JP2003162090A - Toner, toner producing method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent central blanking or scattering at the transfer time in a high-speed tandem type transfer process where a distance from a 1st transfer position to a 2nd transfer position is short, to prevent filming on a photoreceptor and a transfer body even in a long-term use and to prevent offset property while maintaining high OHP light transmissivity though oil is not applied. <P>SOLUTION: The toner is constituted by performing the mixing processing of toner base material including at least binding resin, a colorant and a fixing assistant and then performing the melting and kneading processing thereof by strong shearing force, and performing the surface reforming processing of toner particles processed to be fined by hot blast or the globing processing thereof by mechanical impact force. <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 copying machine, a laser printer, a plain paper FAX, a color PPC, a toner used for a color laser printer and a color FAX, a method for producing the toner, and an image forming apparatus.

[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, 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 light transmitting property. 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 case of a resin structure having a melting property of sharp melt due to the expression of light transmittance, the offset resistance is deteriorated and the toner adheres to the surface of the fixing roller to cause an offset, 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 releasability 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.

As the releasing agent added for the purpose of improving the fixing property, Japanese Patent Laid-Open No. 2-266372 discloses a free fatty acid type carnauba wax and / or a montan ester wax, and an oxidized rice wax having an acid value of 10 to 30. Use of,
Further, in JP-A-9-281748, a melting point of 85-1
Vinyl-based copolymer polymerized at 00 ° C in the presence of natural gas-based Fischer-Tropsch wax, JP-A-10-
In 327196, a polyhydric alcohol component, a dicarboxylic acid, and a polyvalent carboxylic acid compound having a valence of 3 or more are polycondensed, and 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. In Japanese Patent Laid-Open No. 5-333584,
It has been disclosed that the constitution containing a fluorine-modified polyolefin resin such as polypropylene modified with an organic fluorine compound such as perfluorooctyl methacrylate improves the fixability. In JP-A-5-188632, a softening point is 80 to 140 ° C., and a low molecular weight polyolefin containing fluorine, and a melt mixture of low molecular weight olefin and polytetrafluoroethylene are mixed to obtain non-offset property at the time of fixing. The contents to be improved are disclosed, and the contents effective in improving the fixing property are described.

Further, in JP-A-59-148067, an unsaturated ethylenic 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 toners relating to polyester resins, and disclose that good fixing properties can be obtained.

Further, as a charge control agent for imparting chargeability to the toner, Japanese Patent Laid-Open Nos. 2-221967 and 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, a so-called spent that the toner adheres to the carrier during two-component development during long-term use is generated. It tends 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.

Further, when a toner having a constitution of enhancing glossiness and translucency of a color image by using a low melting point release agent and a resin having 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 silicon 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.

First, it is indispensable to realize high transferability in the transfer, and it is possible to improve the transferability by the toner spheroidizing treatment and the polymerized toner.

Further, the transfer residual toner remains on the photosensitive member to some extent, and in the next developing process, if the residual toner in the non-image portion is recovered for development and returned, no problem in terms of image 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 superimposing the color images, which 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.

Further, in a toner to which a releasing agent such as a low melting point wax is added in order to satisfy the above-mentioned non-offset property at the time of fixing, the compatibility of the resin and the wax is poor, so that the wax particles in the toner become coarse. To do. Therefore, the fluidity tends to decrease, the transferability is not good, and the toner cohesiveness is so strong that it is difficult to collect during development in the cleanerless process. I will remain. Further, when this toner is subjected to a spheroidizing treatment by heat or impact force to improve transferability, an effect of improving transferability can be seen, but a coarse wax bleeds on the toner surface, which is a photoreceptor, carrier, There is a problem that the developing roller and the transfer body are contaminated, and the charging, the life, etc. are deteriorated.

Further, it is very important that the transfer residue and the reverse transfer toner have a normal polarity when passing through the charging portion.

On the other hand, as for the charger, a charging roller system, a corona discharge system and the like have been put into practical use. In the process of achieving cleanerlessness, in the charging roller system in which the electrostatic charge image carrier is brought into contact with the electrostatic latent image carrier, an image defect occurs due to the contamination of the charging roller due to the presence of transfer residual toner and / or reverse transfer toner. The use of a non-contact corona discharge type device has the drawbacks that ozone is generated and the size is increased although the contamination of the charging member is reduced. Especially in the case of negative corona discharge, the amount of ozone generated is about one digit higher than that in positive corona discharge. The amount of ozone that humans can perceive as odor is 0.02 ppm, and the permissible concentration is set to 0.1 ppm or less. Copiers and printers use an ozone filter coated with activated carbon to remove ozone and meet this standard. However, recently, a movement to reduce the amount of ozone generated has become active, especially in Europe, to about 1/10 of the current level. Therefore, in the case of the corona discharge method, it is becoming difficult to meet these standards even if an ozone filter is added. Further, the charging device must also be provided with a function of normalizing the transfer residual toner and / or the reverse transfer toner.

When the ion generator is used, the charging member may be contaminated by the transfer residual toner and / or the reverse transfer toner on the electrostatic image carrier. When an ion generator is used, the distance from the electrostatic image carrier is 2 to 3 mm, which is equivalent to the corona discharge method, but there is a large difference in applied voltage. A typical applied voltage when using an ion generator is DC
Although AC of about 3 kV is superimposed on -600 V, DC-5 to 6 kV is applied in the case of corona discharge. When there is weakly charged or oppositely charged toner on the electrostatic image carrier, by using an ion generator with a small DC component and superposed AC, a charger is provided as compared to a corona discharge system with a large DC component. Is not easily contaminated, but it cannot be said to disappear at all. Therefore, how to reduce the transfer residual toner or the reverse transfer toner becomes a major issue.

[0031]

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.

In view of the above problems, it is an object of the present invention to provide a toner having a uniform charge distribution and capable of stabilizing an image for a long time, a method for producing the toner, and an image forming method.

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

An image forming station having a plurality of photoconductors and developing units is arranged side by side, and an endless transfer member is brought into contact with the photoconductors to transfer toners of respective colors successively to the transfer member. In the tandem color process that executes the process, it prevents dropouts and scattering at the time of transfer, high transfer efficiency is obtained, and filming on the transfer body is avoided.
An object of the present invention is to provide a toner, a toner manufacturing method and an image forming method capable of preventing fusion to a transfer member or a cleaning unit.

Even in the cleanerless process, high transfer efficiency is obtained, the charge amount and the fluidity are not deteriorated, the collection in the development is easy and the memory is not generated, the cleanerless process is enabled, and the global environment is prevented and resources are prevented. It is an object of the present invention to provide a toner, a toner manufacturing method, and an image forming method that enable reuse of the toner.

Even if the toner having a release agent such as wax having a low melting point added thereto is spheroidized, contamination of the photosensitive member, carrier, developing roller and transfer member due to bleeding such as wax bleeding can be prevented and uniform charging can be achieved. An object of the present invention is to provide a toner having a distribution and capable of stabilizing an image for a long period of time, a method for producing the toner, and an image forming method.

It is an object of the present invention to provide a full-color electrophotographic toner and an electrophotographic apparatus that exhibit high translucency and glossiness by oilless fixing without applying oil to a 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 capable of avoiding filming on a transfer body and the like, and capable of preventing filming on a photoconductor, a transfer body, etc. even during long-term use under high humidity, a method for producing a toner, and an image forming method. And

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,
Further, it is an object of the present invention to provide a toner, a toner manufacturing method and an image forming method that are compatible with both development and transfer properties.

[0039]

In view of the above problems, the structure according to the present invention has a structure in which a toner base material containing at least a binder resin, a colorant, and a fixing aid is mixed and then rotated in different directions to form a gap. The toner is subjected to a kneading process between two rolls having a temperature difference and a rotation speed difference facing each other, and the toner particles subjected to the micronization treatment are surface-modified with hot air.

Further, in the constitution according to the present invention, after the toner base material containing at least the binder resin, the colorant and the fixing aid is mixed, the mixture is rotated in different directions to form a gap and a temperature difference facing each other. It is a toner produced by performing a kneading process between two rolls provided with a difference in rotation speed, and spheroidizing by a mechanical impact force.

Further, in the constitution according to the present invention, the step of mixing the toner base material containing at least the binder resin, the colorant, and the fixing aid, and then rotating in different directions, and providing a gap to face the temperature difference. And kneading treatment between two rolls having a difference in rotation speed, a step of pulverizing and pulverizing, a step of classifying if necessary, and then a surface modification treatment of the pulverized toner particles with hot air. A method for producing a toner, which comprises a step of applying.

Further, in the constitution according to the present invention, the step of mixing the toner base material containing at least the binder resin, the colorant, and the fixing aid, and thereafter, rotating in different directions and providing a gap to face the temperature difference. Including a step of performing a kneading process between two rolls having a difference in rotational speed, a step of spheroidizing and crushing by a mechanical impact force, a step of classifying if necessary, and a step of externally adding thereafter. Is a manufacturing method.

Further, in the structure according to the present invention, at least the image carrier, the charging means for forming an electrostatic latent image on the image carrier, and the electrostatic latent image formed on the image carrier are formed at least. After mixing the toner base material containing the resin, the colorant, and the fixing aid, the toner is rotated in different directions and mixed and melted between two rolls having a gap and a temperature difference and a rotation speed difference facing each other. A plurality of toner image forming stations including a kneading process and a developing process in which the toner particles that have been subjected to the micronization treatment are visualized with the toner that has been subjected to the surface modification treatment with hot air,
The image forming apparatus includes a transfer unit that sequentially and continuously transfers the visualized toner image to a transfer medium.

Further, in the constitution according to the present invention, at least the image carrier, the charging means for forming the electrostatic latent image on the image carrier, and the electrostatic latent image formed on the image carrier are at least formed. A toner base material containing a binder resin, a colorant, and a fixing aid is mixed and then rotated in different directions, and a melt-kneading process is performed between two rolls provided with a gap and facing each other with a temperature difference and a rotation speed difference. And a toner image forming station including a developing step of visualizing the toner with a toner formed by a spheroidizing treatment by a mechanical impact force, and the toner images thus visualized are successively transferred in succession. The image forming apparatus includes a transfer unit that transfers the image onto the image forming apparatus.

Further, in the structure according to the present invention, at least the image carrier, the charging means for forming an electrostatic latent image on the image carrier, and the electrostatic latent image formed on the image carrier are at least formed. After mixing the toner base material containing the resin, the colorant, and the fixing aid, the toner is rotated in different directions and melt-kneaded between two rolls having a gap and a temperature difference and a rotation speed difference facing each other. A plurality of toner image forming stations including a developing step of developing the toner particles subjected to the surface modification treatment with hot air to visualize the toner particles subjected to the finer treatment,
A primary transfer unit that sequentially transfers the visualized plurality of toners to the transfer member by bringing an endless transfer member into contact with the image carrier, and a multi-layered toner image formed on the transfer member. An image forming apparatus including a secondary transfer unit that collectively transfers the image to a transfer body.

Further, in the constitution according to the present invention, at least the image carrier, the charging means for forming the electrostatic latent image on the image carrier, and the electrostatic latent image formed on the image carrier are formed at least. A toner base material containing a binder resin, a colorant, and a fixing aid is mixed and rotated in different directions, and melt-kneaded between two rolls having a gap and a temperature difference and a rotation speed difference facing each other. A plurality of toner image forming stations including a developing process in which the toner is subjected to a sphering process by a mechanical impact force and then visualized with a toner, and an endless transfer member is brought into contact with the image carrier. Then, a primary transfer unit that sequentially and successively transfers the visualized plurality of toners to the transfer member, and a secondary transfer that collectively transfers the multilayer toner images formed on the transfer member to a transfer medium. And an image forming apparatus composed of That.

Further, in the constitution according to the present invention, at least the image carrier, the charging means in which the constituent elements composed of the ion generating electrode and the induction electrode formed by sandwiching the dielectric material are integrated, and the image carrier. The electrostatic latent image formed on the toner base material containing at least a binder resin, a colorant, and a fixing aid is mixed and rotated in different directions, and a gap is provided to face the temperature difference and rotation speed. A plurality of toner image forming stations including a developing step in which a melt kneading process is performed between two rolls provided with a difference, and the toner is visualized by a toner formed by a spheroidizing process by a mechanical impact force; For example, transfer means for transferring the visualized toner image onto a transfer medium via an intermediate transfer body or not, and toner attached to the image carrier (for example, toner remaining after transfer and / or image carrier). Reverse transcription to the body An image forming device comprising a means for collecting toner) in the developing process.

Further, the structure according to the present invention comprises at least an image carrier, a charging means in which constituent elements composed of an ion generating electrode and an induction electrode sandwiching a dielectric material are integrated, and the image carrier. The electrostatic latent image formed on the toner base material containing at least a binder resin, a colorant, and a fixing aid is mixed and rotated in different directions, and a gap is provided to face the temperature difference and rotation speed. A plurality of toner image forming stations including a developing step of performing a melt-kneading process between two rolls provided with a difference, and at least developing with a toner formed by a spheroidizing process by a mechanical impact force;
(For example, a transfer unit that transfers the visualized toner image onto a transfer medium via an intermediate transfer body or not), and a toner attached to the image carrier (for example, a transfer residual toner and / or an image). And a means for collecting (toner reversely transferred to the carrier) in a developing process.

[0049]

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.

(Wax) The wax added to the toner of this embodiment has an iodine value of 25 or less and a saponification value of 30.
~ 300 wax, acid value 1 ~ 70mg
1-2 with respect to 100 parts by weight of the binder resin which is KOH / g
By adding 0 parts by weight, the repulsion due to the charge action of the toner is alleviated during the multi-layer transfer of the toner, and the transfer efficiency is reduced.
It is possible to suppress blank characters and image distortion during transfer.

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. When the saponification value becomes smaller than 30,
The presence of unsaponifiable substances and hydrocarbons increases, causing filming of the photoconductor and deterioration of chargeability. 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 70 mgKOH / g, the environmental resistance is deteriorated and the fogging is increased.

As the wax, in the molecular weight distribution in gel permeation chromatography (GPC),
Number average molecular weight 100-5000, weight average molecular weight 2
00 to 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 1.01 to 8, Z
The ratio of the average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10 ² to 1 × 1.
A wax having at least one maximum molecular weight peak in the region of 0 ⁴ , an iodine value of 25 or less, and a saponification value of 30 to 300. The wax has an acid value of 1 to 70 mgK
1 to 20 with respect to 100 parts by weight of the binder resin which is OH / g
It is a structure in which a part is added.

As the wax, an ester wax composed of a higher fatty acid, a higher alcohol and an ester bond is preferably used and has an iodine value of 25 or less and a saponification value of 30 to 30.
0, the one having a melting point of 50 to 100 ° C. according to the DSC method is preferable. More preferably, the iodine value is 15 or less, the saponification value is 50 to 250, the melting point by the DSC method is 55 to 90 ° C., and further preferably, the iodine value is 5 or less and the saponification value is 70 to.
200, having a melting point of 60 to 85 ° C. according to the DSC method.

When the iodine value is larger than 25, the environmental dependency is large, and the change of the chargeability of the material is large during continuous long-term use, which impairs the stability of the image. Saponification value is 3
When it is less than 0, the filming of the photoconductor and the deterioration of the charging property are likely to occur. When it is more than 300, the dispersibility in the resin is deteriorated, resulting in increased fog and toner scattering.

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 addition amount is 1 to 20 with respect to 100 parts by weight of the binder resin.
It is preferable to add parts by weight. If it is 0.1 part by weight or less, the effect of improving the fixing property cannot be obtained, and if it is 20 parts by weight or more, there is a problem in storage stability.

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.

Regarding the molecular weight in GPC, the number average molecular weight is 100 to 5,000 and the weight average molecular weight is 200.
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 1.02. Those of 10 are preferable. More preferably, the number average molecular weight is 500 to 4500, the weight average molecular weight is 600 to 9000, the ratio of the weight average molecular weight and the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 7, Z
The ratio of the average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 9, more preferably the number average molecular weight is 700 to 4000, and the weight average molecular weight is 800 to 80.
00, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.06, and the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02. 8

When the number average molecular weight is less than 100 and the weight average molecular weight is less than 200, the 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 as well as the fixing aid 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.

As fixing aids, meadowfoam oil derivatives, carnauba wax, jojoba oil derivatives, 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 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 to
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.

Materials such as hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters, polyhydric alcohol fatty acid esters such as sorbitan fatty acid esters 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.

As the glycerin fatty acid ester, glycerin = monotristearate, glycerin = docosanoate and the like are preferable materials.

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.

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.

Examples of the meadowfoam oil derivative include meadowfoam oil fatty acid, metal salts of meadowfoam oil fatty acid,
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 comprises a fatty acid 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.

Meadow foam oil fatty acid esters include, for example, esters of methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, trimethylolpropane, and the like, and particularly, meadow foam oil fatty acid pentaerythritol monoester, meadow foam oil fatty acid. Pentaerythritol triester, meadowfoam oil fatty acid trimethylolpropane ester and the like are preferable.

Furthermore, the esterification reaction product of the meadowfoam oil fatty acid and the 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 make 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.

As the jojoba oil derivative, jojoba oil fatty acid, metal salt of jojoba oil fatty acid, jojoba oil fatty acid ester, hydrogenated jojoba oil, jojoba oil amide, homojojoba oil amide, jojoba oil triester, 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 saponifying 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 the jojoba oil fatty acid ester 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.

Hydrogenated jojoba oil is obtained by hydrogenating jojoba oil to make 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.

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.

Further, 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.
30% 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 size is smaller than 0.1 μm,
When the number of particles of less than 0.1 μm is more than 30% 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.

In this embodiment, an aliphatic amide type fixing aid 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.

As the aliphatic amide-based fixing aid, palmitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, arachidic acid amide, eicosenoic acid amide, behenic acid amide, erucic acid amide, liglinoseric acid amide, etc. A saturated or monovalent unsaturated aliphatic amide having 16 to 24 carbon atoms and having a melting point of 70 to 110 ° C. 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.

Further, 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-based fixing aids of saturated or mono- and divalent unsaturated fatty acids such as amide, ethylenebiserucic acid amide, propylenebiserucic acid amide, 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, the surface smoothness of the fixed image can be improved and the color image can be further improved by forming the fixing aid with the aliphatic amide type and the alkylenebis fatty acid amide type in the ratio of 3: 7 to 7: 3. It is possible to further improve both the high translucency 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 as the compatibility with the resin progresses, the offset resistance and the storage stability are lowered, and further, the transfer 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 and the Z average molecular weight is 15.
00-9000, 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 the Z-average molecular weight to the number-average molecular weight (Z-average molecular weight / number-average molecular weight) has 1.5 to 6.5, 1 × 10 ^{3 to} 3 × 10 ⁴ at least one molecular weight maximum peak, and the acid Value 5-80mgKOH / g, melting point 80-120 ° C, 25 ° C
The wax obtained by reacting a long-chain alkyl alcohol having 5 to 100 carbon atoms having a penetration degree of 4 or less with an unsaturated polyvalent carboxylic acid or its anhydride and a hydrocarbon wax, or a long-chain alkylamine Wax obtained by reaction with saturated polycarboxylic acid or anhydride thereof and hydrocarbon wax, or obtained by reaction of long-chain fluoroalkyl alcohol with unsaturated polycarboxylic acid or anhydride and hydrocarbon wax The wax is particularly effective for improving the separability of the paper from the fixing roller and the belt in an image in which three layers of toner are formed on thin paper.

Without deteriorating the high temperature offset property,
It is effective in improving the transparency of OHP. 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.

Further, by improving the state of dispersion when this is added to the binder resin, fixability such as releasability and translucency, and developability such as charge stabilization can be further improved. 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 an anhydride thereof 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 wax such as polyethylene and polypropylene, higher fatty acid such as stearic acid, palmitic acid, lauric acid, aluminum stearate, barium stearate, zinc stearate and zinc palmitate, or a metal thereof can be preferably used.

(Binder Resin) GP is used as the binder resin of this embodiment.
In the molecular weight distribution in C, at least one peak of the molecular weight is present in the region of 2 × 10 ^{3 to} 3 × 10 ⁴ , and 3 × 10 ⁴ or more of the molecular weight component as a component present in the high molecular weight region is a binder resin. 5% or more with respect to the whole, weight average molecular weight of 10,000 to 300,000, Z average molecular weight of 20,000 to 500,000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 3 ˜100, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 10 to 2
000, polyester having a melting temperature (hereinafter softening point) of 80 to 150 ° C., an outflow starting temperature of 80 to 120 ° C., and a glass transition point of resin in the range of 45 to 68 ° C. It is preferable to use a resin 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.

Further, 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.

[0104] 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 the 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 at the time of kneading and impairs translucency. 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 fixing aid 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.

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 fixability is deteriorated and the light transmitting property is reduced. descend.

Further, 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 with respect to the entire 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.

Further, 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 photoreceptor 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 ultra high 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. In addition, the cleaning property of the transfer body is improved, vertical stripes are not generated on the developing roller, and by using the fatty acid-treated fine powder as an external additive together, the image disturbance at the time of transfer and the void can be prevented, and the highly efficient transfer property can be obtained. 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 hinders the light transmission.
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 is used.
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 that have not been heretofore available. 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 appropriate 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 8,000 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 fixing aid decreases, resulting in poor offset resistance and high temperature storage stability.
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.

The trivalent or higher carboxylic acid component is 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.

[0136]

[Chemical 1]

Examples of the trihydric or higher alcohol component 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 polyhydric carboxylic acid and polyhydric alcohol are usually used in a proportion of the number of hydroxyl groups to the number of carboxyl groups (OH / COOH) of 0.8 to 1.4.

The molecular weights of resins, waxes and toners 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 determined by a flow tester (CFT500) manufactured by Shimadzu Corporation while heating a 1 cm ³ sample at a temperature rising 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 decreasing 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, R ¹ is a hydrogen atom or a lower alkyl group, R ² is a hydrogen atom, a hydrocarbon group having up to 12 carbon atoms, or a hydroxylalkyl group in the following general formula (Formula 2). , Vinyl ester group or aminoacryl group. The acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, methacrylic acid. Acid-2-ethylhexyl, β-hydroxyacrylate, γ-hydroxyacrylate propyl α-hydroxyacrylate, β-hydroxymethacrylate, γ-aminopropyl acrylate, γ-N, N-
Examples include propyl diethylaminoacrylate, ethylene glycol dimethacrylic acid ester, tetraethylene glycol dimethacrylic acid ester, and the like. 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.

[0147]

[Chemical 2]

Further, the binder resin preferably used in the present invention has a long-chain alkyl group represented by (Chemical Formula 3) with a styrene-based (meth) acrylic acid-based monomer (meth).
The thing which copolymerized the acrylic acid type monomer is used suitably. This remarkably improves the dispersibility of a release agent such as wax, improves the fixability and anti-offset property, and stabilizes the charge, increases the charge under high temperature and low humidity, and improves the two-component development under high humidity. This has the effect of suppressing environmental problems such as poor toner concentration control that keeps the mixing ratio of the carrier and toner constant. With respect to 100 parts by weight of the binder resin, 0.
01 to 8 parts by weight are added. If it is too small, the effect cannot be obtained,
If it is too large, the durability of the resin will decrease.

[0149]

[Chemical 3]

Further, as the binder resin according to the present invention,
What copolymerized the (meth) acrylic-acid type monomer which has the amino group shown in (Chemical formula 4) with the styrene-type and (meth) acrylic-acid type monomer is used suitably. For example,
It is a vinyl-based monomer having an amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylaminoethyl (meth) acrylate. As a result, the dispersibility of the release agent such as wax is remarkably improved, overcharge is suppressed under high temperature and low humidity, the charge is stabilized, and the image quality is stable. 0.01 to 5 parts by weight is added to 100 parts by weight of the binder resin. If it is too small, the effect cannot be obtained, and if it is too large, the moisture resistance decreases.

[0151]

[Chemical 4]

As the method for producing the polymer, 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.

(Charge Control Agent) In the present embodiment, in order to control the charge of the toner and to make the oilless fixing more robust, the above-mentioned fixing aid and charge control agent are used in combination in the binder resin. As a preferable material, a metal salt of a salicylic acid derivative shown in Chemical formula 5 is used.

[0154]

[Chemical 5]

Further, in the present embodiment, in order to control the charge of the toner and make the oilless fixing more robust, the above-mentioned fixing aid and charge control agent are used in combination in the binder resin. As a preferable material, a metal salt of a benzylic acid derivative shown in Chemical formula 6 is used.

[0156]

[Chemical 6]

With this structure, it is possible to secure a wide range of non-offset temperature range in oilless fixing and prevent image disturbance due to the charging action during fixing. This is considered to be the effect of the charge polarity of the metal salt and the functional group having the acid value of the fixing aid. 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 is 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 more than 5 parts by weight, color turbidity in a color image becomes noticeable.

(External Additive) Further, in this embodiment, as the external additive,
Fine powder of metal oxide such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite and magnetite,
Titanates such as barium titanate, calcium titanate, and strontium titanate, zirconates such as barium zirconate, calcium zirconate, and strontium zirconate, or a mixture thereof are 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 due to 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.

Furthermore, the BET specific surface area is 5 to 80 m ^2.
/ G of inorganic fine powder such as silica and BET specific surface area of 10
It is also preferable to use a mixture with 0 to 300 m ² / g of an inorganic fine powder such as silica. It can be configured to have both the fluidity and durability functions.

(External Additive Coverage) The transferability can be improved by specifying the coverage of the external additive that covers the surface of the toner base as the external additive of the present embodiment. In particular, by combining with the above-mentioned spheroidizing treatment, the effect of its transferability is exhibited. The coverage E of the toner base due to the external additive is represented by the following (Equation 3).

[0167]

[Equation 3]

The value of S in the equation is obtained from (Equation 4).

[0169]

[Equation 4]

The definition of each parameter in the above equation is as follows.

C: concentration of external additive (for example, hydrophobic silica), ρx: density of external additive (for example, hydrophobic silica), ρ
t: toner density, dx: external additive (for example, hydrophobic silica)
, Average toner particle diameter, dt: toner average particle diameter.

In this embodiment, the coverage is 70% or more, preferably 70% to 100%, more preferably 80% to 100%.
By this, the transfer efficiency is improved. In particular, when a dot image such as a halftone image is formed, the toner is scattered and easily aggregates due to the pressure during transfer, and the transfer efficiency is likely to decrease. Even in the tandem color process, if the distance between transfer and the time are shortened, the transfer tends to be difficult due to the influence of charge relaxation. At this time, by setting the coverage of the external additive to a certain value or more, the deterioration of the transfer is alleviated. Furthermore, the transfer efficiency is 1 when used in combination with the spheroidized toner described above.
Improves to near 00%. If it is less than 70%, the effect of transfer improvement is weakened.

(Pigment) As the pigment used in the present embodiment, carbon black, iron black, graphite, nigrosine, a metal complex of azo dye, C.I. I. Pigment
Acetoacetic acid arylamide-based monoazo yellow pigments such as yellow 1, 3, 74, 97, 98, C.I. I. Pigment
Acetoacetic acid arylamide disazo yellow pigments such as yellow 12, 13, 14, 17 and the like, 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: 1,81,122,5 and the like red pigments, C.I. I. Solvent Red 49,52,5
Red dyes such as 8 and 8, C.I. I. Pigment Blue 1
Blue dyes and pigments of phthalocyanine and its derivatives such as 5: 3 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.

(Powder Physical Properties of Toner) In the toner of this embodiment, the volume average particle diameter of the toner is 4 to 9 μm, preferably 4 to 8 μm, and more preferably 4 to 6 μm. 9 μm
If it is larger than 4 μm, the resolution will decrease and high image quality will not be obtained.
If it is smaller, aggregation of the toner becomes stronger and the background fog increases.

The coefficient of variation of the volume particle size distribution of the toner is 1
It is preferable that the coefficient of variation of the number particle size distribution is 5 to 35% and the number particle size distribution is 20 to 40%. More preferably, the variation coefficient of volume particle size distribution is 15 to 30%, and the variation coefficient of number particle size distribution is 2.
0 to 35%, more preferably, the variation coefficient of volume particle size distribution is 15 to 25%, and the variation coefficient of number particle size distribution is 20 to 3
It is 0%.

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.

In the particle size distribution of the toner, the particle size is 2 ×
It is preferable to contain 5 to 50% by number of particles of 10 ^{−6 to} 5 × 10 ⁻⁶ m. The fine powder in the toner affects the fluidity of the toner, the image quality, the storage stability, the filming on the photosensitive member, the developing roller, and the transfer member, the characteristics over time, the transfer property, particularly the multi-layer transfer property in the tandem system. 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.

When 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.

The fine powder amount can be controlled by a mechanical classification method in which the centrifugal force of the rotor is used in the classification step, or an air flow type classification method in which a vortex flow is generated by suction and the centrifugal force acts on the toner particles. A multi-stage classification device utilizing the Coanda effect can also be used. This is because the toner particles can be satisfactorily dispersed in the fine powder classifying step, and thus the classification accuracy of the ultrafine toner and the free matter is improved.

The particle size distribution is measured by Coulter counter TA
-Using type II (Coulter Counter, Inc.), number distribution,
Measurement is performed by connecting an interface (made by Nikkaki) that outputs the volume distribution and a personal computer. 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 an aperture of 70 × 10 ⁻⁶ m was used with a Coulter counter TA-II type. The aperture system 70 × 10 ^-6 m, but the particle size distribution measurement range is ^{1.26 × 10 -6 m~50.8 × 10 -6} m, 2.0 × 10 -6 area of less than m outpatient It is not practical because measurement accuracy and measurement reproducibility are low due to the influence of noise and the like. Therefore, the measurement area is 2.0 × 10 ⁻⁶ m to 50.8 × 1
It was set to 0 ^-6 m. In this area, the toner volume average particle diameter Dv and 2
It was calculated toner number% of ^{× 10 -6 m~5 × 10 -6 m} .
The volume average particle diameter Dc of the carrier was measured by using Microtrac of Nikkiso Co., Ltd.

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.

(Kneading Method) The wax to be added can be finely dispersed by kneading with a high shearing force or 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, and the roll temperature of one roll (RL1) and 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 less than 1.1 times, an appropriate shearing force is not generated, the dispersibility is not improved, and the translucency is deteriorated. On the other hand, when it is more than 2.5 times, the productivity is drastically lowered, the dispersibility is not improved, and the developability is deteriorated.

At this time, by kneading under a condition that the ratio of the load current values applied to the two rolls is in the range of 1.25 to 10, an appropriate 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.

The surface temperature of the heated roll is set lower than the resin softening point of the binder resin. Then, it is necessary to set the difference between the resin softening point and the heated roll surface temperature to 10 ° C. or higher. Since the resin is quickly melted and wound around a roll at the time of feeding the material, if the temperature is raised, shearing force is not applied during kneading, resulting in non-uniform dispersion, so that a temperature difference of 10 ° C. or more is necessary. However, if the temperature is higher than 70 ° C., the resin is conveyed without being completely melted, which also lowers the dispersibility.

Further, by setting the temperature difference between the two rolls to be at least ½ of the glass transition point of the resin, it is possible to knead and disperse the ultrahigh molecular weight molecules during kneading in an appropriate state. In particular, it is possible to realize both the translucency and the offset resistance of the color toner.

In order to further improve the uniformity of dispersion and to achieve high transferability, developability and fixability at the same time, one roll is provided with a temperature gradient between the first half and the second half, and the difference in temperature is determined by the glass of resin. The effect is enhanced by setting the temperature at 40 ° C. lower than the transition point or higher. If the temperature is lower than that, the stress on the resin is weakened and the detachability from the roll is deteriorated. On the contrary, it was found that the fog tends to increase when the temperature is set higher than the glass transition point by 30 ° C. Although details cannot be pursued, it is presumed that the internal additive aggregates due to the temperature difference during cooling.

By kneading with a high shearing force, properties such as fixing property, developing property and durability are further improved.

Further, it is preferable that the difference between the surface temperature of the molten toner film in the state where the binder resin is melted and wound around the roller and the heating surface temperature of the roller is 5 ° C. or more and 50 ° C. or less.
If the temperature is higher than 50 ° C., the molten film of toner may separate from the roller surface, and may fall at worst. Therefore, sufficient kneadability cannot be obtained, which leads to increased fog and reduced translucency.
If the temperature is lower than 5 ° C, the shearing force at the time of kneading with the binder resin is weakened, the dispersibility is not improved, and the light transmittance is deteriorated.

After the molten film of the toner is formed on the surface of the heated roll, the heating temperature of the roll is lowered, and the kneading stress becomes stronger in the melted state. If the temperature range to be lowered at this time is too large, the molten layer of the toner peels off on the roll, and the chips are scattered. Therefore, the range from 10 ° C. to the glass transition temperature of the resin is suitable.

Further, although the raw material is put into two rolls, the phenomenon that the material is scattered and thrown up during the feeding is inevitable. Particularly, a charge control agent having a low specific gravity is likely to fly up. If the dusted material does not collect dust locally, it will contaminate peripheral equipment and cause toner contamination. Therefore, it is necessary to devise a method for introducing this raw material. In this configuration, when the toner constituent material is charged between the two rolls from the raw material supply feeder, the raw material feeder is inserted from the cooling side roll (RL2) side, and the charging place is the heating side roll (RL1) and the roll. From the closest contact point of (RL2) to the roll (RL1)
It was decided to drop it on the surface of the roll (RL1) within the range of 20 ° to 80 ° in the direction opposite to the rotating direction. The rise is affected by the convection due to the heat between the rollers.By placing the backside of the feeder at the rising point of the convection of the heat generated between the rollers, it is possible to soften the rise of the air, which causes the rise of the material. It can be suppressed. Further, by providing a cover having an area ratio of 1.2 to 2 times the opening of the raw material supply feeder above the opening, it is possible to further suppress the rise.

Further, by making the opening for dropping the toner raw material from the raw material supply feeder a length of a certain width or more, there is an effect of suppressing soaring. The length of the opening in the axial direction of the roll (RL1) is not less than 1/2 and not more than twice the diameter of the roll (RL1). When the opening is shortened, the dropping point becomes a dot shape, and the amount of dropping the raw material without being melted increases. By lengthening it, it is possible to reduce the amount of falling in a plane on the roller, smoothly melting, and dropping. On the contrary, if it is too long, the uniformity of the raw material is lost at the time of charging, and the concentration of the mixing ratio changes depending on the place.

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 through the opening 614 from the constant amount feeder through the raw material supply feeder 613 and the toner raw material is fed with an 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 drop 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 larger 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.

From the constant quantity feeder 601 the toner raw material falls through the opening 614 while passing through the feeding feeder 613. 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.

(Surface Modification Treatment) Further, the toner of the present invention is structured such that the surface modification treatment is carried out by hot air. This stabilizes the fluidity and developability of the toner and improves the durability. Air that has a temperature necessary to melt the surface of the toner, and has a temperature that is equal to or higher than the softening point of the binder resin and that has an air volume of 0.35 Nm ³ / min or more at an air pressure of 3 × 10 ⁴ Pa. It is a thing.

[0200] Further, it is also possible to use a structure in which one or more kinds of hydrophobic silica, metal oxide fine powder, and metal salt fine powder are externally added and mixed to the toner base, and then surface modification treatment is carried out by hot air. Indicates. Further, even if one or more kinds of hydrophobic silica, metal oxide fine powder and metal salt fine powder are externally added and mixed after the surface modification treatment, better characteristics are exhibited.

Not only the toner base is made spherical by the surface modification treatment, but also by fixing these external additives,
It is possible to prevent separation from the toner base.

When a releasing agent such as wax having a low melting point is added to the binder resin, bleeding is exuded on the surface of the toner due to heat, and this bleeds out to the photosensitive member, transfer member, developing roller,
Fusing and filming easily occur on the developing blade. However, since the wax is finely dispersed by the above-mentioned high shearing force kneading, bleeding bleeding on the toner surface due to heat is small, and even if there is any, it has little effect on the photosensitive member and the developing roller blade.

Description will be made with reference to the drawings. FIG. 5 is a schematic view of a surface modification treatment apparatus using hot air. The toner particles 401 are made into a predetermined particle size distribution by pulverization and classification, and the toner particles 401 are fixed in the constant quantity feeder
No. 02, it is sent by compressed air 403 to a dispersion nozzle 404, which is a dispersion means of particles, and is ejected in the direction of about 45 degrees. In the present invention, the four distribution nozzles 404 are arranged at symmetrical positions. This is because the toner can be processed more uniformly by ejecting the toner from a plurality of nozzles. Toner 4 ejected from the dispersion nozzle 404
Since hot air is emitted to 01, hot air 406 is emitted from the hot air generator 405. The present invention uses a heater. This is not limited to a device such as a device heated by propane gas as long as it can generate hot air. The toner 401 passes through the hot air 406 while being dispersed, and is subjected to a surface modification treatment. The surface-modified toner is hood 40
It is taken into the inside 7 and sent to the cyclone 410 and is collected and collected in the collection box 411. 412 is a bug filter,
414 is a blower, 413 is an air flow meter, and 415 is a thermometer.

The surface-modified particles to be treated taken into the hood 407 can be subjected to cooling treatment with the cooling air 409 generated from the cooling air generator 408. This rapid cooling stabilizes the processing state. The air flow rate is appropriately determined depending on the processing amount. The distance from the position where the particles are treated with hot air to the position where the cooling air is applied is determined depending on the treatment amount, but is 10 to 100c.
m, preferably 20 to 80 cm. The cooling treatment is preferably a method using air cooled to 10 ° C. or lower by a cooler, but is not limited thereto. There are a method of cooling with water, a method of arranging a cooled solid substance around the pipe such as dry ice, and the like.

When the method described in the present invention is used, the production efficiency is improved because of the continuous method. Further, since the surface is modified in a dispersed state, particles do not fuse with each other or coarse particles are not generated. In addition, it has a very simple structure and is compact. There is no rise in the machine wall temperature and the product recovery rate is high. Since it is an open type, there is almost no possibility of dust explosion. Since the treatment is carried out with hot air instantly, the carrier particles as a whole are uniformly treated without aggregation of the particles. The hot air temperature of the treatment at this time is 60 ° C to 60 ° C.
0 ° C is preferred. The temperature is preferably 100 ° C to 500 ° C, more preferably 150 ° C to 350 ° C. When the temperature is 60 ° C or lower, the effect of the surface modification treatment cannot be obtained. When the temperature is 600 ° C. or higher, aggregation of toner base particles easily occurs, which is not suitable. Hot air volume is 0.35 at wind pressure 3-5 × 10 ⁴ Pa
1.0 Nm ³ / min, the raw material supply dispersed air volume is 1 to 3
A preferable range is 0.05 to 0.5 Nm ³ / min at × 10 ⁴ Pa. The ratio of the hot air volume to the raw material supply dispersed air volume is 10:
A range of 1 to 4: 1 is preferred. If the amount of hot air is too large, the raw material is repelled and uniform treatment cannot be performed. If the raw material supply dispersed air volume is too large, the raw material crosses the hot air and cannot be uniformly processed.

In this heat treatment, hydrophobic silica may be externally attached to the toner base and then heat treated to fix the toner on the toner base. Withdrawal of external additives is suppressed,
More durable. This makes it possible to further improve the fixing property, prevent the toner from being overcharged during long-term use, and maintain low fog in the non-image area and high image density for a long time.

In this embodiment, hot air temperature: 350 ° C., hot air flow rate: 1.0 Nm ³ / min (air pressure 5 × 10 ⁴ Pa),
Raw material supply dispersed air volume: 0.5 Nm ³ / min (wind pressure 3 × 1
0 ⁴ Pa), hot air temperature: 400 ° C, hot air flow rate: 0.8
Nm ³ / min (wind pressure 4.5 × 10 ⁴ Pa), raw material supply dispersed air volume: 0.5 Nm ³ / min (wind pressure 3 × 10 ⁴ Pa),
Hot air temperature: 300 ° C, hot air flow rate: 1.0 Nm ³ / mi
n (wind pressure 5 × 10 ⁴ Pa), raw material supply dispersed air volume: 0.5
The treatment was performed under the conditions of Nm ³ / min (wind pressure 3 × 10 ⁴ Pa).

(Mechanical Impact Force) As a device for spheroidizing the toner according to the present invention by a mechanical impact force, a hybridization system manufactured by Nara Machinery Co., Ltd., a mechanofusion system manufactured by Hosokawa Micron Co., Ltd., a product manufactured by Kawasaki Heavy Industries, Ltd. There is a Kryptron system.

Particularly, spheroidization by the Kryptron system is preferable. This is a device in which spheroidization by a mechanical impact force is composed of a rotating body on a cylinder having unevenness on the surface and rotating at high speed, and a fixed body having unevenness on the surface with a narrow gap with the rotating body, By setting the gap between the convex portion of the rotating body and the convex portion of the fixed body to 0.5 to 6 mm, the crushing efficiency and the spheroidizing action can be further enhanced. If it is smaller than 0.5 mm,
Since the contact between the particles, the rotating body and the fixed body is significantly increased,
The frictional heat is remarkably generated, the above-mentioned phenomenon of seizure with the tip portion occurs, and the frequency at which safe driving is impaired increases. 6
If it is larger than mm, a violent flow of high-speed air flow cannot be generated, and sufficient spheroidization 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 advantage 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 reduced, 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, high flowability can be obtained by adding a small amount of silica, the generation of floating silica can be suppressed, and white spots of silica on a solid black image area, silica on an intermediate transfer member or a photoreceptor, 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.

An example of the toner spheroidizing apparatus of this embodiment shown in FIG. 6 will be described.

The raw material 503 obtained by roughly pulverizing the kneaded material is fed from the constant quantity feeder 508, and is sent to the spheroidization processing section 500 by the cooling air 511 supplied by the cooler 509. A raw material 503 is introduced from an inlet 504, rotates at a high speed and has an uneven portion 506 on the surface, and a fixed body 502 having an uneven portion 507 on the surface located in a narrow gap with the rotating body 501. Be transported to the space
Along with the flow of the high-speed airflow generated between the rotating body rotating at a high speed and the fixed body, the raw material particles are crushed by a strong collision to be spheroidized. The spherical particles 510 exit from the outlet 505 and are sent to the coarse powder classifier 513, and the coarse particles are again sent to the inlet 504 by the air 511. The product is sent to the cyclone 515 and the collection container 411
Will be collected.

In this embodiment, the peripheral speed of the rotating body is 130 m.
/ S, gap between rotating body and fixed body: 1.5 mm, raw material supply rate: 5 kg / h, cooling air temperature: 0 ° C., discharge section temperature: 4
5 ° C., peripheral speed of rotating body: 120 m / s, gap between rotating body and fixed body: 1 mm, feed rate of raw material: 5 kg / h, cooling air temperature: 0 ° C., discharge part temperature: 40 ° C.

(Development) In the development process of this embodiment, an elastic blade made of 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, thereby forming a photosensitive member. It is configured to develop by contact or non-contact. As the 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, and toner is supplied from the supply roller to the developing roller,
An elastic rubber or stainless steel doctor blade is brought into contact with the developing roller, or a metallic roller is rotated and brought into contact with the developing roller in the same direction to form a thin layer of toner. A developing method in which a toner image is formed by applying a direct current or an alternating current with or without contact with the photoconductor is preferably used.

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 supplying 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 amount of toner supplied from the toner reservoir onto the developing roller when the amount of toner supplied is controlled to a constant amount, a sponge-like supplying 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 this conventional toner, in this developing structure, when used for a long period of time, scratches on the developing roller and image defects due to vertical streaks on the image due to foreign matter adhering to the blade tend 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 is reduced during long-term continuous use, and when a solid black image is taken, the density of the latter half of the image is partially reduced, 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. Further, in the two-component development used by mixing with a carrier, it is necessary to prevent overcharge and stabilize the charge.

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 allows 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 smaller than | 5 | μC / g, toner scattering increases. If it is larger 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).

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 0.3 to 1.2 wt% of the carrier particle weight.

As the resin used for the resin coating layer, a fluorine resin or a silicone 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 4
It is preferably 0 to 100 × 10 ⁻⁶ m. When the average particle size of the carrier is less than 40 × 10 ⁻⁶ m, the carrier is easily developed on the photoreceptor, and the average particle size of the carrier is 100 × 10 ⁻⁶ m.
If it becomes larger, the toner holding power of the carrier becomes weaker, so that toner scattering occurs.

(Tandem Color Process) Further, in order to form a color image at a high speed, in this embodiment, a plurality of toner image forming stations including a photoconductor, a charging unit and a toner carrier are provided and the toner image is formed on the image carrier. The primary transfer process in which the toner image in which the electrostatic latent image formed on the image is visualized is transferred to the transfer member by bringing the endless transfer member into contact with the image carrier is successively executed, A secondary transfer process is performed in which a multi-layered transfer toner image is formed on a transfer body, and then the multi-layered toner image formed on the transfer body is collectively transferred onto a transfer medium such as paper or OHP. In the transfer process, 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
In the case of (mm / s), the transfer position configuration is such that d1 / v ≦ 0.65. For example, after the first color yellow toner is primarily transferred, the second color magenta toner is primary. The time until transfer 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 charged by the charge effect of the yellow toner. Repulsion causes problems such as a reduction in transfer efficiency and a blank character 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 once, image repulsion occurs due to repulsion between charges of toner.

Therefore, by adopting the toner constitution of this embodiment, the internal additives such as wax in the resin are 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.

(Cleanerless Process) Further, in the present embodiment, a cleaner for carrying out the following charging, exposing and developing processes without having a cleaning process step of collecting the toner remaining on the photoconductor after the transfer process by cleaning. It is preferably used for an electrophotographic apparatus having a basic process of a less process.

By using the toner of this 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.

(Charger) FIG. 17 shows the structure of the ion generator. An ion generating electrode 702 and an induction electrode 703 are provided on both surfaces of a dielectric 701 made of ceramic, glass, or the like, and the induction electrode 703 has a structure covered with an insulator such as ceramic or glass. Further, the ion generating electrode 70
Although not shown, 2 is coated with glass for the purpose of environmental stability and prevention of deterioration due to discharge. Further, a heating member 704 is provided in order to further enhance discharge stability, and a switch AC 705 is operated in the circuit configuration as shown to apply a driving AC voltage 706 between the ion generation electrode 702 and the induction electrode 703. Further, a DC bias voltage 707 is applied to the ion generating electrode 702. The alternating voltage has a frequency of several kHz to several 100 kHz and an output voltage of 0.
Since a high frequency and high voltage of 5 to 5 kVp-p are applied, when an AC voltage 706 is applied between these electrodes with a dielectric 710 sandwiched between them, a creeping discharge occurs between the induction electrode 703 and the ion generation electrode 702, and ion generation occurs. The air around the electrode 702 is ionized, and positive and negative ions are generated near this.
Here, as shown in FIG. 17, when a negative DC bias voltage 707 is applied, only negative ions 7011 are extracted from the ion generator and fall onto the photoconductor 712 to be charged. When the DC bias voltage 707 is positive, positive ions are extracted. At the same time as these electrifications, the power source 708 provided as the power source of the heater 704 for heating is also driven by the heating means to drive 12 to 24V.
A DC voltage of a certain degree is applied. At the same time, the grid voltage 709 may be added.

(Oilless Color Fixing) FIG. 16 is a diagram showing the structure of the fixing unit used in this embodiment.
The present embodiment is preferably used for an electrophotographic apparatus having a fixing process in which a belt-type fixing medium is used 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. In addition, compared to the conventional rigid fixing roller, the elastic belt type has a problem of shortening the life due to scratches due to no oil.

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.

The characteristics of the binder resin used in the examples are shown in (Table 1). 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.

[0241]

[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.

(Table 2) (Table 3) (Table 4) (Table 5) show the wax used in this example and the physical properties thereof. Mnr
Is the number average molecular weight of the wax, Mwr is the weight average molecular weight of the wax, and Mzr is the Z average molecular weight of the wax. T
w (° C.) is the melting point by the DSC method, Ct (%) is the melting point +1
Volume increase rate (%) at 0 ° C, Ck (wt%) is 220 ° C
The heating weight loss of is shown.

[0244]

[Table 2]

[0245]

[Table 3]

[0246]

[Table 4]

[0247]

[Table 5]

(Table 6) shows the pigments used in this example.

[0249]

[Table 6]

Table 7 shows the charge control agents used in this example.

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.

[0252]

[Table 7]

Table 8 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
Blown in a) for 1 minute.

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.

[0256]

[Table 8]

The kneading conditions in this example are shown in (Table 9). 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.

[0258]

[Table 9]

Tables 10 and 11 show the toner material composition and physical property values used in this example.

[0260]

[Table 10]

[0261]

[Table 11]

The weight average particle diameter of each toner is TM1.
~ 3 is 8μm in average particle size, TM4,5 is 6μm in average particle size
m. The same applies to Y, C, and BK toners. Trials were made so that the variation coefficient of the volume particle size distribution was 20 to 25% and the variation coefficient of the number particle size distribution was 25 to 30%. TM1,
Numerals 2 and 5 were spheronized by mechanical impact force, and TMs 3 and 4 were spheronized by hot air. The same applies to Y, C, and BK toners. The kneading PCM30 is a conventional twin-screw extruder, kneading temperature is 110 ° C., rotation speed is 200 min ⁻¹ , and supply rate is 5 kg / h.
Processed in.

The blending ratio of the pigment, charge control agent and wax is shown in parentheses as the blending ratio (parts by weight) to 100 parts by weight of the binder resin. 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 12) and (Table 13) show the molecular weight characteristics of the toner after the kneading treatment in this example. The toner was comparatively evaluated with magenta toner TM1 to 3 toner. 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, and Wmv is the weight average molecular weight Mw of the toner.
v and the number average molecular weight Mnv ratio Mwv / Mnv and Wzv indicate the ratio Mzv / Mnv of the Z average molecular weight Mzv and the number average molecular weight Mnv of the toner.

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.

[0266]

[Table 12]

[0267]

[Table 13]

The molecular weight distribution characteristics are shown in FIGS.

FIG. 5a and FIG. 5b show the binder resin PES, respectively.
-1, molecular weight distribution characteristics of toner TM-1, FIGS. 6a and 6b are binding resin PES-2, respectively, molecular weight distribution characteristics of toner TM-2, FIGS. 7a and 7b are binding resin P, respectively.
The molecular weight distribution characteristics of ES-3 and Toner TM-3 are shown.

In the binder resin PES-1, a high molecular weight component of 3 × 10 ⁴ or more is present in an amount of 5% or more in the area ratio with respect to the entire binder resin molecular weight distribution. 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 is also 3 × 1
A high molecular weight component of 0 ⁴ or more is present in an area ratio of 5% or more with respect to the entire binder resin molecular weight distribution. Also 3 × 10 ^{5 to} 9
It has a high molecular weight component of × 10 ^{6 in} an area ratio of 1% or more with respect to the entire binder resin molecular weight distribution.

It can be seen that the toner is molecularly cleaved by the 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 No. 4 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 to the entire toner molecular weight distribution, and the high molecular weight component of 1 × 10 ⁶ or more is hardly contained.

10 and 11 show examples of molecular weight distribution characteristics. FIG. 10 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. 11 shows M10 and M of the molecular weight distribution characteristics of Toner TM-3.
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.

FIG. 12 shows the molecular weight distribution characteristics of the fixing aid WA-1 and FIG. 13 shows the molecular weight distribution characteristics of the fixing aid WA-9.

(Embodiment 1) FIG. 14 is a sectional view showing the arrangement of an image forming apparatus for full-color image formation used in this embodiment. In FIG. 14, 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 1.0 to 9.8 on the photoconductor 1 via the transfer belt 12.
The toner on the photoconductor is transferred onto the belt by being pressed by the pressing force of (N). 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 will occur, and if it is greater than 9.8 (N), transfer character omission will occur.

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

The toner on the transfer belt 12 is transferred onto the paper 19 by +1300 V 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 unit 205. The toner is conveyed to a fixing unit configured and fixed there.

FIG. 16 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 is a hollow pipe having a wall thickness of 1 mm and an outer diameter of 20 mm. 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 which is equal to the peripheral speed of the photoconductor) and the moving speed of the transfer belt 12 are such that the photoconductor speed is 0.5 to 1.5 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 by 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 superposed to form a color image. After the final B toner image is transferred, the four color toner images are fed from a paper feed cassette (not shown) at the same timing.
9 is collectively transferred to the sheet 9 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. 15 shows a tandem system in which the paper 19 is carried on the paper carrying belt 17 and the toner on the OPC is directly transferred without performing the primary transfer to the belt.

In Table 14, the electrophotographic apparatus shown in FIG.
The results of image rendering are shown below. In Table 15, 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.

[0299]

[Table 14]

[0300]

[Table 15]

When an image was formed using the toner manufactured as described above by the image forming apparatus shown in FIG. 15, 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 with the image forming apparatus shown in FIG.

However, the toners of tm6, ty6, tc6, and tb6 caused filming of the photoconductor, transfer failure, scattering of characters during transfer, and much 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 16), 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.

[0305]

[Table 16]

The 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 tm6 clumped in the storage stability test, and the non-offset temperature range was narrow.

[0308]

As described above, from the first transfer position to the second transfer position.
In order to achieve transferability and oilless fixing in a tandem type transfer process with a short distance to the transfer position of, after mixing processing of the toner base material containing at least a binder resin, a colorant, and a fixing aid, , A toner subjected to a melt-kneading process with a high shearing force and subjected to a surface modification process on the toner particles subjected to a fine treatment, or a toner base material containing at least a binder resin, a colorant, and a fixing auxiliary agent After that, melt kneading with high shearing force is applied, and the toner that is created by spheroidizing with mechanical impact force is used to prevent hollowing and scattering during transfer and to obtain high transfer efficiency. Is possible. 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.

The offset property can be prevented while maintaining high OHP translucency without applying oil with a silicone or fluorine type fixing means (roller or belt). Further, even if the belt is used for a long period of time, a good non-offset property can be maintained without causing a surface deterioration phenomenon of the belt.

[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 surface treatment used in an example of the present invention.

FIG. 6 is a configuration diagram of a toner sphering process used in 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 the molecular weight distribution characteristics of the toner of the example of the invention.

FIG. 11 is a diagram showing the molecular weight distribution characteristics of the toner of the example of the invention.

FIG. 12 is a diagram showing the molecular weight distribution characteristics of the fixing aid of the example of the present invention.

FIG. 13 is a diagram showing the molecular weight distribution characteristics of the fixing aid of the example of the present invention.

FIG. 14 is a cross-sectional view showing the configuration of an image forming apparatus used in an example of the present invention.

FIG. 15 is a cross-sectional view showing the configuration of an image forming apparatus used in an example of the present invention.

FIG. 16 is a cross-sectional view showing the configuration of a fixing unit used in an example of the present invention.

FIG. 17 is a cross-sectional view showing the configuration of the ion generator used in the examples 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 front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B02C 23/32 G03G 9/08 365 365 4G035 G03G 9/08 365 374 4G036 374 375 4G037 375 15/02 102 15 / 02 102 15/16 15/08 507 103 15/16 9/08 381 103 331 15/08 507B F term (reference) 2H005 AA01 AA06 AA08 AB02 AB04 CA08 CA14 CB07 CB13 EA03 EA05 EA06 EA10 2H077 AA37 AC11 AC16 AD06 2H200 GA12 GA23 GA44 GA47 GA60 HA14 HA16 HA28 HB12 HB20 HB22 JA01 JA26 JC03 JC16 MB04 MB05 MB06 4D063 FF14 FF21 FF37 GA10 4D067 EE12 EE22 GA16 GA20 4G035 AB48 4G036 AC42 AC45 4G037 CA05 EA02

Claims (31)

[Claims] 1. A toner base material containing at least a binder resin, a colorant and a fixing aid is mixed and then rotated in different directions, and a gap is provided to provide a temperature difference and a rotation speed difference facing each other. A toner characterized in that a kneading process is performed between rolls of a book, and then the finely divided toner particles are subjected to a surface modification process with hot air. 2. A toner base material containing at least a binder resin, a colorant, and a fixing aid is mixed and then rotated in different directions, and a gap is provided to provide a temperature difference and a rotation speed difference facing each other. A toner characterized by being kneaded between rolls of a book and spheroidized by a mechanical impact force. 3. A step of mixing a toner base material containing at least a binder resin, a colorant, and a fixing aid, followed by rotating in different directions and providing a gap to provide a temperature difference and a rotation speed difference facing each other. A step of performing a kneading process between two rolls,
A method for producing a toner, comprising a step of subjecting to finely pulverizing treatment, a step of classifying if necessary, and a step of subjecting the finely divided toner particles to a surface modification treatment with hot air. 4. A step of mixing a toner base material containing at least a binder resin, a colorant, and a fixing aid, followed by rotating in different directions, and providing a gap to provide a temperature difference and a rotational speed difference facing each other. A step of performing a kneading process between two rolls,
Then, a method for producing a toner, comprising a step of spheroidizing and pulverizing with a mechanical impact force, a step of classifying if necessary, and a step of externally adding thereafter. 5. An image carrier, at least a charging unit for forming an electrostatic latent image on the image carrier, and an electrostatic latent image formed on the image carrier, at least a binder resin, a colorant, and a fixing agent. After a mixing process of a toner base material containing an auxiliary agent, a process of rotating in different directions and performing a melt-kneading process between two rolls having a gap and a temperature difference and a rotation speed difference facing each other, and miniaturization A plurality of toner image forming stations including a developing step for developing the treated toner particles with a toner subjected to a surface modification treatment with hot air, and the visualized toner images are successively and sequentially transferred onto a transfer medium. An image forming apparatus comprising: a transfer unit for transferring. 6. At least a binder resin, a coloring agent, and a fixing member, which comprises at least an image bearing member, a charging unit for forming an electrostatic latent image on the image bearing member, and an electrostatic latent image formed on the image bearing member. After mixing the toner base material containing the auxiliary agent, the toner base material is rotated in different directions, and a kneading process is performed between two rolls having a gap and a temperature difference and a rotation speed difference facing each other. A plurality of toner image forming stations including a developing process for developing a toner image by a spheroidizing process, and a transfer unit for successively transferring the visualized toner image to a transfer medium. An image forming apparatus characterized by the following. 7. At least an image bearing member, a charging unit that forms an electrostatic latent image on the image bearing member, and an electrostatic latent image formed on the image bearing member, at least a binder resin, a colorant, and a fixing agent. After mixing the toner base material containing the auxiliary agent, the toner base material is rotated in different directions, melted and kneaded between two rolls having a gap and facing each other with a temperature difference and a rotation speed difference, and then subjected to a micronization treatment. A plurality of toner image forming stations including a developing step of developing the toner particles with a toner surface-modified with hot air, and an endless transfer member is brought into contact with the image carrier to transfer the toner particles. A primary transfer unit that sequentially transfers the visualized plurality of toners to the body, and a secondary transfer unit that collectively transfers the multi-layered toner images formed on the transfer body to a transfer medium. An image forming apparatus characterized by. 8. An image carrier, at least a charging unit for forming an electrostatic latent image on the image carrier, and an electrostatic latent image formed on the image carrier, at least a binder resin, a colorant, and a fixing agent. A toner base material containing an auxiliary agent is mixed and rotated in different directions, and a kneading process is performed between two rolls having a gap and a temperature difference and a rotation speed difference facing each other. A plurality of toner image forming stations including a developing process for developing a toner image by a spheroidizing process, and an endless transfer member is brought into contact with the image carrier so that the transfer image is visualized on the transfer member. An image characterized by comprising a primary transfer means for sequentially successively transferring a plurality of converted toners, and a secondary transfer means for collectively transferring the multi-layered toner image formed on the transfer body onto a transfer medium. Forming equipment. 9. At least an electrostatic latent image formed on the image carrier is bound by at least an image carrier, a charging unit having an ion generating electrode and an induction electrode formed by sandwiching a dielectric material, and an electrostatic latent image formed on the image carrier. A toner base material containing a resin, a colorant, and a fixing aid is mixed and then rotated in different directions, and a kneading process is performed between two rolls having a gap and a facing temperature difference and a rotation speed difference. A plurality of toner image forming stations including a developing step of developing the toner by a spheroidizing process using a mechanical impact force, and a transfer means for transferring the visualized toner image onto a transfer medium. An image forming apparatus comprising: and a means for collecting the toner attached to the image carrier in a developing process. 10. A charging unit having at least an image carrier, a component composed of an ion generating electrode and an induction electrode formed by sandwiching a dielectric, and an electrostatic latent member formed on the image carrier. The image is rotated in different directions after mixing processing of a toner base material containing at least a binder resin, a colorant, and a fixing aid, and two images are provided with a gap and a temperature difference and a rotation speed difference facing each other. A plurality of toner image forming stations including a developing process in which a kneading process is performed between rolls and at least a spheroidizing process is performed by a mechanical impact force to visualize the toner, and the visualized toner image is transferred. An image forming apparatus comprising: a transfer unit that transfers the image onto a medium; and a unit that collects the toner attached to the image carrier in a developing process. 11. In the transfer process, d1 / v ≦ 0 when the distance from the first transfer position to the second transfer position is d1 (mm) and the peripheral speed of the photoconductor is v (mm / s). .65
9. The image forming apparatus according to claim 7, wherein the image forming apparatus satisfies the condition of. 12. The transfer body is a transfer belt, the transfer belt has a surface resistance of 10 ⁷ to 10 ¹² Ω / □, and a volume resistance of 10 ⁷ to 10 ¹² Ω · cm. The image forming apparatus described. 13. The resistance value of the transfer roller for the first transfer is 10
² in ~10 ⁶ Ω · cm, the image forming apparatus in accordance with claim 7-10 resistance value of the transfer roller to be used for the second transfer is 10 ² ~10 ⁶ Ω · cm. 14. The binder resin comprises at least a polyester resin, and the polyester resin comprises a polyhydric alcohol and a carboxylic acid component containing an aromatic dicarboxylic acid and a trivalent or higher polyvalent carboxylic acid or a lower alkyl ester thereof. The toner according to claim 1, which is a polyester resin obtained by condensation polymerization of. 15. The binder resin contains at least a polyester resin, and the polyester resin is a polyhydric alcohol.
The toner according to claim 1 or 2, which is a polyester resin obtained by polycondensation of an aliphatic dicarboxylic acid and a carboxylic acid component containing a trivalent or higher polyvalent carboxylic acid or a lower alkyl ester thereof. 16. The binder resin has a molecular weight distribution of 2 × 10 ^{3 to} 3 in gel permeation chromatography (GPC).
Kneading by a high shearing force, containing a polyester resin having at least one maximum molecular weight peak in the region of × 10 ⁴ and having a high molecular weight component of 3 × 10 ⁵ or more in an amount of 0.5 parts by weight or more based on the binder resin. The molecular weight distribution in the GPC chromatogram of the toner created by the treatment is
^{3. 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 maximum peak or shoulder in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ^6. Toner. 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.
The toner according to claim 1 or 2, wherein M10 / M90 is 0.5 to 8, where M10 is a molecular weight corresponding to 10% and a molecular weight corresponding to 10% of the height of the maximum molecular weight peak or shoulder is M10. 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.
% (M10-M90) / M90 is 0.1 to 7, where M90 is the molecular weight corresponding to 10% and the molecular weight corresponding to 10% of the peak of the molecular weight peak or shoulder is M10. Toner. 19. The fixing aid has a weight average molecular weight of 200 to 10,000, Z in the molecular weight distribution in GPC.
Average molecular weight is 1500 to 20000, 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 1.02-10, molecular weight 1
× at least one molecular weight maximum peak in 10 ³ to 3 × 10 ⁴ region, melting point 60 to 130 ° C., 25 penetration at ° C., characterized in that it comprises a wax is 4 or less claim 1 or 2. The toner according to 2. 20. The fixing aid has at least 5 to 1 carbon atoms.
Obtained by reacting a long chain alkyl alcohol of 00 with an unsaturated polycarboxylic acid or an anhydride thereof and a hydrocarbon wax, and having a weight average molecular weight of 1,000 to 6 in a molecular weight distribution in gel permeation chromatography (GPC).
000, Z average molecular weight is 1500 to 9000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to 3.8, 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, having at least one peak of molecular weight in the region of molecular weight 1 × 10 ^{3 to} 3 × 10 ⁴ , and having an acid value of 5 to 80 mgKOH
/ G, melting point 80-120 ° C, penetration at 25 ° C is 4
The toner according to claim 1 or 2, further comprising the following wax. 21. The fixing aid has a number average molecular weight of 100 to 5,000, a weight average molecular weight of 200 to 10,000, and a ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) in GPC molecular weight distribution. Is 1.
01-8, ratio of Z average molecular weight and number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02-10, molecular weight 5 × 1
It has at least one maximum molecular weight peak in the region of 0 ² to 1 × 10 ⁴ , an iodine value of 25 or less, and a saponification value of 30 to 3
3. The toner according to claim 1, further comprising a wax of No. 00. 22. The fixing aid is one or two of a derivative of hydroxystearic acid, a glycerin fatty acid ester, a glycol fatty acid ester, a polyhydric alcohol fatty acid ester of sorbitan fatty acid ester, a meadow foam oil derivative, and a jojoba oil derivative. The toner according to claim 1 or 2, including the above. 23. The fixing aid is a saturated or monovalent unsaturated aliphatic amide having a carbon number of 16 to 24 and a melting point of 70 to 110 ° C., an alkylene of a saturated or monovalent unsaturated fatty acid. The toner according to claim 1, containing one or more of bis fatty acid amides. 24. The toner according to claim 1, wherein the toner base is treated with an external additive, and the coverage of the toner base with the external additive is 70% or more. 25. The external additive has an average particle diameter of 35 to 100 n.
23. Silica or titanium oxide fine powder which is m.
The toner, the toner manufacturing method, and the image forming apparatus described above. 26. The toner according to claim 22, wherein the external additive contains silica or titanium oxide fine powder having an average particle diameter of 8 to 35 nm. 27. Two rolls facing each other with a narrow gap capable of rotating in different directions and capable of heating or cooling,
A temperature difference is provided between the roll temperature of one roll (RL1) and the roll temperature of the other roll (RL2), and the roll (RL1) and the roll (RL2) are rotated at different peripheral speeds to remove the toner material. The method for producing a toner according to claim 3, wherein kneading is performed between the two rolls. 28. Two rolls facing each other with a narrow gap capable of rotating in different directions and capable of heating or cooling,
One roll (RL1) has a temperature difference between the first half and the second half, and a temperature difference is provided between the roll temperature of the first half of the roll (RL1) and the roll temperature of the other roll (RL2), and Roll (RL1) and the roll (RL2)
5. The method for producing a toner according to claim 3, wherein the toner materials are kneaded between the two rolls by rotating the rollers at different peripheral speeds. 29. When the peripheral speed of the roll (RL1) is Rw1 and the peripheral speed of the roll (RL2) is Rw2, the processing is performed so as to satisfy the relationship of (Equation 1). Manufacturing method of toner. [Equation 1] 30. When the load current value during rotation of the roll (RL1) is Dr1 and the load current value of the roll (RL2) is Dr2, processing is performed so as to satisfy the relationship of (Equation 2). Item 29. A method for producing a toner according to item 27 or 28. [Equation 2] 31. Sphericalization by a mechanical impact force comprises a rotating body on a cylinder having an uneven surface and rotating at a high speed, and a fixed body having an uneven surface on the surface with the rotating body with a narrow gap. The method for producing a toner according to claim 4, which is performed by a spheronizing device.