JP2003270850A - Toner and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make a toner pulverizable into small grain sized toner, to sharpen the distribution on the rough toner side, to attain an image of high image quality and to prevent voids and scattering at a transfer in a high-speed tandem transfer process wherein a distance from a 1st transfer position to a 2nd transfer position is short, to prevent a reverse transfer, to obtain high transfer efficiency, besides, to attain an oil-less fixation capable of preventing offset while maintaining high OHP translucency. <P>SOLUTION: After mixing, melting and kneading the toner containing at least binding resin and wax, the toner is pulverized into the small-grain sized toner by a rotary pulverizing means while imparting an vibrating means and a means for mitigating aggregation of the additive put in. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a copying machine, a laser printer, a plain paper FAX, a color PPC, a color laser printer and a color FAX.

[0002]

2. Description of the Related Art In recent years, electrophotographic apparatuses have been shifting from office use to personal use, and there is a demand for a technology that realizes downsizing, high speed operation, high image quality, and maintenance-free operation. Therefore, without using the cleanerless process that collects the waste toner during development without cleaning the residual toner after transfer, the tandem color process that enables high-speed output of color images, and the use of fixing oil to prevent offset during fixing In both cases, oilless fixing that achieves both clear color image having high glossiness and high translucency and non-offset property is required together with conditions such as good maintainability and low ozone exhaust. It is necessary to make these functions compatible at the same time, and not only the process but also the improvement of the toner characteristics is an important factor.

In a color printer, an image bearing member (hereinafter referred to as "photosensitive member") is charged by corona discharge by a charging charger, and then a latent image of each color is irradiated on the photosensitive member as an optical signal to form an electrostatic latent image. , The first color, for example, yellow toner is developed to visualize the latent image. After that, the transfer member charged with the opposite polarity to the charging of the yellow toner is brought into contact with the photosensitive member,
The yellow toner image formed on the photoconductor is transferred. The photoconductor is destaticized after cleaning the toner remaining at the time of transfer, and finishes development and transfer of the first color toner.
After that, the same operation as that for the yellow toner is repeated for magenta and cyan toners, and the color toner images are superimposed on the transfer body to form a color image. A four-pass type color process in which these superposed toner images are transferred to paper charged with a polarity opposite to that of the toner has been put into practical use.

Further, a plurality of image forming stations each having a charger, a photoconductor, a developing unit, etc. are arranged side by side, and an endless transfer member is brought into contact with the photoconductor to successively transfer toners of respective colors to the transfer member. A secondary transfer color toner image is formed on the transfer body by executing the primary transfer process, and then the multilayer toner images formed on the transfer body are collectively transferred to a transfer medium such as paper or OHP collectively. There have been proposed a tandem color process configured to execute a transfer process and a tandem color process of directly transferring directly to a transfer medium such as paper or OHP without using a transfer body.

This system is characterized in that it can output a color image at a high speed, but since the toner images of four colors are superposed on the transfer body, the toner layer becomes thick, and there is a difference in pressure between the toner layer that is absent or thin. It is easy to occur. Therefore, due to the toner aggregating effect, a "middle void" phenomenon in which a part of the image is not transferred and becomes a hole is likely to occur. Furthermore, if a material having a high toner releasing effect is used for the transfer member in order to surely clean the residual toner, hollow defects will appear conspicuously and the image quality will be significantly deteriorated. Further, in the case of characters and lines, edge development is performed, and the amount of toner increases and the toner particles agglomerate due to pressurization, resulting in more noticeable voids. Particularly, it appears more remarkably in an environment of high humidity and high temperature.

Further, in order to reduce the size and speed of the machine, it is required that the distance between the image forming stations (corresponding to the distance between the photoconductors) is shorter and the printing is performed at high speed. As a result, for example, after the yellow toner is first transferred,
The time until the second transfer of the next magenta toner is extremely short, charge relaxation of the transfer body and charge relaxation of the transferred toner hardly occur, and when the magenta toner is transferred onto the yellow toner, The magenta toner is repelled by the charge action of the yellow toner, which causes problems such as image disturbance due to scattering of the toner image, reduction in transfer efficiency, and blank characters at the time of transfer.

Further, in the structure using the intermediate transfer member, when the toner of the last color of the fourth color is primary-transferred and then secondary-transferred collectively on paper or the like, the toner image is disturbed due to the repulsion due to the mutual charge of the toner. Occurs.

Further, in order to improve the dot reproducibility in the transfer, the resistance of the transfer member is made high, so that the toner image is disturbed and the tendency of the transfer failure is more remarkable.

Further, it is desired to reduce the particle size of the toner in order to improve the resolution. However, simply reducing the particle size of the toner is not sufficient to improve the image quality, and also leads to a decrease in productivity and an increase in production cost. To improve the image quality, sharpening the cutting property on the coarse powder side and the amount of particles on the fine powder side have a strong influence. In terms of productivity, it is necessary to improve the method of crushing and reducing the particle size without reducing the production amount. In particular, in order to realize an oilless fixing color toner to be described later, a configuration in which wax is added is adopted. The problem with this configuration is that the wax has strong toner cohesiveness,
Since the toner is not loosened and is aggregated and conveyed to the crushing area, it is difficult to crush small particles, and it becomes difficult to cut sharply on the coarse powder side. Further, it is strongly adhered to the pipe during air conveyance, which is also a factor that lowers productivity and pulverizability.

Further, in order to enable oilless fixing without using oil at the time of fixing which will be described later, a toner composition in which a release agent such as wax is added to a sharp melt resin has a strong charge retention property and also has a toner cohesive property. Since the toner has strong characteristics, toner image disorder and transfer failure tend to occur more significantly, and it becomes difficult to achieve both transfer and fixing. Further, in a toner to which a wax having a polar group is added in order to improve the dispersibility in the polyester resin, the cohesiveness becomes stronger, and it becomes extremely difficult to achieve both oilless fixing and transferability.

In the fixing process, in the color image, it is necessary to melt and mix the color toners to enhance the translucency. When toner melting failure occurs, light scattering occurs on the surface or inside the toner image, impairing the original color tone of the toner dye, and at the overlapping portion, light does not enter the lower layer, resulting in poor color reproducibility. Therefore, it is a necessary condition that the toner has a perfect melting property and has a light-transmitting property that does not disturb the color tone. The need for greater light transmission on OHP paper is increasing due to the increasing opportunities for color presentations.

However, in the resin constitution having the melting property of sharp melt due to the expression of the light transmission property, the offset resistance is lowered and an offset occurs by adhering to the surface of the fixing roller, so that a large amount of oil or the like must be applied to the fixing roller. This complicates handling and device configuration. Therefore, an oilless color fixing structure that does not require oil is required.

Further, a fluorine-based material is used for improving the releasing property and durability of the fixing roller and the belt. However, before entering the fixing section, an unfixed toner image is apt to electrostatically repel the fixing roller, resulting in image distortion. On the contrary, the toner may fly to the fixing roller before entering the fixing nip portion to cause a halftone offset. In particular, the influence of the charging property is likely to occur in the configuration where the release oil is not applied. Further, in a toner to which a release agent is added for the purpose of improving the offset property, the fixing roller is likely to be scratched due to the poor dispersion of the internal additive, which causes a vertical streak in the image.

As is well known, the toner for electrostatic charge development used in the electrophotographic method is generally a resin component which is a binder resin, a coloring component comprising a pigment or a dye and a plasticizer,
It is composed of a charge control agent and, if necessary, an additive component such as a release agent. As the resin component, a natural or synthetic resin may be used alone or may be mixed at an appropriate time.

Then, the above additives are premixed in an appropriate ratio, heated and kneaded by hot melting, finely pulverized by an airflow type collision plate system, and finely powdered to complete a toner base.
Thereafter, an external additive such as hydrophobic silica is externally added to the toner base to complete the toner. In one-component development,
Although it is composed only of toner, a two-component developer can be obtained by mixing the toner and a carrier composed of magnetic particles.

In Japanese Patent Application Laid-Open No. 2-271364, an external additive charging means for charging an external additive into a high-speed gas stream and a collision plate provided in a flow path of the high-speed gas stream on which the pulverized raw material and the external additive are placed. The crushed raw material collides with the collision plate to pulverize, and the external additive collides with the pulverized raw material in the vicinity of the collision plate to mix, so that the pulverized body and the additive component can be easily mixed homogeneously. The effect that can be achieved is disclosed. However, this structure is intended to be mixed homogeneously with the additive components, and has a small particle size for the purpose of the present application, a sharp cut property on the coarse powder side, and a pulverized product in the structure of an oilless fixing toner containing wax. There is no suggestion of improving sex. In particular, in a crusher using a collision plate method in which a toner to which wax is added at a high concentration is used, the wax is excessively exposed on the toner surface, which causes filming on the photoreceptor.

Further, in Japanese Patent Application Laid-Open No. 6-89045, coarse particles for toner are subjected to intermediate pulverization treatment, and the average particle diameter obtained is 1.
A mixture powder of intermediate particles for toner of 0 to 50 μm and modifying fine particles having an average particle diameter of 1 μm or less is subjected to friction pulverization by a mechanical pulverizer to obtain a toner in which the modifying fine particles are fixed to the toner particles. According to the configuration obtained, the effect that the modifying fine particles are satisfactorily adhered to the toner particles and the toner having high fluidity and excellent durability can be produced with high efficiency is disclosed. However, there is no suggestion of reduction in particle size for the purpose of the present application, sharp cut property on the coarse powder side, and further improvement in pulverization productivity in the constitution of an oilless fixing toner containing wax.

Further, a configuration is disclosed in which the toner capable of improving the image quality is specified by specifying the particle size distribution of the toner.
As means for embodying the particle size distribution constitution, for example, means for simultaneously cutting coarse powder and fine powder by an elbow jet classifier is shown. However, there is no disclosure of the content of means for adjusting the amount of coarse powder to a predetermined amount in the pulverization step, and there is a problem that the production yield is lowered by the coarse powder classification. In addition, toner that achieves oilless fixing is used to prevent high temperature offset,
The resin is made to have a high viscosity, and further pulverization efficiency is desired.

As the releasing agent and wax to be added, Japanese Patent Laid-Open No. 2-266372 discloses a free fatty acid type carnauba wax and / or montan ester wax,
Use of oxidized rice wax having an acid value of 10 to 30, and in JP-A-9-281748, a melting point of 85 to 100 ° C,
Vinyl-based copolymer polymerized in the presence of natural gas-based Fischer-Tropsch wax, JP-A-10-3271
In JP 96, polycondensation of a polyhydric alcohol component with a dicarboxylic acid and a polyvalent carboxylic acid compound having a valence of 3 or more, the average dispersed particle diameter of the release agent is 0.1 to 3 μm, and the particle diameter of the external additive is It is disclosed that 1 to 5 parts by weight is added at 4 to 200 nm. Japanese Unexamined Patent Publication No. 5-333584 discloses that fixing property is improved by a constitution containing a fluorine-modified polyolefin resin such as polypropylene modified with an organic fluorine compound such as perfluorooctyl methacrylate. . In JP-A-5-188632, a non-offset property at the time of fixing is improved by blending a low-molecular-weight polyolefin having a softening point of 80 to 140 ° C., containing fluorine, and a melt mixture of low-molecular-weight olefin and polytetrafluoroethylene. The contents to be disclosed are disclosed, and the contents effective for improving the fixing property are described.

Further, in JP-A-59-148067, an unsaturated ethylene polymer having a low molecular weight and a high molecular weight portion in a resin and having a low molecular weight peak value and Mw / Mn is used to soften the resin. A toner containing a point-specified polyolefin is disclosed. As a result, it is said that the fixability and the offset resistance are secured. In addition, JP-A-5
Japanese Patent Publication No. 6-158340 discloses a toner containing a resin composed of a specific low molecular weight polymer component and a high molecular weight polymer component as a main component. The purpose is to secure the fixability by the low molecular weight component and the offset resistance by the high molecular weight component. Further, in JP-A-58-223155, it is 10
Disclosed is a toner having a maximum value in a molecular weight range of 100,000 to 100,000 and 200,000 to 1,000,000 and containing a resin composed of an unsaturated ethylene polymer having Mw / Mn of 10 to 40 and a polyolefin having a specific softening point. Has been done. The low molecular weight component is used to secure the fixing property, and the high molecular weight component and polyolefin are used to secure the offset resistance.

Further, JP-A-63-56659 and JP-A-2000-98661 disclose a toner relating to a polyester resin, which discloses that a good fixing property can be obtained.

Further, as a charge control agent for imparting chargeability to the toner, Japanese Patent Laid-Open No. 221967/1990 and Japanese Patent Laid-Open No. 7-
No. 84409, JP-A-5-72812, and JP-A-5-165257 disclose toners using a metal salt of a benzylic acid derivative. In addition, JP-A-53-1
No. 27726, JP-A-55-42752, JP-A-7-2171097 and the like disclose toners using a metal salt of a salicylic acid derivative.

However, if the melt viscosity of the binder resin is lowered or a resin having a low molecular weight is used in order to increase the fixing strength, the pulverizability becomes easy, but if two-component development is carried out during a long-term use, the toner can be developed. The so-called spent, which adheres to the carrier, is likely to occur. The stress resistance of the developer is reduced.
In addition, an offset in which toner adheres to the heat roller is likely to occur during fixing. Further, blocking occurs in which the toner particles are fused with each other during long-term storage.

In contrast to a resin composition in which a high molecular weight component and a low molecular weight component are blended or copolymerized, a release agent having a low melting point, such as polyethylene or polypropylene wax, has a releasability from the heat roller at the time of fixing. It is added for the purpose of improving the offset resistance. However, it is difficult to improve the dispersibility of these release agents in the binder resin, the reverse polarity toner is likely to be generated due to poor dispersion, and fog is generated on the non-image area. Further, an image defect such as being scratched by a brush occurs at the rear end portion of the solid black image portion, which deteriorates the image quality. Further, there is a problem that the carrier, the photoconductor, and the developing sleeve are contaminated with filming.

When a toner having a constitution of enhancing the glossiness and translucency of a color image by using a low melting point release agent and a resin having a low softening property, vertical stripes are generated on the developing roller during development. , Poor cleaning of transfer body and occurrence of filming,
If the dispersibility is improved due to poor scraping of the cleaning roller of the transfer body, the effect of releasability is reduced and the non-offset region becomes narrow, which is difficult to achieve at the same time.

Further, in the contact type one-component developing system in which an elastic blade for regulating the toner layer is used in contact with a developing roller made of silicone or urethane and a supply roller made of urethane or the like for supplying toner to the developing roller is provided, In toners to which a low-melting-point release agent is added, the charge rising property deteriorates,
Deterioration of charge retention property occurs during long-term continuous use. Further, by using the toner containing the above-mentioned low melting point release agent,
When using several thousand sheets, vertical streaks gradually occur on the developing roller, which causes image defects such as white spots and black streaks. This is damage to the developing roller due to poor dispersion of the release agent, fusion to the blade,
It is considered that the cause is agglomeration due to friction between the supply roller and the developing roller.

It is important to realize a cleanerless process without a cleaning process in order to reduce the size of equipment and save resources. After the electrostatic latent image formed on the photoconductor is transferred to the transfer body or paper by the transfer means, the toner remaining on the photoconductor is usually cleaned by means such as a blade or a fur brush. Are collected to be waste toner. At this time, the cleanerless process performs the following charging, exposure, and development processes without this cleaning process step. The transfer residual toner remains on the photosensitive member to some extent, and in the next development process, if the residual toner in the non-image portion is recovered for development and returned, no image problem occurs.

Further, in the case of outputting a color image, the toner of the previous color may be reversely transferred to the photoconductor in the transfer step of superposing the color images, and it may become an abnormal image as a memory. Therefore, it is an important point to take measures against the residual toner and the reversely transferred toner.

[0029]

As described above, the toner is
The above problems must be satisfied in a comprehensive manner.In the case of an oilless fixing toner that does not use oil for the fixing roller, the toner itself has the oil function used for the fixing member. Achieves oil-less fixing using a release agent such as wax, and maintains transferability even in tandem color processes.
Furthermore, it is necessary to satisfy the cleanerless process. Furthermore, in order to realize high resolution, it is necessary to reduce the toner particle size without lowering the productivity and to sharpen the coarse powder side to improve the image quality.

In view of the above problems, the present invention reduces the particle size of the toner without lowering the productivity to improve the image quality, and arranges image forming stations having a plurality of photoconductors and developing units side by side to form a transfer medium. In the tandem color process, in which toner of each color is continuously executed in sequence, it is possible to prevent hollowing and scattering at the time of transfer, to obtain high transfer efficiency, avoid filming on the transfer body, etc. It is an object of the present invention to provide a toner, a method for producing the toner, and an image forming apparatus capable of preventing fusion to a cleaning means.

It is an object of the present invention to provide a full-color electrophotographic toner and an image forming apparatus that exhibit high translucency and glossiness by oilless fixing without applying oil to the fixing roller. And even in the case of color toners using low-melting sharp-melt resin, developing rollers, doctor blades,
An object of the present invention is to provide a toner and an image forming apparatus capable of avoiding filming on a transfer body or the like and preventing filming on the photoconductor, the transfer body or the like even when used for a long time under high humidity.

Even when used in the one-component developing method, no vertical stripes are formed on the developing roller, and even when continuously used, the layer regulation blade and the developing roller do not cause thermal fusion or aggregation of the toner, thereby suppressing a decrease in charge amount. Another object of the present invention is to provide a toner and an image forming apparatus capable of improving the dispersibility of an additive and maintaining stable developability without deteriorating the resin characteristics.

Further, even in the cleanerless process, high transfer efficiency is obtained, the charge amount and the fluidity are not deteriorated, the recovery in the development is facilitated, the memory is not generated, and the toner and the image formation which enable the cleanerless process are made. The purpose is to provide a device.

In a toner to which a releasing agent such as wax having a low melting point is added, contamination of the photosensitive member, carrier, developing roller and transfer member due to bleeding of wax can be prevented and a uniform charge distribution can be obtained. It is an object of the present invention to provide a toner and an image forming apparatus capable of achieving long-term stability.

Further, in the fixing process using a belt, and also in the belt fixing using a roller having a large fixing curvature with a low fixing pressure and a long fixing nip, the non-wrapping property of the paper on the belt is improved, Furthermore, it is possible to prevent chipping of the image area that occurs when the belt and paper are separated,
Furthermore, it is an object of the present invention to provide a toner and an image forming apparatus that can achieve both development and transfer properties.

[0036]

In view of the above problems, the structure according to the present invention has a structure in which the toner composition containing at least a binder resin, a colorant and a wax is melted and kneaded, and then has unevenness on the surface and rotates at high speed. A cylindrical rotating body, and a cylindrical fixed body that is fitted to the outside of the rotating body with a gap of 0.5 mm to 40 mm, shares a central axis with the rotating body, and has irregularities on the surface; A toner to be pulverized into a predetermined particle size distribution by a pulverizer having a supply port for inflowing the pulverized material to be toner and an outlet for discharging the pulverized toner pulverized product. It is a toner which is provided with a means for relaxing the agglomeration of the pulverized material to be toner before being introduced from the supply port, and is introduced from the supply port to be pulverized into a predetermined particle size distribution.

Further, in the constitution according to the present invention, after a toner composition containing at least a binder resin, a colorant, and a wax is melt-kneaded, a cylindrical rotating body having irregularities on the surface and rotating at a high speed, A cylindrical fixed body which is fitted on the outer side of the rotating body with a gap of 0.5 mm to 40 mm, shares a central axis with the rotating body, and has irregularities on the surface, and a supply for inflowing the pulverized material to be toner. A toner which is pulverized to a predetermined particle size distribution by a pulverizer having a port and an outlet for discharging the pulverized toner pulverized product, and the toner is pulverized to a predetermined particle size distribution before the toner pulverized product is introduced from the supply port. This is a toner in which a vibrating means is added to the pulverized material to be toner, and the pulverized material is introduced from the supply port and pulverized into a predetermined particle size distribution.

Further, in the constitution according to the present invention, after a toner composition containing at least a binder resin, a colorant and a wax is melt-kneaded, a cylindrical rotating body having irregularities on its surface and rotating at a high speed, A cylindrical fixed body which is fitted on the outer side of the rotating body with a gap of 0.5 mm to 40 mm, shares a central axis with the rotating body, and has irregularities on the surface, and a supply for inflowing the pulverized material to be toner. A toner that is pulverized into a predetermined particle size distribution by a pulverizer having a port and an outlet that discharges the pulverized toner pulverized product, and is an inorganic material before the pulverized product to be toner flows in from the supply port. It is a toner in which fine powder is supplied to and mixed with the pulverized material to be toner, flowed from the supply port and pulverized to a predetermined particle size distribution.

Further, in the constitution according to the present invention, after a toner composition containing at least a binder resin, a colorant and a wax is melt-kneaded, a cylindrical rotating body having irregularities on its surface and rotating at a high speed, A cylindrical fixed body which is fitted on the outer side of the rotating body with a gap of 0.5 mm to 40 mm, shares a central axis with the rotating body, and has irregularities on the surface, and a supply for inflowing the pulverized material to be toner. A toner that is pulverized into a predetermined particle size distribution by a pulverizer having a port and an outlet that discharges the pulverized toner pulverized product, and evaporates before the pulverized product of the toner flows from the supply port. A toner that supplies a volatile medium to the pulverized product to be mixed with or adheres to the pulverized product, and then flows from the supply port to pulverize into a predetermined particle size distribution.

Further, in the constitution according to the present invention, the content of 5 μm or less in the number distribution of the toner containing at least the binder resin, the colorant and the wax is 60 number% or more, and the content of 3.17 μm or less in the number distribution. The content is 5 to 35% by number, and the toner particles having a particle diameter of 6.35 to 10.1 μm are contained in an amount of 55% by volume or less, and a spherical equivalent to a volume average particle diameter. Specific surface area value St (St = 6 / (true specific gravity × volume average particle size)) and specific surface area ratio SSt (SSt = (St / specific surface area value of pulverized toner) 0.4 to 0.9 A toner.

Further, in the constitution according to the present invention, after a toner composition containing at least a binder resin, a colorant and a wax is melt-kneaded, a cylindrical rotating body having irregularities on its surface and rotating at a high speed, It is fitted on the outer side of the rotating body with a gap of 0.5 mm to 40 mm, shares the central axis with the rotating body,
A cylindrical fixed body having irregularities on its surface, a supply port through which the pulverized material for toner is introduced, and a means for alleviating aggregation of the pulverized material for toner before the pulverized product for toner is introduced from the supply port. With the addition of a crusher equipped with a discharge port for inflowing from the supply port, crushing, and discharging the pulverized toner pulverized product, the content of 5 μm or less in the number distribution is 60 number% or more, The content of 3.17 μm or less in the number distribution is 5 to 35 number%,
5 toner particles having a particle size of 6.35 to 10.1 μm
The specific surface area value St (S
Specific surface area ratio S with t = 6 / (true specific gravity × volume average particle diameter))
The toner is pulverized so that St (SSt = (St / specific surface area value of pulverized toner)) is 0.4 to 0.9.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION Digital image quality improvement, high-definition color reproducibility colorization, high translucency and offset resistance can be achieved without using offset preventing oil in the fixing roller. This makes it possible to prevent the generation of vertical stripes due to roller scratches and blade fusion in one component of development, and to achieve both stable transferability in the cleanerless process and the tandem color process.

(Embodiment 1: Wax) As a wax to be added to the toner of this embodiment, an iodine value of 25 or less,
By adding 1 to 20 parts by weight of a wax having a saponification value of 30 to 300 to 100 parts by weight of the binder resin, repulsion due to the charge action of the toner during toner multi-layer transfer is reduced, and transfer efficiency is reduced. , It is possible to suppress blank characters and reverse transfer during transfer. More preferably, the binder resin has an acid value of 1 to 40 mgKOH / g.

The addition amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. If the amount is less than 0.1 parts by weight, the effect of improving fixability cannot be obtained, and
If it is more than 1 part by weight, there is a problem in storage stability.

When the iodine value is larger than 25, the repulsion due to the charge action of the toner is less likely to be alleviated during the toner multi-layer transfer in the primary transfer. It greatly depends on the environment, and the chargeability of the material changes greatly during long-term continuous use, which impairs image stability. When the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases and the photoconductor filming,
The chargeability is deteriorated. Further, the dispersibility with the charge control agent becomes poor, which causes filming, fusion, and deterioration of the charging property during continuous use. When it is more than 300, the dispersibility of the wax in the resin is deteriorated, and the repulsion due to the charge action of the toner is less likely to be alleviated. In addition, fog and toner scattering increase. When the resin acid value is less than 1 mgKOH / g, the repulsion due to the charge action of the toner is less likely to be alleviated during the toner multi-layer transfer. When the resin acid value is more than 40 mgKOH / g, the environmental resistance is deteriorated and the fogging is increased. In particular, the transferability is liable to decrease under low humidity, and at this time, the transferability can be maintained by using it together with an external additive.

It is preferable that the melting point is 50 to 100 ° C. by the DSC method. More preferably, the iodine value is 15 or less, the saponification value is 50 to 250, and the melting point by the DSC method is 55 to 9
The temperature is 0 ° C., more preferably, the iodine value is 5 or less, the saponification value is 70 to 200, and the melting point by the DSC method is 60 to 85 ° C.

Further, a material having a volume increase rate of 2 to 30% when the temperature changes by 10 ° C. at a temperature equal to or higher than the melting point is preferable. When it changes from solid to liquid, it expands rapidly, and when it fuses with the heat of fixing, the adhesion between toners is further strengthened, the fixing property is further improved, and the releasability from the fixing roller is also improved. The offset property is also improved. When it is less than 2, the effect is small, and when it is more than 30, the dispersibility at the time of kneading decreases.

The heating loss of the wax at 220 ° C. is preferably 8% by weight or less. When the heating loss is more than 8% by weight, it remains in the binder resin during heating and kneading, greatly lowering the glass transition point of the binder resin and impairing the storage stability of the toner. It adversely affects the developing characteristics and causes fogging and filming of the photoconductor intermediate transfer member.

Iodine value is 25 or less, saponification value is 30 to 3
The wax having a composition of 00 has a molecular weight characteristic in gel permeation chromatography (GPC), a number average molecular weight of 100 to 5000, and a weight average molecular weight of 200 to 1000.
0, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, and the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.
It is preferable to have at least one maximum molecular weight peak in the region of 02 to 10 and molecular weight of 5 × 10 ² to 1 × 10 ⁴ . More preferably, the number average molecular weight is 500 to 450.
0, the weight average molecular weight is 600 to 9000, the ratio between the weight average molecular weight and the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 7, the ratio between the Z average molecular weight and the number average molecular weight (Z average molecular weight / number The average molecular weight) is 1.02 to 9, more preferably the number average molecular weight is 700 to 4000, the weight average molecular weight is 800 to 8000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1. 0
1 to 6, and the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 8.

When the number average molecular weight is less than 100 and the weight average molecular weight is less than 200, storage stability deteriorates. When the maximum molecular weight peak is located in a range smaller than 5 × 10 ² , the dispersibility of the charge control agent with the wax deteriorates. The storage stability of the toner is deteriorated, filming on the photoconductor and the transfer body, vertical streaks on the developing roller, scraping failure on the cleaning roller, and the like occur.

The number average molecular weight is more than 5,000, the weight average molecular weight is more than 10,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is more than 8, and the Z average molecular weight and the number average molecular weight are When the ratio (Z average molecular weight / number average molecular weight) is larger than 10 and the maximum molecular weight peak is located in a range larger than the region of 1 × 10 ⁴ , the releasing action becomes weak, and the fixing property, offset resistance, etc. The fixability function deteriorates.

Examples of the wax include meadowfoam oil derivative, carnauba wax, jojoba oil derivative, wood wax, beeswax, ozokerite, carnauba wax, candelia wax, montan wax, ceresin wax,
Materials such as natural wax such as rice wax and synthetic wax such as Fischer-Tropsch wax are preferable, and one kind or a combination of two or more kinds can be used. In particular, carnauba wax having a melting point of 76 to 90 ° C. by the DSC method, candelilla wax of 66 to 80 ° C., hydrogenated jojoba oil of 64 to 78 ° C., 64 to 78
More preferably, at least one wax or two or more waxes selected from the group consisting of hydrogenated meadow foam oil having a temperature of 0 ° C or rice wax having a temperature of 74 to 90 ° C is used.

Saponification number refers to the number of milligrams of potassium hydroxide KOH required to saponify 1 g of sample. It is the sum of acid value and ester value. To measure the saponification value, the sample is saponified in an alcoholic solution of about 0.5N potassium hydroxide and then the excess potassium hydroxide is titrated with 0.5N hydrochloric acid.

The iodine value means the amount of halogen absorbed when a halogen is applied to a sample, converted into iodine and expressed in g per 100 g of the sample. Fat 100
It is the number of grams of iodine absorbed in g, and the larger this value is, the higher the degree of unsaturation of the fatty acid in the sample is. Iodine and mercury (II) chloride alcohol solution or iodine chloride glacial acetic acid solution was added to chloroform or carbon tetrachloride solution of the sample, and iodine left unreacted after standing was titrated with sodium thiosulfate standard solution to absorb iodine. Calculate the amount.

The weight loss of the sample cell was measured with 0.1
Precisely weigh (W1mg) to mg
g, and weigh accurately to 0.1 mg (W2 mg). The sample cell is set on a differential thermal balance, the weighing sensitivity is set to 5 mg, and measurement is started. The temperature is controlled by the following program. After the measurement, the weight loss at the time when the sample temperature reached 220 ° C. is read to 0.1 mg (W3 mg) on the chart. Device, vacuum Riko TGD-3000, heating rate 10 ° C / m
in, maximum temperature 220 ° C., holding time 1 min, heating loss (%) = W3 / (W2-W1) × 100.

Meadowfoam oil derivatives include meadowfoam oil fatty acids, metal salts of meadowfoam oil fatty acids,
Meadow foam oil fatty acid ester, hydrogenated meadow foam oil, meadow foam oil amide, homo meadow foam oil amide, meadow foam oil triester, epoxidized maleic acid derivative of meadow foam oil, isocyanate polymerization of meadow foam oil fatty acid polyhydric alcohol ester , A halogenated modified meadow foam oil is a preferred material. These can be used alone or in combination of two or more.

The meadowfoam oil fatty acid obtained by saponifying and cracking the meadowfoam oil consists of fatty acids having 18 to 22 carbon atoms. The metal salts are sodium, potassium, calcium, magnesium, barium, zinc,
Metal salts such as lead, manganese, iron, nickel, cobalt and aluminum can be used.

Meadowfoam oil fatty acid esters are, for example, esters of methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, trimethylolpropane, and the like, and in particular, meadowfoam oil fatty acid pentaerythritol monoester, meadowfoam oil fatty acid. Pentaerythritol triester, meadowfoam oil fatty acid trimethylolpropane ester and the like are preferable.

Furthermore, an esterification reaction product of the meadowfoam oil fatty acid and a polyhydric alcohol such as glycerin, pentaerythritol and trimethylolpropane is treated with tolylene diisocyanate (TDI), diphenylmethane-
An isocyanate polymer of a meadow foam oil fatty acid polyhydric alcohol ester obtained by crosslinking with an isocyanate such as 4,4′-diisocyanate (MDI) can also be preferably used.

The hydrogenated meadowfoam oil is obtained by hydrogenating the meadowfoam oil to convert unsaturated bonds into saturated bonds.

The meadowfoam oil amide is obtained by hydrolyzing meadowfoam oil and then esterifying it to give a fatty acid methyl ester, which is then reacted with a mixture of concentrated aqueous ammonia and ammonium chloride. Further, by adding hydrogen to this, the melting point can be adjusted. It is also possible to add hydrogen before hydrolysis. A product having a melting point of 75 to 120 ° C. is obtained. Homo-meadow foam oil amide is obtained by hydrolyzing meadow-foam oil, reducing it to alcohol, and then passing through nitril.

Examples of jojoba oil derivatives include jojoba oil fatty acid, metal salts of jojoba oil fatty acid, jojoba oil fatty acid ester, hydrogenated jojoba oil, jojoba oil amide, homojojoba oil amide, jojoba oil triester, and maleic acid of epoxidized jojoba oil. Derivatives, an isocyanate polymer of jojoba oil fatty acid polyhydric alcohol ester, and halogenated modified jojoba oil are preferred materials. These can be used alone or in combination of two or more.

The jojoba oil fatty acid obtained by saponification of jojoba oil comprises fatty acids having 18 to 22 carbon atoms. The metal salts are sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese,
Metal salts such as iron, nickel, cobalt and aluminum can be used.

Examples of jojoba oil fatty acid esters include:
Esters such as methyl, ethyl, butyl and glycerin, pentaerythritol, polypropylene glycol, and trimethylolpropane, especially jojoba oil fatty acid pentaerythritol monoester, jojoba oil fatty acid pentaerythritol triester, jojoba oil fatty acid trimethylolpropane ester, etc. preferable.

Furthermore, jojoba oil fatty acid and glycerin,
An esterification reaction product with a polyhydric alcohol such as pentaerythritol or trimethylolpropane is converted into tolylene diisocyanate (TDI), diphenylmethane-4,4′-
An isocyanate polymer of jojoba oil fatty acid polyhydric alcohol ester obtained by crosslinking with an isocyanate such as disisocyanate (MDI) can also be preferably used.

The hydrogenated jojoba oil is obtained by hydrogenating jojoba oil to convert unsaturated bonds into saturated bonds.

Jojoba oil amide is obtained by hydrolyzing jojoba oil and then esterifying it to give a fatty acid methyl ester, which is then reacted with a mixture of concentrated aqueous ammonia and ammonium chloride. Further, by adding hydrogen to this, the melting point can be adjusted. It is also possible to add hydrogen before hydrolysis. Melting point is 75
The thing of -120 degreeC is obtained. Homo jojoba oil amide is obtained by hydrolyzing jojoba oil, reducing it to alcohol, and then passing through nitrile.

Materials such as hydroxystearic acid derivatives, polyhydric alcohol fatty acid esters such as glycerin fatty acid ester, glycol fatty acid ester and sorbitan fatty acid ester are preferable, and one kind or a combination of two or more kinds can be used.

As derivatives of hydroxystearic acid, methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol = mono 12-hydroxystearate, glycerin = mono 1
2-Hydroxystearate, ethylene glycol = mono-12-hydroxystearate and the like are suitable materials. It has an effect of preventing paper wrapping in the oilless fixing and an effect of preventing belt filming.

As the glycerin fatty acid ester, glycerin = monotristearate and glycerin = docosanoate are suitable materials. It has the effect of easing the cold offset property at low temperature in oilless fixing and preventing the transfer property from decreasing.

Suitable glycol fatty acid esters are propylene glycol = monopalmitate, propylene glycol = monostearate and other propylene glycol fatty acid esters, and ethylene glycol = monostearate and other ethylene glycol fatty acid esters. In addition to the oilless fixing property, it has the effect of preventing slippage by improving slippage during development.

As the sorbitan fatty acid ester, sorbitan = monopalmitate, sorbitan = monostearate and sorbitan = monotristearate are preferable materials. Furthermore, materials such as a stearic acid ester of pentaerythritol and a mixed ester of adipic acid and stearic acid or oleic acid are preferable, and one kind or a combination of two or more kinds can be used. It has an effect of preventing paper wrapping in the oilless fixing and an effect of preventing belt filming.

In this embodiment, an aliphatic amide wax is internally added to the polyester resin. As a result, the translucency of a color image can be greatly improved. In particular, the smoothness of the surface of the fixed image can be promoted and a high quality color image can be obtained. Further, it is possible to prevent the copy sheet from being wrapped around the fixing roller at the time of fixing, to achieve both the light-transmitting property and the offset resistance, and to prevent the hollow portion at the time of transfer.

Examples of the aliphatic amide type wax include carbons such as palmitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, arachidic acid amide, eicosenoic acid amide, behenic acid amide, erucic acid amide and ligrinoseric acid amide. It is a saturated or monovalent unsaturated aliphatic amide having the number 16 to 24 and a melting point of 70 to 110 ° C. is preferable. More preferably 70 to 10
The temperature is 0 ° C, more preferably 75 to 95 ° C. The addition amount is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin. When the melting point is lower than 70 ° C., the dispersibility in the resin is lowered and filming on the photoconductor is likely to occur. When the melting point is higher than 110 ° C., the smoothness of the surface of the fixed image is deteriorated and the translucency is deteriorated. The addition amount is 10
If it is more than the amount by weight, the storage stability deteriorates. If the amount added is less than 0.5 parts by weight, the function cannot be exhibited.

Furthermore, methylenebisstearic acid amide, ethylenebisstearic acid amide, propylenebisstearic acid amide, butylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisoleic acid amide, propylenebisoleic acid amide, butylenebisoleic acid amide. Acid amide, methylenebislauric acid amide, ethylenebislauric acid amide, propylenebislauric acid amide, butylenebislauric acid amide, methylenebismyristate amide, ethylenebismyristate amide, propylenebismyristate amide, butylenebismyristate amide , Methylene bispalmitate amide, ethylene bispalmitate amide, propylene bispalmitate amide, butylene bispalmitate amide, methylenebis Lumitoleic acid amide, ethylene bispalmitoleic acid amide, propylene bispalmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bis arachidic acid amide, ethylene bis arachidic acid amide, propylene bis arachidic acid amide, butylene bis arachidic amide , Methylenebiseicosenoic acid amide, ethylenebiseicosenoic acid amide,
Propylene bis-eicosenoic acid amide, butylene bis-eicosenoic acid amide, methylene bis-behenic acid amide, ethylene bis-behenic acid amide, propylene bis-behenic acid amide, butylene bis-behenic acid amide, methylene bis-erucic acid Preferred are alkylenebisfatty acid amide waxes of saturated or mono- and divalent unsaturated fatty acids such as amide, ethylenebiserucic acid amide, propylenebiserucic acid amide and butylenebiserucic acid amide.

As a result, it becomes possible to improve the translucency in a color image and the offset resistance to the roller. The addition amount is preferably 0.1 to 9 parts by weight with respect to 100 parts by weight of the binder resin. If the melting point is lower than 100 ° C, the effect of offset resistance decreases. Melting point 14
If it is higher than 5 ° C, the dispersibility in the resin is deteriorated and the fog is increased. If the addition amount is less than 0.1 parts by weight, the function cannot be exhibited, and if it is more than 9 parts by weight, fog increases.

Further, by composing the wax of the aliphatic amide type and the alkylenebis fatty acid amide type in the ratio of 3: 7 to 7: 3, the surface smoothness of the fixed image can be improved and the color image can be further improved. It is possible to further improve both the transparency and the offset resistance. It is necessary that the melting point of the alkylenebisfatty acid amide is higher than that of the aliphatic amide. When the melting point of the alkylene bis fatty acid amide type is lowered, not only the offset resistance is lowered, but also the resin itself is in a low-softening state and over-pulverization at the time of pulverization progresses, resulting in an increase in fine powder and a decrease in productivity.

Particularly, since the aliphatic amide type is a low melting point material, the resin itself is plasticized when the compatibility with the resin progresses, the offset resistance and the storage stability are deteriorated, and further, the transfer of the resin during long-term use is prevented. The hollow is getting worse. Therefore, by using in combination with the alkylenebis fatty acid amide, which has a higher melting point than the aliphatic amide, plasticization of the resin itself can be suppressed, and the high transparency and surface smoothness of the aliphatic amide can be achieved. It is possible to prevent the dropout of transfer during long-term use without loss, and to maintain offset resistance and storage stability.

In the molecular weight distribution in GPC, the weight average molecular weight is 1000 to 6000, the Z average molecular weight is 1500 to 9000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to.
3.8, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.5 to 6.5, 1 × 10 ^{3 to} 3
It has at least one maximum molecular weight peak in the region of × 10 ⁴ , an acid value of 5 to 80 mgKOH / g, and a melting point of 80 to 120.
5 to 1 carbon atoms with a penetration of 4 or less at 25 ° C and 25 ° C
00 obtained by reacting a long-chain alkyl alcohol with an unsaturated polycarboxylic acid or an anhydride thereof and a hydrocarbon wax, or a long-chain alkylamine with an unsaturated polycarboxylic acid or an anhydride and a hydrocarbon wax The wax obtained by the reaction with the wax, or the wax obtained by the reaction of the long-chain fluoroalkyl alcohol with the unsaturated polycarboxylic acid or its anhydride and the hydrocarbon wax, forms a three-layer color toner on thin paper. It is particularly effective in improving the separability of the paper from the fixing roller or the belt in the image. OH without deteriorating the high temperature offset property
It is effective in improving the permeability of P. In addition, the addition of wax can exhibit fixing properties, particularly non-offset property in oilless fixing, high glossiness, and high translucency, and does not deteriorate the high temperature storage stability. Even if a fluorine-based or silicon-based member is used for the fixing roller, halftone offset can be prevented. Further, the charging stability during continuous use can be obtained, and both the fixing property and the developing charging stability can be achieved.

Furthermore, by improving the state of dispersion when this is added to the binder resin, it is possible to further improve fixability such as releasability and translucency, and developability such as charge stabilization. It may be considered that the dispersibility of other internal additives may be reduced by the addition of a release agent, but the composition of the additive of the present embodiment does not reduce the dispersibility of both of them and seeks to achieve both the fixability and the developability. be able to.

When the number of carbon atoms of the long-chain alkyl of the wax is less than 5, the releasing action is weakened and the separability and the high temperature non-offset property are deteriorated. Long chain alkyl has 100 carbon atoms
If it is larger, the dispersibility in the binder resin deteriorates. If the acid value is less than 5 mgKOH / g, the charge amount of the toner may be reduced during long-term use. If the acid value is greater than 80 mgKOH / g, the moisture resistance will decrease and fogging under high humidity will increase. When the melting point is lower than 80 ° C., the storage stability of the toner is deteriorated. When the melting point is higher than 120 ° C., the releasing action becomes weak and the non-offset temperature width becomes narrow. If the penetration at 25 ° C. is greater than 4, the toughness is reduced, and filming occurs on the photoconductor and the intermediate transfer member during long-term use.

The weight average molecular weight is less than 1000,
Z average molecular weight less than 1500, weight average molecular weight /
When the number average molecular weight is smaller than 1.1, the Z average molecular weight / number average molecular weight is smaller than 1.5, and the maximum molecular weight peak is located in a range smaller than 1 × 10 ³ , the storage stability of the toner is improved. Deterioration, filming on photoreceptor, intermediate transfer body,
Vertical stripes on the developing roller and scraping defects on the cleaning roller may occur.

The weight average molecular weight is larger than 6000,
Z average molecular weight greater than 9000, weight average molecular weight / number average molecular weight greater than 3.8, Z average molecular weight /
When the number average molecular weight is larger than 6.5 and the maximum molecular weight peak is located in a range larger than the region of 3 × 10 ⁴ , the releasing action is weakened and the fixing offset property is deteriorated.

More preferably, the weight average molecular weight is 1000.
~ 5000, Z average molecular weight is 1700 to 8000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to 2.8, ratio of Z average molecular weight to number average molecular weight (Z average Molecular weight / number average molecular weight) is 1.5 to
It is preferable to have at least one molecular weight maximum peak in the region of ^4.5 , 1 × 10 ³ to 1 × 10 ⁴ , and more preferably, the weight average molecular weight is 1000 to 2500, the Z average molecular weight is 1900 to 3000, and the weight average molecular weight. And the number average molecular weight ratio (weight average molecular weight / number average molecular weight) is 1.2 to
1.8, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.7 to 2.5, 1 × 10 ^{3 to} 3
It has at least one maximum molecular weight peak in the region of × 10 ³ .

As the alcohol, those having a long alkyl chain such as octanol, dodecanol, stearyl alcohol, nonacosanol and pentadecanol can be used. Further, N-methylhexylamine as amines,
Nonylamine, stearylamine, nonadecylamine and the like can be preferably used. Fluoroalkyl alcohols include 1-methoxy (perfluoro-2-methyl-1)
-Propene), hexafluoroacetone, 3-perfluorooctyl-1,2-epoxypropane and the like can be preferably used. As the unsaturated polycarboxylic acid or anhydride thereof, one or more of maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like can be used. Among them, maleic acid and maleic anhydride are more preferable. As the synthetic hydrocarbon wax, polyethylene, polypropylene, Fischer-Tropsch wax, α-olefin and the like can be preferably used.

An unsaturated polycarboxylic acid or its anhydride is polymerized with an alcohol or an amine, which is then synthesized in the presence of a dihydromiperoxide or tertiary butyl peroxyisopropyl monocarbonate. It can be obtained by adding it to wax.

The addition amount is 1 with respect to 100 parts by weight of the binder resin.
-20 parts by weight is preferred. When it is 1 or less, the releasing effect is difficult to be obtained. When it is 20 or more, not only the fluidity of the toner is lowered, but also when more is added, the toner is saturated and the effect is not improved.

Polyolefin, polypropylene, and other polyolefin waxes, higher fatty acids such as stearic acid, palmitic acid, lauric acid, aluminum stearate, barium stearate, zinc stearate, zinc palmitate, and metallic substances thereof can be preferably used.

The amount of addition is 100 parts by weight of the binder resin,
0.5 to 20 parts by weight is preferable. If it is less than 0.5, the effect of improving translucency cannot be obtained. When it is more than 20, not only the fluidity of the toner is lowered, but also when it is added more than that, the toner is saturated and the effect is not improved.

Also, the dispersion average particle diameter of the wax in the binder resin is 0.1 to 1.5 μm, and the dispersion particle diameter distribution is 0.1.
35% by number or less of particles less than μm, 0.1 to 2.0 μm
65% by number or more, and particles exceeding 2.0 μm are 5
It is preferably not more than a few percent. The particle size and the number thereof were obtained from the cross-sectional photograph of the toner by TEM.

The dispersion average particle diameter is smaller than 0.1 μm,
When the number of particles of less than 0.1 μm is more than 35% by number, the releasing effect as a releasing agent is small and the fixing ability cannot be exhibited. Dispersion average particle size is greater than 1.5 μm, 2.0 μ
When the number of particles exceeding m is more than 5% by number, the dispersibility of the wax in the resin is deteriorated and the repulsion due to the charge action of the toner is less likely to be alleviated. In addition, fog and toner scattering increase.

(Embodiment 2: Binder Resin) The binder resin of this embodiment has a molecular weight distribution of 2 × 10 ³ to GPC.
It has at least one maximum molecular weight peak in the 3 × 10 ⁴ region and 3 × as a component existing in the high molecular weight region.
It has a molecular weight component of 10 ⁴ or more in an amount of 5% or more with respect to the entire binder resin, has a weight average molecular weight of 10,000 to 300,000, a Z average molecular weight of 20,000 to 500,000, and a ratio of the weight average molecular weight to the number average molecular weight ( Weight average molecular weight / number average molecular weight) is 3 to 100, ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 10 to 2000, and 1 by Koka type flow tester
/ 2 method melting temperature (hereinafter softening point) 80-150
C., the outflow starting temperature is 80 to 120.degree. C., and the resin preferably has a glass transition point of 45 to 68.degree. C. as a component.

The weight average molecular weight is preferably 10,000 to 12
10,000, Z average molecular weight 20,000 to 300,000, weight average molecular weight / number average molecular weight 3 to 50, Z average molecular weight / number average molecular weight 10 to 1000, softening point 90 to 140 ° C., outflow starting temperature 85 to It is preferable to use a polyester resin having a glass transition point of 115 ° C. and a glass transition point of 52 to 65 ° C. as a component. More preferably, the weight average molecular weight is 10,000 to 40,000, the Z average molecular weight is 20,000 to 100,000, the weight average molecular weight / number average molecular weight is 3 to 20, and the Z average molecular weight / number average molecular weight is 10 to 1.
00, the softening point is 105 to 135 ° C, and the outflow starting temperature is 90.
It is preferable to use a polyester resin having a glass transition point of -120 ° C and a glass transition point of 58-65 ° C as a component.

As a component existing in the high molecular weight region,
It is preferable to have a molecular weight component of 1 × 10 ⁵ or more in an amount of 3% or more based on the entire binder resin. Further, as a component existing in the high molecular weight region, it is preferable to have a molecular weight component of 3 × 10 ⁵ or more in an amount of 0.5% or more based on the entire binder resin.

[0095] Preferably the components present in the high molecular weight region, a 8 × 10 ⁴ ~1 × 10 ⁷ molecular weight component with respect to the entire binder resin 3% or more, and 1 × 10 ⁷ or more components does not contain The configuration is preferred.

More preferably, as a component existing in the high molecular weight region, a high molecular weight component of 3 × 10 ^{5 to} 9 × 10 ⁶ is contained in an amount of 1% or more based on the entire binder resin, and a component of 9 × 10 ⁶ or more. Is not contained.

More preferably, as a component existing in the high molecular weight region, a high molecular weight component of 7 × 10 ^{5 to} 6 × 10 ⁶ is contained in an amount of 1% or more based on the entire binder resin, and a component of 6 × 10 ⁶ or more. Is not contained.

If the amount of the high molecular weight component is too large, or if it is too large, the large molecular weight component remains during kneading, which impairs the light transmitting property. In addition, the production efficiency of the resin itself is reduced. Unnecessary scratches are applied to the developing roller supply roller, causing vertical streaks in the image. In addition, the dispersibility of the wax decreases.

The weight average molecular weight of the binder resin is less than 10,000, the Z average molecular weight is less than 20,000, and the weight average molecular weight /
Number average molecular weight less than 3, Z average molecular weight / number average molecular weight less than 10, softening point less than 80 ° C, outflow starting temperature less than 80 ° C, glass transition point 45 ° C.
When it is smaller, the dispersibility at the time of kneading decreases, resulting in increased fog and poor durability. Further, the kneading stress during kneading is not sufficiently applied, and the molecular weight cannot be maintained at an appropriate value. The dispersibility of the wax and charge control agent in the resin deteriorates, and the repulsion due to the charge action of the toner is less likely to be alleviated. In addition, fog and toner scattering increase. In addition, offset resistance and high-temperature storability are deteriorated, further, cleaning failure on the transfer member and filming on the photosensitive member occur.

The binder resin has a weight average molecular weight of more than 300,000, a Z average molecular weight of more than 500,000, a weight average molecular weight / number average molecular weight of more than 100, and a Z average molecular weight /
Number average molecular weight is greater than 2000 and softening point is 150 ° C.
If the outflow starting temperature is higher than 120 ° C. and the glass transition point is higher than 68 ° C., the load during the processing of the machine becomes excessive and the productivity is extremely lowered, or the transparency of the color image is lowered. This leads to a decrease in fixing strength.

Further, the molecular weight distribution in GPC of the toner after being melt-kneaded and pulverized and classified is 2 × 10 ^{3 to} 3
× at least one molecular weight maximum peak in 10 ^fourth region, the region of 5 × 10 ⁴ to 1 × 10 ⁶ is that a structure having at least one molecular weight maximum peak or shoulder.

The maximum molecular weight existing on the low molecular weight side of the toner
The peak is preferably 3 × 10³~ 2 x 10^FourIn the area of
Have at least one, more preferably 4 × 10³~ 2x
10 ^FourIt is a structure having at least one in the area.

The position of the maximum molecular weight peak or shoulder on the high molecular weight side of the toner is preferably 6 × 10 5.
It has at least one in the region of ^{4 to} 7 × 10 ⁵ , and more preferably has at least one peak or shoulder of the maximum molecular weight in the region of 8 × 10 ^{4 to} 5 × 10 ⁵ .

When the maximum molecular weight peak position of the molecular weight distribution of the toner existing on the low molecular weight side is smaller than 2 × 10 ³ , the durability is deteriorated, and when it is larger than 3 × 10 ⁴ , the fixing property is deteriorated and the light transmitting property is reduced. descend.

Also, the molecules of the toner existing on the high molecular weight side
The position of the maximum molecular weight peak or shoulder in the mass distribution is 5
× 10^FourIf it becomes smaller, the offset resistance will decrease,
Storage stability deteriorates. Deterioration of developability and waste toner recycling
The rolling property is also reduced. 1 x 10 ⁶Grindability becomes larger
Decrease, leading to a decrease in production efficiency.

Further, it is preferable that the content of the high molecular weight component of 5 × 10 ⁵ or more as the component existing in the high molecular weight region of the toner is 10 wt% or less based on the whole binder resin. The large amount of components existing in the high molecular weight region of 5 × 10 ⁵ or more, or the huge state is a result of the problem that the kneading state fails because uniform kneading stress is not applied to the toner constituent materials during kneading. This significantly impairs the translucency. Also, increase in fog due to poor dispersion, developing roller,
The supply roller is damaged, the pulverizability of the toner is deteriorated, and the manufacturing efficiency is reduced.

More preferably, the content of the high molecular weight component of 5 × 10 ⁵ or more is 5% or less with respect to the entire binder resin,
More preferably, the content of the high molecular weight component of 1 × 10 ⁶ or more is 1% or less based on the entire binder resin, or the high molecular weight component is not contained.

In the molecular weight distribution in the GPC chromatogram of the toner, the height of the molecular weight distribution of the maximum molecular weight peak existing in the region of 2 × 10 ^{3 to} 3 × 10 ⁴ is Ha, 5 ×.
Letting Hb be the maximum molecular weight peak or shoulder height existing in the region of 10 ⁴ to 1 × 10 ⁶ , Hb / Ha is 0.
It is set to 15 to 0.9.

When Hb / Ha is smaller than 0.15, the offset resistance is deteriorated, the storage stability is also deteriorated, and the filming on the developing sleeve or the photosensitive member is promoted. When it is larger than 0.9, the developing roller supply roller is scratched, the pulverizability is deteriorated, the productivity is lowered, and the cost is increased. More preferably, Hb / Ha is 0.15 to 0.7, and even more preferably Hb / Ha is 0.2 to 0.6.

In the molecular weight distribution of GPC of the toner, at least one molecular weight maximum peak is in the region of 2 × 10 ^{3 to} 3 × 10 ⁴ , and at least one molecular weight maximum peak is in the region of 5 × 10 ⁴ to 1 × 10 ^6. Or, in the structure having a shoulder, focusing on the molecular weight curve in a region larger than the maximum peak of the molecular weight distribution existing in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ⁶ or the molecular weight value corresponding to the shoulder, the molecular weight distribution Maximum peak or shoulder height as standard 10
As 0%, the molecular weight corresponding to a height of 90% of the peak of the molecular weight or shoulder was M90, and the molecular weight corresponding to a height of 10% of the peak of the molecular weight or shoulder was M10. In this case, it can be realized by setting M10 / M90 to 0.5 to 8. Furthermore, (M1
By setting 0-M90) / M90 to 0.1 to 7, high translucency can be secured, and oilless fixing capable of preventing offset can be realized without requiring fixing oil.

The above M10 / M90, and (M10
Defining the value of (-M90) / M90 (the slope of the molecular weight distribution curve) can quantify the state of molecular cleavage of the ultrahigh molecular weight component, and this value is within the range described above (the slope of the molecular weight distribution curve. Is abrupt), the ultra-high molecular weight component that inhibits the translucency disappears due to cutting during kneading, resulting in high translucency. Further, the high molecular weight component forming a peak or shoulder appearing on the high molecular side contributes to the anti-offset property, and it is possible to prevent the offset of the color toner from occurring without using oil.

Further, when the ultrahigh molecular weight component is molecularly cut, it is possible to uniformly disperse the wax and the charge control agent in the binder resin, so that the charge amount becomes uniform and a clear resolution is obtained. It does not deteriorate the durability even if it is used continuously for a long period of time. Further, the cleaning property of the transfer member is improved, the vertical stripes are not generated on the developing roller, and the image disturbance at the time of transfer and the void can be prevented, and the highly efficient transfer property can be obtained.

When the value of M10 / M90 is larger than 8 or (M10-M90) / M90 is larger than 7, the ultrahigh molecular weight component still remains and impairs the translucency.
The value of M10 / M90 is smaller than 0.5, or (M1
When 0-M90) / M90 is smaller than 0.1, the mechanical load during kneading becomes excessive and the productivity decreases. Toner durability is reduced. More preferably M10 / M90
Has a value of 0.5 to 6, and (M10-M90) / M90
Is 0.1 to 4.5. More preferably, M10 /
The value of M90 is 0.5 to 4.5, and (M10-M9
0) / M90 is 0.1 to 3.5.

As a result, the digital image quality is improved, the color reproducibility is improved, and the developing roller for contact-type one-component development,
The supply roller can be used stably for a long period of time, and high translucency and offset resistance can be achieved without using offset preventing oil on the fixing roller.Furthermore, a cleaner process is realized, short distance between transfer, It is possible to prevent hollow defects in the transfer process and achieve high transferability in a short-time tandem transfer process.

By kneading the above-mentioned binder resin with a high shearing force in the melt-kneading process, it becomes possible to exhibit characteristics which have never been obtained. By fixing without using oil, it is possible to achieve both high transparency of the color toner and offset resistance. In other words, the binder resin to which the ultra-high molecular weight component has been imparted has a high shearing force, whereby the ultra-high molecular weight component is made to have a low molecular weight, thereby exhibiting high translucency. Offset property can also be satisfied. Further, since it has an ultra-high molecular weight component, a high shearing force is applied during kneading, so that the wax can be more uniformly dispersed, the translucency is improved, non-offset property, high image quality, high color reproducibility, Good transferability can be obtained.

After the melt-kneading treatment, the toner has a weight average molecular weight of 8,000 to 180,000 and a Z average molecular weight of 18,000 to 45.
The weight average molecular weight to number average molecular weight ratio (weight average molecular weight / number average molecular weight) is 3 to 80, and the Z average molecular weight to number average molecular weight ratio (Z average molecular weight / number average molecular weight) is 10 to 1.
000.

By kneading the toner in this suitable range with a high shearing force, it is possible to achieve both high light-transmitting property and offset resistance of the color toner by fixing without using oil.

The weight average molecular weight is preferably 8000 to 1.
It is preferable that the number average molecular weight is 0,000, the Z average molecular weight is 18,000 to 300,000, the weight average molecular weight / number average molecular weight is 3 to 60, and the Z average molecular weight / number average molecular weight is 10 to 500.

More preferably, the weight average molecular weight is 10,000 to
It is preferable that the weight average molecular weight is 40,000, the Z average molecular weight is 20,000 to 80,000, the weight average molecular weight / number average molecular weight is 3 to 30, and the Z average molecular weight / number average molecular weight is 10 to 50.

The weight average molecular weight is less than 8000, and Z
Average molecular weight less than 18,000, weight average molecular weight /
When the number average molecular weight is less than 3 and the Z average molecular weight / number average molecular weight is less than 10, the kneading stress is not sufficiently applied and the molecular weight cannot be maintained at an appropriate value. The dispersibility of the wax is reduced and the offset resistance and the high temperature storage stability are deteriorated.
Further, cleaning failure on the intermediate transfer member and filming on the photosensitive member occur.

When the weight average molecular weight is more than 180,000, the Z average molecular weight is more than 450,000, the weight average molecular weight / number average molecular weight is more than 80, and the Z average molecular weight / number average molecular weight is more than 1000, the shear force pressure is increased. On the contrary, the internal additives such as the charge control agent coagulate with each other, leading to a decrease in dispersibility, resulting in an increase in fogging during the cleaner process, a decrease in image density, and a transfer failure. Further, the fixing strength is lowered, and the light-transmitting property and the glossiness are lowered.

The binder resin contains 5% by weight of THF insoluble component.
Hereinafter, it is preferable that the composition has no THF-insoluble component. If the amount of the THF-insoluble component is more than 5% by weight, it becomes a factor of deteriorating the translucency of the color image, which deteriorates the image quality.

As the binder resin preferably used in this embodiment, a polyester resin obtained by polycondensation of an alcohol component and a carboxylic acid component such as carboxylic acid, carboxylic acid ester and carboxylic acid anhydride is preferably used. .

Examples of the divalent carboxylic acid or lower alkyl ester include aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid and hexahydrophthalic anhydride.
Maleic acid, maleic anhydride, fumaric acid, itaconic acid,
Examples thereof include aliphatic unsaturated dibasic acids such as citraconic acid, aromatic dibasic acids such as phthalic anhydride, phthalic acid, terephthalic acid, and isophthalic acid, and their methyl esters, ethyl esters, and the like. Among these, aromatic dibasic acids such as succinic acid, phthalic acid, terephthalic acid and isophthalic acid, and lower alkyl esters thereof are preferable. It is preferable to use a combination of succinic acid and terephthalic acid or phthalic acid and terephthalic acid.

As the trivalent or higher carboxylic acid component, 1,
2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalene tricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexatricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, Examples thereof include pyromellitic acid, enpol trimer acid, acid anhydrides thereof, and alkyl (C1-12) esters.

Examples of the dihydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol and 1,4.
-Butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and other diols, glycerin, trimethylolpropane, trimethylolethane, etc. Examples are triols and mixtures thereof. Especially in this
Bisphenol A represented by (Chemical Formula 1), its derivative, its alkylene oxide adduct, neopentyl glycol, and totimethylol propane are preferable.

[0127]

[Chemical 1]

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,
4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-
Butanetriol, 1,2,5-pentanetriol,
Examples thereof include glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzene.

For the polymerization, known polycondensation, solution polycondensation and the like can be used. As a result, a good toner can be obtained without impairing the vinyl chloride matting resistance and the color of the color material of the color toner.

The ratio of polyhydric carboxylic acid and polyhydric alcohol used is generally 0.8 to 1.4 in terms of the ratio of the number of hydroxyl groups to the number of carboxyl groups (OH / COOH).

The molecular weights of the resin, wax and toner are values measured by gel permeation chromatography (GPC) using several kinds of monodisperse polystyrene as standard samples.

The equipment is HPLC8120 series manufactured by Tosoh Corporation, and the column is TSKgel super HM-H H4.
000 / H3000 / H2000 (7.8 mm diameter, 15
0 mm × 3), eluent THF (tetrahydrofuran),
Flow rate 0.6 ml / min, sample concentration 0.1%, injection rate 2
0 μL, detector RI, measurement temperature 40 ° C. The pretreatment for measurement is to dissolve the sample in THF and filter with a 0.45 μm filter to measure the resin component from which additives such as silica have been removed. The measurement conditions are such that the molecular weight distribution of the target sample falls within a range in which the logarithm of the molecular weight and the count number are linear in the calibration curve obtained from several kinds of monodisperse polystyrene standard samples.

The softening point of the binder resin was measured by a flow tester (CFT500) manufactured by Shimadzu Corporation while heating a 1 cm ³ sample at a heating rate of 6 ° C./min with a plunger of about 9.8 × 10 ⁵ N. / Mm ² load is applied and the product is extruded from a die with a diameter of 1 mm and a length of 1 mm, and the temperature at which the piston stroke begins to rise begins to flow out due to the relationship between the piston stroke of this plunger and the temperature rise temperature characteristic of the temperature. The temperature (Tfb), 1/2 of the difference between the minimum value of the curve and the outflow end point is calculated, and the temperature at the point where the minimum value of the curve and that of the curve are added is the melting temperature (softening point Tm) in the 1/2 method. .

The glass transition point of the resin was measured by using a differential scanning calorimeter, the temperature was raised to 100 ° C., left at that temperature for 3 minutes, and then cooled to room temperature at a temperature lowering rate of 10 K / min. The temperature at the intersection of the extension line of the base line below the glass transition point and the tangent line showing the maximum slope from the rising part of the peak to the apex of the peak when the heat history is measured at 10 K / min. Say

For the melting point of the endothermic peak by DSC, a differential calorimeter DSC-50 manufactured by Shimadzu Corporation was used. 5K /
The temperature was raised to 200 ° C. for 5 minutes, rapidly kept at 10 ° C. for 5 minutes, allowed to stand for 15 minutes, then raised at 5 K / min, and determined from the endothermic (melting) peak. The amount of sample put into the cell was 10 mg ± 2 mg.

As the binder resin preferably used in this embodiment, homopolymers or copolymers of various vinyl monomers can also be preferably used. For example, styrene, O-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn butyl styrene, p-tert-butyl styrene, pn
-Hexyl styrene, pn-octyl styrene, p-
Examples thereof include styrene and derivatives thereof such as n-hexylstyrene and P-chlorostyrene, and styrene is particularly preferable.

As the acrylic monomer, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate,
Methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, β-hydroxyacrylate, γ-hydroxyacrylate propyl α-hydroxyacrylate, β-hydroxymethacrylate, γ-aminopropylacrylate, γ Examples thereof include -N, N-diethylamino acrylate propyl ester, ethylene glycol dimethacrylate ester, and tetraethylene glycol dimethacrylate ester. The styrene-acrylic copolymer suitable for the purpose of the present invention is a styrene / butyl acrylate copolymer, and particularly preferably a styrene / butyl acrylate copolymer containing 75 to 85% by weight of styrene and 15 to 25% by weight of butyl acrylate. used.

The polymer is produced by bulk polymerization,
Known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. A method in which bulk polymerization is performed to a polymerization rate of 30 to 90% by weight and then a solvent and a polymerization initiator are added and the reaction is continued by solution polymerization is also preferable.

(Third Embodiment: Charge Control Agent) In the present embodiment, a charge control agent is added for the purpose of charge control of the toner and for strengthening oilless fixing. A preferred material is an acrylic sulfonic acid type polymer,
A vinyl copolymer of a styrene monomer and an acrylic acid monomer having a sulfonic acid group as a polar group is preferable. Particularly, a copolymer with acrylamido-2-methylpropanesulfonic acid can exhibit preferable characteristics.

As a preferable material, a metal salt of a salicylic acid derivative shown in Chemical formula 2 is used.

[0141]

[Chemical 2]

As a preferred material, the metal salt of the benzylic acid derivative shown in Chemical formula 3 is used.

[0143]

[Chemical 3]

With this structure, a wide non-offset temperature range can be secured in oilless fixing, and image disturbance due to the charging action at the time of fixing can be prevented. It is considered that this is due to the effect of the functional group having the acid value of the wax and the charge polarity of the metal salt. In addition, it is possible to prevent the charge amount from decreasing during continuous use. Blade fusion during development can be suppressed.

The amount of addition was 100 parts by weight of the binder resin,
0.5 to 5 parts by weight is preferable. It is more preferably 1 to 4 parts by weight, and further preferably 3 to 4 parts by weight. If the amount is less than 0.5 parts by weight, the charging effect is lost. If it is 5 parts by weight or more, color turbidity in a color image becomes noticeable.

(Fourth Embodiment: External Additive) Further, in the present embodiment, as the external additive, fine powder of metal oxide such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite, magnetite, barium titanate, titanic acid is used. A titanate such as calcium or strontium titanate, a zirconate such as barium zirconate, calcium zirconate or strontium zirconate, or a mixture thereof is used. The external additive is hydrophobized if necessary.

Examples of the silicone oil type material treated with silica include dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, cyclic dimethyl silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, carbinol modified silicone. At least one of oil, methacryl modified silicone oil, mercapto modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, amino modified silicone oil, chlorophenyl modified silicone oil Silica treated as described above is preferably used. For example, Toray Dow Corning Silicone S
H200, SH510, SF230, SH203, BY
16-823, BY16-855B and the like. The treatment is carried out by mixing the inorganic fine powder and a material such as silicone oil with a mixer such as a Henschel mixer, spraying the silicone oil-based material onto silica, or dissolving or dispersing the silicone oil-based material in a solvent. After that, there is a method of preparing by removing the solvent after mixing with silica fine powder. It is preferable to add 0.1 to 10 parts by weight of the silicone oil-based material to 100 parts by weight of the inorganic fine powder.

As the silane coupling agent, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzylmethylchlorosilane,
Examples include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane. The silane coupling agent treatment is a dry treatment of reacting a vaporized silane coupling agent with a fine powder made into a cloud by stirring or the like, or a wet treatment of dropping a silane coupling agent in which fine powder is dispersed in a solvent. It is processed according to the law.

It is also preferable to treat the silicone oil type material after the silane coupling treatment.

The inorganic fine powder having a positive electrode charging property is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil. Further, in order to enhance the hydrophobic treatment, it is preferable to use a combination of treatments with hexamethyldisilazane, dimethyldichlorosilane and other silicone oils. For example, it is preferable to treat with at least one of dimethyl silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil.

At this time, the inorganic fine powder is B by nitrogen adsorption.
ET specific surface area is 5-300 m²/ G is preferred. Better
A good specific surface area is 10 to 250 m²/ G, more preferred
20 to 150 m²It is preferably in the range of / g.
Specific surface area is 5m²If less than / g, the fluidity of the toner
It does not improve and the storage stability decreases. Specific surface area is 300m
²If it is larger than / g, the agglomeration will worsen and uniform external additive treatment will be possible.
It gets harder. In addition, it is easy to induce filming on the photoconductor
Become 0.1 to 100 parts by weight of toner base particles
5 parts by weight, preferably 0.2 to 3 parts by weight is blended.
If it is less than 0.1 parts by weight, the fluidity of the toner cannot be improved,
If it is more than 5 parts by weight, the amount of floating silica increases and the inside of the machine is contaminated.
To do.

The BET specific surface area is 5 to 80 m ² / g.
Inorganic fine powder such as silica and BET specific surface area of 100 to
It is also preferable to use a mixture with 300 m ² / g of inorganic fine powder such as silica. It can be configured to have both the fluidity and durability functions.

When the toner is crushed, the inorganic fine powder is supplied to and mixed with the pulverized product of the toner before the pulverized product of the toner is introduced from the supply port, and the inorganic fine powder is introduced from the supply port and pulverized to a predetermined particle size distribution. Take a configuration. As a result, the pulverized material for toner enters the pulverizing portion having the rotating body in a uniformly dispersed state, and the pulverized material for toner is uniformly pulverized by the vortex flow generated by the rotating body. As a result, it becomes possible to reduce the size of the particles and to grind the coarse powder in a state where it is sharply cut.

The inorganic fine powder supplied and mixed at this time has an average particle size of 8 to 40 nm and a loss on ignition of 0.5 to 10 w.
Silica or titanium oxide fine powder with t% is preferred. Further, silica or titanium oxide fine powder which is surface-treated with one or more of fatty acid ester, fatty acid amide and fatty acid metal salt is preferable. Furthermore, as the inorganic fine powder, silica or titanium oxide fine powder obtained by surface-treating silicone oil is a preferable material. Further, an inorganic fine powder having a charge polarity opposite to that of the toner base particles is also an effective means for relaxing the charge of the pulverized material to be toner.

If the average particle size is smaller than 8 nm, quantitative cutout becomes unstable. If the average particle size is larger than 40 nm, uniform pulverizability will not be improved. If the loss on ignition is less than 0.5 wt%, fine powder will be scattered. Ignition loss is 10w
If it is larger than t%, the agglomeration of the fine powder becomes strong, and the uniform supply of the pulverized material to be toner deteriorates.

For the loss on drying (%), about 1 g of a sample is placed in a container which has been dried, allowed to cool, and precisely weighed, and precisely weighed. Dry for 2 hours in a hot air dryer (105 ° C ± 1 ° C). After allowing to cool for 30 minutes in a desiccator, the weight is accurately weighed and calculated from the following formula.

Loss on drying (%) = loss on drying (g) /
Sample amount (g) × 100 For ignition loss, about 1 g of the sample is placed in a magnetic crucible that has been dried, allowed to cool, and precisely weighed, and the weight is precisely weighed. Ignite for 2 hours in an electric furnace set at 500 ° C. After cooling in a desiccator for 1 hour, the weight is precisely weighed and calculated from the following formula.

Loss on ignition (%) = loss on ignition (g) /
Sample amount (g) × 100 For the measurement of the hydrophobicity, 0.2 g of the product to be tested is weighed out in 50 ml of distilled water charged in a 250 ml beaker. Methanol is dripped at the tip from a buret that is immersed in the liquid until the total amount of the inorganic fine powder becomes wet. At that time, the mixture is stirred slowly with a magnetic stirrer. The degree of hydrophobicity is calculated by the following equation from the amount of methanol a (ml) that is essential for completely wetting.

Hydrophobicity = (a / (50 + a)) × 100 (%) Further, the water adsorption amount of the treated inorganic fine powder is preferably 1 wt% or less. Preferably 0.5 wt% or less,
It is more preferably 0.1 wt% or less, still more preferably 0.05 wt% or less. If it is more than 1 wt%, the charging property is deteriorated and filming on the photoconductor during durability occurs.
The water adsorption amount was measured by using a continuous vapor adsorption device (BELSORP18: Nippon Bell Co., Ltd.) for the water adsorption device.

(Fifth Embodiment: Pigment) Further, as the pigment used in the present embodiment, carbon black, iron black, graphite, nigrosine, a metal complex of azo dye, C.I.
I. Pigment Yellow 1,3,74,97,98 and the like, acetoacetic acid arylamide monoazo yellow pigments, C.I.
I. Pigment Yellow 12, 13, 14, 17 and the like, acetoacetic acid arylamide disazo yellow pigments, C.I.
I. Solvent Yellow 19, 77, 79, C.I. I. Disperse Yellow 164, C.I. I. Pigment Red 48,49: 1,53: 1,57,57: 1,8
Red pigments such as 1,122,5, C.I. I. Solvent Red 49, 52, 58, 8 and other red dyes, C.I. I. Pigment Blue 15: 3 and other phthalocyanines and their blue derivative pigments are blended in one kind or two or more kinds.
The addition amount is preferably 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin.

(Sixth Embodiment: Physical Properties of Toner Powder) By the pulverizing means of the present embodiment, the content of 5 μm or less in the number distribution of the toner containing the binder resin, the colorant and the wax is 60 or less.
It is contained in a number% or more, and the content of 3.17 μm or less in the number distribution is 5 to 35 number% and is 6.35 to 10.1.
It is possible to realize a particle size distribution structure in which toner particles having a particle size of μm are contained at 55% by volume or less without deteriorating the processing capacity.

If the content of 5 μm or less is 60% by number or more, the image quality is remarkably improved. 3.17 μm in number distribution
If the following content is 5 to 35% by number, fine powder classification cutting is hardly required, leading to an improvement in yield. 6.35
When toner particles having a particle diameter of 10.1 μm are 55% by volume or less, toner scattering during development can be reduced.

Further, the specific surface area value St (St = 6 / (true specific gravity × volume average particle diameter)) corresponding to the true sphere converted from the volume average particle diameter SSt (SSt = (St / milled The specific surface area of the toner) can be 0.4 to 0.9, preferably 0.5 to 0.85, and more preferably 0.55.
It is 0.8. If it is larger than 0.9, spheroidization is promoted, the chargeability is deteriorated, and problems such as scattering at the time of transfer are caused.
If it is less than 0.4, the shape becomes too irregular, or the amount of finely pulverized powder is large.

The volume average particle diameter of the toner can be set to 4 to 6.5 μm. Coefficient of variation of volume particle size distribution of toner is 15 to 35%, coefficient of variation of number particle size distribution is 20 to 40%
Is preferred. More preferably, the coefficient of variation of the volume particle size distribution is 15 to 30%, the coefficient of variation of the number particle size distribution is 20 to 35%, and even more preferably, the coefficient of variation of the volume particle size distribution is 15 to 25%. The coefficient of variation of distribution is 20 ~
30%.

The coefficient of variation is the standard deviation in the particle size of the toner divided by the average particle size. It is based on the particle size measured using a Coulter counter (Coulter Co.). The standard deviation is the square of the difference from the average value of the measured values (n-
It is expressed as the square root of the value divided by 1).

That is, the coefficient of variation refers to the extent of spread of the particle size distribution, and the coefficient of variation of the volume particle size distribution is 15%.
When the coefficient of variation of the number particle size distribution is less than 20% or less than 20%, it is difficult to be produced and the cost is increased.
If the variation coefficient of the volume particle size distribution is more than 35% or the variation coefficient of the number particle size distribution is more than 40%, the cohesiveness of the toner becomes strong when the particle size distribution becomes broad, and filming and transfer to the photoconductor are performed. Defective, it becomes difficult to collect the residual toner in the cleanerless process.

The fine powder in the toner causes the fluidity of the toner, the image quality,
It affects storage stability, filming on the photosensitive member, the developing roller, and the transfer member, aging characteristics, transferability, and in particular, tandem multi-layer transferability. Furthermore, it affects the non-offset property, glossiness, and translucency in oilless fixing. In a toner containing a release agent such as wax to realize oilless fixing, the amount of fine powder affects the compatibility with tandem transferability.

If the amount of fine powder is excessive, the wax that cannot be completely dispersed is exposed on the toner surface, and filming occurs on the photosensitive member, the developing roller and the transfer member. Further, since the fine powder has a large adhesion to the heat roller, it tends to be offset. Further, in the tandem system, toner aggregation is likely to be strong, and a transfer failure of the second color is likely to occur during multi-layer transfer. When the amount of fine powder decreases, the image quality deteriorates.

Particle size distribution is measured by Coulter counter TA
-Using a type II (Coulter Counter), an interface (manufactured by Nikkaki) that outputs the number distribution and volume distribution and a personal computer are connected to perform measurement. An electrolyte solution containing a surfactant (sodium lauryl sulfate) at a concentration of 1% was added to about 50 ml of toner to be measured, and 2 mg of toner was measured.
Add about 3 times, and the electrolyte with the sample suspended is about 3
A dispersion treatment was carried out for a minute, and a Coulter counter TA-II type aperture having an aperture of 70 μm was used. 70
With the aperture system of μm, the particle size distribution measurement range is 1.2.
Although it is 6 μm to 50.8 μm, a region of less than 2.0 μm is not practical because the measurement accuracy and the reproducibility of measurement are low due to the influence of external noise and the like. Therefore, the measurement area is 2.0 μm to 5 μm.
It was 0.8 μm.

The degree of compression is calculated from the static bulk density and the dynamic bulk density, which is one of the indicators of the toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the toner particle shape, the external additive, and the type and amount of the wax. When the particle size distribution of the toner is narrow and the amount of fine powder is small, when the surface of the toner has few irregularities and the shape is close to a sphere, and when the amount of external additive added is large,
When the particle size of the external additive is small, the degree of compression is small and the fluidity of the toner is high. The degree of compression is preferably 5 to 40%. More preferably, it is 10 to 30%. It is possible to achieve both oilless fixing and tandem multi-layer transfer. If it is less than 5%, the fixability tends to be low, and particularly the light-transmitting property tends to deteriorate. Toner scattering tends to increase from the developing roller. If the transferability is higher than 40%, the transferability is deteriorated, and hollowing and transfer failure occur in the tandem system.

(Embodiment 7: Kneading method) The wax to be added can be finely dispersed by kneading with a high shearing force and a high compression shearing force. A high dispersion treatment can be achieved by treating the roll temperature setting and temperature gradient, the kneading conditions of the rotation speed and the load current, and the softening point and the glass transition point of the binder resin under optimum conditions. The high shear force is a kneading force that acts on a toner material such as a binder resin by rotating rolls facing each other in a narrow gap at a high speed, and has a rotation speed difference with a force generated when the roll is sandwiched in a narrow gap. The shear force received from a rotating roll. It has a kneading force that cannot be exhibited by conventional twin-screw extruders. This makes it possible to reduce the high molecular weight component of the binder resin.

Specifically, it has two opposing rolls that rotate in different directions and can be heated or cooled. The roll temperature of one roll (RL1) and the roll temperature of the other roll (RL2)
The roll temperature of the rolls is different from that of the rolls (RL
This can be realized by rotating 1) and the roll (RL2) at different peripheral speeds and kneading between the two rolls. Further, one roll (RL1) has a temperature difference between the front half and the rear half.

The rotation speed ratio of the two rolls is 1.1 times to 2.5.
When the amount is doubled, an appropriate shearing force is generated at the time of kneading, the molecular cutting of the binder resin, the dispersibility of internal additives such as colorants are improved, and the fixability and the developability are improved. It is configured to increase the rotation ratio of the roll on the side where the toner is heated to melt and wind the toner. When it is 1.1 times or less, an appropriate shearing force is not generated, the dispersibility is not improved, and the translucency is deteriorated. Conversely, 2.
When it is 5 times or more, the productivity is drastically lowered, the dispersibility is not improved, and the developability is deteriorated.

By kneading under a condition that the ratio of the load current values applied to the two rolls at this time is in the range of 1.25 to 10, proper shearing force is applied and the dispersibility of the internal additive is further improved. Is improved. If it is smaller than this range, the dispersibility is not improved and the light-transmitting property is deteriorated. Also, the productivity is reduced. On the other hand, if it is larger than this range, the load applied to the roller becomes too large, and the ultra-high molecular weight component becomes too low in molecular weight, so that the non-offset property deteriorates and offset occurs.

FIG. 1 is a schematic perspective view of the toner melt-kneading process, FIG. 2 is a plan view, FIG. 3 is a front view, and FIG. 4 is a side view. Reference numeral 601 denotes a toner raw material quantitative feeder, 602 a roll (RL1), 603 a roll (RL2), 604 a molten film of toner wound around the roll (RL1), 602-
Reference numeral 1 denotes the first half of the roll (RL1) (upstream in the raw material transport direction), 602-2 denotes the second half of the roll (RL2) (downstream in the raw material transport direction), and 605 denotes the first half of the roll (RL1) 602. Inlet of heat carrier for heating -1; 606
Is an outlet of the heat medium that has heated the front half 602-1 of the roll (RL1), and 607 is the rear half 602 of the roll (RL1).
-2 for heating or cooling the medium, 608 for heating or cooling the latter half 602-2 of the roll (RL1), 609 for heating or cooling the roll (RL2) 603 A medium inlet, 610 is a medium outlet for heating or cooling the roll (RL2) 603, 6
11 is a spiral groove on the surface of the roll, the depth is 2 to 10
Approximately mm, 612 is a toner pool formed between the rolls. The spiral groove 611 is preferable so that the material can be smoothly conveyed from the right end of the raw material input part to the left end of the discharge part when the toner is kneaded.

The toner raw material is fed from the opening portion 614 through the raw material supply feeder 613 from the constant quantity supply device by the arrow 615.
As described above, the roll (RL1) is dropped near the end on the side of 602-1. The length of the feed feeder opening is represented by 616. This length is preferably 1/2 to 4 times the roll radius. If the length is short, the amount of material falling down from the gap between the two rollers increases rapidly before the material to be dropped melts. If it is too long, the raw material will be separated during the transportation by the raw material feeder and uniform dispersion cannot be obtained.

Further, as shown by the arrow in FIG. 4, the dropping position is dropped to a point in the range of 20 ° to 80 ° from the point where the two rolls of the roll (RL1) 602 are closest to each other. Two
If the angle is smaller than 0 °, the amount dropped from the gap between the two rolls increases rapidly. If it is more than 80 °, the toner powder will fly up a lot when it is dropped, and the surroundings will be contaminated. Further, the cover 617 is installed so as to cover an area wider than the opening length 616. Illustration of the cover is omitted in FIG.

The toner raw material is dropped from the opening 614 while passing through the feed feeder 613 from the constant quantity feeder 601. The toner raw material that fell is roll (RL1) 602-1
It is dropped near the end on the side. Then, the resin is melted by the heat of 602-1 and the compressive shearing force of the roll (RL2) 603, and the resin is wound around the front half portion 602-1 of the roll (RL1). That state is the second half 602 of the roll (RL1).
-Extend to the end of -2, the first half 6 of the roll (RL1)
The toner is peeled off from the latter half 602-2 of the roll (RL2) heated or cooled at a temperature lower than 02-1. The roll 603 is cooled to room temperature or lower during the above process. The clearance between the roll (RL1) 602 and the roll (RL2) 603 is 0.1 to 0.9 mm.
Is. In this embodiment, the amount of raw material charged is 10 kg / h, the diameter of the rolls (RL1) (RL2) is 140 mm, and the length is 8
It was performed at 00 mm.

(Embodiment 8: Pulverization) The toner according to the present embodiment is capable of pulverizing with a small particle diameter, and in order to make the distribution on the coarse powder side sharp, after the toner composition is melted and kneaded, irregularities are formed on the surface. And a cylindrical rotating body that rotates at high speed, and a cylindrical rotating body that is fitted with a gap of 0.5 mm to 40 mm outside the rotating body, shares the central axis with the rotating body, and has irregularities on the surface. It is pulverized into a predetermined particle size distribution by a pulverizer having a fixed body, a supply port for introducing the toner pulverized product, and an outlet for ejecting the pulverized toner pulverized product. At this time, before the pulverized material to be toner is introduced from the supply port, a means for relaxing the aggregation of the pulverized material to be toner is added, and the pulverized product is introduced from the supply port and pulverized to a predetermined particle size distribution.

As means for alleviating the agglomeration of the pulverized material to be toner, an evaporative medium such as water vapor, ethanol, iso-propyl alcohol, etc. may be added to the pulverized material to be toner before the pulverized material to be toner is introduced from the supply port. The purpose is to be able to remove the charge of the powder with n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, or the like.
This is a method of spraying and supplying the toner to be pulverized in the form of mist so that the toner is mixed or adhered, and then flowed from the pulverization supply port.

Further, before the pulverized material to be toner is made to flow in from the supply port, a vibrating means is added to the pulverized material to be supplied to supply the pulverized material. As the vibrating means, there are ultrasonic vibration, vibration vibration and the like. Before the pulverized material to be toner passes through the pipe and flows in from the pulverizing part supply port, the pipe part is provided with a vibrating device to disperse the pulverized material to be supplied from the supply port.

Further, before the pulverized material to be toner is made to flow in from the supply port, an inorganic fine powder is supplied to and mixed with the pulverized material to be toner in the pulverized material to be toner, and is made to flow in and pulverized from the supply port. There is. The above-mentioned materials are suitable as the inorganic fine powder. The inorganic fine powder adheres to the toner surface in an electrostatically attached state without being fixed to the toner base. Less than about half of the input amount is taken to the bag filter. The supply amount of the inorganic fine powder is preferably about 0.1 to 5 wt% of the supply amount of the pulverized material to be toner.

Crushing efficiency and spheroidization are achieved by setting the gap between the convex portion of the rotating body and the convex portion of the fixed body to 0.5 to 40 mm, preferably 0.5 to 10 mm, more preferably 0.5 to 6 mm. The action can be further enhanced. If it is smaller than 0.5 mm, the contact between the particles and the rotating body and the fixed body is remarkably increased, so that the frictional heat is remarkably generated and the toner is fused at the above-mentioned tip portion. If it is larger than 40 mm, a violent flow of high-speed airflow cannot be generated, and sufficient pulverizability cannot be obtained.

When this method is used, the spheroidizing treatment can be performed at the same time as the pulverization, so that there is a great merit that the manufacturing process can be shortened. According to this method, the toner has a finely rounded corner and is spherical, so that the fluidity is dramatically improved.

When the fluidity of the toner is low, unevenness is generated in the solid image portion, the triboelectric chargeability is lowered, the amount of reverse polarity toner is increased, and the toner is strongly adhered to the non-image portion of the photoconductor and cannot be removed. The image becomes ground fog and deteriorates the image, and the transfer efficiency is lowered. Increasing the amount of silica as an external additive to improve the fluidity of the toner makes the triboelectric charge uniform and reduces the background fog.
The increase in image density and the unevenness in the solid black image portion tend to be eliminated. However, problems such as filming of silica or toner on the photoconductor and adhesion of white spots on the solid black image portion of silica aggregates occur.

Therefore, a high flowability can be obtained with a small amount of silica added, the generation of floating silica can be suppressed, and white spots of silica on solid black image areas, silica on intermediate transfer members and photoconductors, and toner The occurrence of filming is suppressed. Further, it is possible to suppress the occurrence of unevenness in the solid black image portion, which is seen with the low-fluidity toner, to obtain uniform transferability, and to suppress the generation of reverse polarity toner to a low level, which is a factor of improving transfer efficiency.

Further, at the time of transfer, especially at high temperature and high humidity,
Even when the toner such as characters or lines is concentrated, even if the toner is transferred with a predetermined pressing force, the high fluidity of the toner makes it difficult for the toner particles to aggregate with each other, and a clear image with no voids can be obtained.

One example of the toner crushing device of the present embodiment shown in FIG. 5 will be described.

The kneaded product is roughly crushed to a mesh size of about 1 to 5
Toner pulverized product 503 that has passed mm is a constant amount supply device 508.
The cooling air 511 supplied from the cooling unit 509 is sent to the crushing supply unit, and the crushing processing unit 5
It is crushed with 00. The raw material 503 is introduced from the inlet 504, rotates at a high speed, and has the uneven portion 506 on the surface thereof.
01 and a fixed body 502 having a concave and convex portion 507 on the surface of the rotating body 501 and a narrow gap, and a high-speed airflow generated between the rotating body and the fixed body rotating at high speed. Along with the flow of, the raw material particles are pulverized by a strong collision and are spheroidized. The spherical particles 510 exit from the outlet 505 and are sent to the coarse powder classifier 513, and the coarse particles are reintroduced by the air 511 into the inlet 50.
Sent to 4. The product is sent to the cyclone 515 and collected in the collecting container 520. Reference numeral 512 is a thermometer, 514 is a bag filter, 516 is an air flow meter, and 517 is a blower.

Reference numeral 519 is a vibrator vibration device, and 518 is an inorganic fine powder supply device. When separated by coarse powder classification and supplied again to the crushing section, it is preferable to supply the inorganic fine powder supply from the rear. As a result, the inorganic fine powder is uniformly mixed when it collides with the pulverized product. Instead of the inorganic fine powder, an evaporative solvent can be supplied as the medium. In this embodiment, the crushing condition is a peripheral speed of the rotating body: 130 m / s, a gap between the rotating body and the fixed body: 1.5 mm, and a supply amount of the pulverized material to be toner:
5 kg / h, supply amount of inorganic fine powder: 0.03 kg / h,
Cooling air temperature: 0 ° C., discharge part temperature: 45 ° C., crushing condition Peripheral speed of rotating body: 120 m / s, gap between rotating body and fixed body:
1 mm, toner pulverized material supply rate: 5 kg / h, inorganic fine powder supply rate: 0.02 kg / h, cooling air temperature: 0 ° C.,
The discharge temperature was 40 ° C.

(Embodiment 9: Two-component development, carrier)
In the developing process of this embodiment, the resistance of resin coating on magnetite or ferrite particles is 1 × 10 ⁹ to 1 × 1.
It is suitable for two-component development by mixing with a carrier having a particle size of 0 ¹⁴ and a particle size of 30 to 80 μm.

An AC bias as well as a DC bias is applied between the photoconductor and the developing roller.

At that time, the frequency is 1 to 10 kHz, the AC bias is 1.0 to 2.5 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.2 to 1 :. Two
Is preferred.

More preferably, the frequency is 3.5-8 kHz.
z, the AC bias is 1.2 to 2.0 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.5.
˜1: 1.8.

Further preferably, the frequency is 5.5 to 7 kHz.
z, the AC bias is 1.5 to 2.0 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.6.
˜1: 1.8.

By using this developing process configuration and the toner of the present embodiment, dots can be reproduced faithfully and the development γ characteristic can be repelled. Both high-quality images and oil-less fixability can be achieved. Further, it is possible to prevent charge-up even in a high-resistance carrier under low humidity, and to obtain a high image density even in continuous use. This is because it is possible to reduce the adhesion with the carrier, maintain the image density, reduce the fog, and faithfully reproduce the dots, by using a toner that can express high chargeability, and the combination of the carrier configuration and the AC bias. .

If the frequency is lower than 1 kHz, dot reproducibility deteriorates and halftone reproducibility deteriorates. Frequency is 10
When the frequency is higher than kHz, it cannot follow in the developing area,
No effect. In the range of this frequency, in two-component development using a high resistance carrier, it works for the reciprocal action between the carrier and the toner rather than between the developing roller and the photoconductor, and has the effect of releasing the toner minutely from the carrier. Good reproducibility and halftone reproducibility are achieved, and high image density can be obtained.

If the AC bias is smaller than 1.0 kV (p-p), the effect of suppressing charge-up cannot be obtained, and if the AC bias is larger than 2.5 kV (p-p), fog increases. When the peripheral speed ratio between the photoconductor and the developing roller is less than 1: 1.2 (the developing roller becomes slow)
Image density is difficult to obtain. When the peripheral speed ratio between the photoconductor and the developing roller becomes larger than 1: 2 (the developing roller speed increases)
And toner scattering increases.

The carrier used in the two-component development is prepared by providing a resin coating layer on the surface of ferrite particles. The main material of the ferrite is Fe ₂ O ₃ and NiO, CuO, CoO, MgO, ZnO, MnC.
O ₃ , BaCO ₃ , and SrCO ₃ are mixed and used as a raw material.
The ferrite particles are prepared by a wet method or a dry method, and the dry method is preferable. In the dry method, the raw materials are mixed and then calcined,
It is pulverized in water by a ball mill or the like, and polyvinyl alcohol, a defoaming agent and a dispersant are further added as a binder to prepare a granulating chiller. The chiller is granulated while being dried by heating with a spray dryer, and is then subjected to main firing. Main firing is 900
It is performed at ˜1400 ° C. for 10 to 30 hours, and then crushed and classified to obtain ferrite particles.

For the coating layer, known methods such as a spray method and a dipping method are used. The coating amount is 0.1 to 2 wt% of the carrier particle weight. The resin used for the resin coating layer is
Fluorine-based resin or silicone-based resin is used. As the carbon black contained in the resin coating layer, carbon blacks produced by various production methods are used, and oil furnace carbon acetylene black is preferable. The average particle size of the carrier is preferably 30 to 70 μm. When the average particle size of the carrier is less than 30 μm, the carrier is easily developed on the photosensitive member, and when the average particle size of the carrier is more than 70 μm, the toner holding force of the carrier becomes weak and toner scattering occurs.

(Embodiment 10: One-component development) In the developing process of this embodiment, an elastic blade such as rubber or metal is brought into contact with an elastic or rigid developing roller at a constant pressure to form a thin layer of toner. It can be suitably used as a one-component developing method in which the toner is formed and developed by contact or non-contact with the photoreceptor. As a one-component developing method, a sponge-type supply roller made of urethane resin and a developing roller made of silicon resin or urethane resin are brought into contact with each other at a constant biting amount,
Toner is supplied from the supply roller to the developing roller, and an elastic rubber or metallic stainless steel doctor blade is brought into contact with the developing roller, or the metallic roller is rotated and brought into contact with the developing roller in the same direction. A developing method is preferably used in which a thin layer of toner is formed, and a toner image is formed by applying the thin layer of the toner to or from the photoreceptor with or without contact with the photoreceptor.

At this time, the frequency of the AC bias is 0.5
-10 kHz, AC bias is 0.3-1.2 kV (p
-P), and the peripheral speed ratio between the photoconductor and the developing roller is 1:
By setting 1.2 to 1: 1.8, dots can be faithfully reproduced, good development γ characteristics can be obtained, and a high quality image can be realized. Then, low ground fog and high image density can be obtained. Frequency is 0.5 to 5 kHz, AC bias is 0.3 to 1.
0 kV (p-p), and the peripheral speed ratio between the photoconductor and the developing roller is more preferably 1: 1.2 to 1: 1.5, further preferably 0.5 to 2 kHz and AC bias. It is 0.5 to 0.9 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.2 to 1: 1.4.

At this time, if the frequency is lower than 0.5 kHz, dot reproducibility deteriorates and halftone reproducibility deteriorates. When the frequency is higher than 10 kHz, it is impossible to follow the development area, and the effect does not appear. AC bias is 0.
When it is smaller than 3 kV (pp), the solid tracking ability maintaining effect cannot be obtained, and when the AC bias is larger than 1.2 kV (pp), fog increases. When the peripheral speed ratio between the photoconductor and the developing roller is smaller than 1: 1.2 (the developing roller becomes slow), it is difficult to obtain the image density. When the peripheral speed ratio between the photoconductor and the developing roller becomes larger than 1: 1.8 (the developing roller speed increases), the toner scattering increases.

The supply roller and the developing roller are rotated in the same direction, and the peripheral speeds of the developing roller and the supplying roller are 1: 1 to 0.8 :.
The developing roller speed is increased at a rate of 0.2. The developing roller is 9.8 to 9.8 × 10 on the surface of the photoconductor.
The electrostatic latent image on the photoconductor is developed by pressing with a pressure of ² (N). The elastic blade is pressed against the developing roller with a pressure of 5 to 5 × 10 ² (N) to form a toner layer.

Further, in order to control the toner supply amount on the developing roller when the toner supply amount supplied from the toner reservoir is conveyed onto the developing roller, a sponge-like supply roller made of urethane resin or the like is used. The contact is made with the developing roller with a constant biting amount of 0.1 to 1 mm with respect to the developing roller.

In order to control the amount of toner supplied from the toner reservoir onto the developing roller when the amount of toner supplied is to be constant, a sponge-like supplying roller made of urethane resin or the like is used as the developing roller. The structure provided in contact with is taken. This is an effective means for regulating the toner conveyance amount to a fixed amount.

However, with the conventional toner, in this developing structure, when it is used for a long period of time, image defects such as scratches on the developing roller and vertical streaks on the image due to foreign matter adhering to the blade are likely to occur. In particular, in order to improve the color fixing property, the use of a binder resin having a low softening property and the toner containing a low melting point release agent occur more remarkably.

Further, the toner conveyance amount on the developing roller decreases during long-term continuous use, and when a solid black image is taken, the density of the latter half of the image partially decreases, and a solid followability defect is likely to occur. . When the charge amount of the toner on the developing roller was measured by a suction method, it was found that the charge amount was significantly reduced. Pursuing further, the charge amount of the toner on the supply roller unit has greatly increased, that is, the decrease in the image density does not mean that the charge amount of the toner has decreased, but the supply roller unit before it is supplied to the developing roller unit. This is because the charging capacity has been increased and the supply capacity from the supply roller to the developing roller has decreased. Therefore, it is necessary to have a configuration capable of ensuring the image density while preventing the toner from scattering. It is also effective to increase the contact pressure of the doctor blade to increase the charging ability of the toner, but the toner is likely to be fused and the developing roller is damaged.

Therefore, it has been found that, by adopting the toner constitution of the present embodiment, it is possible to prevent the generation of vertical stripes on the developing roller, the poor followability of solids, and the fusion of toner without sacrificing the fixing characteristics. It was

This enables uniform dispersion in the resin,
The charge distribution is stabilized, overcharge of the toner on the supply roller is suppressed, the fluidity is stabilized, and the followability of a solid image is improved. Due to the uniform dispersion, the fluidity of the toner can be maintained, the toner can be smoothly conveyed on the developing roller, and the conveying state can be always stabilized. In particular, it is very effective in stabilizing the transportation state under high humidity. At this time, it is preferable that the toner charge amount on the developing roller by the suction type Faraday cage method is | 5 | to | 45 | μC / g. If it is | 5 | μC / g or less, toner scattering increases. If it is more than | 45 | μC / g, it is difficult to obtain the image density.

To measure the charge amount of the toner by the suction type Faraday cage method, the toner on the developing roller is sucked while rotating, and the sucked toner is collected by the filter,
Obtain its weight W (g). Further, the voltage V (V) induced in the capacitor is measured as the charge amount when the charged toner moves during suction, and Q (μC / g) = C (F) × V (V)
The charge amount is calculated from / W (g).

(Embodiment 11: Tandem Color Process) In order to form a color image at high speed, this embodiment has a plurality of toner image forming stations including a photoconductor, a charging unit and a toner carrier, A primary transfer process in which a toner image obtained by visualizing an electrostatic latent image formed on an image carrier is transferred to the transfer medium by bringing an endless transfer medium into contact with the image carrier is successively executed. Then, a multi-layer transfer toner image is formed on the transfer body, and then the multi-layer toner image formed on the transfer body is collectively transferred to a transfer medium such as paper or OHP in a secondary transfer process. In the transfer process configured as described above, when the distance from the first primary transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photoconductor is v (mm / s), d1 / v ≤
The transfer position configuration is 0.65. For example, after the first color yellow toner is primarily transferred,
The time until the primary transfer of the magenta toner of the color is extremely short, charge relaxation of the transfer body or charge relaxation of the transferred toner hardly occurs, and when the magenta toner is transferred onto the yellow toner, the magenta toner is The yellow toner is repelled by the charge action, which causes problems such as a decrease in transfer efficiency and blank characters at the time of transfer. Further, during the primary transfer of the cyan toner of the third color, when the toner is transferred onto the previous yellow and magenta toners, the scattering of the cyan toner, the transfer failure, and the omission of transfer occur remarkably. Further, the toner of a specific particle size is selectively developed during repeated use, and if the fluidity of each toner particle is greatly different, the chances of frictional electrification are different, resulting in variations in the amount of electrification and further deterioration of transferability. Will be invited.

Further, the distance from the primary transfer position of the fourth color of the last black toner to the secondary transfer position is d2 (m
m), when the peripheral speed of the photoconductor is v (mm / s), d
With the transfer position configuration of 2 / v ≦ 0.75, when secondary transfer is performed on a copy sheet at a time, image disturbance occurs due to repulsion caused by mutual charges of toner.

Therefore, by adopting the toner constitution of this embodiment, the internal additive such as wax in the resin is uniformly dispersed,
Since the charge distribution is stabilized and the toner overcharge on the supply roller is suppressed and the fluidity fluctuation can be suppressed, the transfer efficiency can be prevented from being lowered and the character dropout at the time of transfer can be prevented without sacrificing the fixing property. can do.

(Twelfth Embodiment: Cleanerless Process) In the present embodiment, the following charging, exposure, and development are performed without the cleaning process step of collecting the toner remaining on the photoconductor after the transfer process by cleaning. It is suitable for use in an electrophotographic apparatus having a cleanerless process as a basic structure.

By using the toner of the present embodiment, aggregation of the toner can be suppressed, overcharge can be prevented, and chargeability can be stabilized.
It is possible to obtain high transfer efficiency. Further, due to the improved uniform dispersibility in the resin, the good charging property, and the releasing property of the material, the toner remaining in the non-image area can be favorably collected by the development. Therefore, there is no development memory in which the image pattern before the non-image area remains.

(Thirteenth Embodiment: Oilless Color Fixing) This embodiment is preferably used for an electrophotographic apparatus having a fixing process of using a belt type fixing medium as a means for fixing toner. As the belt, a nickel electroformed belt or a polyimide belt having heat resistance and deformability is used. In order to improve the releasability, silicone rubber, fluororubber, or fluororesin is used as the surface layer. Release oils have been applied to these fixing belts to prevent offset. A toner having releasability without using oil eliminates the need to apply release oil. However, if the release oil is not applied, the toner tends to be charged, and if the unfixed toner image approaches the belt, the toner may fly due to the influence of the charging. Especially, it tends to occur at low temperature and low humidity. In addition, when the toner has a certain amount of high molecular weight component added to prevent high-temperature offset and has a certain amount of elastic element, the paper with the fine vertical line pattern of the toner is drawn at the tip of the paper when it is separated from the belt with a large curvature. May cause a tip offset that may be brought to the belt. Also, compared to the conventional rigid fixing roller, the elastic belt type
Oilless causes a problem of shortened life due to scratches.

Therefore, by using the toner of the present embodiment, it is possible to prevent the occurrence of offset without using oil and to obtain high color translucency. Further, the overcharge property of the toner can be suppressed, and the toner fly due to the charging action with the belt can be suppressed. Further, it is possible to prevent the offset toner from being separated from the belt by the effect of the molecular weight distribution and slipperiness of the offset toner which is brought to the belt.

Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to this.

Table 1 shows the properties of the binder resin used in the examples. As the resin, a polyester resin containing bisphenol A propyl oxide adduct, terephthalic acid, trimellitic acid, succinic acid, and fumaric acid as main components was used, and a resin having different thermal characteristics depending on the compounding ratio and the polymerization conditions was used.

[0221]

[Table 1]

Mnf is the number average molecular weight of the binder resin, Mwf
Is the weight average molecular weight of the binder resin, Mzf is the Z average molecular weight of the binder resin, Wmf is the ratio Mwf / Mnf of the weight average molecular weight Mwf to the number average molecular weight Mnf, and Wzf is the Z of the binder resin.
Ratio of average molecular weight Mzf and number average molecular weight Mnf Mzf / M
nf and AV represent resin acid values.

[0223] Tables 2 and 3 show the waxes used in this example and the physical properties thereof. Mnr represents the number average molecular weight of the wax, Mwr represents the weight average molecular weight of the wax, and Mzr represents the Z average molecular weight of the wax. Tw
(° C.) is the melting point by the DSC method, Ct (%) is the melting point +10
The volume increase rate (%) and Ck (wt%) at 220 ° C. represent the heating loss of 220 ° C.

[0224]

[Table 2]

[0225]

[Table 3]

[0226]

[Table 4]

(Table 5) shows the pigments used in this example.

[0228]

[Table 5]

Table 6 shows the charge control agents used in this example and the physical properties thereof.

Examples of the metal salt of salicylic acid derivative include an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. A butyl group and the like. As the metal Y, zinc, nickel,
Examples thereof include cobalt, copper and chromium, with zinc and chromium being preferred. Examples of the metal salt of the benzylic acid derivative include benzene rings for R ^{1 to} R ⁴ , and examples of the alkali metal X include lithium, sodium and potassium, with potassium being preferred.

[0231]

[Table 6]

Table 7 shows the external additives used in this example. The charge amount is measured by a blow-off method of frictional charging with a non-coated ferrite carrier. Two
50 g of carrier and 0.1 g of silica are mixed in a 100 ml polyethylene container in an environment of 5 ° C. and 45% RH, and the mixture is stirred longitudinally at a speed of 100 min ⁻¹ for 5 minutes and 30 minutes, and then 0.3 g is collected. Nitrogen gas 1.96 × 10 ⁴ (P
It was blown for 1 minute in a).

In the case of positive charging, the value at 5 minutes after stirring for 5 minutes is +1.
The value at 30 minutes after stirring for 30 minutes at +00 to +800 μC / g is preferably +50 to +400 μC / g.
Silica in which the charge amount at the 30-minute value maintains 40% or more of the charge amount at the 5-minute value is preferable. If the rate of decrease is large, the amount of charge changes greatly during long-term continuous use, and it becomes impossible to maintain a constant image.

In the negative chargeability, the value at 5 minutes is -100 to -800.
A value of 30 minutes in μC / g is preferably −50 to −600 μC / g. Highly charged silica can exhibit its function with a small amount of addition.

[0235]

[Table 7]

The kneading conditions in this example are shown in (Table 8). T
rj1 (° C.) is the heating temperature of the first half of the roll (RL1),
Trk1 (° C.) is the heating temperature of the second half of the roll (RL1), Tr2 (° C.) is the heating temperature of the roll (RL2), and Rw1
Is the rotational speed of the roll (RL1), Rw2 is the roll (RL1)
The rotation speed of 2), the load current value when the roll (RL1) is rotating are shown as Dr1, and the load current value of the roll (RL2) is shown as Dr2. Raw material input is 15 kg / h, roll (RL
1) (RL2) diameter is 140mm, length is 800mm
I went there.

[0237]

[Table 8]

(Table 9) and (Table 10) show the grinding conditions in this example.

Inorganic fine powder to be supplied before pulverization and its supply amount, vibration of a vibrator, and solvent spraying are applied.

[0240]

[Table 9]

[0241]

[Table 10]

Tables 11 and 12 show the toner material composition and physical property values used in this example.

[0243]

[Table 11]

[0244]

[Table 12]

In the figure, Ss is a specific surface area value of the crushed toner, St is a value expressed by St = 6 / (true specific gravity of toner × volume average particle diameter), and SSt is St that is Ss (crushed It is a value obtained by dividing by the specific surface area value of the toner.

The kneading PCM30 is a conventional twin-screw extruder,
Kneading temperature 110 ° C, rotation speed 200min ^-1 , supply amount 5kg
/ H.

Regarding the compounding ratio of the pigment, charge control agent and wax, the compounding ratio (parts by weight) to 100 parts by weight of the binder resin is shown in parentheses. The external additive indicates the blending amount (parts by weight) with respect to 100 parts by weight of the toner base. External addition processing is FM20B
At stirring blade Z0S0 type, rotation speed 2000min
^-1 , the treatment time was 5 min, and the charged amount was 1 kg.

(Table 13) and (Table 14) show the molecular weight characteristics of the toner after the kneading treatment in this example. As toners, TM1 to TM7 toners of magenta toner were compared and evaluated. Similar results are obtained with yellow, cyan and black toners. Mnv is the number average molecular weight of the toner, Mwv is the weight average molecular weight of the toner, Wmv is the ratio Mwv / Mnv, Wz of the weight average molecular weight Mwv of the toner and the number average molecular weight Mnv.
v is the Z-average molecular weight Mzv and the number-average molecular weight Mnv of the toner
The ratio Mzv / Mnv of is shown.

ML is a molecular weight value showing a maximum molecular weight peak on the low molecular weight side in the molecular weight distribution, MH is a molecular weight value showing a maximum molecular weight peak on the high molecular weight side, Sm is Hb / Ha, S
K1 is M10 / M90, SK2 is (M10-M90) /
M90 is shown.

[0250]

[Table 13]

[0251]

[Table 14]

The molecular weight distribution characteristics are shown in FIGS.

FIGS. 6 and 7 show the binder resin PES-, respectively.
1. Molecular weight distribution characteristics of toner TM-1, FIGS. 8 and 9 are binding resin PES-2, respectively, and molecular weight distribution characteristics of toner TM-2, FIGS. 10 and 11 are binding resin PES-, respectively.
3, toner TM-3 molecular weight distribution characteristics, FIG. 12, FIG.
Are the binding resin PES-4 and the toner TM-4 molecular weight distribution characteristics, respectively, and FIGS. 14 and 15 are the binding resin PES and the binding resin PES, respectively.
-5, toner TM-5 molecular weight distribution characteristics, FIG. 16, FIG.
7 shows the molecular weight distribution characteristics of the binder resin PES-6 and toner TM-6, and FIGS. 18 and 19 show the binder resin pe.
7 shows the molecular weight distribution characteristics of s-7 and toner tm-7. Indicates.

In the binder resin PES-1, a high molecular weight component of 3 × 10 ⁴ or more is present in an area ratio of 5% or more with respect to the entire molecular weight distribution of the binder resin. Further, 3 × 10 ^{5 to} 9 × 10 ⁶ high molecular weight components are used in an area ratio of 1 to the entire binder resin molecular weight distribution.
% Or more. Similarly, PES-2, 3, 4, 5, 6
Also, a high molecular weight component of 3 × 10 ⁴ or more exists in an area ratio of 5% or more with respect to the entire binder resin molecular weight distribution. Also 3 × 1
It has a high molecular weight component of 0 ^{5 to} 9 × 10 ^{6 in} an area ratio of 1% or more with respect to the entire molecular weight distribution of the binder resin.

It can be seen that the toner is molecularly cleaved by kneading and appears as a peak or a shoulder on the side of the polymer component. That is, the component that inhibits the light-transmitting property disappears due to the cutting and appears as a steep slope on the polymer side, which is a factor that maintains the offset resistance without hindering the light-transmitting property. 3x1 for Toner TM-1
The amount of the high molecular weight component of 0 ⁵ or more is 5% or less in the area ratio with respect to the entire toner molecular weight distribution, and the high molecular weight component of 1 × 10 ⁶ or more is hardly contained. Similarly, TM-2, 3,
In 4, 5, and 6 as well, the amount of the high molecular weight component of 3 × 10 ⁵ or more is 5% or less in terms of the area ratio with respect to the entire toner molecular weight distribution.
Almost no high molecular weight component of 0 ⁶ or more is contained.

20 and 21 show examples of molecular weight distribution characteristics. FIG. 20 schematically shows M10 and M90 which have a characteristic of having a sharp molecular weight peak on the polymer component side.
The maximum peak height of the molecular weight distribution is 100%.
FIG. 21 shows M10 and M of the molecular weight distribution characteristics of Toner TM-4.
90 is shown schematically. It appears as a shoulder shape on the side of the polymer component, and the height of the apex of the shoulder of this shoulder portion is used as a reference of 100%. This is the binder resin P
This is because the high molecular weight component of ES3 was molecularly cut by kneading and appeared as a shoulder on the high molecular component side.

The peak height of the distribution on the polymer side is 100
%, The molecular weight curve in a region larger than the molecular weight value corresponding to the maximum peak or shoulder, that is, the region where the slope of the molecular weight distribution curve in this region is negative,
That is, in the right part of the distribution curve, when the height of the peak or shoulder of the molecular weight distribution is 100%, the molecular weight corresponding to 90% of the peak or shoulder of the molecular weight is M90, and the peak or shoulder of the molecular weight is 90%. The molecular weight corresponding to 10% of the height of M is defined as M10. Here, the value of M10 / M90 (the slope of the molecular weight distribution curve) can quantify the molecular cleavage state of the ultrahigh molecular weight component. The small value of M10 / M90 means that the slope of the molecular weight distribution curve is steep, and the component obstructing the light-transmitting property disappears due to the cutting, resulting in high light-transmitting property. Furthermore, the peak appearing on the polymer side contributes to the offset resistance.

Further, FIG. 22 shows the molecular weight distribution characteristic of the wax WA-1, and FIG. 23 shows the molecular weight distribution characteristic of the wax WA-9.

(Embodiment) FIG. 24 is a sectional view showing the arrangement of an image forming apparatus for full-color image formation used in this embodiment. In FIG. 24, the outer casing of the color electrophotographic printer is omitted. The operation of attaching / detaching the transfer belt unit 2 in the printer and inspecting / maintenance of the inside of the printer at the time of paper jam, etc. are performed by tilting the front plate open to largely open the inside of the printer. The transfer belt unit 17 is designed to be attached / detached in a direction parallel to the rotation axis generatrix direction of the photoconductor.

The transfer belt unit 17 is the transfer belt 1
2. First color (yellow) transfer roller 10 made of an elastic body
Y, second color (magenta) transfer roller 10M, third color (cyan) transfer roller 10C, fourth color (black) transfer roller 10K, drive roller 11 made of an aluminum roller, second transfer roller 14 made of an elastic body, Second transfer driven roller 1
3, a belt cleaner blade 16 for cleaning the toner image remaining on the transfer belt 12, and a roller 15 at a position facing the cleaner blade.

At this time, from the first color (Y) transfer position to the second color
The distance to the color (M) transfer position is 42 mm (second color (M)
The transfer position is the third color (C) transfer position, the third color (C) transfer position is the same as the fourth color (K) transfer position), and the peripheral speed of the photoconductor is 100 mm / s.

The transfer belt 12 is used by kneading a conductive filler in an insulating polycarbonate resin and forming a film with an extruder. In this example, as an insulating resin, a film obtained by adding 5 parts by weight of conductive carbon (eg, Ketjen black) to 95 parts by weight of a polycarbonate resin (for example, Iupilon Z300 manufactured by Mitsubishi Gas Chemical Co., Inc.) was used. Also, the surface is coated with fluororesin,
Thickness is about 120 μm and volume resistance is 10 ⁷ to 10 ¹² Ω · c.
m, and the surface resistance is 10 ⁷ to 10 ¹² Ω / □. It is also for improving dot reproducibility. The transfer belt 12 is for effectively preventing loosening and charge accumulation due to long-term use, and the surface of the transfer belt 12 is coated with a fluororesin so that the toner filming on the surface of the transfer belt due to long-term use can be prevented. This is to enable effective prevention. When the volume resistance is less than 10 ⁷ Ω · cm, retransfer easily occurs, and when it is more than 10 ¹² Ω · cm, the transfer efficiency is deteriorated. The first transfer roller is a carbon conductive urethane foam roller having an outer diameter of 14 mm and has a resistance value of 10 ² to 10 ⁶ Ω. During the first transfer operation, the first transfer roller 10 is pressed against the photoconductor 1 through the transfer belt 12 with a pressing force of 1.0 to 9.8 (N), and the toner on the photoconductor is transferred onto the belt. To be done. When the resistance value is smaller than 10 ² Ω, retransfer is likely to occur. Larger than 10 ⁶ Ω, transfer defects are more likely to occur. If it is less than 1.0 (N), transfer failure occurs, and 9.
If it is larger than 8 (N), the transfer character omission occurs.

The second transfer roller 14 is a carbon conductive urethane foam roller having an outer diameter of 20 mm and a resistance value of 10 ² to.
It is 10 ⁶ Ω. The second transfer roller 14 is the transfer belt 1.
It is pressed against the transfer roller 13 via the transfer medium 19 such as 2 and paper, OHP or the like. The transfer roller 13 is configured to be rotatable following the transfer belt 12. The second transfer roller 14 and the counter transfer roller 13 in the second transfer have 5.0 to 2
Pressed with a pressing force of 1.8 (N), the recording material such as paper 19
Toner is transferred from the transfer belt to. Resistance value is 10 ²
If it is smaller than Ω, retransfer is likely to occur. Larger than 10 ⁶ Ω, transfer defects are more likely to occur. If it is less than 5.0 (N), transfer failure will occur, and if it is more than 21.8 (N), the load will be large and jitter will easily occur.

In FIG. 24, four sets of image forming units 18Y, 18M, 18C and 18K for each color of yellow (Y), magenta (M), cyan (C) and black (B) are connected in series as shown in the figure. Are arranged in a shape.

Image forming units 18Y, 18M, 18
C and 18K are composed of the same constituents except for the developer contained therein, so the image forming unit 18Y for Y will be described and the description for the units for other colors will be omitted for the sake of simplicity.

The image forming unit is constructed as follows. 1 is a photoconductor, 3 is pixel laser signal light, 4 is JIS
-Outer diameter 18 mm made of silicone rubber with A hardness of 60 °
The developing roller is pressed against the photoconductor with a force of 21 N and rotates in the direction of the arrow. Reference numeral 6 is a supply roller made of a conductive urethane sponge having an outer diameter of 14 mm, and supplies the toner in the toner hopper to the developing roller. A metal blade 5 forms a toner layer on the developing roller. Although the power supply is omitted, the developing roller 4 has a direct current of -230 V, and
An alternating voltage of V (pp) and a frequency of 1 kHz is applied. A DC bias of −330 V is applied to the supply roller 6.

A charging roller 2 made of epichlorohydrin rubber and having an outer diameter of 12 mm is applied with a DC bias of -1 kV. The surface of the photoreceptor 1 is charged to -450V. Reference numeral 8 is a cleaner, 9 is a waste toner box, and 7 is toner.

The paper is conveyed from below the transfer unit 17, and the paper 19 is fed by the paper feeding roller (not shown) to the nip portion where the transfer belt 12 and the second transfer roller 14 are in pressure contact with each other. A paper transport path is formed in the.

The toner on the transfer belt 12 is transferred to the paper 19 by + 1300V applied to the second transfer roller 14, and is transferred from the fixing roller 201, the pressure roller 202, the fixing belt 203, the heating medium roller 204, and the induction heater section 205. The toner is conveyed to a fixing unit configured and fixed there.

FIG. 26 shows the fixing process diagram. The belt 20 is provided between the fixing roller 201 and the heat roller 204.
It is multiplied by 3. Fixing roller 201 and pressure roller 2
A predetermined weight is applied to the belt 20 and the belt 20.
A nip is formed between the pressure roller 202 and the pressure roller 202. The ferrite core 20 is provided on the outer peripheral surface of the heat roller 204.
6, an induction heater unit 2 including a coil 207
05 is provided, and a temperature sensor 208 is arranged on the outer surface.

The belt is made of Ni of 30 μm as a base material, silicone rubber of 150 μm on it, and PF on it.
It has a structure in which A tubes of 30 μm are superposed.

The pressure roller 202 is pressed against the fixing roller 201 by the pressure spring 209. Toner 210
The recording material 211 having a mark moves along the guide plate 212.

The fixing roller 201 as a fixing member has a length of 250 mm, an outer diameter of 14 mm, and a thickness of 1 mm, which is a hollow roller core metal 213 made of aluminum, and has a rubber hardness (JIS-A) of 20 degrees according to JIS standard. An elastic layer 214 made of silicone rubber having a thickness of 3 mm is provided. A silicone rubber layer 215 having a thickness of 3 mm is formed thereon to have an outer diameter of about 20 mm. It receives a driving force from a driving motor (not shown) and rotates at 100 mm / s.

The heat roller 204 has a thickness of 1 mm and an outer diameter of 2
It consists of a 0 mm hollow pipe. The surface temperature of the fixing roller was controlled to 170 ° C. using a thermistor.

The pressure roller 202 as a pressure member has a length of 250 mm and an outer diameter of 20 mm. This is outer diameter 16
mm, 1 mm thick aluminum hollow roller core metal 216 has a rubber hardness (JIS-
An elastic layer 217 having a thickness of 2 mm and made of silicone rubber having A of 55 degrees is provided. The pressure roller 202 is rotatably installed, and has a width of 5.0 m between the pressure roller 202 and the fixing roller 201 by a spring-loaded spring 209 on one side 147N.
forming a nip width of m.

The operation will be described below. In full-color mode, all Y, M, C, K first transfer rollers 1
0 is pushed up and presses the photoconductor 1 of the image forming unit via the transfer belt 12. At this time, a direct current bias of +800 V is applied to the first transfer roller. An image signal is sent from the laser beam 3 and is incident on the photoconductor 1 whose surface is charged by the charging roller 2 to form an electrostatic latent image. The toner 7 on the developing roller 4 which is in contact with the photoconductor 1 and rotates in the opposite direction visualizes the electrostatic latent image formed on the photoconductor 1.

At this time, the image forming speed of the image forming unit 18Y (100 mm / s equal to the peripheral speed of the photosensitive member) and the moving speed of the transfer belt 12 are such that the photosensitive member speed is 0.5 to 1.5 higher than the transfer belt speed. % It is set to be slow.

In the image forming step, the Y signal light 3Y is input to the image forming unit 18Y, and the image is formed with the Y toner. Simultaneously with image formation, the Y toner image is transferred from the photoconductor 1Y to the transfer belt 12 by the action of the first transfer roller 10Y. At this time, + 800V is applied to the first transfer roller 10Y.
DC voltage was applied.

With a time lag between the first transfer of the first color (Y) and the first transfer of the second color (M), the M signal light 3M is input to the image forming unit 18M, and the image formation by the M toner is performed. At the same time as the image formation, the M toner image is transferred from the photoconductor 1M to the transfer belt 12 by the action of the first transfer roller 10M. At this time, the M toner is transferred on the first color (Y) toner. Similarly, C (cyan), K
An image is formed by the (black) toner, and at the same time when the image is formed, YMCK is performed by the action of the first transfer rollers 10C and 10B.
A toner image is formed on the transfer belt 12. This is a so-called tandem system.

On the transfer belt 12, four color toner images were positionally aligned and overlaid to form a color image. After the final transfer of the B toner image, the four color toner images are fed from a paper feed cassette (not shown) at the same timing.
Are collectively transferred by the action of the second transfer roller 14. At this time, the transfer roller 13 was grounded, and a DC voltage of +1.3 kV was applied to the second transfer roller 14. The toner image transferred on the paper was fixed by the pair of fixing rollers 201 and 202. The paper was then ejected out of the apparatus via a pair of ejection rollers (not shown). The transfer residual toner remaining on the intermediate transfer belt 12 is cleaned by the action of the cleaning blade 16 to prepare for the next image formation.

FIG. 25 shows a tandem system in which the paper 19 is carried on the paper carrying belt 17 without the primary transfer to the belt and the toner on the OPC is directly transferred.

In Table 15, the electrophotographic apparatus of FIG.
The results of image rendering are shown below. In Table 16, the toner is 3
The state of transfer failure at the character portion in the full-color image with overlapping colors and the wrapping property of the paper on the fixing belt during fixing were evaluated.

[0283]

[Table 15]

[0284]

[Table 16]

An image was formed using the toner manufactured as described above by the image forming apparatus shown in FIG. 25. As a result, there was no disturbance of horizontal lines, scattering of toner, voids in characters, etc., and a solid black image was uniform. , An image of extremely high resolution and high quality in which even 16 lines / mm of image lines were reproduced, and a high-density image with an image density of 1.3 or more was obtained. Further, the background fog in the non-image area did not occur. Further, even in the long-term durability test of 10,000 A4 sheets, the fluidity and the image density showed little change and showed stable characteristics. Further, the uniformity when a solid image was taken on the entire surface during development was also good. There is no development memory. Even after continuous use, no abnormal image of vertical stripes was generated. Also, in the transfer, the void is at a level where there is no practical problem, and the transfer efficiency is about 98%. Further, the filming of the toner on the photoconductor and the transfer belt was at a level where there was no practical problem. The cleaning failure of the transfer belt did not occur either. In addition, the toner is not disturbed and the toner does not fly during fixing. Further, even in the cleaner process in which the residual toner at the time of transfer is recovered by the development as it is without using the cleaning blade 8, the recovery can be smoothly performed, and the history of the previous image is not left. Also, in the case of a full-color image in which three colors are overlapped, no transfer failure occurred and paper did not wind around the fixing belt at the time of fixing. Similar results were obtained by the image forming apparatus shown in FIG.

However, the toners tm7, ty7, tc7, and tb7 caused filming of the photoconductor, defective transfer, scattering of characters during transfer, and a lot of fog. Filming of the transfer belt and poor cleaning occurred. When a solid image was taken on the entire surface at the time of development, blurring occurred in the latter half. The wax was fused to the developing blade during continuous use, and an abnormal image of vertical stripes was generated. Wrapping of paper around the fixing belt occurred when outputting images of three colors. Toner skipping occurred during fixing.

Next, as shown in (Table 17), the amount of adhesion on OHP paper is 1.2.
Solid image of g / cm ² or more, process speed 100 mm /
s, a non-offset test was conducted with a fixing device using a belt to which no oil was applied. No OHP jam occurred in the fixing nip portion. In the whole solid green image on plain paper, offset did not occur up to the 122,000th sheet. Even if the silicone or fluorine fixing belt is not coated with oil, the surface deterioration phenomenon of the belt is not observed.

The transmittance and the offset property at high temperature were evaluated. Process speed is 100mm / s, fixing temperature is 180 ℃
And the transmittance is spectrophotometer U-3200 (Hitachi),
The transmittance of 700 nm light was measured. The results of fixability, offset resistance, and storage stability are shown.

[0289]

[Table 17]

OHP translucency shows 80% or more,
Further, the non-offset temperature width was 40 to 60 K, which showed good fixing properties in a fixing roller not using oil. Further, almost no aggregation was observed in the storage stability at 60 ° C. for 5 hours.

However, the toner of tm7 had a lump in the storage stability test, and the non-offset temperature range was narrow.

[0292]

As described above, in the crushing means by the rotating body, the addition of the means for alleviating the agglomeration enables the crushing of the small particle size and the sharp distribution on the coarse powder side.
Furthermore, in order to achieve transferability and oilless fixing in the tandem transfer process, even in toner containing a specific binder resin, charge control agent, and wax, high image quality due to small particle size It is possible to prevent omission and scattering and obtain high transfer efficiency. Filming of the photoconductor and the transfer body can be prevented even during long-term use under high humidity. The cleaning property of the transfer member can be improved. Even in a cleanerless process that does not use a cleaning blade or the like, the transfer residual toner can be smoothly collected, and the history of the previous image can be prevented from remaining. Further, it is possible to realize oilless fixing that prevents offset properties while maintaining high OHP translucency without applying oil.

[Brief description of drawings]

FIG. 1 is a schematic perspective view of a toner melt-kneading process used in an example of the present invention.

FIG. 2 is a plan view of a toner melt-kneading process used in an example of the present invention.

FIG. 3 is a front view of a toner melt-kneading process used in an example of the present invention.

FIG. 4 is a sectional view of a toner melt-kneading process used in an example of the present invention.

FIG. 5 is a configuration diagram of a toner crushing process used in an example of the present invention.

FIG. 6 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 7 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 8 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 9 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 10 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 11 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 12 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 13 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 14 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 15 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 16 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 17 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 18 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 19 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 20 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 21 is a diagram showing molecular weight distribution characteristics of a binder resin and a toner according to an example of the present invention.

FIG. 22 is a diagram showing the molecular weight distribution characteristics of the wax of the example of the present invention.

FIG. 23 is a diagram showing the molecular weight distribution characteristics of the wax of the example of the present invention.

FIG. 24 is a cross-sectional view showing the configuration of the image forming apparatus used in the examples of the present invention.

FIG. 25 is a cross-sectional view showing the configuration of the image forming apparatus used in the examples of the present invention.

FIG. 26 is a cross-sectional view showing the configuration of a fixing unit used in an example of the present invention.

[Explanation of symbols]

1 photoconductor 3 laser signal light 4 developing roller 5 blade 10 first transfer roller 12 transfer belt 14 second transfer roller 13 drive tension roller 17 transfer belt units 18B, 18C, 18M, 18Y image forming unit 18 image forming unit group 201 fixing Roller 202 Pressure roller 203 Fixing belt 205 Induction heater section 206 Ferrite core 207 Coil 602 Roll (RL1) 603 Roll (RL2) 604 Melted film of toner wound on roll (RL1) 605 Heat medium inlet 606 Heat medium Outlet of

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 331 F term (reference) 2H005 AA01 AA06 AA08 AA21 AB04 CA08 CA12 CA14 CA30 CB07 CB13 EA03 EA05 EA06 EA07 EA10

Claims (33)

[Claims] 1. A toner which contains at least a binder resin, a colorant and a wax, and has a cylindrical rotating body having irregularities on its surface and rotating at a high speed, and 0.5 mm outside the rotating body.
A cylindrical fixed body fitted with a gap of about 40 mm, sharing the central axis with the rotating body, and having irregularities on the surface, a supply port for introducing a pulverized material to be toner, and a pulverized toner A supply means for discharging the pulverized material is provided, and a means for alleviating agglomeration of the pulverized material to be toner is added before the pulverized material to be toner is introduced from the supply port. A toner characterized in that it is made to flow from the mouth and is pulverized into a predetermined particle size distribution. 2. A toner which contains at least a binder resin, a colorant and a wax, has a cylindrical rotating body having irregularities on its surface and rotates at a high speed, and 0.5 mm outside the rotating body.
A cylindrical fixed body fitted with a gap of about 40 mm, sharing the central axis with the rotating body, and having irregularities on the surface, a supply port for introducing a pulverized material to be toner, and a pulverized toner A crushing unit having at least a discharge port for discharging the crushed product is provided. Before the crushed product to be toner is introduced from the supply port, a vibrating unit is added to the crushed product to be toner to allow the crushed product to flow from the supply port. A toner characterized by being pulverized into a predetermined particle size distribution. 3. A toner which contains at least a binder resin, a colorant and a wax, and has a cylindrical rotating body having irregularities on its surface and rotating at a high speed, and 0.5 mm outside the rotating body.
A cylindrical fixed body fitted with a gap of about 40 mm, sharing the central axis with the rotating body, and having irregularities on the surface, a supply port for introducing a pulverized material to be toner, and a pulverized toner It is created by a pulverizing means having at least a discharge port for discharging the pulverized product, and before the pulverized product to be toner is introduced from the supply port, the inorganic fine powder is supplied to and mixed with the pulverized product to be toner, and the supply is performed. A toner characterized in that it is made to flow from the mouth and is pulverized into a predetermined particle size distribution. 4. A toner which contains at least a binder resin, a colorant and a wax, and has a cylindrical rotating body having irregularities on its surface and rotating at a high speed, and 0.5 mm outside the rotating body.
A cylindrical fixed body fitted with a gap of about 40 mm, sharing the central axis with the rotating body, and having irregularities on the surface, a supply port for introducing a pulverized material to be toner, and a pulverized toner It is made by a crushing means having at least a discharge port for discharging the pulverized material, and an evaporative medium is supplied to the toner pulverized material to be mixed or attached before the toner pulverized material is flown in from the supply port. A toner which is made to flow from the supply port and pulverized to a predetermined particle size distribution. 5. A toner containing at least a binder resin, a colorant, and a wax has a content of 5 μm or less in the number distribution of 60% by number or more, and 3.17 μ in the number distribution.
The content of m or less is 5 to 35% by number, and is 6.35 to 1
The specific surface area value St (St = 6 / (true specific gravity × x) is a particle size distribution structure in which toner particles having a particle size of 0.1 μm are contained in an amount of 55% by volume or less, and the value is equivalent to a true sphere converted from the volume average particle size. Volume average particle diameter)) and specific surface area ratio SSt (SSt =
(St / specific surface area value of pulverized toner)) is 0.4 to
A toner having a value of 0.9. 6. A cylindrical rotating body which is a toner containing at least a binder resin, a colorant and a wax, and has a surface having irregularities and which rotates at a high speed, and 0.5 mm outside the rotating body.
A cylindrical fixed body fitted with a gap of about 40 mm, sharing the central axis with the rotating body, and having irregularities on the surface, a supply port for introducing a pulverized material to be toner, and a pulverized toner The content of 5 μm or less in the number distribution is obtained by a pulverizing means having at least an outlet for discharging the pulverized material and a means for alleviating the agglomeration of the pulverized material for the toner before the pulverized material for the toner flows in from the supply port. Quantity is 60%
In the particle size distribution configuration, the content of the toner particles is not less than 3.17 μm in the number distribution and is 5 to 35% by number, and the toner particles having a particle size of 6.35 to 10.1 μm is contained at 55% by volume or less. And a specific surface area value St (St = 6 / (true specific gravity × volume average particle diameter)) corresponding to a true sphere converted from the volume average particle diameter SSt (SSt = (St / crushed toner The specific surface area of the toner) is 0.4 to 0.9 and the toner is pulverized. 7. A volatile medium is supplied to and mixed with or adhered to the pulverized material to be toner before the pulverized material to be toner is made to flow into the pulverized material to be supplied from the supply port, and the volatile medium is made to flow into the pulverized material from the supply port to have a predetermined particle size distribution. The toner according to claim 6, which is pulverized. 8. A vibrating means is added to the toner pulverized product before the toner pulverized product is introduced from the supply port,
7. The toner according to claim 6, wherein the toner is made to flow from the supply port and is pulverized to have a predetermined particle size distribution. 9. An inorganic fine powder is supplied to and mixed with the pulverized product to be toner before the pulverized product to be toner is made to flow into the pulverized product from the supply port, and is made to flow into the pulverized product from the supply port to be pulverized to a predetermined particle size distribution. 7. The toner according to claim 6, wherein 10. The inorganic fine powder has an average particle size of 8 to 40.
10. The toner according to claim 3 or 9, comprising silica or titanium oxide fine powder having a loss on ignition of 0.5 to 10 wt%. 11. The inorganic fine powder is a fatty acid ester,
10. The toner according to claim 3 or 9, which contains silica or titanium oxide fine powder surface-treated with one or more of fatty acid amides and fatty acid metal salts. 12. The toner according to claim 3, wherein the inorganic fine powder contains silica or titanium oxide fine powder surface-treated with silicone oil. 13. The binder resin has an acid value of 1 to 40 mg.
Polyester resin with KOH / g and wax at least gel permeation chromatography (GPC)
In the molecular weight distribution in, the number average molecular weight is 100 to
5000, weight average molecular weight is 200 to 10,000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number Average molecular weight) is 1.02-1
An ester wax having at least one maximum molecular weight peak in the region of 0 and a molecular weight of 5 × 10 ² to 1 × 10 ⁴ , an iodine value of 25 or less, and a saponification value of 30 to 300 is contained. 7. The toner according to any one of 1 to 6. 14. The binder resin has an acid value of 1 to 40 mg.
A KOH / g polyester resin, wherein the wax is obtained by a reaction with a long-chain alkyl alcohol having at least 5 to 100 carbon atoms, an unsaturated polyvalent carboxylic acid or an anhydride thereof, and a hydrocarbon wax, and has an acid value of 5 to 5. 80 mgK
7. The toner according to claim 1, further comprising a wax having an OH / g, a melting point of 90 to 120 ° C., and a penetration of 4 or less at 25 ° C. 15. The wax is one or more selected from derivatives of hydroxystearic acid, glycerin fatty acid ester, glycol fatty acid ester, polyhydric alcohol fatty acid ester of sorbitan fatty acid ester, meadowfoam oil derivative and jojoba oil derivative. 7. The toner according to claim 1, further comprising: 16. The wax has a melting point of 70 to 110.
1 or 2 of a saturated or monovalent unsaturated aliphatic amide having 16 to 24 carbon atoms which is ℃, and an alkylenebis fatty acid amide system of a saturated or monovalent unsaturated fatty acid
7. The toner according to claim 1, which comprises one or more kinds. 17. The GPC molecular weight distribution of the toner has at least one molecular weight maximum peak in the region of molecular weight 2 × 10 ^{3 to} 3 × 10 ⁴ , and at least one molecular weight in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ^6. A peak having a maximum peak or shoulder, and a peak having a maximum molecular weight distribution in a region having a molecular weight of 5 × 10 ⁴ to 1 × 10 ⁶ , which is larger than a molecular weight value corresponding to the maximum peak or shoulder having a molecular weight distribution. Alternatively, when the shoulder height is 1, the maximum molecular weight peak or shoulder height is 90.
% When M10 is the molecular weight corresponding to 10% of the maximum molecular weight peak or shoulder height, and M10 / M90 is 0.5-8. The toner according to any one of 1. 18. The GPC molecular weight distribution of the toner has at least one molecular weight maximum peak in the molecular weight range of 2 × 10 ^{3 to} 3 × 10 ⁴ , and at least one molecular weight peak in the molecular weight range of 5 × 10 ⁴ to 1 × 10 ^6. A peak having a maximum peak or shoulder, and a peak having a maximum molecular weight distribution in a region having a molecular weight of 5 × 10 ⁴ to 1 × 10 ⁶ , which is larger than a molecular weight value corresponding to the maximum peak or shoulder having a molecular weight distribution. Alternatively, when the shoulder height is 1, the maximum molecular weight peak or shoulder height is 90.
% Is M10 and the molecular weight corresponding to 10% of the peak of the molecular weight peak or shoulder is M10, (M10-M90) / M90 is 0.1 to 7. Item 7. The toner according to any one of items 1 to 6. 19. At least a binder resin, a colorant, and a wax, at least an image carrier, a charging unit for forming an electrostatic latent image on the image carrier, and an electrostatic latent image formed on the image carrier. And the content of 5 μm or less in the number distribution is 60% by number or more and 3.17 μm in the number distribution.
The following content is 5 to 35% by number, 6.35 to 1
The specific surface area value St (St = 6 / (true specific gravity × x) is a particle size distribution structure in which toner particles having a particle size of 0.1 μm are contained in an amount of 55% by volume or less, and the value is equivalent to a true sphere converted from the volume average particle size. Volume average particle diameter)) and specific surface area ratio SSt (SSt =
(St / specific surface area value of pulverized toner)) is 0.4 to
A plurality of toner image forming stations including developing means for developing with a toner of 0.9, and transfer means for successively and successively transferring the visualized toner images onto a transfer medium. A characteristic image forming apparatus. 20. At least a binder resin, a colorant and a wax, at least an image carrier, a charging unit for forming an electrostatic latent image on the image carrier, and an electrostatic latent image formed on the image carrier. And a cylindrical rotating body having irregularities on its surface and rotating at a high speed, and 0.5 to the outside of the rotating body.
A cylindrical fixed body fitted with a gap of mm to 40 mm, sharing a central axis with the rotating body, and having irregularities on the surface, a supply port for introducing a pulverized material to be toner, and a pulverization treatment. With a pulverizing means having at least an outlet for discharging the pulverized toner and a means for relaxing the agglomeration of the pulverized toner before the pulverized toner is introduced from the supply port, Content is 60
Number% or more content, content of 3.17 μm or less in number distribution is 5 to 35 number% content, 6.35 to 10.1 μm
The specific surface area value St (St = 6 / (true specific gravity × volume average particle) has a particle size distribution configuration in which the toner particles having a particle size of 55% by volume or less are included, and the value is equivalent to a true sphere converted from the volume average particle size. Diameter)) and a specific surface area ratio SSt (SSt = (St / specific surface area value of pulverized toner)) of 0.4 to 0.9. An image forming apparatus comprising: a plurality of toner image forming stations including means; and a transfer means for successively and successively transferring the visualized toner images to a transfer medium. 21. A toner containing at least a binder resin, a colorant and a wax, which has a cylindrical rotating body having irregularities on its surface and rotating at a high speed, and 0.5 m outside the rotating body.
a cylindrical fixed body fitted with a gap of m to 40 mm, sharing the central axis with the rotating body, and having irregularities on the surface;
A supply port for inflowing the pulverized material to be toner, an outlet for discharging the pulverized toner pulverized product, and a means for alleviating agglomeration of the pulverized material to be toner before inflowing the pulverized material to be toner from the supply port. The content of 5 μm or less in the number distribution is 60% by number or more, the content of 3.17 μm or less in the number distribution is 5 to 35% by number, and the content is 6.35 to 10.1 μm. The specific surface area value St (St = 6 / (true specific gravity × volume average particle size) is a particle size distribution configuration in which the toner particles having a particle size are contained in an amount of 55% by volume or less and which is converted from the volume average particle size. )) Specific surface area ratio SSt (SSt = (St / specific surface area value of pulverized toner) 9 is 0.4 to 0.9. Multiple tons including and An image forming station, a primary transfer means for contacting an endless transfer member to the image bearing member to sequentially and successively transfer the visualized toners to the transfer member, and a primary transfer unit formed on the transfer member. An image forming apparatus comprising: a secondary transfer unit that collectively transfers a multi-layered toner image onto a transfer medium. 22. Before the pulverized material to be toner is flown in through a supply port, an evaporative medium is supplied to the pulverized material to be toner to be mixed or adhered, and is flowed in through the supply port to have a predetermined particle size distribution. The image forming apparatus according to claim 20, which is crushed. 23. Before the pulverized material to be toner is made to flow in from a supply port, a vibrating means is added to the pulverized material to be toner, and it is made to flow in from the supply port and pulverized to a predetermined particle size distribution. The image forming apparatus according to claim 20 or 21. 24. Before feeding the pulverized material to be toner from a supply port, inorganic fine powder is supplied to and mixed with the pulverized material to be toner, flowed from the supply port and pulverized to a predetermined particle size distribution. 22. The image forming apparatus according to claim 20, wherein: 25. The inorganic fine powder has an average particle size of 8 to 40.
25. The image forming apparatus according to claim 24, which contains silica or titanium oxide fine powder having a loss on ignition of 0.5 to 10 wt%. 26. The inorganic fine powder is a fatty acid ester,
25. The image forming apparatus according to claim 24, further comprising silica or titanium oxide fine powder surface-treated with one or more of fatty acid amide and fatty acid metal salt. 27. The image forming apparatus according to claim 24, wherein the inorganic fine powder contains silica or titanium oxide fine powder surface-treated with silicone oil. 28. The binder resin has an acid value of 1 to 40 mg.
Polyester resin with KOH / g and wax at least gel permeation chromatography (GPC)
In the molecular weight distribution in, the number average molecular weight is 100 to
5000, weight average molecular weight is 200 to 10,000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number Average molecular weight) is 1.02-1
An ester wax having at least one maximum molecular weight peak in the region of 0 and a molecular weight of 5 × 10 ² to 1 × 10 ⁴ , an iodine value of 25 or less, and a saponification value of 30 to 300 is contained. The image forming apparatus according to any one of 19 to 21. 29. The binder resin has an acid value of 1 to 40 mg.
A KOH / g polyester resin, wherein the wax is obtained by a reaction with a long-chain alkyl alcohol having at least 5 to 100 carbon atoms, an unsaturated polyvalent carboxylic acid or an anhydride thereof, and a hydrocarbon wax, and has an acid value of 5 to 5. 80 mgK
22. The image forming apparatus according to claim 19, further comprising a wax having an OH / g, a melting point of 90 to 120 [deg.] C., and a penetration of 4 or less at 25 [deg.] C. 30. The wax is one or more of a hydroxystearic acid derivative, a glycerin fatty acid ester, a glycol fatty acid ester, a polyhydric alcohol fatty acid ester of a sorbitan fatty acid ester, a meadow foam oil derivative, and a jojoba oil derivative. The image forming apparatus according to claim 19, further comprising: 31. The wax has a melting point of 70 to 110.
1 or 2 of a saturated or monovalent unsaturated aliphatic amide having 16 to 24 carbon atoms which is ℃, and an alkylenebis fatty acid amide system of a saturated or monovalent unsaturated fatty acid
The image forming apparatus according to any one of claims 19 to 21, wherein the image forming apparatus includes one or more kinds. 32. The GPC molecular weight distribution of the toner has at least one molecular weight maximum peak in the molecular weight range of 2 × 10 ^{3 to} 3 × 10 ⁴ , and at least one molecular weight peak in the region of 5 × 10 ⁴ to 1 × 10 ^6. A peak having a maximum peak or shoulder, and a peak having a maximum molecular weight distribution in a region having a molecular weight of 5 × 10 ⁴ to 1 × 10 ⁶ , which is larger than a molecular weight value corresponding to the maximum peak or shoulder having a molecular weight distribution. Alternatively, when the shoulder height is 1, the maximum molecular weight peak or shoulder height is 90.
% When M10 is the molecular weight corresponding to 10% of the molecular weight maximum peak or shoulder height, and M10 / M90 is 0.5-8. The image forming apparatus according to any one of 1. 33. The GPC molecular weight distribution of the toner is such that at least one molecular weight maximum peak is in the molecular weight range of 2 × 10 ^{3 to} 3 × 10 ⁴ , and at least one molecular weight peak is in the region of molecular weight of 5 × 10 ⁴ to 1 × 10 ^6. A peak having a maximum peak or shoulder, and a peak having a maximum molecular weight distribution in a region having a molecular weight of 5 × 10 ⁴ to 1 × 10 ⁶ , which is larger than a molecular weight value corresponding to the maximum peak or shoulder having a molecular weight distribution. Alternatively, when the shoulder height is 1, the maximum molecular weight peak or shoulder height is 90.
% Is M10 and the molecular weight corresponding to 10% of the peak of the molecular weight peak or shoulder is M10, (M10-M90) / M90 is 0.1 to 7. The image forming apparatus according to any one of Items 19 to 21.