles or friction with a suitable charging member, and the thus charged toner particles are carried by the developing sleeve of the developing apparatus and then adhered to the latent image on the photosensitive member surface. To form a toner image.
Up to now, in the formation of the toner image, in particular, in the case of the one-component developer, for example, the developer is allowed to stand for a long time, so that the fluidity of the developer is lowered, thereby enhancing the adhesion between the toner particles and charging the toner particles satisfactorily. As a result, even if the latent image is uniform, a so-called "non-uniform image" or "dimmed image" may occur, a phenomenon in which the visible image is formed unevenly. As a method for preventing this, conventionally, a method of imparting fluidity by agitating the developer first in a developing apparatus has been widely used.
However, over stirring the developer may promote toner deterioration, which may shorten the life of the developer.
The two-component developer is a mixture of magnetic carrier particles and synthetic resin non-magnetic toner particles in a suitable mixing ratio. The toner particles are charged at the time of mixing with the carrier particles, and the thus charged toner particles are carried by the developing sleeve of the developing apparatus, and then attached to the latent image portion on the surface of the photosensitive member to form a toner image. As a developing method using the two-component developer, so-called magnetic brush developing methods are disclosed in Japanese Patent Laid-Open Nos. 55-32060 and 59-165082, wherein a two-component developer composed of carrier particles and toner particles A magnetic brush is formed on the surface of the developing sleeve with the magnet disposed therein, and the magnetic brush formed on the photosensitive drum opposite to the developing sleeve is rubbed or approached, while maintaining a small developing gap, and between the developing sleeve and the photosensitive drum. The alternating electric field is applied continuously (between SD) to toner particles are repeatedly displaced from the developing sleeve side to the photosensitive drum side or vice versa to perform development.
In the magnetic brush developing method using a two-component developer, the toner particles are given triboelectric charge when mixed with the carrier particles. Since the carrier particles have a higher specific gravity than the toner particles, they are subjected to high mechanical stress due to friction with the carrier particles at the time of mixing, so that repeated performance of the developing mechanism tends to promote deterioration of the toner.
When such toner deterioration occurs, specifically, the concentration of the fixed image changes as a result of long-term use, and a part of the toner particles adheres to the non-image part, which causes "fog" to occur, resulting in a deterioration in image reproducibility. .
As a result of extensive research, the present invention has found that the deterioration of the toner is related to the following three phenomena.
The first development is crushing and granulation of toner particles.
In the commonly used grinding method toners, when the toner particles are curved, and when the toners having different shapes are stirred in the developing apparatus for a long time, the toner particles are formed due to the collision between the toner particles and the developer carrier or toner particles. In particular, it shows that their convex surface is crushed and it becomes a fine particle.
The second phenomenon is that the external additive particles are embedded in the toner particle surface ("surface" as used herein means the outermost portion).
When the particles of the toner are curved and each type uses a different toner, the fine particles used as the external additive particles are buried on the convex surface of the toner, while the external additives are not buried on the concave side. On the other hand, as a representative example of the polymerization toner, for example, when toner particles having a spherical particle shape are used, the toner particles are not crushed and granulated, and the fine particles added as external additives are uniformly embedded on the surface of the toner particles. Appears to be.
The third development is a nonuniformity of the charging characteristics of the toner particles.
In the use of conventionally known toner particles, the charge distribution thereof is measured, and it appears that the charge distribution can be wider than before stirring if the toner particles are stirred in the developing apparatus for a long time.
It is an object of the present invention to solve the above problem.
Another object of the present invention is a toner that does not deteriorate even after long-term use, has excellent image density stability and fine detail reproducibility, and can obtain an image without fog, a two-component developer using the same, and an image forming method. , And an apparatus unit.
In order to achieve the above object, the present invention
In the particle size distribution according to the circular distribution and the diameter corresponding to the circular shape of the particles measured by the flow type particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and the diameter corresponding to the circular shape is 3.0 μm to Containing 8.0 to 30.0% by volume of particles having a diameter 0.60 μm to less than 2.0 μm, corresponding to a circle, having a maximum value Y in the area of 0.60 μm to 2.00 μm, corresponding to a maximum X in the region of 9.0 μm and a circle;
The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And the number average length of at least 30-600 micrometers non-spherical inorganic fine powder (B) containing,
A toner comprising a binder resin and a colorant, and a toner containing an external additive fine powder.
In addition, the present invention
As a two-component developer comprising (I) a toner particle containing a binder resin and a colorant, a toner containing an external additive fine powder, and (II) a carrier,
In the particle size distribution according to the circular distribution of the particles and the diameter corresponding to the circular shape measured by the flow particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and an area of 3.0 µm to 9.0 µm in diameter corresponding to the circular shape. Contains from 8.0 to 30.0% by weight of particles having a maximum diameter of 0.60 μm to less than 2.0 μm corresponding to a circle having a maximum value Y in a region of maximum diameter X and a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape,
The external additive fine powder is formed by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles and having a shape coefficient SF-1 of greater than 150. It is to provide a two-component developer comprising at least an aspheric inorganic fine powder (B) having a number average long diameter of 30 m to 600 m m.
In addition, the present invention
(I) charging the latent electrostatic image bearing member for supporting the latent electrostatic image,
(II) forming an electrostatic latent image on the charged latent image bearing member,
(III) developing the electrostatic latent image on the latent image bearing member with toner to form a toner image, and
(IV) transferring the toner image formed on the latent image bearing member to the transfer member;
As an image forming method,
Wherein the toner comprises at least toner particles containing at least a binder resin and a colorant, and at least an external additive fine powder,
In the particle size distribution according to the circular distribution of the particles and the diameter corresponding to the circular shape measured by the flow particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and an area of 3.0 µm to 9.0 µm in diameter corresponding to the circular shape. Contains from 8.0 to 30.0% by weight of particles having a maximum diameter of 0.60 μm to less than 2.0 μm corresponding to a circle having a maximum value Y in a region of maximum diameter X and a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape,
The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And an at least spherical inorganic fine powder (B) having a number average long diameter of 30 m to 600 m m.
In addition, the present invention
A toner as a one-component developer containing at least toner particles containing a binder resin and a colorant, and an external additive fine powder,
A developing container for containing the one-component developer, and
A developer carrying member for transporting a developer to a developing region by carrying a one-component developer to be contained in the developing container.
An apparatus unit detachably mounted to an image forming apparatus main body, comprising:
Wherein the toner comprises toner particles containing at least a binder resin and a colorant, and an external additive fine powder,
In the particle size distribution according to the circular distribution of the particles and the diameter corresponding to the circular shape measured by the flow particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and an area of 3.0 µm to 9.0 µm in diameter corresponding to the circular shape. Contains from 8.0 to 30.0% by weight of particles having a maximum diameter of 0.60 μm to less than 2.0 μm corresponding to a circle having a maximum value Y in a region of maximum diameter X and a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape,
The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And an apparatus unit including at least an aspheric inorganic fine powder (B) having a number average long diameter of 30 m to 600 m m.
1 illustrates an image forming apparatus capable of implementing an image forming method using the toner of the present invention.
2 illustrates another image forming apparatus that can implement the image forming method using the toner of the present invention.
Fig. 3 illustrates another image forming apparatus capable of implementing the image forming method using the toner of the present invention.
Fig. 4 illustrates another image forming apparatus which can implement the image forming method using the toner of the present invention.
Fig. 5 illustrates another image forming apparatus which can implement the image forming method using the toner of the present invention.
Fig. 6 illustrates a developing apparatus using a nonmagnetic one-component developing method using the toner of the present invention.
7 illustrates a developing apparatus using a two-component developing method using the toner of the present invention.
FIG. 8 illustrates an image forming apparatus which uses a belt-shaped intermediate transfer member instead of the drum-type intermediate transfer member of the image forming apparatus shown in FIG.
9 shows the pattern used to evaluate the reproducibility of the detail image.
Fig. 10 schematically illustrates the particle form of the non-spherical inorganic fine powder (B).
Fig. 11 is a block diagram when the image forming apparatus of the present invention is applied to a printer of a fax apparatus.
<Explanation of symbols for the main parts of the drawings>
(1) photosensitive drum (latent image bearing member)
(2) charging roller
(3) core (intermediate transcript means)
(4) developing machine
(5) intermediate transcript
(6) cleaning mechanism
(7) tray
(8) transfer means
(9) Fuser
(9a) fixing roller
(9b) pressure roller
(L) light source device
(E) laser light
(119) Photosensitive Drum (Latent Image Carrier)
120 developing device
(121) Develop sleeve (developer carrier)
122 sleeve body
123 magnets
124, 125 shipping screw
126 developing containers
127 developing blade
(128) developer
(129) Supply Toner
As a result of extensive research by the present inventors, when an external additive fine powder used in a toner having a specific circularity distribution and a specific particle size distribution according to a diameter corresponding to a circular shape is used, two or more fine powders having a specific shape and a specific number of average long diameters are used. It has been found that even after long-term use, the toner deterioration does not occur, the stability of the image density and the fine detail reproducibility are excellent, and an image without fog generation can be obtained.
The detailed reason why such an effect can be obtained is not clear, but is estimated as follows.
As a result of extensive research, the inventors have found that the deterioration of the developer is associated with the following three phenomena.
The first development is crushing and granulation of toner particles, the second development is that particles of external additives are embedded in the surface of the toner particles, and the third development is uneven charging characteristics of the toner particles.
The present invention has been made based on the above phenomenon.
Embodiments of the present invention are described in detail below.
The toner of the present invention has an average circularity of 0.950 to 0.995, preferably 0.960 to 0.995 in the circularity distribution of the particles measured by the flow particulate measuring device. At this time, a flow type particle measuring apparatus means the apparatus which statistically analyzes the picked-up particle | grain image. The average circularity is calculated as the average of the malleability of the circularity obtained according to the following equation using the above apparatus.
Circularity = circumferential length of the corresponding circle / circumferential length of the particle projection image
In the above formula, the circumferential length of the particle projection means the length of the contour formed by connecting the edge points of the binary coded particles. The circumferential length of the corresponding circle means the circumferential length of the circle having the same area as the binary coded particulate.
When the toner's average circularity is less than 0.950, the friction between the toner particles or between the toner particles and the member (e.g., the toner carrier) that charges the toner increases, causing the toner particles to crush and become fine particles, resulting in fog. , An image having a high definition can be obtained. When the average circularity of the toner is larger than 0.995, the toner cannot be charged due to friction, and an image with poor uniformity can be obtained.
In one particle size distribution according to a diameter corresponding to a circle measured using a flow particulate analyzer, the toner of the present invention has a maximum value X and a diameter of 0.60 μm corresponding to a circle in an area of 3.0 μm to 9.0 μm in diameter corresponding to the circle. It contains 8.0 to 30.0% by number of particles having a maximum value Y in the region of from 2.00 μm to a diameter of 0.60 μm to less than 2.0 μm, corresponding to a circle. At this time, the particles constituting the maximum value Y serves to lower the fluidity to an appropriate value.
In the particle size distribution along the diameter corresponding to the circle measured using the flow particulate measuring instrument, since the spherical toner having only a single peak has too good fluidity, the triboelectric charging of the toner is not sufficiently performed in the initial stage, The image becomes uneven. Even when the content of particles having a diameter of 0.60 mu m or more and less than 2.00 mu m corresponding to the circular shape is less than 8.0 number%, the initial image becomes uneven because the fluidity of the toner is too good. When the toner content of particles having a diameter of 0.60 µm or more and less than 2.00 µm corresponding to a circular shape is more than 30.0% by number, the effect of lowering fluidity is too great, and the toner is poor in fluidity, which may result in poor initial image quality after long standing. have.
The fluidity lowering effect can be more prominent in an image forming method using an intermediate transfer member, and therefore, the present invention is preferable to such an image forming method. His detailed mechanism is unclear. For example, when using a color toner to form a full color image on the intermediate transfer member, the toner whose fluidity is adjusted to an appropriate value is hardly affected by the fine vibration generated from the drive system, It is presumed that the toner image on the carcass can be prevented from becoming fine.
In the present invention, there is no particular limitation on the method of obtaining the maximum values X and Y in one particle size distribution according to the diameter corresponding to the circle and the method of adjusting the content of particles having a diameter corresponding to the circle of 0.60 μm or more and less than 2.00 μm. . For example, a method of properly adding particles which do not adversely affect toner deterioration, a method of using all of the emulsified particles formed as by-products when the toner particles are produced by polymerization, and a part of the emulsified particles formed as by-products It is possible to use some of the emulsified particles by removing them by wet fractionation or wind fractionation.
In the present invention, the toner having the specific average circularity is, for example, when the toner particles produced by the pulverization method are spherical, toner particles are produced by adjusting the processing conditions. When manufactured by the polymerization method, it can be produced by a method of producing toner by adjusting the polymerization conditions.
The following method can be implemented by the method of spheroidizing the toner particle manufactured by the grinding | pulverization method. A uniformly dispersed mixture is prepared by uniformly dispersing toner constituent materials such as a binder resin and a colorant and, if necessary, a release mixer and a charge control agent using a dry mixer such as a Henschel mixer or a median disperser, and the resulting mixture is kneaded. Melt kneading using a kneading machine such as a machine or an extruder, and after cooling the obtained kneaded material, it is pulverized by a pulverizer such as a hammer mill, and the pulverized product is pulverized by using a pulverizer which impinges on the target under a jet stream to pulverize it. The particle size distribution is controlled by further classifying the obtained pulverized product with a classifier to remove coarse powder and fine powder. The particles whose particle size distribution has been adjusted can be spherical by a hot bath method in which toner particles are dispersed in water and heated, a heat treatment method in which toner particles are passed in hot air, or a mechanical collision method in which toner particles impart a collision force by mechanical energy. Can be. Processing conditions such as processing temperature, processing time, and processing energy used to spheronize the toner particles can be appropriately adjusted, thereby adjusting the toner roundness.
As a method for producing toner particles by the polymerization method, there are the following methods.
In the polymerizable monomer, a colorant and, if necessary, toner constituent materials such as a release agent and a charge control agent are added together with the polymerization initiator, and these are uniformly dissolved or dispersed in a mixer such as a homogenizer or an ultrasonic disperser to prepare the monomer composition. do. This monomer composition is dispersed in a water phase containing a dispersion stabilizer using a homomixer. Particle production is stopped at the stage where the droplets from the monomer composition have the desired size of toner particles. After particle production, the particle state is maintained by the action of the dispersion stabilizer and stirred to the extent that the sedimentation of the particles can be prevented. The polymerization can be carried out at a polymerization temperature set at 40 ° C or higher, usually 50 to 90 ° C. In order to control the molecular weight distribution of the binder resin for toner, the temperature can be increased in the second half of the polymerization reaction. In addition, the aqueous medium may be partially evaporated after the end of the reaction or after the end of the reaction to remove unreacted polymerizable monomers and by-products. After completion of the reaction, the produced toner particles are cleaned, filtered and recovered. In the suspension polymerization method, it is usually preferable to use 300 to 3,000 parts by weight of water as the dispersion medium with respect to 100 parts by weight of the monomer composition.
When producing toner particles by the polymerization method, the toner circularity can be adjusted by changing the polymerization conditions such as the type and amount of the dispersion stabilizer, the stirring conditions, the pH of the aqueous phase and the polymerization temperature.
In the present invention, the circularity distribution and the particle size distribution of the diameter corresponding to the prototype of the toner are measured as follows using the flow type particulate analyzer FPIA-1000 (manufactured by Toa Iyou Denshi K.K.).
For the measurement, the fine dust is removed through the filter, resulting in interface with ion-exchanged water having up to 20 particles in the measuring range (e.g., 0.60 µm to less than 159.21 µm in diameter corresponding to the circle) in 10 ^-3 water. About 10 ml of a solution (20 ° C.) is prepared by adding 0.1-5% by weight of an active agent (preferably CONTAMINON ™; available from Wako Pure Chemical Industries, Ltd.). About 0.02 g of a measurement sample is added to this solution, and it disperse | distributes uniformly, and prepares a sample dispersion. Ultrasonic disperser UH-50 (manufactured by KK SMT, vibrator with titanium alloy chips having a diameter of 5 mm) is used for a dispersion time of about 5 minutes or more, at which time the dispersion medium is appropriately cooled so that its temperature does not exceed 40 ° C. . Using the flow particulate analysis device, particle size distribution and circularity distribution of particles having a diameter corresponding to a circular shape of 0.60 µm or more and less than 159.21 µm are measured.
An outline of the measurement method is described in the catalog (June 1995 edition) of the FPIA-1000 issued by Toa Iyou Denshi K.K., the operating manual of the measuring device and Japanese Patent Laid-Open No. 8-136439.
Pass the sample dispersion through a channel (extending along the flow direction) of a flat transparent flow cell (thickness: about 200 μm). A strobe and a CCD (charge pair device) camera are mounted at positions opposite to each other with respect to the flow cell so as to form an optical path that crosses over the thickness of the flow cell. While the sample dispersion is flowing, the strobe light is irradiated at intervals of 1/30 seconds to obtain an image of the particles passing through the flow cell, so that each particle is photographed as a two-dimensional image having a certain range parallel to the flow cell. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the diameter corresponding to the circle. The circularity of each particle is calculated by dividing the circumferential length of a particular circle (corresponding circle) in which the two-dimensional image of each particle has the same area by the circumferential length of the two-dimensional image of each particle.
As shown in Table 1 below, the range of 0.06 to 400 μm is obtained by dividing by 226 channels divided by 30 channels for one octave. In actual measurement, the diameter corresponding to a circular shape is measured in the range of 0.60 micrometer or more and less than 159.21 micrometers.
In Table 1 below, the upper limit in each particle diameter range does not include the number itself (ie, means "less than").

The toner of the present invention has the above toner particles and the external additive fine powder. The external additive fine powder has at least an inorganic fine powder (A) in which each particle is present individually or in an aggregated state, and a non-spherical inorganic fine powder (B) formed by combining a plurality of particles. This allows the toner to have improved fluidity and prevent the toner from deteriorating due to the operation.
More specifically, the external additive fine powder (A) functions to properly move around the surface of the toner particles to equalize the charge on the surface of the toner particles, sharpen the charge amount distribution of the toner, and improve the fluidity of the toner. The non-spherical inorganic fine powder (B) functions as a spacer of the toner particles to suppress the toner particles from being embedded in the inorganic fine powder (A).
In general, when the toner particles having a less uneven surface and near spherical surface come into contact with a member that imparts a triboelectric charge to the toner, such as a developing sleeve, a narrow passage for the external additive fine powder externally added to the surface of the toner particles will escape. It tends to be buried on the surface of the toner particles, and the toner particles tend to deteriorate.
The toner of the present invention is a near-spherical toner having an average circularity of 0.950 to 0.995 as described above. However, since the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) are included on the toner particle surface as the external additive fine powder, the inorganic fine powder (A) is buried in the toner particle surface by the non-spherical inorganic fine powder (B). Can be effectively prevented.
The inorganic fine powder (A) is a primary particle on the toner particles, and the number average long diameter is 1 m to 30 m, preferably 1 m to 25 m. This is good because the charge amount distribution of the toner and the fluidity of the toner can be improved.
When the number average long diameter of the primary particles of the inorganic fine powder (A) is less than 1 m m, the inorganic fine powder (A) is likely to be buried on the toner surface, and the toner used for a long time may deteriorate.
If the average length of the number of primary particles of the inorganic fine powder (A) is 30 m 占 퐉 or more, the ability to equalize the charge on the surface of the toner particles becomes poor, thereby widening the charge amount distribution of the toner, and causing problems such as toner scattering and fog. May occur.
When the inorganic fine powder (A) is dispersed on the surface of the toner particles, the inorganic fine powder (A) has a ratio of the primary long diameter / short diameter (ratio of the long diameter to the short diameter) on the surface of the toner particles. It may be preferred to be 1.0 to 1.5, more preferably 1.0 to 1.3.
If the inorganic fine powder (A) has a ratio of the long diameter / short diameter of the primary particles of 1.5 or more, the cohesive force of the inorganic fine powder (A) becomes excessive, and the inorganic fine powder (A) is placed on the surface of the toner particles using a widely used stirring mixer. It may be difficult to disperse uniformly in a preferred form.
The inorganic fine powder (A) is a primary particle on the surface of the toner particles and may have a shape factor SF-1 of 100 to 130, preferably 100 to 125, which moves properly on the toner particles to impart good fluidity to the toner. Good in terms of
If the primary particle shape coefficient SF-1 of the inorganic fine powder (A) exceeds 130, the ability of the inorganic fine powder (A) to properly move on the surface of the toner particles is reduced, resulting in poor density uniformity and fine image reproducibility. This can be obtained.
In the present invention, SF-1, which indicates the shape factor, randomly samples 100 particles in a particle image using FE-SEM (S-4700; field-emission scanning electron microscope manufactured by Hitachi Ltd.), and this image It is a value obtained by introducing into an image analysis device (LUZEX-III; manufactured by Nikkor) through an interface to analyze information, and calculating the data according to the following formula.
SF-1 = (MXLNG) ² / AREA × π / 4 × 100
In the above formula, MXLNG represents the absolute maximum length of toner particles on the image, and AREA represents the projected area of the toner particles.
The shape factor SF-1 of the inorganic fine powder (A) is measured at 10,000 times magnification on the FE-SEM.
The inorganic fine powder (A) is preferably 50 to 150 m ² / g, more preferably 60 to 140 m ² when measured by nitrogen adsorption according to the BET method so that the charging performance of the toner particles can be easily and stably maintained. It is preferred to have a specific surface area (BET specific surface area) of / g.
If the BET specific surface area of the inorganic fine powder (A) is smaller than 50 m ² / g, the inorganic fine powder (A) can be easily separated from the surface of the toner particles, causing problems such as toner scattering and fog. In addition, the uniformity of image density becomes poor.
If the BET specific surface area of the inorganic fine powder (A) is larger than 150 m ² / g, the toner may have unstable charging characteristics, particularly when left in a high humidity environment for a long time, and may cause problems such as toner scattering and fog.
In the present invention, the BET specific surface area of the fine powder is measured by the following method using Autosorb I, a specific surface area measuring instrument manufactured by Quantec Rom.
About 0.1 g of the measurement sample is weighed in a cell and degassed for at least 12 hours at 40 ° C. under vacuum of 1.0 × 10 ⁻³ mmHg or less. Thereafter, nitrogen gas is adsorbed while the sample is cooled with liquid nitrogen, and the value is measured by multiple assay.
The non-spherical inorganic fine powder (B) used in the present invention is 150 or more, preferably 190 or more, in order to prevent itself from moving on the toner particle surface and to prevent the inorganic fine powder (A) from being buried on the toner particle surface. More preferably, it may have 200 or more toner particulate shape coefficient SF-1.
If the shape coefficient SF-1 of the non-spherical inorganic fine powder (B) is 150 or less, the non-spherical inorganic fine powder (B) itself may be buried on the surface of the toner particles so that the inorganic fine powder (A) is buried on the surface of the toner particles. It may be less effective at limiting.
The shape coefficient SF-1 of the non-spherical inorganic fine powder (B) on toner particles is measured at a magnification of 50,000 times in FE-SEM.
As the particle shape of the non-spherical inorganic fine powder (B), the particles may be formed not only of non-spherical particles such as rod-shaped particles or agglomerated particles, but also formed of a combination of a plurality of particles as shown in FIG. 10. This is effective to prevent the inorganic fine powder (A) from being buried on the toner particle surface. The reason is estimated as follows. Particles of the non-spherical inorganic fine powder (B) formed by the coalescing of a plurality of particles have a shape with a bent portion, and therefore, the non-spherical inorganic fine powder (B) can be prevented from being buried in the toner particles, and aspheric The inorganic fine powder (B) can act as a spacer on the toner particles to prevent the inorganic fine powder (A) from being buried in the toner particles.
The non-spherical inorganic fine powder (B) is also preferably 30 to 600 m 탆, more preferably 30 to 300 m 탆, even more preferably 35 to 300 m so as to perform a function as a spacer on the toner particles well. It may have a number average long diameter of μm.
If the non-spherical inorganic fine powder (B) has a number average long diameter of less than 30 m μm, the effect of adding it is similar to the effect obtained when only the inorganic fine powder (A) is added alone, thereby preventing the investment of the inorganic fine powder (A). It can be difficult to prevent.
If the non-spherical inorganic fine powder (B) has a number average long diameter greater than 600 m µm, the inorganic fine powder (A) is buried on the surface of the toner particles due to the friction between the toner particles and the non-spherical inorganic fine powder (B), and the toner Can deteriorate.
The non-spherical inorganic fine powder (B) is preferably at least 1.7, more preferably at least 2.0, and even more preferably at least 3.0 particulate long diameter / short diameter in order to effectively suppress the inorganic fine powder (A) from being buried on the surface of the toner particles. May have rain.
If the non-spherical inorganic fine powder (B) has a long diameter / short diameter ratio of less than 1.7, the non-spherical inorganic fine powder (B) may have a less bent structure, and therefore, the non-spherical inorganic fine powder (B) itself may have a toner particle surface. The effect of suppressing buried in the inorganic fine powder (A) on the surface of the toner particles may be less.
The non-spherical inorganic fine powder (B) also contains a plurality of primary particles having a minimum width of the average Feret diameter on the toner particles, preferably 20 m to 200 m m, more preferably 30 m to 200 m m. It is good in that it produces | generates by coalescence which can suppress the embedment of the inorganic fine powder (A) to the toner particle surface effectively.
If the minimum width of the average ferret diameter of the primary particles constituting the coalesced particles of the non-spherical inorganic fine powder (B) is less than 20 m µm, the cohesiveness of the non-spherical inorganic fine powder (B) increases, and the stirring mixer is widely used. It is difficult to uniformly disperse the non-spherical inorganic fine powder (B) on the toner particle surface by using.
When the minimum width of the average ferret diameter of the primary particles constituting the aggregated particles of the non-spherical inorganic fine powder (B) exceeds 200 m 탆, it may have a less curved curved structure, in addition, the toner particles and the acetabular particles Due to the friction of the shaped inorganic fine powder (B), the inorganic fine powder (A) may be undesirably buried on the surface of the toner particles.
The non-spherical inorganic fine powder (B) preferably has a specific surface area (BET specific surface area) by nitrogen adsorption according to the BET method of 20 to 90 m 2 / g, more preferably 25 to 70 m 2 / g. It is good at preventing the addition effect of A).
When the BET specific surface area of the non-spherical inorganic fine powder (B) is less than 20 m 2 / g, during the stirring operation using a widely used stirring mixer, the non-spherical inorganic fine powder (B) causes the inorganic fine powder (A) to surface on the toner particles. Since the phase is already buried, the effect of adding the inorganic fine powder (A) may be lowered.
When the BET specific surface area of the non-spherical inorganic fine powder (B) exceeds 90 m 2 / g, the inorganic fine powder (A) is introduced into the pores of the non-spherical inorganic fine powder (B) to reduce the effect of adding the inorganic fine powder (A). Can be.
In the present invention, when observing an electron micrograph magnification of the toner, the sum of the number of primary particles of the inorganic fine powder (A) present individually or in an aggregated state per area of 0.5 µm X 0.5 µm is preferably averaged. 20 or more, more preferably 25 or more, are present on the surface of the toner particles, and the aspheric inorganic fine powder (B) per area of 1.0 μm × 1.0 μm is averaged, preferably 1 to 20, more preferably It may be desirable to be present on the surface of 2 to 18 toner particles. The total number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles means the total number of primary particles constituting the aggregate and the primary particles present individually.
If the sum of the primary particles of the inorganic fine powder (A) present on the toner particles is on average less than 20, the fluidity may be poor, resulting in an image having poor uniformity.
Number of External Additive Powders The average long diameter, the ratio of the long diameter to the short diameter, and the average width of the average ferret diameter and the number of particles of the external additive fine powder present on the toner particle surface are measured as follows.
The numerical values of the inorganic fine powder (A) were taken by scanning electron microscope FE-SEM (S-4700, manufactured by Hitachi Ltd.) and photographed the toner particle surface magnified 100,000 times. It measures by measuring the particle | grains which are m micrometers. The long diameter and the width of the primary particles are appropriately measured within the magnification in the range of 100,000 to 500,000 times as described above.
The average length of the primary particle of the inorganic fine powder (A) measures the length of the primary particle of the inorganic fine powder (A) on 10 views in an enlarged photograph, and makes the average value its average length. Similarly, the average value of the primary short diameters of the inorganic fine powder (A) is determined as the average width, and the ratio of the average long diameter / average short diameter is calculated as the long diameter / short diameter ratio of each primary particle of the inorganic fine powder (A). In this case, the length of the primary particles corresponds to the distance between the largest parallel lines of a series of parallel lines drawn in contact with the contour of the primary particles of the inorganic fine powder (A), and the width of the primary particles is the least parallel lines among the parallel lines. Corresponds to the distance.
When the diameter measured at the time of measuring the length and width of the inorganic fine powder (A) is 1 mm or less in actual scale, the magnification of the enlarged photograph of the surface of the toner particles is appropriately enlarged and measured in the range of 500,000 times or less.
The number of particles of the inorganic fine powder (A) on the surface of the toner particles increases the number of primary particles of the inorganic fine powder (A) per unit area of 0.5 μm × 0.5 μm (50 mm × 50 mm in a 100,000-fold magnification) of the toner particle surface. Photo 10 Counts on the field of view and determines its average value. When counting the number of particles of the inorganic fine powder (A), the number of primary particles counts the inorganic fine powder (A) present in the portion corresponding to 0.5 µm X 0.5 µm in the center of the enlarged photograph, and the inorganic fine powder in the aggregated state. For (A), the number of primary particles constituting the aggregate is counted.
The numerical values of the non-spherical inorganic fine powder (B) were photographed on the surface of the toner particles magnified 50,000 times by scanning electron microscope FE-SEM (manufactured by S-800, Hitachi Ltd.). It measures by measuring the particle | grains which are 1-40 mmicrometer.
The average long diameter of the particles of the non-spherical inorganic fine powder (B) measures each long diameter of the non-spherical inorganic fine powder (B) on 10 views in the enlarged photograph, and sets the average value thereof to the average long diameter. Similarly, the average value of the short diameters of the non-spherical inorganic fine powder (B) is determined as the average short diameter, and the ratio of the average long diameter / average short diameter is calculated as the long diameter / short diameter ratio of the particles of the non-spherical inorganic fine powder (B). At this time, the length of the particles corresponds to the distance between the largest parallel lines of the series of parallel lines drawn in contact with the contour of each particle of the non-spherical inorganic fine powder (B), and the width of the primary particles is the least parallel of the parallel lines. Corresponds to the distance.
The number of particles of the non-spherical inorganic fine powder (B) on the surface of the toner particles is the number of particles of the non-spherical inorganic fine powder (B) per unit area of 1.0 μm X 1.0 μm (50 mm × 50 mm in 50,000 times magnification) of the toner particle surface. Is counted on the magnified photograph 10 field of view and determined by calculating the average value. When counting the number of non-spherical inorganic fine powders (B), it counts with respect to the non-spherical inorganic fine powder (B) which exists in the area corresponding to 1.0 micrometer x 1.0 micrometer of the center part of an enlarged photograph.
The minimum width of the average ferret diameter of the primary particles constituting the aggregated particles of the non-spherical inorganic fine powder (B) is obtained by sampling 20 or more particles of the non-spherical inorganic fine powder (B) on multiple views in the enlarged photograph, and the non-spherical inorganic fine powder (B). The minimum width of the ferret diameter of all the sampled particles capable of measuring the minimum width of the ferret diameter of the primary particles constituting the coalesced particles of the same) is measured in the field of view, and the average value thereof is the average width of the average ferret diameter. At this time, the smallest distance between a series of parallel lines drawn in contact with the contour of the primary particles constituting the coalesced particles of the non-spherical inorganic fine powder (B) is called the minimum width of the ferret diameter.
The identification of the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) in the scanning electron micrograph is judged according to the difference in the particle shape in the scanning electron micrograph when the particle shape between the inorganic fine powder is clearly different. Use the method. Alternatively, when there is a difference in composition of the inorganic fine powders, a method of detecting the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) by using only the specific element designated by the X-ray micronizer can be used.
In the present invention, the inorganic fine powder (A) and / or the non-spherical inorganic fine powder (B) preferably contains a silicone oil. Treatment of the inorganic fine powder with silicone oil improves the water resistance of the inorganic fine powder (s), and prevents the charging member from being damaged by the inorganic fine powder in the nonmagnetic one-component development system, and as a result, the charging characteristics of the toner are uneven. Can be prevented. At this time, it is estimated that silicone oil is extracted with a very small amount of inorganic fine powder (s) to serve as a lubricant.
In the present invention, the inorganic fine powder (A) and / or the non-spherical inorganic fine powder (B) is preferably an inorganic compound (s). In the case where the inorganic fine powder (A) is an organic compound, the particles may be deformed and adhered to the surface of the toner particles due to prolonged use. On the other hand, when the non-spherical inorganic fine powder (B) is an organic compound, it deforms or disintegrates due to friction with the charging member, and thus cannot serve as a spacer particle sufficiently.
As the inorganic fine powders (A) and (B) used in the present invention, conventionally known materials can be used. In order to improve charge stability, developability, flowability, and preservation, it may be preferable to select from silica, alumina, titania, or a complex oxide thereof. In particular, fine silica powders are preferred because the formation of primary particles or coalesced primary particles can be arbitrarily controlled to some extent. For example, silica includes dry silica or fumed silica produced by vapor phase oxidation of silicon halides or alkoxides and wet silica prepared from alkoxides or sucrose, either of which may be used. Dry silicas with less silanol groups on the surface and inside and less manufacturing residues such as Na ₂ O and SO ₃ ^2- are preferred.
It may be preferable to prepare the non-spherical inorganic fine powder (B) by the following manufacturing method especially.
Taking the fine silica powder as an example, silicon halides are gas-phase oxidized to produce silica fine powders, and the obtained fine silica powder is subjected to a water resistance treatment to prepare non-spherical silica fine powders. In particular, during gas phase oxidation, it may be desirable to heat at a high temperature such that primary particles of silica coalesce.
This non-spherical inorganic fine powder (B) classifies the coalesced particles in which the primary particles are coalesced with each other to obtain relatively coarse particles, and provides a particle size distribution so as to satisfy the condition of the number average length in the state present on the toner particle surface. It is preferable to adjust.
The toner of the present invention may have 0.1 to 3 parts by weight of inorganic fine powder (A), preferably 0.2 to 2 parts by weight, and 0.1 to 3 parts by weight of non-spherical inorganic fine powder (B) based on 100 parts by weight of toner particles. Parts, preferably 0.2 to 1.5 parts by weight.
If the amount of the inorganic fine powder (A) in the toner is less than 0.1 part by weight, the fluid may not be provided to the toner sufficiently, resulting in an uneven image.
If the amount of the inorganic fine powder (A) in the toner exceeds 3 parts by weight, the inorganic fine powder (A) is separated from the surface of the toner particles, thereby forming a large number of aggregates of the inorganic fine powder (A) to form fog on paper and to clean it. This results in an image with poor line expressability.
When the amount of the non-spherical inorganic fine powder (B) included in the toner is less than 0.1 part by weight, the effect of adding the non-spherical inorganic fine powder (B) cannot be obtained, and the uniformity of the image may be degraded when used for a long time.
When the amount of the non-spherical inorganic fine powder (B) contained in the toner exceeds 3 parts by weight, the non-spherical inorganic fine powder (B) is separated from the surface of the toner particles, thereby forming a plurality of aggregates of the non-spherical inorganic fine powder (B) to form a paper image. Fog is formed on the surface, which results in an image with poor fine line expressability.
If necessary, an external additive may be added to the toner of the present invention in addition to the inorganic fine powder (A) and the non-spherical inorganic fine powder (B).
As such fine particles, organic or inorganic fine particles generally known as external additives can be used.
Examples of the inorganic fine particles include metal oxides (eg, aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide), nitrides (eg silicon nitride), carbides (eg For example, silicon carbide), metal salts (eg calcium sulfate, barium sulfate and calcium sulfate), fatty acid metal salts (eg zinc stearate and calcium stearate), carbon black and silica, and any of the above Is available. Examples of the organic fine particles include homopolymers or copolymers of monomer components used in binder resins for toners such as styrene, acrylic acid, methyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate obtained by emulsion polymerization or spray drying. There is.
The fine particles used in the toner of the present invention may be treated with a silane coupling agent or subjected to a surface treatment in which an alumina coating is formed on the surface of the fine particles in order to increase the water resistance, further improve the environmental characteristics, and improve the operability of particle size and shape control. Can be.
Specifically, the silane coupling agent may include hexamethyldisilazane or a compound represented by Formula 1 below.
R _m SiY _n
(Wherein R is an alkoxyl group or a chlorine atom; m is an integer of 1 to 3; Y is a hydrocarbon group containing an alkyl group or a vinyl group, glycidoxyl group or methacryl group; n is 1 to 3)
Representative examples of the compound represented by the formula (1) include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimeth Methoxysilane, vinyltriacetoxysilane, divinylchlorosilane and dimethylvinylchlorosilane.
The method for processing a silane coupling agent includes a dry method in which a fine powder made into a cloud state by stirring is reacted with a silane coupling agent, and a wet method in which the fine powder is dispersed in a solvent, and the silane coupling agent is added dropwise thereto to carry out the reaction. It can be carried out by any one of the two methods can be used.
The alumina coating is a method of adding aluminum chloride, aluminum nitrate or aluminum sulfate in an aqueous solution or solvent, immersing the fine particles therein and drying, or hydrous alumina, hydrous alumina-silica, hydrous alumina-titania, hydrous alumina-titania-silica or The hydrous alumina-titania-silica-zinc oxide can be added by an aqueous solution or a solvent, and the fine particles are immersed therein and dried by a method.
The toner particles contained in the toner of the present invention contain at least one binder resin and a colorant.
Binder resins used in the present invention include homopolymers of styrene and derivatives thereof such as polystyrene and polyvinyl toluene; Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, With styrene-methyl vinyl ether copolymer, styrene-ethyl vinyl ether copolymer, styrene-methyl vinyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer and styrene-maleate copolymer Same styrene copolymers; Polymethyl methacrylate; Polybutyl methacrylate; Polyvinyl acetate; Polyethylene; Polypropylene; Polyvinyl butyral; Polyacrylic acid resins; rosin; Denatured rosin; Terpene resins; Aliphatic or cycloaliphatic hydrocarbon resins; Aromatic petroleum resins; Paraffin wax; There is carnauba wax. Any of these may be used alone or in the form of a mixture.
As the colorant used in the present invention, the black colorant uses a carbon black, a magnetic material, and a colorant made black using the yellow / magenta / cyan colorant shown below.
As the yellow colorant, representative compounds such as condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168 and 180 can be preferably used.
As a magenta coloring agent, a condensed azo compound, a diketopyrropyrrole compound, an anthraquinone compound, a quinacridone compound, a base dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound are used. Specifically, C.I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185 , 202, 206, 220, 221 and 254 are particularly preferred.
As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds and base dye lake compounds can be used. Specifically, C.I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62 and 66 may be particularly preferably used.
Any of these colorants can be used alone, in the form of a mixture, or in solid solution.
In the case of a color toner, the colorant of the present invention is selected in consideration of color angle, saturation, lightness weather resistance, transparency on OHP film, and dispersibility in toner. The addition amount of a coloring agent is used in the quantity of 1-20 weight part with respect to 100 weight part of resin.
As the toner of the present invention, a charge control agent can be used as necessary.
As a charge control agent used for this invention, a well-known thing can be used. In the case of color toners, charge control agents are particularly colorless, have a high charging speed of the toner, and stably maintain a constant charge amount.
Specific compounds include, as negative charge control agents, metal compounds of salicylic acid, naphthoic acid, dicarboxylic acid or derivatives thereof, high molecular compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds and Carissaren and the like. Positive charge control agents include quaternary ammonium salts, polymeric compounds having quaternary ammonium salts in the side chain, guanidine compounds and imidazole compounds.
It may be preferable to use the charge control agent in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the binder resin. However, in the present invention, the addition of the charge control agent is not essential. In the case of using the two-component developing method, triboelectric charging using a carrier can be used. In addition, when using the nonmagnetic one-component blade coating developing method, the triboelectric charging which uses a blade member or a sleeve member is used. Therefore, it is not essential that the charge control agent is contained in the toner particles.
In the toner of the present invention, wax may be used as the low softening point material, if necessary.
Low softening point materials used in the toners of the present invention include paraffin waxes, polyolefin waxes, fine-clean waxes and Fischer-Tropsch waxes, amide waxes, higher fatty acids, long chain alcohols, ester waxes and graft compounds and block compounds thereof. Derivatives. It may be desirable for these low molecular weight components to be removed and the maximum endothermic peak of the DSC moist heat curve to be sharp.
Waxes which can be preferably used are straight chain alkyl alcohols having 15 to 100 carbon atoms, straight chain fatty acids, straight chain acidamides, straight chain esters or montan derivatives. It is also desirable to remove impurities such as liquid fatty acids from these waxes.
More preferably, the wax may be a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or polymerization using a Ziegler catalyst or any other catalyst under low pressure; Alkylene polymers obtained by thermal decomposition of high molecular weight alkylene polymers; Dispersion and purification of low molecular weight alkylene polymers formed as by-products upon polymerization of alkylene; Polymethylene wax obtained by extracting and fractionating a specific component from a distillation residue of a hydrocarbon polymer obtained by the arge method from a synthesis gas composed of carbon monoxide and hydrogen or from a synthetic hydrocarbon obtained by hydrogenating a distillation residue may be included.
The low softening point material used in the present invention preferably has an endothermic main peak at a temperature in the range of 40 to 90 ° C., more preferably 45 to 85 ° C. in the endothermic curve measured by DSC (differential scanning calorimetry). The endothermic main peak is preferably a low softening point material having a narrow melting point range in which half of the width is within 10 ° C, more preferably within 5 ° C. In particular, an ester wax mainly composed of an ester compound of 15 to 45 long-chain alkyl alcohols having 15 to 45 carbon atoms and a long-chain alkylcarboxylic acid having 15 to 45 carbon atoms is preferable in view of transparency of the OHP sheet and low temperature fixability and high temperature offset resistance at the time of fixing. .
In the present invention, the measurement method of DSC uses, for example, DSC-7 (manufactured by Perkin Elmer Co.). In the detection section of the device, the temperature is corrected based on the melting point of indium and zinc and the calorific value is corrected using the heat of indium fusion. The sample is measured while raising the temperature from 20 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min as a control by using a pan placed in a pan made of aluminum and nothing.
The low softening point material preferably contains 3 to 40 parts by weight, more preferably 5 to 35 parts by weight with respect to 100 parts by weight of the binder resin in the toner particles.
When the content of the low softening point material is less than 5 parts by weight, it is difficult to obtain sufficient high temperature offset characteristics. Also, when fixing the image on both sides of the recording material, the first (surface) image may be offset at the time of fixing the second (backside).
When the content of the low softening point material exceeds 40 parts by weight, when toner particles are produced by a pulverization method at the time of toner production, fusion of the toner component is likely to occur in the toner manufacturing apparatus, and primary particles are formed by a polymerization method. In the case of preparation, the granulation performance may be reduced during the preparation of the particles, and the toner particles may be coalesced with each other.
In the present invention, when the toner particles are obtained by the polymerization method, the polymerizable monomers used may include styrene monomers such as styrene, o-, m- or p-methylstyrene, and m- or p-ethylstyrene; Methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, butyl acrylate or methacrylate, octyl acrylate or methacrylate, dodecyl acrylate or methacrylate, With stearyl acrylate or methacrylate, behenyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, dimethylaminoethyl acrylate or methacrylate and diethylaminoethyl acrylate or methacrylate Acrylic or methacrylic ester monomers; And olefin monomers such as butadiene, isoprene, cyclohexene, acrylo- or methacrylonitrile and acrylic acid amide, any of which may be used. The polymerizable monomers may be used alone or in general, or in the publications of POLYMER HANDBOOK, 2nd Edition, III pp. It may be used in the form of a suitable mixture mixed such that the theoretical glass transition temperature (Tg) is from 40 to 80 ° C. as described in 139-192 (John Wiley & Sons, Inc.). If the theoretical glass transition temperature is lower than 40 ° C, problems arise in terms of storage stability of the toner or durability of the developer. When it exceeds 80 ° C, the fixing point of the toner may be high. In particular, in the case of a toner for a full color image, the color mixing performance of each color toner may not be sufficient at the time of fixing, resulting in poor color reproducibility and seriously lowering the transparency of the OHP image. Therefore, such a temperature is not preferable for a high quality image.
In the method of obtaining toner particles using the polymerization method, it is particularly preferable to simultaneously add polar resins in order to carry out the polymerization reaction of the polymerizable monomer without interruption. As the polar resin used in the present invention, a copolymer of styrene and acrylic acid or methacrylic acid, a maleic acid copolymer, a polyester resin and an epoxy resin may be preferable. It may be desirable that the polar resin does not contain any unsaturated groups in the molecule that can react with the polymerizable monomer.
Examples of the polymerization initiator used in the present invention include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile and 1,1'-azo. Azo polymerization initiators such as bis- (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; And peroxide-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropylperoxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide.
The control of the particle size distribution and particle size of the toner particles is a method of changing the type or amount of dispersant having the action of poorly water-soluble inorganic salts or protective colloids, or mechanical device conditions, such as the rotational speed of the rotor, the number of passes and the stirring blades. It can adjust by stirring conditions and container shape, such as the shape of, or the method of adjusting solid content concentration in aqueous solution.
In the present invention, the toner particles may have a core / shell structure in which the shell portion is formed of a polymer synthesized by polymerization and the core addition is formed of a low softening point material. This is preferable because the fixing property of the toner is improved without lowering the blocking resistance of the toner, and the remaining monomers can be easily removed from the toner particles.
As a specific method of observing the tomographic surface of the toner particles of the present invention, the cured product obtained by sufficiently dispersing the toner particles in a room temperature curable epoxy resin and then curing for 2 days in an atmosphere at a temperature of 40 ° C. Stained with triruthenium tetraoxide combined with, and cut samples into flakes using a microtome with a diamond cutter to observe the cross-sectional shape of the toner particles using a projection electron microscope (TEM). In the present invention, it may be preferable to use a triruthenium tetraoxide dyeing method to form a contrast between materials using the difference in crystallinity between the low softening point material constituting the core portion and the resin constituting the shell portion.
The toner of the present invention may be used as a one-component developer containing toner, or the toner may be mixed with a carrier for use as a two-component developer.
In the case of using the toner of the present invention as a two-component developer, as a carrier, for example, surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium and rare earth elements, and alloys or oxides thereof There are particles of magnetic metals such as and ferrite, and any of these can be used. There is no particular limitation on the method for producing these.
Moreover, for the purpose of charge control etc., it is preferable to coat the surface of a carrier particle with a resin containing coating material. As this method, any conventionally well-known method, such as a method which melt | dissolves or suspends a resin containing coating | cover material in a solvent, apply | coats, and adheres to a carrier particle, or simply mixes in powder form, can be used, for example. In order to make a coating layer stable, the method of apply | coating after melt | dissolving a coating material in a solvent is preferable.
The coating material that can be coated on the carrier particle surface may vary depending on the material of the toner. Examples of toner materials include, for example, aminoacrylate resins, acrylic resins, copolymers of any of these resins with styrene resins; And silicone resins, polyester resins, fluorine-based resins, polytetrafluorine-based ethylene, monochlorotrifluorine-based ethylene polymers, and polyvinylidene fluoride may be preferably used, but are not limited thereto. The coating amount of these compounds can be suitably determined to satisfy the charge-imposing performance of the carrier, and generally can range from 0.1 to 30% by weight, preferably 0.3 to 20% by weight of the total amount, based on the weight of the carrier. .
As a carrier material used in the present invention, ferrite particles having a composition of Cu-Zn-Fe [composition ratio: (5 to 20): (5 to 20): (30 to 80)] of 98% or more may be representative. There is no particular limitation as long as the performance of the carrier is not impaired. In addition, the carrier may be in the form of a resin carrier composed of, for example, a binder resin, a metal oxide, and a magnetic metal oxide.
When the carrier is mixed with toner particles, excellent results can be obtained by mixing in a two-component developer at a ratio such that the toner is in a concentration of 2 to 9% by weight, preferably 3 to 8% by weight. If the toner concentration is less than 2% by weight, the image density is low, making it practical. If the toner concentration is more than 9% by weight, fog and scattering in the machine frequently occur to shorten the life of the developer.
An image forming method and apparatus unit using the toner of the present invention will be described below with reference to the drawings.
1 to 8 schematically illustrate an image forming apparatus in which multiple toner images are collectively transferred to a recording medium by the image forming method of the present invention using an intermediate transfer member.
1 schematically illustrates an image forming apparatus in which multiple toner images are collectively transferred to a recording medium by the image forming method of the present invention using an intermediate transfer member.
The rotatable charging roller 2 as the charging member to which the charging bias voltage is applied is brought into contact with the surface of the photosensitive drum 1 as the latent image bearing while rotating the charging roller 2 to perform uniform primary charging of the photosensitive drum surface. do. Subsequently, the first electrostatic latent image is formed on the photosensitive drum 1 by being exposed to the laser light E generated from the light source L as the exposure means. Thus, the first electrostatic latent image formed is developed using the black toner contained in the black developer 4Bk as the first developer, provided in the rotatable rotary unit 4, to form a black toner image. The black toner image formed on the photosensitive drum 1 is electrostatically primary transferred to the intermediate transfer drum 5 by the action of a transfer bias voltage applied to the conductive support of the intermediate transfer member. Subsequently, a second electrostatic latent image is formed on the surface of the photosensitive drum 1 in the same manner as described above, and the rotary unit 4 is rotated so that the second electrostatic by yellow toner contained in the yellow developer 4Y as the second developer. The latent image is developed to form a yellow toner image. The yellow toner image is electrostatically primary transferred onto the black toner image primaryly transferred onto the intermediate transfer drum 5. Similarly, the third and fourth electrostatic latent images are formed while the rotary unit 24 rotates, and the magenta toner contained in the magenta developer 4M as the third developer and the cyan toner contained in the cyan developer 4C as the fourth developer are The respective magenta toner images and the cyan toner images formed are sequentially transferred by using each one sequentially. Thus, the toner images of each color are first transferred onto the intermediate transfer drum 5. The toner image firstly transferred as the multiple toner image on the intermediate transfer drum 5 is recorded on the recording medium by the action of the transfer bias voltage applied from the second transfer apparatus 8 located on the corresponding side via the opening medium P. The batch secondary transfer is electrostatically on (P). The multiple toner images secondarily transferred onto the recording medium P are heat-fixed to the recording medium P by the fixing device 3 having the heating roller 3a and the pressure roller 3b. The transfer residual toner remaining on the surface of the photosensitive drum 1 after the transfer is recovered by a cleaner having a cleaning blade in contact with the surface of the photosensitive drum 1, whereby the photosensitive drum 1 is cleaned.
In the primary transfer from the photosensitive drum 1 to the intermediate transfer drum 5, the transfer current applies a bias from a power supply (not shown) to the conductive support of the intermediate transfer drum 5 provided as the first transfer device. Thereby forming a toner image.
The intermediate transfer drum 5 consists of a conductive support 5a that is a rigid body and an elastic layer 5b covering its surface.
The conductive support 5a can be formed using, for example, a metal such as aluminum, iron, copper or stainless steel, or a conductive resin in which carbon or metal particles are dispersed. In these shapes, the support may be cylindrical, having a shaft penetrated through the center of the cylinder, and a cylinder reinforced inside.
The elastic layer 5b includes styrene-butadiene rubber, higher styrene rubber, butadiene rubber, isoprene rubber, ethylene-propylene copolymer, nitrile butadiene rubber (NBR), chloroprene rubber, butyl rubber, silicone rubber, fluorine rubber, nitrile rubber, urethane It may be desirable to form using elastomer rubbers including, but not limited to, rubbers, acrylic rubbers, epichlorohydrin rubbers and norbornane rubbers. It is also possible to use resins such as polyolefin resins, silicone resins, fluorine resins, polycarbonate resins, and copolymers or mixtures thereof.
In addition, on the surface of the elastic layer, highly lubricious and aqueous-repellent lubricant powder can be dispersed in any binder to form the surface layer.
There is no particular limitation on the lubricant. Various fluorine-based rubbers, fluorine-based elastomers, carbon fluorides including fluorine-bonded graphite, such as polytetrafluorine-based ethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluorine-based ethylene copolymers (ETFE) and Fluorine compounds such as tetrafluoroethylene-perfluorofluoroalkyl vinyl ether copolymers (PFA), for example silicone resin particles, silicone rubbers such as silicone rubber and silicone elastomers, polyethylene (PE), polypropylene (PP), polystyrene (PS ), Acrylic resins, polyamide resins, phenol resins, and epoxy resins may be preferred.
In the binder of the surface layer, a conductive agent may be appropriately added to control the resistance. Examples of the conductive agent include various conductive inorganic particles, carbon black, ionic conductive agent, conductive resin, and resin in which conductive particles are dispersed.
Multiple toner images on the intermediate transfer drum 5 are secondarily transferred onto the recording medium P by the second transfer device 8 collectively. Non-contact electrostatic transfer means using a corona charger as the transfer means, or contact electrostatic transfer means using a transfer roller or transfer belt are available.
In the fixing apparatus 3, instead of the thermal roller fixing apparatus having the heating roller 3a and the pressing roller 3b, the film in contact with the toner image on the recording medium P is heated to form a film on the recording medium P. The film heat fixing apparatus in which multiple toners on the recording medium P are enthusiastically adhered by heating the toner image can be used.
Instead of an intermediate transfer drum as an intermediate transfer member used in the image forming apparatus shown in Fig. 1, an intermediate transfer belt can be used to collectively transfer multiple toner images onto a recording medium. This intermediate transfer belt is constructed as shown in FIG.
In the process of passing the toner image formed and held on the photosensitive drum 1 through the nip between the photosensitive drum 1 and the intermediate transfer belt 10, the intermediate transfer belt 10 is passed through the primary transfer roller 12. The primary transfer is successively transferred to the outer circumferential surface of the intermediate transfer belt 10 with the aid of the applied primary transfer bias.
The primary transfer bias for sequential superimposition transfer of the first to fourth color toner images on the intermediate transfer belt 10 has a reverse polarity with respect to the polarity and is applied from the bias power supply 14.
Reference numeral 13b denotes a secondary transfer roller, which is axially supported in parallel with the secondary transfer counter roller 13a and is provided so as to be separated from the lower surface portion of the intermediate transfer belt 10.
In the first transfer step of the first to third color toner images from the photosensitive drum 1 to the intermediate transfer belt 10, the secondary transfer roller 13b and the intermediate transfer belt cleaner 9 are transferred to the intermediate transfer belt 10. ) Can be located away from.
In order to transfer the synthetic full color toner image transferred on the intermediate transfer belt 10 to the recording medium P, the second transfer roller 13b is brought into contact with the intermediate transfer belt 10, and at the same time the recording medium P Is introduced into the nip between the intermediate transfer belt 10 and the second transfer roller 13b at a predetermined time so that the secondary transfer bias is applied from the virus power source 16 to the second transfer roller 13b. With the help of this second transfer bias, the full color toner image synthesized from the intermediate transfer belt 10 to the recording medium P is secondarily transferred.
After the image transfer to the recording medium P is completed, the charging member 9 for cleaning is brought into contact with the intermediate transfer belt 10, and the bias power source 15 has a bias having a reverse polarity with respect to the polarity of the photosensitive drum 1 Is applied from the photosensitive drum 1 to the toner (transfer residual toner) remaining on the intermediate transfer belt 10 without being transferred to the recording medium P.
The transfer residual toner is electrostatically transferred to the photosensitive drum 1 in the vicinity of the nip between the intermediate transfer belt 10 and the photosensitive drum 1 and the intermediate transfer belt 10 is cleaned.
The intermediate transfer belt 10 includes a belt-shaped base layer and a surface treatment layer provided on the base layer. The surface treatment layer may consist of a plurality of layers.
Rubber, elastomer or resin can be used for the base layer and the surface treatment layer. For example, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene copolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, acrylo as rubbers and elastomers Nitrile butadiene rubber, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine-based rubber, polysulfide rubber, polynorbornane rubber, hydrogenated rubber, and thermoplastic elastomers ( For example, one or more materials selected from the group consisting of polystyrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, polyamide-based, polyester-based, and fluororesin-based elastomers may be used, but are limited to these materials. It is not. As the resin, resins such as polyolefin resin, silicone resin, fluorine resin and polycarbonate resin can be used. In addition, any copolymer or mixture of these resins may be used.
As a base layer, any of said rubber | gum, elastomer, and resin formed from the film can be used. A core layer having a woven fabric shape, a nonwoven fabric shape, a filamentous or film shape on any one or both surfaces of the rubber, elastomer and resin coated, adsorbed or sprayed can be used.
Materials constituting the core layer include, for example, natural fibers such as cotton, silk and lignin; Regenerated fibers such as chitin fibers, alginic acid fibers and regenerated cellulose fibers; Semisynthetic fibers such as acetic acid fibers; Polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyurethane fiber, polyalkylparaoxybenzoate fiber, polyacetal fiber, aramide fiber, poly Synthetic fibers such as fluoroethylene fiber and phenol fiber; Inorganic fibers such as carbon fiber, glass fiber and boron fiber; And one or more materials selected from the group consisting of metal fibers such as iron fibers and copper fibers, but are not limited thereto.
In addition, a conductive agent may be added to the base layer and the surface treatment layer in order to control the resistance of the intermediate transfer belt. There is no particular limitation on such a conductive agent. For example, carbon powders, metal powders such as aluminum or nickel powders, metal oxides such as titanium oxide, and polymethyl methacrylates containing quaternary ammonium salts, polyvinyl aniline, polyvinyl pyrrole, polydiacetylene, polyethyleneimine, boron One or more conductive agents selected from the group consisting of a containing high molecular compound and a conductive high molecular compound such as polypyrrole can be used, but the present invention is not limited thereto.
Optionally, lubricants are added to improve the lubricity of the intermediate transfer belt to improve its transfer performance.
There is no particular limitation on the lubricant. Various fluorine-based rubbers, fluorine-based elastomers, carbon fluorine compounds including fluorine bonded graphite, polytetrafluoromethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluorine-based ethylene copolymers (ETFE) and tetrafluorine-based ethylene- Fluorine compounds such as perfluoroalkyl vinyl ether copolymers (PFA), silicone resin particles, silicone compounds such as silicone rubber and silicone elastomers, polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylic resins, polyamides It is preferable to use resin, a phenol resin, an epoxy resin, and the like.
An image forming method of forming toner images of different colors in each of the plurality of image forming portions, and transferring them to the same transfer medium while sequentially superimposing them will be described with reference to FIG.
In the above method, the first, second, third, and fourth image forming portions 29a, 29b, 29c, and 29d are arranged in parallel, and each image forming portion has a dedicated latent image bearing member therein, that is, Photosensitive drums 19a, 19b, 19c, and 19d, respectively.
The photosensitive drums 19a to 19b have latent image forming means 23a, 23b, 23c and 23d, developing means 17a, 17b, 17c and 17d on their outer periphery, respectively. ), Transfer discharge means 24a, 24b, 24c and 24d, and cleaning means 18a, 18b, 18c and 18d.
Under this structure, first, a latent image of yellow component color is formed by the latent image forming means 23a on the photosensitive drum 19a of the first image forming portion 29a. This latent image is converted into a visible image (toner image) using the yellow toner-containing developer of the developing means 17a, and the toner image is transferred to the transfer medium S and the recording medium by the transfer means 24a.
In the process of transferring the yellow toner image to the transfer medium S as described above, in the second image forming portion 29b, a latent image of the magenta component is formed on the photosensitive drum 19b, followed by the developing means 17b. The magenta toner-containing developer is converted into a visible image (toner image). This visible image (magenta toner image) is superimposed at a predetermined position on the transfer medium S at the time when the transfer medium S on which the transfer in the first image forming portion 29a is completed is carried into the transfer means 24d. Is transferred.
Then, cyan and black toner images are formed in the third and fourth image forming portions 29c and 29d, respectively, in the same manner as described above, and the cyan and black toner images are superimposed on the same transfer medium S. Is transferred. After this image forming process is finished, the transfer medium S is conveyed to the fixing unit 22 so that the toner image on the transfer medium S is fixed. Thus, a multicolor image is obtained on the transfer medium S. FIG. Each of the photosensitive drums 19a, 19b, 19c, and 19d on which transfer has been completed is cleaned by cleaning means 18a, 18b, 18c, and 18d to remove residual toner, respectively. And the latent image formation performed subsequently.
In the image forming apparatus, the conveyance belt 25 was used to convey the recording medium and the transfer medium S. FIG. As shown in Fig. 2, the transfer medium S is conveyed from right to left, and in this conveying process, the transfer means 24a of each of the image forming sections 29a, 29b, 29c, and 29d, respectively. ), (24b), 24 (c) and 24 (d).
In this image forming method, a conveyance belt composed of a mesh made of testosterone fibers and a conveyance belt composed of a thin film dielectric sheet made of polyethylene terephthalate resin, polyamide resin or urethane resin is processed as a conveying means for conveying a transfer medium. It is used in terms of ease and durability.
After the transfer medium S passes through the fourth image forming portion 29d, an AC voltage is applied to the static eliminator 20 so that the transfer medium S is discharged, separated from the belt 68, and then the fuser ( 22), the toner image is fixed and finally discharged through the paper discharge port 26.
In this image forming method, the image forming section is provided with each independent latent image bearing member, and can be configured to send the transfer medium sequentially to the transfer region of each latent image bearing member by the belt-shaped conveying means.
In such an image forming method, a common latent image bearing member is provided in each image forming portion, and the transfer medium is repeatedly sent to the transfer area of the latent image bearing member by using a drum-type conveying means so that toner images of each color are formed. The transfer medium may be configured to be received.
However, since the conveyance belt has a high volume resistance, the conveyance belt continues to increase the charge amount in the course of the transfer repeated several times as in the case of the color image forming apparatus. Therefore, uniform transfer cannot be maintained unless the transfer current is increased in sequence for each transfer.
The toner of the present invention has excellent transfer performance because the transfer performance of the toner for each transfer can be made uniform under the same transfer current even if the charging of the charging means is increased for each transfer iteration, so that an image having a good quality and a high quality level can be obtained. Has
An image forming method of a full color image according to another embodiment will be further described with reference to FIG. 3.
The electrostatic latent image formed on the photosensitive drum 33 by suitable means can be visualized by the developer contained in the developing unit 36 provided to the developing means, attached to the rotating developing unit 39 rotating in the direction of the arrow. Therefore, the color toner image (first color) formed on the photosensitive drum 33 is retained on the transfer drum 48 by the gripper 47 by the transfer charger 44, the green medium S. Is transferred to. The transfer residual toner remaining on the surface of the photosensitive drum 33 after the transfer is recovered by a cleaner having a cleaning blade in contact with the surface of the photosensitive drum 33 so that the photosensitive drum 33 is cleaned.
As the transfer charger 44, a corona charger or a contact transfer charger is used. When the corona charger is used as the transfer charger 44, a voltage of -10 kV to +10 kV is applied and the transfer current is set to -500 µA to +500 µA. On the outer circumferential surface of the transfer drum 48, a holding member is mounted. This retaining member is formed of a film-like dielectric sheet such as a polyvinylidene fluoride resin film or a polyethylene terephthalate film. For example, a sheet having a thickness of 100 μm to 200 μm and a volume resistance of 10 ¹² to 10 ¹⁴ Ω · cm is used.
In the case of the second color, the rotary developing unit rotates until the developer 35 opposes the photosensitive drum 33. Then, the second color latent image is developed by the second developer contained in the developing device 35, and the formed color toner image is transferred to the transfer medium and the recording medium S as described above.
The same operation is also repeated for the third and fourth colors. Therefore, the transfer drum 48 is rotated a predetermined number of times while keeping the transfer medium and the recording medium S gripped, so that the toner images corresponding to the predetermined number of colors are multiplexed onto the recording medium. It is preferable that the transfer current for electrostatic transfer be provided so as to be higher in order of first color <second color <third color <fourth color so that toner is hardly left on the photosensitive drum after transfer.
On the other hand, a high transfer current is not preferable because the image to be transferred may be blurred. However, the toner of the present invention has excellent transfer performance so that second, third and fourth color images to be multiplexed can be reliably transferred. Therefore, images of all colors are neatly formed, and a multicolor image of vivid color tone can be obtained. In addition, in full color images, excellent images with excellent color reproducibility can be obtained. Moreover, since the transfer current no longer needs to be so large, less image blurring in the transfer phase can occur. When the recording medium S is separated from the transfer drum 48, the electric charge is removed by the separated charger 45, and when the transfer current is large, the recording medium S is electrostatically severely attracted to the transfer drum. And the transfer medium cannot be separated unless the current increases further at the same time as the separation. In the case where the current increases further, such a current has a reverse polarity with respect to the polarity of the transfer current, so that the toner image may be blurred, or the toner may be scattered from the transfer medium and contaminate the inside of the image forming apparatus. Since the toner of the present invention can be easily transferred, the transfer medium can be easily separated without increasing the separation current, so that image blur and toner scattering simultaneously with separation can be prevented. Therefore, the toner of the present invention can be particularly preferably used in an image forming method for forming a multicolor image or a full color image including multiple transfer steps.
The recording medium S on which multiple transfers have been completed is separated from the transfer drum 48 by a separating charger 45. Then, the toner image retained thereon is fixed by a heat-pressing roller fixing unit 32 having a web impregnated with silicone oil, and at the time of fixing, the additive colors are mixed to form a full color copy image.
The multi-development batch transfer method will be described with reference to Fig. 4 showing an example of the full-color image forming apparatus.
The electrostatic latent image formed on the photosensitive drum 103 by the charger 102 and the exposure portion 101 using the laser light uses toner by the developing devices 104, 105, 106, and 107. Visualized by sequentially performed phenomena. In the developing process, non-contact developing is preferably used. In the non-contact development, the developer layer formed in the developer does not rub against the surface of the image forming photosensitive drum 103 so that the development can be performed in the second and subsequent developing steps without blurring the image formed in the preceding developing step. Can be.
The toner image for the multicolor image or the full color image formed on the photosensitive drum 103 is transferred to the transfer medium and the recording medium S by the transfer charger 109. In the transfer step, electrostatic transfer is preferably used when corona discharge transfer or contact transfer is used. In the former corona discharge transfer method, a transfer charger 109 for generating a corona discharge is provided on the opposite side of a toner image, and a transfer medium recording medium S is inserted therebetween, and the corona discharge acts on the rear side of the recording medium. The toner image is electrostatically transferred. The latter contact transfer method causes the transfer roller or transfer belt to contact the photosensitive drum 103 and then applies an bias to the roller or by electrostatic charging from the back side of the belt with the transfer medium recording medium S inserted therebetween. The toner image is transferred. By such electrostatic transfer, the multicolor toner image held in the photosensitive drum 103 is simultaneously transferred to the transfer medium and the recording medium S. FIG. Since the toner transferred in such a batch transfer system is a large amount, the toner may remain in a large amount after the transfer, resulting in uneven transfer, and color unevenness in a full-color image.
However, the toner of the present invention has excellent transfer performance so that any color image of a multicolor image can be neatly formed. In full color images, excellent images with excellent color reproducibility can be obtained. Moreover, even at a low current, the toner can be transferred with excellent efficiency, so that image blur can be prevented from occurring. Moreover, since the recording medium can be easily separated, any toner scattering can also be prevented from occurring. In addition, excellent transfer performance can be realized in the contact transfer means due to the excellent release property. Therefore, the toner of the present invention can be preferably used also for an image forming method having multiple image batch transfer steps.
The recording medium S on which the multicolor toner image is transferred at one time is separated from the photosensitive drum 103, and then fixed by the heating roller fixing unit 112, as a result of which a multicolor image is formed.
The transfer residual toner remaining on the surface of the photosensitive drum 103 after the transfer is recovered by a cleaner 108 having a cleaning blade capable of contacting the surface of the photosensitive drum 1 so that the photosensitive drum 103 is removed. It is cleaned. The cleaning blade of the cleaner 108 is separated from the surface of the photosensitive drum 103 while waiting, and the toner image is transferred to the photosensitive drum 103 when the toner image is transferred from the photosensitive drum 103 to the transfer medium and the recording medium S. FIG. It can be operated for contact.
FIG. 5 illustrates an image device using a transfer belt as second transfer means when the fourth color toner image primarily transferred to the intermediate transfer drum is collectively transferred to the recording medium by using the intermediate transfer drum.
In the apparatus system shown in Fig. 5, the developer with cyan toner, the developer with magenta toner, the developer with yellow toner and the developer with black toner are developed by developers 244-1, 244-2, Contained in (244-3) and (244-4), respectively. The electrostatic latent image formed on the photosensitive member 241 is developed to form toner images of respective colors on the photosensitive member 241. The photosensitive member 241 is a photosensitive drum or photosensitive belt having a photosensitive insulating material layer formed of a-Se, CdS, ZnO ₂ , OPC or a-Si. The photosensitive member 241 is rotated by a driving device (not shown).
As the photosensitive member 241, it is preferable to use the photosensitive member 241 having an amorphous silicon photosensitive layer or an organic photosensitive layer.
The organic photosensitive layer may be a monolayer type in which the photosensitive layer contains a charge generating material or a charge transfer material in the same layer, or may be a functionally separated photosensitive layer consisting of a charge transfer layer and a charge generating layer. A multilayer photosensitive layer comprising a conductive substrate and a charge generating layer and a charge transfer layer formed on the substrate in this order is a preferred example.
As the binder resin of the organic photosensitive layer, polycarbonate resin, polyester resin or acrylic resin has particularly excellent transfer performance and cleaning performance, and rarely causes poor cleaning, melt adhesion of toner to the photosensitive member and film formation of external additives. Do not.
The charging step may be in a non-contact manner with the photoreceptor 241 using a corona charger, or a contact type using a roller or the like. You can use both of these methods. It is desirable to use the contact type system shown in FIG. 5 to enable efficient and uniform charging, to simplify the system, and to reduce ozone generation.
The charging roller 242 is basically composed of the core 242b and the conductive elastic layer 242a forming the outer circumference thereof. The charging roller 242 is in contact with the surface of the photosensitive member 241 with pressure, and rotates together as the photosensitive member 241 rotates.
When using a charging roller, the charging process is carried out at a roller contact pressure of 5 to 500 g / cm, and an AC voltage of 0.5 to 5 kVpp, an AC frequency of 50 Hz to 5 kHz when an AC voltage is formed in addition to the DC voltage and When using a DC voltage of ± 0.2 to ± 1.5 kV, and a DC voltage, it may be desirable to carry out under the conditions of a DC voltage of ± 0.2 to ± 5 kV.
As a charging means different from a charging roller, there exists a method of using a charging blade and the method of using a conductive brush. Such contact charging means does not require a high voltage, for example, and has an effect of reducing ozone generation.
As the contact charging means, the charging roller and the charging blade may be preferably made of conductive rubber, and may provide a release film on the surface thereof. The release film can be formed using any of nylon resin, PVDF (polyvinylidene fluoride) or PVDC (polyvinylidene chloride).
The toner image on the photosensitive member 241 is transferred to the intermediate transfer drum 245 when a voltage (for example, ± 0,1 to ± 5 kV) is applied. The surface of the photosensitive member 241 is cleaned by the cleaning means 249 having the cleaning blade 248.
The intermediate transfer drum 245 consists of a pipe-type conductive core 245b and a medium resistance elastic body layer 245a formed on the outer circumferential surface thereof. The core 245b may comprise a plastic pipe provided with a conductive coating thereon.
The medium resistance elastomer layer 245a is made of an elastic material such as silicone rubber, Teflon rubber, chloroprene rubber, urethane rubber, or EPDM (ethylene-propylene-diene terpolymer), and is made of carbon black, zinc oxide, tin oxide or carbonization. Conductive additives such as silicon are blended and dispersed to adjust the electrical resistance (volume resistance) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm.
The intermediate transfer drum 245 is provided in contact with the lower surface of the photosensitive member 241 which is supported in parallel in the axial direction with respect to the photosensitive member 241, and is half as indicated by the arrow at the same circumferential speed as the photosensitive member 241. Rotate clockwise.
The first cyan toner image formed and retained on the surface of the photosensitive member 241 is applied to the intermediate transfer drum 245 in the course of passing through the transfer nip portion where the photosensitive member 241 and the intermediate transfer drum 245 contact. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer drum 245 with the help of an electric field formed at the transfer nip portion by the transfer bias.
If necessary, after the toner image is transferred to the transfer member, the surface of the intermediate transfer drum 245 can be cleaned with cleaning means that can be in contact with or separated from the intermediate transfer drum. When toner is present on the intermediate transfer drum 245, the cleaning means is spaced apart from the surface of the intermediate transfer drum so as not to blur the toner image.
The transfer means 247 is mounted in contact with the lower surface portion of the intermediate transfer drum 245 which is supported axially in parallel with the intermediate transfer drum 245. The transfer means 247 is, for example, a transfer roller or a transfer belt and rotates counterclockwise as indicated by an arrow at the same circumferential speed as the intermediate transfer drum 245. The transfer means may be mounted in direct contact with the intermediate transfer drum, or may be arranged to be in contact with and between the intermediate transfer drum and the transfer means such as a belt.
The transfer roller is basically composed of a conductive elastic layer forming a core at the center and its outer circumference.
The intermediate transfer drum and the transfer roller may be formed from generally available materials. The elastic layer of the transfer roller can be manufactured to have a volume resistance set less than the volume resistance of the elastic layer of the intermediate transfer drum, so that the voltage applied to the transfer roller can be reduced, thereby forming an excellent toner image on the transfer member. The transfer body can prevent bending around the intermediate transfer drum. In particular, it may be desirable for the elastic layer of the intermediate transfer drum to have a volume resistance of at least 10 times the volume resistance of the elastic layer of the transfer roller.
The hardness of the intermediate transfer drum and the transfer roller is measured according to JIS K-6301. The intermediate transfer drum used in the present invention may preferably be composed of an elastic layer having a hardness in the range of 10 to 40. In the hardness of the transfer roller, the transfer roller preferably has elasticity having a hardness higher than the hardness of the elastic layer of the intermediate transfer drum in order to prevent the transfer body from being rolled around the intermediate transfer drum, and has a value of 41 to 80. If the intermediate transfer drum and the transfer roller have reverse hardness, a concave surface is formed on the transfer roller surface so that the transfer member tends to curl around the intermediate transfer drum.
As shown in FIG. 5, the transfer belt 247 is disposed below the intermediate transfer drum 245. The transfer belt 247 is laid over two rollers provided parallel to the axis of the intermediate transfer drum 245, that is, the bias roller 247a and the tension roller 247c, and are driven through driving means (not shown). . The transfer belt 247 is configured to be movable in the direction of the arrow on the surface of the bias roller 247a around the tension roller 247c, so that it can be brought into contact with or separated from the intermediate transfer drum 245 above and below the direction of the arrow. . In the bias roller 247a, a desired secondary transfer bias is applied by the secondary transfer bias power supply 247b. The tension roller 247c is grounded.
The transfer belt 247 used in the embodiment of the present invention is a thermosetting urethane which can be controlled such that carbon black is dispersed to have a thickness of about 300 μm and a volume resistance of 10 ⁸ to 10 ¹² Ω · cm (when applied at 1 kV). It is a rubber comprising an elastomer, and its surface is covered with a 20 μm thick fluorine-based rubber so that it can be controlled to have a strain resistance of 10 ⁵ Ω · cm (when 1 kV is applied). It has a tube shape with an outer size of 80 mm long and 300 mm wide.
The transfer belt 247 described above is stretched about 5% by the tension applied with the aid of the bias roller 247a and the tension roller 247c.
The transfer belt 247 rotates at a speed set equal to or different from the circumferential speed of the intermediate transfer drum 245. The transfer member 246 is conveyed between the intermediate transfer drum 245 and the transfer belt 247, and at the same time a bias having reverse polarity with respect to the polarity of the toner is applied from the transfer bias applying means to the transfer transfer belt 247, The toner image on the intermediate transfer drum 245 is transferred to the surface of the transfer member 246.
The transfer rotating body can be made of the same material used for the charging roller. The transfer process may preferably be carried out under roller contact pressures of 5 to 500 g / cm and DC voltage conditions of ± 0.2 to ± 10 kV.
The conductive elastic layer 247a ₁ of the bias roller 247a has a volume resistance of 10 ⁶ to 10 ¹⁰ Ω cm, such as polyurethane and ethylene-propylene-diene terpolymer (EPDM), in which conductive materials such as carbon are dispersed. Is an elastomer. A bias is applied to the core 247a ₂ by a constant voltage power supply. The bias condition is preferably ± 0.2 to ± 10 kV.
Subsequently, the transfer material 246 is transported to a fixing unit 281 having a heating roller in which a heating element, such as a halogen heater, is built, and a pressure roller of an adjacent elastic body under pressure, and passed between the heating roller and the pressure roller to toner. The image is heated and press-fixed to the transfer material. A method of fixing by a heater through a film can also be used.
1 to 5, one of the one-component developing method using the one-component developer or the two-component developing method using the two-component developer containing the toner and the carrier can be applied. Can be.
The developing method using the one-component nonmagnetic developer using the toner of the present invention is explained based on the schematic configuration diagram shown in FIG.
The developing apparatus 170 supports a developing container 171 for accommodating the nonmagnetic one-component developer 176 as a non-magnetic toner, and a one-component nonmagnetic developer 176 to be accommodated in the developing container 171 to develop the developing region. A developer carrier 172 for transporting to the developer, a supply roller 173 for supplying a one-component magnetic developer onto the developer carrier, and a developer layer thickness for regulating the developer layer thickness on the developer carrier And a stirring member 175 for stirring the one-component magnetic developer 176 in the elastic blade 174 of the regulating member and the developing container 171.
Reference numeral 169 is a latent image bearing member for supporting an electrostatic latent image, and latent image formation is used for electrophotographic process means or electrostatic recording means, not shown. Reference numeral 172 denotes a developing sleeve that functions as a developer carrying member, and is composed of a nonmagnetic sleeve made of aluminum or stainless steel.
The developing sleeve may be manufactured by using a tubular tube of aluminum or stainless steel by itself, and preferably, by spraying glass beads, mirror-processing the surface thereof, or coating the surface thereof with resin to uniformly roughen its surface. Can be. In particular, the method of coating the sleeve surface with a resin can be preferably used because it disperses various particles in the resin so that the surface roughness and the conductivity of the sleeve can be easily adjusted and the lubricity can be easily given.
There is no restriction on the resin used to coat the sleeve surface and the various particles added to the resin. As the resin, a thermoplastic resin, for example, styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluorine resin, cellulose resin and acrylic resin; And thermosetting or photocurable resins such as epoxy resins, polyester resins, alkyd resins, phenolic resins, melamine resins, polyurethane resins, urea resins, silicone resins and polyamide resins.
As various particles to be added, PMMA, acrylic resin, polybutadiene resin, polystyrene resin, polyethylene, polypropylene, polybutadiene, or the above copolymer, benzoguanamine resin, phenol resin, polyamide resin, nylon, fluorine series Resins, silicone resins, epoxy resins and polyesters; Carbon blacks such as furnace black, lamp black, thermal black, acetylene black and channel black; Metal oxides such as titanium oxide, tin oxide, zinc oxide, molybdenum oxide, potassium titanate, antimony oxide and indium oxide; Metals such as aluminum, copper, silver and nickel; And inorganic fillers such as graphite, metal fibers and carbon fibers.
The one-component nonmagnetic developer 176 is stored in the developing container 171 and is supplied onto the developer carrying member 172 by a supply roller 173. The feed roller 85 is composed of a foam such as a polyurethane foam, and rotates at a non-zero relative speed in the forward or reverse direction with respect to the developer carrier, so that the developer can be supplied onto the developer carrier, It is also possible to remove the developer (which is not used for development) remaining on the development carrier after being transferred. The one-component nonmagnetic developer supplied on the developer carrying member 172 is uniformly coated in a thin layer using the elastic blade 174 as the developer layer thickness regulating member.
In order for the elastic coating blade to contact the developer carrier, a pressure of 0.3 to 25 kg / m, preferably 0.5 to 12 kg / m, is effective at a linear pressure in the bus direction of the developer carrier. If the adjacent pressure is less than 0.3 kg / m, it is difficult to uniformly coat the one-component nonmagnetic developer, resulting in a wide charge distribution of the one-component nonmagnetic developer, resulting in fog or dark spots around the linear image. . When the adjacent pressure exceeds 25 kg / m, overpressure is applied to the one-component nonmagnetic developer to deteriorate the one-component nonmagnetic developer and the one-component nonmagnetic developer is combined, so that the pressure is not preferable and the developer It is not preferable because a large torque is required to drive the carrier. In other words, the adjoining pressure of 0.3 to 25 kg / m makes it possible to effectively loosen the aggregation of the one-component nonmagnetic developer and to raise the charging amount of the one-component nonmagnetic developer simultaneously.
As elastic blades, there are silicone rubbers, urethane rubbers and rubber elastomers such as NBR, elastomers such as polyethylene terephthalate and polyamides, and metal elastomers such as stainless steel, steel and phosphated bronze. Complexes of the above materials may also be used. It may be desirable to include metal sheets of stainless steel or phosphated bronze, provided by rubber molding, such as urethane or silicone rubber, or various types of elastomers, such as polyamide elastomers.
In the one-component nonmagnetic developing method, in a system in which the one-component nonmagnetic developer is thin-coated on a developing sleeve by a blade, the thickness of the one-component nonmagnetic developer on the developing sleeve is determined by the gap α between the developing sleeve and the latent image bearing interface. It can be smaller and alternating electric field can be applied to this gap. This is desirable to obtain sufficient image density. More specifically, a developing bias formed by superimposing the alternating electric field or the DC electric field on the alternating electric field may be applied on the latent image bearing member 169 from the developing sleeve 172. This makes it easy for the one-component nonmagnetic developer to move from the developing sleeve surface to the surface of the latent image bearing member, so that a better image can be obtained.
In the present invention, the gap α between the latent image bearing member and the developer carrier may preferably be set to, for example, 50 to 500 µm, and the thickness of the developer layer supported on the developer carrier is, for example, 4 to 400 μm.
The developing sleeve is rotated at a circumferential speed of 100 to 200% with respect to the latent image bearing member. The alternating electric field may be applied at a peak-to-peak voltage of preferably 0.1 kV or more, preferably 0.2 to 3.0 kV, more preferably 0.3 to 2.0 kV. The alternating bias can be applied at a frequency of 1.0 to 5.0 kHz, preferably 1.0 to 3.0 kHz, more preferably 1.5 to 3.0 kHz. As the wavelength form of the alternating bias, square waves, sine waves, sawtooth waves, and triangular waves can be used. Asymmetric AC biases with different forward / reverse voltage application times may also be used. It is also desirable to overlap the DC bias.
The two-component developer composed of the toner and the carrier of the present invention has been described based on its schematic configuration diagram shown in FIG.
The developing apparatus 120 is a developing container 126 for accommodating the two-component developer 128, and developing as a developing carrier for supporting and transporting the two-component developer 128 contained in the developing container 126 to the developing unit. And a developing blade 127 as a developer layer thickness regulating means for regulating the layer thickness of the toner layer formed on the developing sleeve 121.
The developing sleeve 121 is disposed with a magnet 123 in the nonmagnetic sleeve body 122.
The interior of the developing container 126 is divided into a developing chamber (first chamber, R1) and a stirring chamber (second chamber, R2) by the partition wall 130. At the top of the stirring chamber R2, the stirring storage chamber R3 is formed on the other side of the partition wall 130. The developer 128 is accommodated in the developing chamber R1 and the stirring chamber R2, and the refilling toner (non-magnetic toner) 129 is contained in the toner storage chamber R3. A supply opening 131 is provided in the toner storage chamber R3 and is added dropwise through the stirring chamber R2 through the supply opening 131 in an amount corresponding to the amount of toner consumed.
The transport screw 124 is disposed in the developing chamber R1. As the transport screw 124 is driven to rotate, the developer 128 accommodated in the developing chamber R1 is transported in the longitudinal direction of the developing sleeve 121. Similarly, the transport screw 125 is disposed in the stirring chamber R2, and as the transport screw 125 is rotated, the toner added dropwise from the supply port 131 to the stirring chamber R2 is formed in the developing sleeve 121. It is transported in the longitudinal direction.
The developer 128 is a two-component developer containing a nonmagnetic toner and a magnetic carrier.
The developing container 126 has an opening disposed at a portion in contact with the photosensitive drum 119, and the developing sleeve 121 protrudes from the opening, where a gap is formed between the developing sleeve 121 and the photosensitive drum 119. A bias applying means 132 for applying a bias voltage is disposed in the developing sleeve 121 formed of a nonmagnetic material.
The magnet roller acting as a magnetic field generating device fixed in the developing sleeve 121, that is, the magnet 123 is a developing magnetic pole S1, a magnetic pole N3 located downstream, a developer S2 for transporting the developer 128, and Has (N1). The magnet 123 is disposed in the manner in which the developing magnetic pole S1 is in contact with the photosensitive drum 119 inside the sleeve body 122. The developing magnetic pole S1 forms a magnetic field in a limited developing portion between the developing sleeve 121 and the photosensitive drum 119, where the magnetic brush is formed by a magnetic field.
The developer layer regulating blade 127 disposed above the developing sleeve 121 and for regulating the layer thickness of the developer 128 on the developing sleeve 121 is made of a nonmagnetic material such as aluminum or SUS316 stainless steel. . The distance A between the end of the nonmagnetic blade 127 and the interface of the developing sleeve 121 is 300 to 1000 mu m, preferably 400 to 900 mu m. If this distance is less than 300 µm, the magnetic carriers are trapped between them, and the developing layer tends to be uneven, and also, the developer required for good development cannot be coated on the sleeve, so that low concentrations and unevenly developed The problem is that only images are obtained. In order to prevent uneven coating due to insoluble particles mixed in the developer, the distance may be preferably 400 μm or more. If this distance exceeds 1000 μm, the amount of developer coated on the developing sleeve 121 amplifies undesirable developer layer thickness regulation, causing a problem that a large amount of magnetic carrier particles adhere to the photosensitive drum 119. In addition, the circulation of the developer, the formation of the nonmagnetic developer layer, and the developing regulation force by the blade 127 become weak, resulting in a lack of triboelectricity of the toner, which causes fog and becomes inefficient.
The development by the two-component developing device 120 is performed while applying an alternating electric field, while the magnetic brush composed of the toner and the magnetic carrier is adjacent to the latent image bearing member (eg, photosensitive drum) 119. Since the magnetic brush is adjacent to the latent image carrier, the transfer residual toner supported on the carrier after low sand is taken out of the magnetic brush and then recovered in the developing chamber R1. The distance B (distance between S-D) between the developer carrying member (developing sleeve) 121 and the photosensitive drum 119 may be preferably 100 to 1000 μm. This is desirable to improve carrier adhesion and dot reproducibility. If the gap is narrower than 100 mu m, the developer is not supplied sufficiently, resulting in low image density. When the gap exceeds 1000 mu m, the line of magnetic force from the magnet S1 is widened, so that the density of the magnetic brush is lowered, the dot reproducibility is poor, or the force that restrains the carrier is weakened, thereby causing carrier adhesion.
The alternating electric field preferably has a peak-to-peak voltage of 500 to 5000 V and a frequency of 500 to 10,000 Hz, preferably 500 to 3,000 Hz, each of which may be appropriately selected and applied. In such a case, the waveform used may be selected from triangle waves, square waves, sinusoids, or waveforms of various duty ratios. When the applied voltage is lower than 500 V, sufficient image density is difficult to be obtained, and fog toner in the non-image portion sometimes cannot be recovered well. If the applied voltage exceeds 5000 V, the latent image is disordered through the magnetic brush, sometimes causing deterioration of image quality.
The two-component developer having a well-charged toner lowers the fog removal voltage Vback, and the photosensitive member is charged low in its primary charging, thereby allowing the photosensitive member to have a longer life. Vback may be 150 V or less, and more preferably 100 V or less, depending on the developing system.
As the contrast potential, a potential of 200 V to 500 V is preferably used to obtain sufficient image density.
If the frequency is less than 500 Hz, charge injection into the carrier occurs, which leads to process speech, which results in carrier attachment or disordered latent images resulting in poor image quality. When it exceeds 10,000 Hz, the toner does not carry the entire length and tends to lower the image quality.
In order to develop sufficient image density, obtaining excellent dot reproducibility, no carrier adhesion, and having the magnetic brush on the developing sleeve 121 adjoin the photosensitive drum 119 with a width of 3 to 8 mm (developing nip C) It may be desirable. If developing nip C is narrower than 3 mm, it may be difficult to satisfy sufficient image density and dot reproducibility. If it is wider than 8 mm, the developer may return to the nip and stop the machine operation, or it may be difficult to sufficiently prevent carrier attachment. As a method for adjusting the developing nip, the nip width is appropriately adjusted by adjusting the distance A between the developer layer thickness regulating blade 127 and the developing sleeve 121 or the distance B between the developing sleeve 121 and the photosensitive drum 119. Can be.
The developing system using a two-component developer can be carried out by a developing simultaneous cleaning method, wherein any cleaning member in contact with the surface of the photosensitive drum is transferred between the transferring part in the transferring step and the charging part in the charging step and in the developing step. The transfer residual toner, which is not provided between the portion and the developing portion and which remains on the photosensitive drum after transfer, is collected by the developing apparatus in the developing step.
In the developing simultaneous cleaning step, the developing part, the transfer part, and the charging part are located in the above order with respect to the moving direction of the latent image bearer, and remove the transfer residual toner present on the surface of the latent image bearer adjacent to the surface of the photosensitive drum. No cleaning member is provided between the transfer portion and the charging portion and between the charging portion and the developing portion.
In the image forming method using the development simultaneous cleaning method, an inversion phenomenon in which the development is performed in a state where the charging polarity of the toner and the charging polarity of the latent image bearing member have the same polarity in the developing step is described as an example. In the case of using a negatively charged photosensitive member and a negatively charged toner, the transfer step can transfer the image visualized by the positive polarity transfer member to the transfer material, where the type of transfer material (thickness, resistance, conductivity, etc. is different). ) And the image area, the charging polarity of the transfer residual toner varies from plus to minus. However, in the case of charging the negatively charged photosensitive member, depending on the charging member of negative polarity, even if the polarity of the transfer residual toner as well as the polarity of the photosensitive member surface is converted to positive polarity in the transfer step, the charging polarity can be made uniform to the negative side. . Therefore, when the reverse development is used as the developing method, the negatively charged transfer residual toner remains and develops in the front potential portion of the toner. The transfer residual toner does not remain in the dark portion potential portion of the undeveloped toner, and is pulled toward the developer magnetic brush or the developer carrier due to the relationship with the developing electric field so that the toner does not remain there.
The device unit of the present invention will be described with reference to FIG.
The apparatus unit of the present invention is detachably mounted from the main body of the image forming apparatus (for example, a copying machine, a laser beam printer or a facsimile apparatus).
In the embodiment shown in Fig. 6, the apparatus unit is the developing apparatus 170 and the developing apparatus is detachably mounted from the main body of the image forming apparatus.
That is, the developing apparatus includes a developer 176, a developing container 171, a developer carrying member 172, a supply roller 173, a developer layer thickness regulating member 174, and a stirring member 175. As the apparatus unit of the present invention, there may be at least a developer 176, a developing container 171, and a developing carrier 172.
The device unit may further be accompanied by a latent image bearing member, cleaning member or charging member as a unitary body.
When the image forming method of the present invention is applied to a printer in a facsimile apparatus, the optical image exposure light L serves as the exposure light used to print received data. 11 shows an example thereof in the form of a block diagram.
The adjuster 91 adjusts the image reading unit 90 and the printer 99. The entire regulator 91 is controlled by the CPU 97. The image data output from the image reading section is sent to another facsimile portion via the transmission circuit 93. Data received from the other part is sent to the printer 99 through the receiving circuit 92. The predetermined image data is stored in the image memory 96. The printer adjuster 98 adjusts the printer 99. Number 94 represents the telephone.
The image received from the line 95 (the image information from the remote terminal connected via the line) is demodulated in the receiving circuit 92 and after the image information is coded by the CPU 97, the image memory 96 Will be remembered successively. Subsequently, when one or more pages of images are stored in the memory 96, image recording for those pages is performed. CPU 97 reads image information for one page from memory 96 and sends coded image information for that page to printer controller 98. Receiving image information for one page from the CPU 97, the printer controller 98 adjusts the printer 99 so that image information for one page is recorded.
The CPU 97 receives information on the next page while the printer 99 is recording.
Images are received and recorded in this manner.
According to the present invention, a fog-free image can be obtained having excellent image density stability and fine image reproducibility without incurring deterioration of the toner even in long-term use.
The present invention will be described below in more detail by the given examples, but the present invention is not limited to these examples.
Example 1
450 parts by weight of a 0.1 M Na ₃ PO ₄ aqueous solution was introduced to 700 parts by weight of ion-exchanged water, heated to 50 ° C., and then 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Stirred. To the resulting mixture, 70 parts by weight of a 1.0 M CaCl ₂ aqueous solution was added in small portions to obtain an aqueous medium containing a calcium phosphate compound.
(Monomer) (parts by weight)
Styrene 170 parts by weight
30 parts by weight of n-butyl acrylate
(coloring agent)
Mr. Child. Pigment Blue 15: 3 15 parts by weight
(Charge control agent)
Salicylic acid metal compound 2 parts by weight
(Polar resin)
20 parts by weight of saturated polyester resin (acid value: 10; peak molecular weight: 150,000)
(Release agent)
Behenyl stearate 30 parts by weight
(Crosslinking binder)
0.5 parts by weight of divinylbenzene
The material was heated to 50 ° C. and uniformly dissolved or dispersed at 9,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). A polymerizable monomer composition was prepared by dissolving 10 parts by weight of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in the obtained mixture.
After the polymerizable monomer composition was introduced into the medium, the polymerizable monomer composition was granulated by stirring the TK homomixer at 8,000 rpm at 50 ° C. under a nitrogen atmosphere.
The granulation product obtained was then stirred with a paddle blade for mixing while raising the temperature to 60 ° C. for 2 hours. After 4 hours, the temperature was raised to 70 ° C. at a rate of temperature rise of 40 ° C. per hour where the reaction was carried out for 5 hours. After the completion of the polymerization, the remaining monomer was evaporated off under reduced pressure, the reaction system was cooled and hydrochloric acid was added thereto to dissolve calcium phosphate to obtain a suspension containing cyan toner particles (1-a).
The average circularity distribution and particle size distribution of the cyan toner particles (1-a) thus obtained were measured by a flow particle imager (manufactured by Toa Iyou Denshi K.K.). As a result, the particles had an average circularity of 0.970 and had a maximum X at 6.1 μm in diameter corresponding to the circle and no maximum Y in a range from 0.6 μm to 2.00 μm in diameter corresponding to the circle. The content of particles having a diameter of 0.60 μm to 2.00 μm corresponding to the circle was 4% by number.
On the other hand, 7 parts by weight of styrene monomer and 3 parts by weight of potassium persulfate as water-soluble initiators were added to 500 parts by weight of ion-exchanged water, and the obtained mixture was stirred with a paddle blade for mixing while raising the temperature to 70 ° C. It was performed for 24 hours. Thus, a suspension containing the particulate polymer (1-b) was obtained.
The average circularity distribution and particle size distribution of the thus obtained particulate polymer (1-b) were measured with a flow particle imager (manufactured by Toa Iyou Denshi K.K.). As a result, the particles had an average circularity of 0.972 and had a maximum only at 0.8 μm in diameter corresponding to the circular shape. The content of particles having a diameter of 0.60 μm to 2.00 μm corresponding to the circle was 72 number%.
The total amount of the suspension containing the particulate polymer (1-b) was added to the suspension containing the cyan toner particles (1-a), and the obtained mixture was stirred with a mixing paddle blade for 2 hours, filtered and washed with water. Subsequently, it dried and obtained cyan toner particle (1) whose weight average particle diameter is 6.5 micrometers.
100 parts by weight of the cyan toner particles (1) thus obtained were treated with silicone oil and 1.0 parts by weight of fine silica powder (A-1) having a BET specific surface area of 110 m ² / g, and a silicone oil and a silane coupling agent and a BET ratio. 0.5 parts by weight of fine silica powder (B-1) having a surface area of 50 m ² / g was added, followed by uniformly stirring using a Henschel mixer (manufactured by Mitsui Mining & Smelting Co., LTD.) To prepare the cyan toner (1). Obtained. This toner was used as a nonmagnetic one-component developer (1).
The fine silica powder (B-1) is surface-treated with 100 parts by weight of commercially available silica fine powder NAX50 (manufactured by Nippon Aerosil Co., Ltd.) with 10 parts by weight of dimethylsilicone oil, and subjected to wind rating to collect relatively coarse particles to obtain a particle size distribution. It was the product obtained by adjusting. In a photograph taken at a magnification of 100,000 times with a transmission electron microscope (TEM) and at a magnification of 30,000 times with a scanning electron microscope (SEM), the fine silica particles (B-1) have a primary particle having a primary particle diameter of 40 mμm. It confirmed that it was a particle | grain formed by combining in plurality. The particle shape of the fine silica powder (B-1) confirmed by this enlarged photograph is shown in FIG.
In the enlarged picture of the cyan toner 1, the primary particles of the fine silica powder A-1 present in the toner particles have a fine silica powder of 117 with a shape coefficient SF-1 (100,000 times magnification) and also present in the toner particles ( The particle | grains of B-1) were 290 in shape coefficient SF-1 (50,000 times enlarged photograph).
In 500,000-fold magnification photographs of cyan toner (1) taken with a scanning electron microscope, the fine silica powder (A-1) had an average long diameter of 7.35 mμm, a long diameter / short diameter ratio of 1.1, and 0.5 μm in a 100,000-fold magnification. It was confirmed that there were 122 particles per unit area of 0.5 mu m. In a 500,000-fold magnification of cyan toner (1) taken with a scanning electron microscope, the fine silica powder (B-1) had an average long diameter of 152 mμm, a long diameter / short diameter ratio of 3.2, and a unit area of 1.0 μm × 1.0 μm. It was confirmed that there existed 6 particle numbers.
In a 100,000-fold magnification photograph of the cyan toner (1) taken with a scanning electron microscope, the primary particles constituting the fine silica powder (B-1) had an average value of the minimum diameter of the ferret (average of the minimum diameter) of 42 mμm. Was found to be.
The average circularity distribution and the particle size distribution of the cyan toner 1 were measured with a flow particle imager (manufactured by Toa Iyou Denshi K.K.). As a result, the toner has an average circularity of 0.970 and the content of particles having a diameter of 0.60 μm to 2.00 μm corresponding to a circle having a maximum X at a diameter of 6.1 μm corresponding to a circle and a maximum Y at a diameter of 0.8 μm corresponding to a circle. 24 number%.
Commercially available laser beam printer CANON LBP-2030 was placed in a retrofit modifier as shown in FIG. In order to evaluate an individual evaluation item, 5,000 running tests were used using this.
The retrofit of the LBP-2030 is configured as shown in FIG. 1. The developing unit 170 of the developing method of the nonmagnetic one-component developing system shown in FIG. 6 is separated by using the black developing unit 4BK, the magenta developing unit 4Y, the magenta developing unit 4M, and the nonmagnetic one-component developing system as the cyan developing unit 4C. Using a rotation unit 4 provided as possible as a developing apparatus, the secondary toner images formed by the respective color toners transferred on the intermediate transfer drum 5 can be secondarily collectively transferred to the recording material P. And heat-fixing with the recording material P afterwards. The fixing unit 9 is also modified to be constructed in the following manner.
A roller composed of an aluminum mandrel covered with two kinds of layers is used as the fixing roller 9a of the fixing unit 9. In the lower layer portion, high temperature vulcanized silicone rubber (HTV silicone rubber) is used as the elastic layer. The elastic layer has a thickness of 2.1 mm and a rubber hardness of 3 ° (JIS-A). In the upper layer, a tetrafluorine ethylene-perfluoro fluorinated alkyl vinyl ether copolymer (PFA) formed into a thin film by spray coating is used as a release layer. The thin film is 20 μm thick.
The pressure roller 9b of the fixing unit 9 is a fixing roller 9a which is coated with a lower layer of silicon high elastic layer and an upper layer of fluorine resin releasing agent formed with the same thickness and physical properties as those of similar materials and formed with the same thickness and properties as the similar materials. The structure is similar
The fin width of the fixing unit is set to 9.5 mm, the fixing pressure is 2.00 × 10 ⁵ Pa, and the fixing roller surface temperature at the standby is set to 180 ° C. The application mechanism of the fixing oil is detachable.
A drum consisting of a surface layer of aluminum cones covered with a 5 mm thick elastic layer formed of a mixture of NBR and epichlorohydrin is used as the intermediate transfer drum 5.
The cyan developer (4C) of the converting machine of LBP-2030 was charged with 160 g of the nonmagnetic one-component developer (1). Commercially available copy paper CLC Paper A4 (manufactured by CANON SALES INC., Basis weight: 81.4 g / m ² ) was placed in the tray 7 as the recording material P, and a continuous operation test was conducted under the following conditions. .
World War I conditions:
From a power supply (not shown), a charge bias voltage formed by applying a DC voltage of -600 V and an AC voltage of 1,150 Hz sine wave at an amplitude of 2 kvpp is applied to the charging roller 2 while discharging to transfer charges and insulated. The photosensitive drum 1 of material was constantly charged.
Latent Image Formation Conditions:
The constant charged photosensitive drum 1 was irradiated and exposed by laser light L to form an electrostatic latent image. The intensity of the laser light was set to provide a surface potential of -200 V on the exposed portion.
Developing condition:
A developing bias voltage formed by applying a DC voltage of -350 V and an AC voltage of 2,300 Hz sine wave with an amplitude of 1.8 kvpp was applied to the developing sleeve of the cyan developer 4C shown in Fig. 1, above each developing sleeve to perform development. An alternating electric field was formed in the interval (distance: 300 µm) between the developing sleeve and the photosensitive drum 1, which was prepared such that the toner (toner layer thickness: 170 µm) was made to fly to the photosensitive drum 1.
Primary transfer condition:
In order to primary transfer the toner image formed on the photosensitive drum 1 by the developing device 4C to the intermediate transfer drum 5, a DC voltage +300 V was applied to the aluminum drum 5a as the primary transfer bias voltage.
Secondary transfer condition:
In order to primary transfer the toner image formed on the intermediate transfer drum 5 to the recording material P, a DC voltage +2,000 V was applied to the transfer means 8 as the secondary transfer bias voltage.
The image density and beta image image density stability after the initial stage and the number of sheets of paper run, the amount of fog on the paper at the initial stage, and the fine line reproducibility after the number of sheets of paper were evaluated in the following manner. .
Burn Density:
The entire beta image was printed on paper and 10 randomly selected image densities from the formed total beta images were measured with a reflective densitometer (REFLECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.).
The measurement was performed three times, and the image density of all 30 points was measured, and the number average of the number of values obtained therefrom was taken as the density of the initial image.
The evaluation of the image density was similarly measured using the above evaluation method in the image after running on the number of sheets of paper, that is, the image when printing 1,000, 3,000, and 5,000 sheets.
Burn Density Stability of Beta Burns:
The entire beta image was printed on one sheet of paper at a temperature of 20 ° C. and a humidity of 30%, and ten randomly selected image densities were formed from the total beta image formed by the REFLECTOMETER MODEL TC-6DS, Tokyo Denshoku Co. , Ltd.).
The measurement was carried out three times to measure the total image density of 30 points, and the difference between the maximum and minimum values obtained therefrom was calculated, and the results were graded as follows.
a: The difference between the maximum value and the minimum value is 0.2 or less.
b: the difference between the maximum and the minimum is 0.2 to 0.4.
c: the difference between the maximum and the minimum is 0.4 to 0.6.
d: The difference between the maximum value and the minimum value is 0.6 to 0.8.
e: The difference between the maximum value and the minimum value is 0.8 or more.
In the above evaluation, the smaller the difference between the maximum value and the minimum value, the more there is no blurry or uneven image in the initial image, and the better image having better image density stability.
The evaluation of the image density stability of the beta image was similarly measured using the evaluation method in the image after running on the number of sheets of paper, that is, the image at 1,000, 3,000 and 5,000 prints.
Fog amount on paper:
Commercially available copy paper CLC paper A4 (manufactured by CANON SALES INC., Basis weight: 81.4 g / m ² ) was used as the recording material, and an image having a beta white image was printed thereon. The reflection density of the beta white image and the reflection density before printing were measured with a reflection densitometer (RELECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.).
The difference between the worst value (Ds) of the white paper portion reflection density after printing and the average value (Dr) of the reflection density of the paper after printing, that is, Ds-Dr was taken as the amount of fog on the paper.
An image with a fog amount of 2% or less on paper is a good image without fog on the paper, and a 5% or more image is an unclear image with distinct fogs on the paper.
a: The amount of fog on the paper is 2% or less when 5,000 sheets of printing are finished.
b: The amount of fog on paper is 5% or less at the end of 3,000 prints, and the amount of fog on paper is 5% or more at the end of 5,000 prints.
c: The amount of fog on paper is 5% or less at the end of 1,000 prints, and the amount of fog on paper is 5% or more at the end of 3,000 prints.
d: The amount of fog on paper is 5% or less at the end of 500 sheets of printing, and the amount of fog on paper is 5% or more at the end of 1,000 sheets of printing.
e: The amount of fog on the paper is 5% or more when 500 sheets have been printed.
Fine Line Reproducibility:
In order to evaluate the fine line reproducibility, the latent image was formed into stripes as shown in Fig. 9, and the image after fixation was evaluated.
A latent image in which the width of the latent image portion is 4 dots (170 μm) and the non-latent image portion is 10 dots (420 μm) at a resolution of 600 dpi is shown in FIG.
Latent images of streaks were formed continuously on 1,000 sheets of paper and stationary phases on 1,000 sheets of paper were used. Fine line reproducibility by randomly selecting five points from the image part was evaluated by the absolute value between the mean value of the five part image widths and the theoretical latent image width (170 μm).
a: 0 μm to 30 μm.
b: 30 μm to 60 μm.
c: 60 μm to 90 μm.
d: 90 µm or more.
The said evaluation was also performed about the image at the time of printing 3,000 sheets and 5,000 sheets.
Various physical properties of the toner are shown in Table 2 [2a to 2b] and the results are shown in Table 4.
Example 2
0.5 parts by weight of the fine silica powder (B-1) used in the cyan toner 2 having various physical properties as shown in Table 2, and the fine silica powder (B-2) having a BET specific surface area of 81 m ² / g (B-2) ) It was obtained in the same manner as in Example 1 except for replacing by 0.4 part by weight. This toner was used as a nonmagnetic one-component developer (2).
Evaluation was carried out in the same manner as in Example 1 using the nonmagnetic one-component developer (2).
The evaluation results are shown in Table 4.
Example 3
1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) used in the cyan toner 3 having various physical properties as shown in Table 2 were surface-treated with silicone oil and BET 1.0 parts by weight of alumina fine powder (A-2) having a specific surface area of 145 m ² / g and 0.6 parts by weight of fine silica powder (B-3) having a BET specific surface area of 70 m ² / g, respectively, were surface-treated with silicone oil. Except that was obtained in the same manner as in Example 1. This toner was used as a nonmagnetic one-component developer (3).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (3).
The evaluation results are shown in Table 4.
Example 4
0.5 parts by weight of fine silica powder (B-1) used in the cyan toner 2 having various physical properties as shown in Table 2 was surface-treated in the order of hexamethyldisilazane and dimethylsilicone oil and the BET specific surface area 73 Obtained in the same manner as in Example 1, except that 0.6 parts by weight of fine silica powder (B-4) having m ² / g was replaced. This toner was used as a nonmagnetic one-component developer (4).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (4).
The evaluation results are shown in Table 4.
Example 5
1.0 parts by weight of the fine silica powder (A-1) and 0.5 parts by weight of the fine silica powder (B-1) used in the cyan toner 5 having various physical properties as shown in Table 2 were subjected to BET without surface treatment with silicone oil. 0.8 parts by weight of fine silica powder (A-3) having a specific surface area of 141 m ² / g, followed by hexamethyldisilazane and dimethylsilicone oil, and fine silica powder having a BET specific surface area of 60 m ² / g (B-5 ) It was obtained in the same manner as in Example 1 except for replacing with 0.6 parts by weight of each. This toner was used as a nonmagnetic one-component developer (5).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (5).
The evaluation results are shown in Table 4.
Example 6
0.5 parts by weight of the fine silica powder (B-1) used in the cyan toner 6 having various physical properties as shown in Table 2 without fine surface-treated titanium dioxide powder (B- with a specific surface area of 86 m ² / g (B- 6) Obtained in the same manner as in Example 1 except for replacing by 0.6 parts by weight. This toner was used as the nonmagnetic one-component developer (6).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (6).
The evaluation results are shown in Table 4.
Example 7
1.0 part by weight of fine silica powder (A-1) and 0.5 part by weight of fine silica powder (B-1) used in the cyan toner (7) having various physical properties as shown in Table 2, fine silica powder (A-1) 1.3 It was obtained in the same manner as in Example 1, except that parts by weight and 0.6 parts by weight of silica fine powder (B-7) having a surface treatment of silicone oil and having a BET specific surface area of 60 m ² / g were respectively replaced. This toner was used as a nonmagnetic one-component developer (7).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (7).
The evaluation results are shown in Table 4.
Example 8
1.0 part by weight of fine silica powder (A-1) and 0.5 part by weight of fine silica powder (B-1) used in the cyan toner 8 having various physical properties as shown in Table 2, fine silica powder (A-1) Obtained in the same manner as in Example 1, except that 4.0 parts by weight and 0.5 parts by weight of fine silica powder (B-1) were each replaced. This toner was used as the nonmagnetic one-component developer (8).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (8).
The evaluation results are shown in Table 4.
Example 9
1.0 part by weight of fine silica powder (A-1) and 0.5 part by weight of fine silica powder (B-1) were used for the cyan toner 9 having various physical properties as shown in Table 2, and fine silica powder (A-1). Obtained in the same manner as in Example 1, except that 0.7 parts by weight and 3.6 parts by weight of fine silica powder (B-1) were each replaced. This toner was used as the nonmagnetic one-component developer (8).
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer (9).
The evaluation results are shown in Table 4.
Example 10
1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) used in the cyan toner 10 having various physical properties as shown in Table 2, fine silica powder (A-1) Obtained in the same manner as in Example 1, except that 2.4 parts by weight and 1.7 parts by weight of fine silica powder (B-1) were each replaced. This toner was used as the nonmagnetic one-component developer 10.
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer 10. As shown in FIG.
The evaluation results are shown in Table 4.
Example 11
450 parts by weight of a 0.1 M Na ₃ PO ₄ aqueous solution was introduced to 700 parts by weight of ion-exchanged water, and then heated to 50 ° C., followed by stirring at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). . To the resulting mixture, 70 parts by weight of a 1.0 M CaCl ₂ aqueous solution was added in small portions to obtain an aqueous medium containing a calcium phosphate compound.
(Monomer) (parts by weight)
Styrene 170 parts by weight
25 parts by weight of n-butyl acrylate
(coloring agent)
Mr. Child. Pigment Blue 15: 3 15 parts by weight
(Charge control agent)
3 parts by weight of BONTORON E-84 (manufactured by Orient Chemical Industries Ltd.)
(Polar resin)
20 parts by weight of saturated polyester resin (acid value: 10; peak molecular weight: 150,000)
(Release agent)
Behenyl stearate 30 parts by weight
(Crosslinking binder)
1.5 parts by weight of divinylbenzene
The material was heated to 50 ° C. and uniformly dissolved or dispersed at 9,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). A polymerizable monomer composition was prepared by dissolving 5 parts by weight of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in the obtained mixture.
After the polymerizable monomer composition was introduced into the medium, the polymerizable monomer composition was granulated by stirring the TK homomixer at 8,500 rpm at 50 ° C. under a nitrogen atmosphere.
The granulated product obtained was then stirred with a paddle blade for mixing while raising the temperature to 60 ° C. for 2 hours. After 4 hours, the temperature was raised to 70 ° C. at a rate of temperature rise of 40 ° C. per hour where the reaction was carried out for 5 hours. After the polymerization was completed, the remaining monomer was evaporated under reduced pressure, the reaction system was cooled, and then, hydrochloric acid was added thereto to dissolve calcium phosphate, followed by filtration and washing with water, followed by drying to obtain cyan toner particles having a weight average particle size of 6.5 μm (2 -a) was obtained.
The average circularity distribution and particle size distribution of the cyan toner particles (2-a) thus obtained were measured with a fluorine particle imager (manufactured by Toa Iyou Denshi K.K.). As a result, the particles have an average circularity of 0.973 and have a maximum X at a diameter of 1.0 μm corresponding to a circular shape, a maximum Y at a diameter of 6.9 μm corresponding to a circular shape, and a content of particles having a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape. 4 number%.
Cyan toner particles (2-a) were wind-divided to remove relatively fine particles to obtain cyan toner particles (2).
To 100 parts by weight of the cyan toner particles (2) thus obtained, 1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) were added in the same manner as in Example 1, followed by a Henschel mixer (Mitsui Mining). &Amp; Smelting Co., LTD.) To obtain a cyan toner (11) having various physical properties as shown in Table 2. This toner was used as the nonmagnetic one-component developer 11.
The average circularity distribution and the particle size distribution of the cyan toner 11 were measured with a flow particle imager (manufactured by Toa Iyou Denshi K.K.). As a result, the toner has an average circularity of 0.970, has a maximum X at a diameter of 1.0 μm corresponding to the circular shape, a maximum Y at a diameter of 6.5 μm corresponding to the circular shape, and a content of particles having a diameter of 0.60 μm to 2.00 μm corresponding to the circular shape. 18 number%.
Evaluation was performed by the same method as Example 1 using this nonmagnetic one-component developer 11.
The evaluation results are shown in Table 4.
Comparative Example 1
180 parts by weight of nitrogen-substituted water and 20 parts by weight of a 0.2% aqueous solution of polyvinyl alcohol were introduced into a four-neck flask, followed by 75 parts by weight of styrene, 25 parts by weight of n-butyl acrylate, 3.0 parts by weight of benzoyl peroxide and divinylbenzene. 0.01 part by weight was added followed by stirring to form a suspension. Subsequently, the inside of the flask was replaced with nitrogen, and then the temperature was raised to 80 ° C. to carry out a polymerization reaction while maintaining the system at that temperature for 10 hours.
The polymer obtained was washed with water and dried in a reduced pressure environment while maintaining the temperature at 65 ° C. to obtain a resin. Subsequently, 88 parts by weight of the obtained resin, metal-containing azo dye C.I. 12 parts by weight of Pigment Blue 15: 3 and 10 parts by weight of paraffin wax were mixed in a fixed-dry dry mixer whose vent holes were connected to the suction pump, and the resulting mixture was melt kneaded in a twin screw extruder while being sucked through the vent holes. .
The melt kneaded product obtained was pulverized with a hammer mill to obtain a pulverized product of the 1 mm mesh passable toner composition. The milled product was further ground into a product having a volume average particle diameter of 20 to 30 μm using a mechanical mill, followed by a jet mill using interparticle collisions in swirl flow, and then the toner composition in the surface modifier was modified by thermal and mechanical shear forces. Subsequently, the resultant was classified with a multi-division classification machine to obtain cyan toner particles 3 having a weight average particle diameter of 7.0 μm.
To 100 parts by weight of the cyan toner particles (3) thus obtained, 1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) were added in the same manner as in Example 1, followed by a Henschel mixer (Mitsui Mining). & Smelting Co., LTD.) To obtain a cyan toner 12 having various physical properties as shown in Table 3 [3 (A)-3 (B)]. This toner was used as the nonmagnetic one-component developer 12.
Evaluation was performed by the same method as Example 1 using this nonmagnetic one-component developer (12).
The evaluation results are shown in Table 4.
Comparative Example 2
1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) used in the cyan toner 13 having various physical properties as shown in Table 3, fine silica powder (B-1) Obtained in the same manner as in Example 1 except for replacing only 0.8 parts by weight. This toner was used as a nonmagnetic one-component developer (13).
Evaluation was performed by the same method as Example 1 using this nonmagnetic one-component developer (13).
The evaluation results are shown in Table 4.
Comparative Example 3
1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) used in the cyan toner 14 having various physical properties as shown in Table 3, fine silica powder (A-1) Obtained in the same manner as in Example 1 except for replacing only 1.4 parts by weight. This toner was used as the nonmagnetic one-component developer 14.
Evaluation was performed by the same method as Example 1 using this nonmagnetic one-component developer 14.
The evaluation results are shown in Table 4.
Comparative Example 4
0.5 parts by weight of fine silica powder (B-1) used in the cyan toner 15 having various physical properties as shown in Table 3 was surface-treated in the order of hexamethyldisilazane and dimethylsilicone oil and the BET specific surface area 38 Obtained in the same manner as in Example 1, except that 0.5 parts by weight of fine silica powder (B-10) having m ² / g was replaced. This toner was used as the nonmagnetic one-component developer 15.
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer 15. As shown in FIG.
The evaluation results are shown in Table 4.
Comparative Example 5
The cyan toner particles 1 having various physical properties as shown in Table 3 were used without the fine silica powder (A-1) used therein and without the fine silica powder (B-1). Obtained in the same manner as in Example 1, except that it was used as such. This toner was used as the nonmagnetic one-component developer 16.
Evaluation was carried out in the same manner as in Example 1 using this nonmagnetic one-component developer 16. As a result, the very poor result of in-machine scattering of the toner apparently obtained was also obtained in all evaluation items of the image density after the initial stage and 1,000 sheets of operation, the image density stability of the beta image, the amount of fog on the paper, and fine line reproducibility. . Therefore, evaluation was stopped when 1,000 sheets were printed.
The evaluation results are shown in Table 4.
Comparative Example 6
Cyan toner particles 4 containing cyan toner particles 1-a without using a suspension containing cyan toner particles 1-b as conditions for producing cyan toner particles 1 therein. The suspension was obtained in the same manner as in Example 1, except that only the suspension was filtered, washed with water and dried.
To 100 parts by weight of the cyan toner particles (4) thus obtained, 1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) were added in the same manner as in Example 1, followed by a Mitsui Mining machine. &Amp; Smelting Co., LTD.) To obtain a cyan toner 17 having various physical properties as shown in Table 3. This toner was used as the nonmagnetic one-component developer 17.
Evaluation was carried out in the same manner as in Example 1 using this nonmagnetic one-component developer 17.
The evaluation results are shown in Table 4.
Comparative Example 7
(Monomer) (parts by weight)
7 parts by weight of styrene monomer
0.2 parts by weight of divinylbenzene
(Initiator)
4 parts by weight of potassium persulfate
The material was added to 500 parts by weight of ion exchanged water and the resulting mixture was stirred with a mixing paddle blade while the temperature was raised to 70 ° C. to perform a soap free polymerization for 72 hours. Thus, a suspension containing the particulate polymer (5-b) was obtained.
The average circularity distribution and particle size distribution of the thus obtained particulate polymer (5-b) were measured with a flow particle imager (manufactured by Toa Iyou Denshi K.K.). As a result, the particles had an average circularity of 0.972 and had a maximum only at a diameter of 2.6 μm corresponding to the circle, and the content of particles having a diameter of 0.60 μm to 2.00 μm corresponding to the circle was 72 number%.
Except that the cyan toner particles 5 were replaced with the particulate polymer (1-b) used therein with the particulate polymer (5-b) and added to the suspension containing the cyan toner particles (1-a). Obtained in the same manner as in Example 1.
To 100 parts by weight of the cyan toner particles (5) thus obtained, 1.0 parts by weight of fine silica powder (A-1) and 0.5 parts by weight of fine silica powder (B-1) were added in the same manner as in Example 1, followed by a Henschel mixer (Mitsui Mining). & Smelting Co., LTD.) To obtain cyan toner 18 having various physical properties as shown in Table 3. This toner was used as the nonmagnetic one-component developer 18.
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer 18. As shown in FIG.
The evaluation results are shown in Table 4.
Comparative Example 8
Classification of cyan toner particles 19 having various physical properties as shown in Table 3 modified so as to collect relatively fine particles to control the particle size distribution of 0.5 parts by weight of fine silica powder (B-1) used therein. Obtained in the same manner as in Example 1, except that it was obtained under conditions and replaced by a fine silica powder (B-8) having a BET specific surface area of 110 m ² / g. This toner was used as a nonmagnetic one-component developer 19.
It evaluated by the method similar to Example 1 using this nonmagnetic one-component developer 19.
The evaluation results are shown in Table 4.
Comparative Example 9
The cyan toner particles 20 having various physical properties as shown in Table 3 were sorted so that 0.5 parts by weight of fine silica powder (B-1) used therein could be collected to collect only coarse particles to control the particle size distribution. Obtained in the same manner as in Example 1, except that the silica fine powder (B-9) having a BET specific surface area of 22 m ² / g and obtained under repeated sorting conditions was repeated. This toner was used as the nonmagnetic one-component developer 20.
Evaluation was carried out in the same manner as in Example 1 using the nonmagnetic one-component developer 20.
The evaluation results are shown in Table 4.


Example 12
Magenta toner particles (6), yellow toner particles (7) and black toner particles (8) are used therein. Mr. Pigment Blue 15: 3. Pigment Red 122 11 parts by weight, C.I. It was produced in the same manner as in Example 1, except that 14 parts by weight of Pigment Yellow 17 and 10 parts by weight of carbon black were each replaced.
1.0 part by weight of fine silica powder (A-1) and 0.5 part by weight of fine silica powder (B-1) were respectively added to 100 parts by weight of the obtained magenta toner particles 6, yellow toner particles 7 and black toner particles 8. Magenta toner 21 and yellow toner having various physical properties as shown in Table 2 by uniformly stirring using a Henschel mixer (manufactured by Mitsui Mining & Smelting Co., LTD.) After the addition in the same manner as in Example 1. (22) and black toner 23 were obtained. This toner was used as nonmagnetic one-component developers (21), (22), and (23).
The nonmagnetic one-component development used in Example 1 in the cyan developer 4C, magenta developer 4M, yellow developer 4Y and black developer 4BK using the same LBP-2030 modifier used in Example 1. 160 g of the agent (21), 160 g of the nonmagnetic one-component developer 22, and 160 g of the nonmagnetic one-component developer 23 were each filled.
Image formation was performed under the conditions shown below.
World War I conditions:
From the power supply (not shown in FIG. 1), the charging roller 2 is discharged by discharging the charge bias voltage formed by applying a DC voltage of -600 V and an AC voltage of 1,150 Hz sine wave at an amplitude of 2 kvpp to discharge charge. In addition, the photosensitive drum 1 of the insulating material was constantly charged.
Latent Image Formation Conditions:
The electrostatic latent image was formed by irradiating and exposing with the laser light L on the constant charged photosensitive drum 1. The intensity of the laser light was set to provide a surface potential of -200 V on the exposed portion.
The electrostatic latent image is advanced in the order of yellow, magenta, cyan, and black, each color toner image is sequentially firstly transferred onto the intermediate transfer drum, and the four-color multi-toner image firstly transferred onto the intermediate transfer drum is recorded. The secondary transfer was carried out on a batch and four toner multiple toner images were heat-fixed onto the recording material to form a full color image.
Developing condition:
The developing sleeve of each of the cyan developer 4C, magenta developer 4M and black developer 4BK shown in FIG. In addition, the distance (distance: 300 μm) between the developing sleeve and the photosensitive drum 1, which is made so that the toner (toner layer thickness: 170 μm) on each developing sleeve is made to fly to the photosensitive drum 1 in order to perform the developing. ), Alternating electric fields were formed.
Primary transfer condition:
In order to primary transfer the toner image formed by the development of the developer 4Y to the intermediate transfer drum 5, a DC voltage +100 V was applied to the aluminum drum 5a as the primary transfer bias voltage. In order to primary transfer the toner image formed by the development of the developing device 4M to the intermediate transfer drum 5, a DC voltage +200 V was applied to the aluminum drum 5a as the primary transfer bias voltage. In order to primary transfer the toner image formed by the development of the developing device 4C to the intermediate transfer drum 5, a DC voltage +300 V was applied to the aluminum drum 5a as the primary transfer bias voltage. In order to primary transfer the developed toner image of the developing device 4BK to the intermediate transfer drum 5, DC voltage +400 V was applied to the aluminum drum 5a as the primary transfer bias voltage.
Secondary electronic conditions:
The intermediate transfer drum 5 applies a DC voltage of +2,000 V to the transfer means 8 as a secondary transfer bias voltage in order to primary transfer the four-color full color toner images transferred to the recording material P firstly. It was.
As a result, even in operation of 5,000 sheets, good results were obtained for the image density of the fixed image, the fog prevention on the paper, and the fine line reproducibility, and a full color image with excellent color reproducibility could be obtained stably.
Example 13
Using the nonmagnetic one-component developer shown in FIG. 6, the developing system 170 of the nonmagnetic one-component development method was developed for each of the developing portions 17a, 17b, 17c, and 17d of the image forming apparatus shown in FIG. Nonmagnetic one-component developer (1) produced in Example 1, and nonmagnetic one-component developer (21) and (22) produced in Example 12, respectively, using a full color image forming apparatus used in ) And (23) were used to form a full color image.
The developing device of the developing part 17a is a nonmagnetic one-component developer 21, the developing device of the developing part 17b is a nonmagnetic one-component developer 1, and the developing device of the developing part 17c is a nonmagnetic one-component system. The developer 22 was filled with the developer of the developing portion 17d with the nonmagnetic one-component developer 23. The electrostatic latent image and the recording material as the residue were subjected to the order of colors of black, cyan, magenta and yellow under the following conditions to form a multi-color toner image of four colors on the recording material, followed by heating and fixing on the recording material to produce a full color image. Formed.
Electrostatic latent image burns formed on the photoreceptor: -150 V
Develop bias voltage:
DC component: -300 V
AC component: 2,000 Hz, amplitude 2 kVpp
Distance between photosensitive drum and developing sleeve: 300 μm
Developer layer thickness on the developing sleeve: 170 μm
Transfer bias voltage:
Transfer section 24a: +100 V
Transfer section 24b: +170 V
Transfer section 24c: +240 V
Transfer section 24d: +310 V
As a result, even in 20,000 sheets of operation over a long time, a result of good image density of the fixed image, fog prevention on paper, and fine line reproducibility was obtained, and a full color image with excellent color reproducibility was stably obtained.
Example 14
Using the nonmagnetic one-component developer shown in FIG. 6, the developing system 170 of the nonmagnetic one-component development method is developed for each of the image forming apparatuses 244-1, 244-2, and 244-2. 3) and the nonmagnetic one-component developer (1) produced in Example 1, and the nonmagnetic developer (21) produced in Example 12, using the full color forming apparatus used in (244-4). , (22) and (23) were used to form a full color image.
The developing unit 244-1 is a nonmagnetic one-component developer 23, the developing unit 244-2 is a nonmagnetic one-component developer 21, and the developing unit 244-3 is a nonmagnetic one-component developer ( In 1), the developer 244-4 was filled with a nonmagnetic one-component developer 22. The development was carried out in the order of the colors black, magenta, cyan and yellow, and each color toner image was successively transferred onto the intermediate transfer drum, and the four color toner images transferred on the intermediate transfer drum were collectively transferred onto the recording material. After heat fixing, a full color image was formed on the recording material.
Middle transfer drum:
Conductor: Aluminum
Elastic layer: styrene-butadiene rubber, 5 mm thick
World War I conditions:
DC component: -600 V
AC component: 2,000 Hz, amplitude 1.8 kVpp
Electrostatic latent image formed on the photosensitive member: -250 V
Develop bias voltage:
DC component: -400 V
AC component: 2,000 Hz, amplitude 1.8 kVpp
Distance between photosensitive drum and developing sleeve: 300 μm
Developer layer thickness on the developing sleeve: 170 μm
Primary transcription condition
DC voltage: +100 V
DC voltage: +150 V
DC voltage: +200 V
DC voltage: +250 V
Secondary transfer condition:
DC voltage: +2,000 V
As a result, even at 15,000 sheets of operation over a long period, the image density of the fixed image, the fog prevention on paper, and fine line reproducibility were obtained, and a full color image with excellent color reproducibility could be stably obtained.
According to the present invention, even after long-term use, the developer is not deteriorated, the image density stability and fine detail reproducibility are excellent, and an image which does not generate fogging can be obtained.

权利要求:
Claims (99)
[1" claim-type="Currently amended] In the particle size distribution according to the circular distribution and the diameter corresponding to the circular shape of the particles measured by the flow type particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and the diameter corresponding to the circular shape is 3.0 μm to Containing 8.0 to 30.0% by volume of particles having a diameter 0.60 μm to less than 2.0 μm, corresponding to a circle, having a maximum value Y in the area of 0.60 μm to 2.00 μm, corresponding to a maximum X in the region of 9.0 μm and a circle;
The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And the number of the average long diameter of which contains at least a non-spherical inorganic fine powder (B) of 30 m ㎛ to 600 m ㎛,
A toner comprising toner particles containing a binder resin and a colorant, and an external additive fine powder.
[2" claim-type="Currently amended] The toner according to claim 1, wherein in the circular distribution of the particles measured by the flow particulate analysis device, the average circularity of the toner is 0.960 to 0.995.
[3" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) has, on toner particles, primary particles having a number average long diameter of 1 m to 25 m m.
[4" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) has a long diameter to short diameter (long diameter / short diameter) of 1.0 to 1.5 on the toner particles.
[5" claim-type="Currently amended] The toner according to claim 1, wherein the non-spherical inorganic fine powder (B) has a number average long diameter of 30 m to 300 m m on toner particles.
[6" claim-type="Currently amended] The toner according to claim 1, wherein on the toner particles, the non-spherical inorganic fine powder (B) is formed by combining a plurality of primary particles having an average value of a minimum width of a ferret diameter of 30 m to 200 m.
[7" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) has a specific surface area of 50 m ² / g to 150 m ² / g as measured by nitrogen adsorption according to the BET method.
[8" claim-type="Currently amended] The toner according to claim 1, wherein the non-spherical inorganic fine powder (B) has a specific surface area of 20 m ² / g to 90 m ² / g as measured by nitrogen adsorption according to the BET method.
[9" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) has a shape factor SF-1 of 100 to 125 on toner particles.
[10" claim-type="Currently amended] The toner according to claim 1, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of greater than 190 on the toner particles.
[11" claim-type="Currently amended] The toner according to claim 1, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of more than 200 on toner particles.
[12" claim-type="Currently amended] The inorganic fine powder (A) according to claim 1, wherein the inorganic fine powder (A) is the primary particles alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was a total of 20 or more in average per unit area of 0.5 μm × 0.5 μm, A toner having an average of 1 to 20 non-spherical inorganic fine powders (B) present on the surface of the toner particles, per unit area of 1.0 μm × 1.0 μm.
[13" claim-type="Currently amended] The inorganic fine powder (A) according to claim 1, wherein the inorganic fine powder (A) is the primary particles alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was 25 or more in total per unit area of 0.5 μm × 0.5 μm, A toner having an average of 2 to 18 non-spherical inorganic fine powders (B) present on the surface of the toner particles, per unit area of 1.0 μm × 1.0 μm.
[14" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) is contained in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of the toner.
[15" claim-type="Currently amended] The toner according to claim 1, wherein the toner comprises the non-spherical inorganic fine powder (B) in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of the toner.
[16" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have particles selected from the group consisting of silica, alumina, titania and complex oxides thereof.
[17" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have silica powder.
[18" claim-type="Currently amended] The toner according to claim 1, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have a silicone oil.
[19" claim-type="Currently amended] The toner according to claim 1, wherein the toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[20" claim-type="Currently amended] The toner according to claim 1, wherein the toner particles are produced by a suspension polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[21" claim-type="Currently amended] The toner according to claim 1, which is a nonmagnetic toner.
[22" claim-type="Currently amended] The toner according to claim 1, which is used as a one-component developer.
[23" claim-type="Currently amended] The toner according to claim 1, which is a nonmagnetic toner and used as a one-component developer.
[24" claim-type="Currently amended] As a two-component developer comprising (I) a toner particle containing a binder resin and a colorant, a toner containing an external additive fine powder, and (II) a carrier,
In the particle size distribution according to the circular distribution of the particles and the diameter corresponding to the circular shape measured by the flow particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and an area of 3.0 µm to 9.0 µm in diameter corresponding to the circular shape. Contains from 8.0 to 30.0% by weight of particles having a maximum diameter of 0.60 μm to less than 2.0 μm corresponding to a circle having a maximum value Y in a region of maximum diameter X and a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape,
The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And at least a non-spherical inorganic fine powder (B) having an average long diameter of 30 m to 600 m µm.
[25" claim-type="Currently amended] 25. The developer according to claim 24, wherein in the circular distribution of the particles measured by the flow particulate analysis device, the average circularity of the toner is 0.960 to 0.995.
[26" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) has a number average long diameter of 1 m to 25 m m as primary particles on toner particles.
[27" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) has a long diameter to short diameter (long diameter / short diameter) of 1.0 to 1.5 on toner particles.
[28" claim-type="Currently amended] The developer according to claim 24, wherein the non-spherical inorganic fine powder (B) has a number average long diameter of 30 m to 300 m m on the toner particles.
[29" claim-type="Currently amended] The developer according to claim 24, wherein the non-spherical inorganic fine powder (B) is formed on the toner particles by combining a plurality of primary particles having an average value of the minimum width of the ferret diameter of 30 m to 200 m.
[30" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) has a specific surface area of 50 m ² / g to 150 m ² / g as measured by nitrogen adsorption according to the BET method.
[31" claim-type="Currently amended] The developer according to claim 24, wherein the non-spherical inorganic fine powder (B) has a specific surface area of 20 m ² / g to 90 m ² / g as measured by nitrogen adsorption according to the BET method.
[32" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) has a shape coefficient SF-1 of 100 to 125 on toner particles.
[33" claim-type="Currently amended] The developer according to claim 24, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of greater than 190 on toner particles.
[34" claim-type="Currently amended] The developer according to claim 24, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of more than 200 on toner particles.
[35" claim-type="Currently amended] The inorganic fine powder (A) according to claim 24, wherein the inorganic fine powder (A) is the primary particles alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was a total of 20 or more in average per unit area of 0.5 μm × 0.5 μm, A developer having an average of 1 to 20 non-spherical inorganic fine powders (B) present on the surface of said toner particles per unit area of 1.0 μm × 1.0 μm.
[36" claim-type="Currently amended] The inorganic fine powder (A) according to claim 24, wherein the inorganic fine powder (A) is the primary particles alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was 25 or more in total per unit area of 0.5 μm × 0.5 μm, A developer having an average of 2 to 18 non-spherical inorganic fine powders (B) present on the surface of the toner particles per unit area of 1.0 μm × 1.0 μm.
[37" claim-type="Currently amended] A developer according to claim 24, wherein the inorganic fine powder (A) is contained in an amount of 0.1 parts by weight to 3.0 parts by weight based on 100 parts by weight of toner.
[38" claim-type="Currently amended] A developer according to claim 24, wherein the developer contains the aspheric inorganic fine powder (B) in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of toner.
[39" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have particles selected from the group consisting of silica, alumina, titania and complex oxides thereof.
[40" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have a silica powder.
[41" claim-type="Currently amended] The developer according to claim 24, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have a silicone oil.
[42" claim-type="Currently amended] The developer according to claim 24, wherein the toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[43" claim-type="Currently amended] The developer according to claim 24, wherein the toner particles are produced by a suspension polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[44" claim-type="Currently amended] A developer according to claim 24, wherein said toner is a nonmagnetic toner.
[45" claim-type="Currently amended] (I) charging the latent electrostatic image bearing member for supporting the latent electrostatic image,
(II) forming an electrostatic latent image on the charged latent image bearing member,
(III) developing the electrostatic latent image on the latent image bearing member with toner to form a toner image, and
(IV) transferring the toner image formed on the latent image bearing member to the transfer member;
As an image forming method,
Wherein the toner comprises at least toner particles containing at least a binder resin and a colorant, and at least an external additive fine powder,
In the particle size distribution according to the circular distribution of the particles and the diameter corresponding to the circular shape measured by the flow particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and an area of 3.0 µm to 9.0 µm in diameter corresponding to the circular shape. Contains from 8.0 to 30.0% by weight of particles having a maximum diameter of 0.60 μm to less than 2.0 μm corresponding to a circle having a maximum value Y in a region of maximum diameter X and a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape,
The external additive fine powder is formed on the toner particles by combining the inorganic fine powder (A) having a number average long diameter of 1 m to 30 m μm and a plurality of particles on the toner particles, and having a shape coefficient SF-1 of greater than 150. And at least an aspheric inorganic fine powder (B) having a number average long diameter of 30 m to 600 m m.
[46" claim-type="Currently amended] 46. The method of claim 45, wherein in the circular distribution of the particles measured by the flow particulate analysis device, the average circularity of the toner is 0.960 to 0.995.
[47" claim-type="Currently amended] 46. The method of claim 45, wherein the inorganic fine powder (A) has, on toner particles, primary particles having a number average length of 1 m to 25 m m.
[48" claim-type="Currently amended] The method according to claim 45, wherein the inorganic fine powder (A) has a long diameter to short diameter (long diameter / short diameter) of 1.0 to 1.5 on toner particles.
[49" claim-type="Currently amended] 46. The method of claim 45, wherein the non-spherical inorganic fine powder (B) has a number average long diameter of 30 m to 300 m m on toner particles.
[50" claim-type="Currently amended] 46. The method according to claim 45, wherein, on the toner particles, the non-spherical inorganic fine powder (B) is formed by combining a plurality of primary particles having an average value of the minimum width of the ferret diameter of 30 m to 200 m.
[51" claim-type="Currently amended] 46. The method of claim 45, wherein the inorganic fine powder (A) has a specific surface area of 50 m ² / g to 150 m ² / g as measured by nitrogen adsorption according to the BET method.
[52" claim-type="Currently amended] 46. The method of claim 45, wherein the non-spherical inorganic fine powder (B) has a specific surface area of 20 m ² / g to 90 m ² / g as measured by nitrogen adsorption according to the BET method.
[53" claim-type="Currently amended] 46. The method of claim 45, wherein the inorganic fine powder (A) has a shape factor SF-1 of 100 to 125 on toner particles.
[54" claim-type="Currently amended] 46. The method of claim 45, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of greater than 190 on toner particles.
[55" claim-type="Currently amended] 46. The method of claim 45, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of greater than 200 on toner particles.
[56" claim-type="Currently amended] 46. The inorganic fine powder (A) according to claim 45, wherein the inorganic fine powder (A) is the primary particles alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was a total of 20 or more in average per unit area of 0.5 μm × 0.5 μm, The number of non-spherical inorganic fine powders (B) present on the surface of the toner particles is an average of 1 to 20 per unit area of 1.0 μm × 1.0 μm.
[57" claim-type="Currently amended] 46. The inorganic fine powder (A) according to claim 45, wherein the inorganic fine powder (A) is the primary particles alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was 25 or more in total per unit area of 0.5 μm × 0.5 μm, The number of aspheric inorganic fine powders (B) present on the surface of the toner particles is an average of 2 to 18 per unit area of 1.0 μm × 1.0 μm.
[58" claim-type="Currently amended] 46. The method of claim 45, wherein the inorganic fine powder (A) is contained in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of toner.
[59" claim-type="Currently amended] 46. The method of claim 45, wherein the non-spherical inorganic fine powder (B) is contained in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of toner.
[60" claim-type="Currently amended] 46. The method of claim 45, wherein said inorganic fine powder (A) and said non-spherical inorganic fine powder (B) each have particles selected from the group consisting of silica, alumina, titania and complex oxides thereof.
[61" claim-type="Currently amended] 46. The method of claim 45, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have silica powder.
[62" claim-type="Currently amended] 46. The method of claim 45, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have a silicone oil.
[63" claim-type="Currently amended] 46. The method of claim 45, wherein the toner particles are produced by a polymerization method wherein a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[64" claim-type="Currently amended] 46. The method of claim 45, wherein the toner particles are produced by a suspension polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[65" claim-type="Currently amended] 46. The method of claim 45, wherein the toner is a nonmagnetic toner.
[66" claim-type="Currently amended] 46. The method of claim 45, wherein the toner is used as a one-component developer.
[67" claim-type="Currently amended] 46. The method of claim 45, wherein the toner is used as a one-component developer as a nonmagnetic toner.
[68" claim-type="Currently amended] 46. The method of claim 45, wherein the nonmagnetic toner is mixed with a carrier and used as a two-component developer.
[69" claim-type="Currently amended] 46. The image forming method according to claim 45, wherein the transfer member is a recording body, wherein a toner image formed on a latent image bearer is transferred directly to the recording body, and the toner image transferred to the recording body is fixed to the recording body.
[70" claim-type="Currently amended] 46. The transfer member according to claim 45, wherein the transfer member includes an intermediate transfer member, wherein the toner image formed on the latent image bearer is first transferred to the intermediate transfer member, and the toner image primary transfer to the intermediate transfer member is secondly transferred to the recording medium. And the toner image secondarily transferred to the recording medium is fixed to the recording medium.
[71" claim-type="Currently amended] The method of claim 45,
(i) charging the latent electrostatic image bearing member for supporting the latent electrostatic image,
(ii) forming an electrostatic latent image on the charged latent image bearing member,
(iii) developing a latent electrostatic image on the latent image bearing member using a color toner selected from the group consisting of cyan toner, magenta toner and yellow toner to form a color toner image, and
(iv) transferring the color toner image formed on the latent image bearing member to the transfer member;
Wherein the steps (i) to (iv) are performed sequentially two or more times using color toners having different colors, respectively, to form a multicolor toner image on the transfer body,
here,
The cyan toner comprises i) cyan toner particles as the toner particles containing at least a binder resin and a cyan colorant, and ii) the external additive fine powder,
The magenta toner comprises i) magenta toner as the toner particles containing at least a binder resin and a magenta colorant, and ii) an external additive fine powder,
The yellow toner comprises i) a yellow toner as the toner particles containing at least a binder resin and a yellow colorant, and ii) an external additive fine powder)
[72" claim-type="Currently amended] 76. The method of claim 71, wherein the steps (i) to (iv) are performed four times using color toners having respective colors using four color toners including black toner in addition to the cyan toner, the magenta toner, and the yellow toner. A full-color image forming method of sequentially performing a four-color toner image on a transfer body,
Wherein the black toner comprises i) black toner particles as the toner particles containing at least a binder resin and a black colorant, and ii) an external additive fine powder.
[73" claim-type="Currently amended] 46. The image forming method according to claim 45, further comprising a cleaning step of recovering toner remaining on the surface of the latent image carrier after the transferring step.
[74" claim-type="Currently amended] 74. The image forming method according to claim 73, wherein said cleaning step uses a pre-development cleaning method of cleaning the surface of the latent image bearer using a cleaning member that contacts the latent image bearer.
[75" claim-type="Currently amended] 75. The image forming method according to claim 74, wherein in the predevelopment cleaning method, the cleaning step is performed after the transfer step and before the charging step.
[76" claim-type="Currently amended] 74. The transfer unit according to claim 73, wherein the transfer unit in the transfer step, the charging unit in the charging step, and the developing unit in the developing step are arranged in the order of the transfer unit, the charging unit, and the developing unit with respect to the surface moving direction of the latent image bearing member. No cleaning member exists between the transfer portion and the charging portion, and between the charging portion and the developing portion, to remove toner remaining on the surface of the latent image bearing member in contact with the surface of the latent image bearing member,
In the cleaning step, in the developing step, the developing apparatus holding the toner develops an electrostatic latent image carried on the latent image bearing member, and at the same time, the developing apparatus recovers the toner remaining on the surface of the latent image bearing member. An image forming method using a developing simultaneous cleaning method for cleaning the surface of a carrier.
[77" claim-type="Currently amended] A toner as a one-component developer containing at least toner particles containing a binder resin and a colorant, and an external additive fine powder,
A developing container for containing the one-component developer, and
A developer carrying member for transporting a developer to a developing region by carrying a one-component developer to be contained in the developing container.
An apparatus unit detachably mounted to an image forming apparatus main body, comprising:
Wherein the toner comprises toner particles containing at least a binder resin and a colorant, and an external additive fine powder,
In the particle size distribution according to the circular distribution of the particles and the diameter corresponding to the circular shape measured by the flow particulate analysis device, the toner has an average circularity of 0.950 to 0.995, and an area of 3.0 µm to 9.0 µm in diameter corresponding to the circular shape. Contains from 8.0 to 30.0% by weight of particles having a maximum diameter of 0.60 μm to less than 2.0 μm corresponding to a circle having a maximum value Y in a region of maximum diameter X and a diameter of 0.60 μm to 2.00 μm corresponding to a circular shape,
The external additive fine powder is formed by combining the inorganic fine powder (A) having a number average long diameter of 1 m µm to 30 m µm and a plurality of particles on the toner particles as primary particles, and having a shape coefficient SF-1 of greater than 150. And at least an aspheric inorganic fine powder (B) having a number average long diameter of 30 m µm to 600 m µm.
[78" claim-type="Currently amended] 78. The apparatus unit of claim 77, wherein in a circular distribution of particles measured with a flow particulate analysis device, the average circularity of the toner is 0.960 to 0.995.
[79" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein the inorganic fine powder (A) has, on toner particles, primary particles having a number average long diameter of 1 m µm to 25 m µm.
[80" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein said inorganic fine powder (A) has a long diameter / short diameter (long diameter / short diameter) of 1.0 to 1.5 on toner particles.
[81" claim-type="Currently amended] 78. An apparatus unit according to claim 77, wherein said non-spherical inorganic fine powder (B) has a number average long diameter of 30 m to 300 m m on toner particles.
[82" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein, on the toner particles, the non-spherical inorganic fine powder (B) is formed by combining a plurality of primary particles having an average value of the minimum width of the ferret diameter of 30 m to 200 m.
[83" claim-type="Currently amended] 78. An apparatus unit according to claim 77, wherein said inorganic fine powder (A) has a specific surface area of 50 m ² / g to 150 m ² / g as measured by nitrogen adsorption according to the BET method.
[84" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein said non-spherical inorganic fine powder (B) has a specific surface area of 20 m ² / g to 90 m ² / g as measured by nitrogen adsorption according to the BET method.
[85" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein said inorganic fine powder (A) has a shape coefficient SF-1 of 100 to 125 on toner particles.
[86" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of greater than 190 on toner particles.
[87" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein the non-spherical inorganic fine powder (B) has a shape factor SF-1 of more than 200 on toner particles.
[88" claim-type="Currently amended] 78. The method of claim 77, wherein on the toner particles, the inorganic fine powder (A) is the primary particles are present alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was a total of 20 or more in average per unit area of 0.5 μm × 0.5 μm, And the number of non-spherical inorganic fine powders (B) present on the surface of the toner particles is an average of 1 to 20 per unit area of 1.0 mu m x 1.0 mu m.
[89" claim-type="Currently amended] 78. The method of claim 77, wherein on the toner particles, the inorganic fine powder (A) is the primary particles are present alone or in an aggregated state,
As observed in the electron micrograph magnification of the toner, the number of primary particles of the inorganic fine powder (A) present on the surface of the toner particles was 25 or more in total per unit area of 0.5 μm × 0.5 μm, And the number of aspheric inorganic fine powders (B) present on the surface of said toner particles is an average of 2 to 18 per unit area of 1.0 mu m x 1.0 mu m.
[90" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein said inorganic fine powder (A) is contained in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of toner.
[91" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein said non-spherical inorganic fine powder (B) is contained in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of toner.
[92" claim-type="Currently amended] 78. An apparatus unit according to claim 77, wherein said inorganic fine powder (A) and said non-spherical inorganic fine powder (B) each have particles selected from the group consisting of silica, alumina, titania and complex oxides thereof.
[93" claim-type="Currently amended] 78. The apparatus unit according to claim 77, wherein the inorganic fine powder (A) and the non-spherical inorganic fine powder (B) each have silica powder.
[94" claim-type="Currently amended] 78. An apparatus unit according to claim 77, wherein said inorganic fine powder (A) and said non-spherical inorganic fine powder (B) each have a silicone oil.
[95" claim-type="Currently amended] 78. The apparatus unit of claim 77, wherein the toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[96" claim-type="Currently amended] 78. The apparatus unit of claim 77, wherein the toner particles are produced by a suspension polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of a polymerization initiator.
[97" claim-type="Currently amended] 78. The apparatus unit of claim 77, wherein said toner is a nonmagnetic toner.
[98" claim-type="Currently amended] 78. The latent image bearer according to claim 77, wherein in addition to said one-component developer, said developing container, and said developer carrier, a latent image bearer for carrying an electrostatic latent image, a charging member for electrostatically charging said latent image bearer, and a latent image bearer The apparatus unit further comprising any member selected from the group consisting of cleaning members for cleaning the surface of the substrate.
[99" claim-type="Currently amended] 78. The apparatus unit of claim 77, further comprising an electrophotographic photosensitive member as a latent image bearing member for carrying an electrostatic latent image, in addition to the one-component developer, the developing container, and the developer carrying member.

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同族专利:

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公开号 | 公开日

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CN100359409C|2008-01-02|

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EP0933685A1|1999-08-04|

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EP0933685B1|2005-10-26|

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DE69927860D1|2005-12-01|

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DE69927860T2|2006-06-22|

---

US6077636A|2000-06-20|

---

CN1237723A|1999-12-08|

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KR100285183B1|2001-03-15|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1998-01-28|Priority to JP98-015452

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1998-01-28|Priority to JP1545298

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1998-06-18|Priority to JP98-171578

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1998-06-18|Priority to JP17157898

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1999-01-28|Application filed by 미따라이 하지메, 캐논 가부시끼가이샤

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1999-08-25|Publication of KR19990068188A

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2001-03-15|Application granted

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2001-03-15|Publication of KR100285183B1

优先权:

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申请号 | 申请日 | 专利标题

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JP98-015452|1998-01-28|

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JP1545298|1998-01-28|

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JP98-171578|1998-06-18|

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JP17157898|1998-06-18|