JP4719028B2 - Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to an image forming method and an image forming apparatus using an electromagnetic induction heating type fixing device suitable for a printer, a copying machine, a facsimile, and the like, and a toner, a developer, a toner-containing container, and a process cartridge used therefor. .

In recent years, market demands for energy saving and high speed are increasing for image forming apparatuses such as printers, copiers, and facsimiles. In order to achieve these performances, it is important to improve the thermal efficiency of the fixing device used in the image forming apparatus.
In an image forming apparatus, an unfixed toner image is formed by an image transfer process or a direct system by an image forming process such as electrophotographic recording, electrostatic recording, magnetic recording, etc. Formed on the recording medium. As a fixing device for fixing an unfixed toner image, a contact heating method such as a heat roller method, a film heating method, and an electromagnetic induction heating method is widely adopted.

  The heat roller type fixing device basically includes a rotating roller pair including a fixing roller having a heat source such as a halogen lamp inside and adjusted to a predetermined temperature, and a pressure roller pressed against the fixing roller. It is said. A recording medium is introduced into a contact portion (so-called nip portion) of these rotating roller pairs and conveyed, and an unfixed toner image is melted and fixed by heat and pressure from a fixing roller and a pressure roller.

As the film heating type fixing device, for example, Patent Document 1 and Patent Document 2 are proposed.
In this film heating type fixing device, a recording medium is brought into close contact with a heating body fixedly supported by a support member through a thin fixing film having heat resistance, and heating is performed while the fixing film is slid relative to the heating body. The heat of the body is supplied to the recording medium through the film material. As the heating body, for example, a ceramic heater provided with a resistance layer on a ceramic substrate such as alumina or aluminum nitride having characteristics such as heat resistance, insulation, and good thermal conductivity is used. Since this fixing device can use a thin film with a low heat capacity as the fixing film, the heat transfer efficiency is higher than that of a heat roller type fixing device, the warm-up time can be shortened, quick start and energy saving can be achieved. It becomes possible.

As the electromagnetic induction heating type fixing device, for example, a technique has been proposed in which Joule heat is generated by an eddy current generated in a magnetic metal member by an alternating magnetic field, and a heating body including the metal member generates electromagnetic induction heat (patent) Reference 3).
Here, the configuration of the electromagnetic induction heating type fixing device will be described. FIG. 1 is a schematic diagram showing a conventional fixing device using an electromagnetic induction heating method. The fixing device includes a film inner surface guide 121 on which a heating body 120 including an exciting coil unit 118 and a magnetic metal member 119 as a heating unit is mounted, and a film inner surface guide 121 in a state where the magnetic metal member 119 is in contact with an inner wall. A pressure roller for rotating the film 117 while forming a nip portion N between the cylindrical film 117 having heat resistance and the film 117 at the position of the magnetic metal member 119 and pressing the film 117. 122.

The film 117 has a heat resistance of 100 μm or less, preferably 50 μm or less and 20 μm or more, and has a single layer film such as PTFE, PFA, FEP or the like, or an outer periphery of a film such as polyimide, polyamideimide, PEEK, PES, PPS, etc. A composite layer film having a surface coated with PTFE, PFA, FEP or the like is used.
The film inner surface guide 121 is made of a member having rigidity and heat resistance formed of a resin such as PEEK or PPS, and the heating body 120 is fitted in a substantially central portion of the film inner surface guide 121 in the longitudinal direction. .
The pressure roller 122 includes a core 122a and a heat-resistant rubber layer 122b having good releasability, such as silicone rubber, provided around the core 122a. The film 117 is held so as to be in pressure contact with the magnetic metal member 119 of the heating body 120. The pressure roller 122 is driven to rotate counterclockwise by driving means (not shown).

By the rotational driving of the pressure roller 122, a frictional force is generated between the pressure roller 122 and the film 117, and the rotational force acts on the film 117. The film 117 is in close contact with the magnetic metal member 119 of the heating body 120. Slide and rotate.
A recording medium having an unfixed toner image T formed by an image forming unit (not shown) between the film 117 in the nip portion N and the pressure roller 122 in a state where the heating body 120 reaches a predetermined temperature. 111 is introduced. The recording medium 111 is sandwiched between the pressure roller 122 and the film 117 and conveyed through the nip portion N, whereby heat of the magnetic metal member 119 is applied to the recording medium 111 via the film 117, and the unfixed toner image T is formed. It is melt-fixed on the recording medium 111. At the exit of the nip portion N, the recording medium 111 that has passed is separated from the surface of the film 117 and conveyed to a paper discharge tray (not shown).

As described above, in the electromagnetic induction heating type fixing device, the magnetic metal member 119 as the induction heating means is disposed near the toner image T of the recording medium 111 via the film 117 by utilizing the generation of eddy current. The heating efficiency is higher than that of the film heating type fixing device.
However, among image forming apparatuses, a fixing device in a full-color image forming apparatus is required to have a capability of sufficiently heating and melting a toner particle layer having a thickness of four or more layers. In order to achieve this requirement, in the electromagnetic induction heating type fixing device, a rubber elastic layer having a certain thickness is required on the surface of the film in order to sufficiently wrap and uniformly melt the toner image. Become. In order to solve these problems, when an elastic layer such as silicone rubber is coated on the surface of the film to some extent, the thermal responsiveness deteriorates due to the low thermal conductivity of the elastic layer, and the inner surface of the film and the toner heated from the heating body When the amount of toner is very large due to a very large temperature difference with the outer surface in contact with the belt, the belt surface temperature decreases rapidly, so that sufficient fixing performance cannot be secured, and so-called cold offset occurs. There is a problem of doing.

  On the other hand, in the image forming method, the electric latent image or the magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and the latent image is developed with toner to form a toner image. Next, the toner image is usually transferred and fixed on a recording medium such as paper.

  The toner used for development is generally colored particles in which a binder, a charge control agent, and other additives are contained in a binder resin. The production methods are roughly classified into a pulverization method and a suspension weight. There is legal. In the pulverization method, a colorant, a charge control agent, an offset preventive agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. . According to this pulverization method, it is possible to produce a toner having excellent characteristics to some extent, but there is a limitation in the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle.

  Therefore, in actuality, when the toner composition is pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, The fine powder having a particle size of 5 μm or less and the coarse powder having a particle diameter of 20 μm or more must be removed by classification, which has the disadvantage that the yield becomes very low. In the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner. Further, the pulverization method has a particle size limit, and cannot cope with further reduction in particle size.

In recent years, in order to overcome these problems in the pulverization method, a toner production method using a suspension polymerization method has been proposed and implemented. As a technique for producing a toner for developing an electrostatic latent image by a polymerization method, for example, there is a suspension polymerization method.
However, the toner particles obtained by the suspension polymerization method are spherical and have the disadvantage of poor cleaning properties. In addition, in development and transfer with a low image area ratio, there is little transfer residual toner and cleaning defects do not become a problem. Toner may be generated on the photosensitive member as untransferred toner, and accumulation will cause image smudges. Further, since the toner has a spherical shape, the contact area between the toners is reduced, and the adhesion is reduced. Therefore, there is a problem that a margin for fixing is easily lowered, and stability at the lower limit of fixing cannot be obtained.

  For this reason, a method of associating resin fine particles obtained by an emulsion polymerization method to obtain irregular toner particles has been proposed (see Patent Document 4). However, in the toner particles obtained by the emulsion polymerization method, a large amount of surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of charging of the toner is impaired. The distribution is widened, and the resulting image is poorly soiled. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited.

Further, in the fixing step of the image forming method, toner particle releasability from the heating member (hereinafter, sometimes referred to as “offset resistance”) is required. The offset resistance can be improved by the presence of a release agent on the toner particle surface. For example, not only the resin fine particles are contained in the toner particles, but also a method for improving the offset resistance due to the resin fine particles being unevenly distributed on the surface of the toner particles has been proposed (Patent Document 5 and Patent Document 5). 6).
However, these proposals have a problem that the fixing lower limit temperature is increased and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

In addition, in the method of obtaining irregular toner particles by associating the resin fine particles obtained by the emulsion polymerization method, in order to improve the offset resistance, when the release agent fine particles are associated, The toner particles are taken into the toner particles, and as a result, the offset resistance cannot be sufficiently improved. Further, since the toner particles are constituted by randomly fusing resin fine particles, release agent fine particles, colorant fine particles, etc., the composition (content ratio of constituent components) between the obtained toner particles, the molecular weight of the constituent resin, etc. Variations occur. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time.
In a low-temperature fixing system that requires low-temperature fixing, fixing inhibition is caused by resin fine particles unevenly distributed on the toner surface, and the fixing temperature range cannot be secured. Moreover, it is common to use a styrene / acrylic resin for any of the suspension polymerization method, the emulsion polymerization method, and the dissolution suspension method, and the polyester resin has difficulty in particle formation, and the particle size, particle size distribution, Shape control was difficult. Further, there is a limit to fixability when aiming at lower temperature fixing.

In addition, for the purpose of heat-resistant storage stability and low-temperature fixing, an attempt has been made to use a polyester resin modified with a urea bond (see Patent Document 7). However, the surface of the toner is not devised, and the environmental charge stability with more severe conditions does not have sufficient performance.
Furthermore, in the field of electrophotography, high image quality has been studied from various angles, and in particular, recognition that reducing the diameter of toner is extremely effective is increasing. However, as the diameter of the toner advances, there is also a problem that the transferability and fixability are lowered, resulting in a poor image.

  In order to stabilize various properties such as toner chargeability, a means for sharpening the particle size distribution of the toner is used. If the average particle size of the toner does not match the specific particle size distribution, A sufficient effect cannot be obtained. That is, it is not sufficient to generalize the relationship between the average particle size and the particle size distribution, and it is necessary to have a particle size distribution and a shape corresponding to the average particle size of each toner.

Further, in an image forming apparatus having a member that cleans a pressure roller by fixing with a fixing device including a heating roller including a heating member and a pressure roller disposed oppositely, a small amount of toner is generated by long-term fixing. There is a problem that the toner accumulated in the cleaning unit and collected by the cleaning roller is melted again.
Therefore, in order to solve the problem that the toner melts again, for example, by making the length of the cleaning roller longer than the pressure roller, the heat storage property at the end of the cleaning roller is increased and the temperature at the end is hardly increased. At the same time, a method has been proposed in which heat accumulated at the end of the cleaning roller can be released from a portion where the cleaning roller and the pressure roller are not in contact (see Patent Document 8).
Further, Patent Document 9 proposes a method of cooling the temperature of the end portion of the cleaning roller by making a hole as a ventilation port that allows exchange of air inside and outside the fixing device.
Patent Document 10 proposes a method of having two switchable cleaning rollers and alternately switching and using the cleaning rollers while controlling the temperature.

  However, these proposals cannot prevent the toner itself from adhering to the cleaning roller. For this reason, in continuous printing for a long time, the toner may melt without the temperature of the cleaning roller being lowered. Further, it is important from the viewpoint of high durability to reduce the absolute amount of the adhesion amount to the cleaning portion, and these improvements are also necessary.

JP-A-63-313182 Japanese Patent Laid-Open No. 1-263679 JP-A-8-22206 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A Japanese Patent Laid-Open No. 11-133667 JP 2000-194223 A JP 2002-123119 A JP 2002-318500 A

An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, according to the present invention, firstly, the amount of adhesion to the cleaning roller can be reduced, the toner collected by the cleaning roller can be prevented from being melted again, and the backflow of the toner can be prevented to solve the image smearing problem. It is an object of the present invention to provide a toner that can be used, a developer using the toner, a container containing toner, a process cartridge, an image forming method, and an image forming apparatus.
A second object of the present invention is to provide an image forming method and an image forming apparatus using an electromagnetic induction heating type fixing device that is excellent in offset resistance and excellent in low-temperature fixability.

Means for solving the problems are as follows. That is,
<1> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A fixing device having a medium and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv) of 3 μm to 7 μm . The ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) (Dv / Dn) is 1.01 to 1.25, and the content ratio of particles having a particle diameter of 0.6 μm to 2.0 μm is The toner base particles having 20% by number or less and an average circularity of 0.93 to 0.99 are included, and 0.3 parts by weight to 5.0 parts by weight of external additives are added to 100 parts by weight of the toner base particles. Ri greens and, external additive is an image forming method characterized by comprising a particle size different hydrophobized silica and hydrophobized titanium oxide.
<2> The image forming method according to <1>, wherein the toner material is granulated by emulsifying or dispersing a solution or dispersion of the toner material in an aqueous medium.
<3> The image forming method according to <2>, wherein the toner material is dissolved or dispersed in an organic solvent, and the organic solvent is removed during granulation or after granulation.
<4> Particles containing at least the adhesive substrate while granulating reacts the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate. The image forming method according to any one of <2> to <3>, wherein the image forming method is performed.
<5> external additive, wherein comprising a hydrophobized silica or titanium oxide having hydrophobicized less than the average primary particle diameter of 20nm, and is hydrophobic treatment above average primary particle diameter of 20nm silica <1 > To <4> .
< 6 > An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A fixing device having a medium and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner prepares a toner solution by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. A dispersion is prepared by emulsifying or dispersing therein, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form particles of the adhesive substrate. Obtained by removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein. An image forming method is characterized.
< 7 > The image forming method according to < 6 >, wherein the polymer capable of reacting with the active hydrogen group-containing compound has an average of 2.1 to 2.8 functional groups per molecule.
< 8 > An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A fixing device having a medium and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner includes an active hydrogen group-containing compound, a polymer that can react with the active hydrogen group-containing compound, and an organic acid compound that is at least one of a carboxylic acid compound and a carboxylic acid anhydride as an organic solvent. A toner solution is prepared by dissolving or dispersing in an aqueous medium, and then the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound and the active hydrogen group are prepared. It is an image forming method characterized in that it is obtained by reacting a containing compound with a polymer capable of reacting to form an adhesive substrate in the form of particles and removing the organic solvent.
< 9 > The image forming method according to <8>, wherein the organic acid compound has a number average molecular weight of 15 to 1,500.
< 10 > An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A fixing device having a medium and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of a component having a molecular weight of 500 or less is 4% by mass or less, and a molecular weight of 3 , 000-9, an image forming method characterized by having one peak in the region of 000.
< 11 > The image forming method according to < 10 >, wherein the unmodified resin includes an unmodified polyester resin.
< 12 > The toner material further comprises an unmodified polyester resin, and the mass ratio of the polymer capable of reacting with the active hydrogen group-containing compound and the unmodified polyester resin (polymer / unreactable with the active hydrogen group-containing compound) The image forming method according to any one of < 9 > to < 9 > and < 11 >, wherein the modified polyester resin) is 5/95 to 80/20.
< 13 > The image forming method according to any one of <1> to < 12 >, wherein the polymer capable of reacting with the active hydrogen group-containing compound contains.
< 14 > The image forming method according to < 13 >, wherein the functional group-containing polyester resin is a polyester resin having a urea group.
Peak molecular weight of <15> unmodified polyester resin 1, 000 to 20, an image forming method according the a 000 to <11> to any one of <14>.
< 16 > The image forming method according to any one of < 11 > to < 15 >, wherein the acid value of the unmodified polyester resin is 10 mgKOH / g to 30 mgKOH / g .
< 17 > The image forming method according to any one of < 11 > to < 16 >, wherein the glass transition temperature (Tg) of the unmodified polyester resin is 35 ° C to 55 ° C.
< 18 > The image forming method according to any one of <1> to < 17 >, wherein the toner includes a wax, the wax is finely dispersed in the toner, and is present in the vicinity of the surface more than the toner central portion. .
< 19 > The image forming method according to any one of <1> to < 18 >, wherein the toner contains a charge control agent.
< 20 > The image forming method according to any one of < 6 > to < 19 >, wherein the toner has a volume average particle diameter of 3 μm to 8 μm .
< 21 > Any one of < 6 > to < 20 >, wherein the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is 1.00 to 1.25. The image forming method described.
< 22 > The image forming method according to any one of < 6 > to < 21 >, wherein the toner has an average circularity of 0.900 to 0.980.
< 23 > The image forming method according to any one of <1> to < 22 >, wherein a T1 / 2 melting temperature of the toner by a flow tester is 140 ° C. to 180 ° C.
< 24 > The image forming method according to any one of <1> to < 23 >, wherein the shape factor SF-1 of the toner represented by the following mathematical formula 1 is 105 to 170.
In Equation 1, MXLNG represents the maximum length of a shape that can be formed by projecting toner onto a two-dimensional plane. AREA represents the area of a figure formed by projecting toner onto a two-dimensional plane.
< 25 > The image forming method according to any one of <2> to < 24 >, wherein the toner is obtained with a volumetric shrinkage of 10 % to 90% in an aqueous medium using a solid fine particle dispersant.
< 26 > An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A medium, and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv) of 3 μm to 7 μm . The ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) (Dv / Dn) is 1.01 to 1.25, and the content ratio of particles having a particle diameter of 0.6 μm to 2.0 μm is The toner base particles having 20% by number or less and an average circularity of 0.93 to 0.99 are included, and 0.3 parts by weight to 5.0 parts by weight of external additives are added to 100 parts by weight of the toner base particles. Ri greens and, external additive is an image forming apparatus characterized by comprising a particle size different hydrophobized silica and hydrophobized titanium oxide.
< 27 > An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A medium, and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner prepares a toner solution by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. A dispersion is prepared by emulsifying or dispersing therein, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form particles of the adhesive substrate. Obtained by removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein. The image forming apparatus is characterized.
< 28 > An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A medium, and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner includes an active hydrogen group-containing compound, a polymer that can react with the active hydrogen group-containing compound, and an organic acid compound that is at least one of a carboxylic acid compound and a carboxylic acid anhydride as an organic solvent. A toner solution is prepared by dissolving or dispersing in an aqueous medium, and then the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound and the active hydrogen group are prepared. An image forming apparatus obtained by reacting a containing compound with a polymer capable of reacting to produce an adhesive base material in the form of particles and removing the organic solvent.
< 29 > An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A medium, and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of a component having a molecular weight of 500 or less is 4% by mass or less, and a molecular weight of 3 , 000-9, an image forming apparatus characterized by having one peak in the region of 000.
< 30 > The image forming apparatus according to any one of < 26 > to < 29 >, wherein the electrostatic latent image carrier includes amorphous silicon.
< 31 > The above-mentioned < 26 > to < 31 > further comprising a charger, wherein the electrostatic latent image carrier is charged by bringing the charger into contact with the electrostatic latent image carrier and applying a voltage to the charger. 30 >. The image forming apparatus according to any one of 30 >.
< 32 > A toner used in the image forming method according to any one of <1> to < 25 >.
< 33 > A developer comprising the toner according to < 32 >.
< 34 > A toner-containing container filled with the toner according to < 32 >.
< 35 > An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner described in < 32 > to form a visible image. It is a process cartridge characterized by having at least.

The image forming method according to the first to fourth aspects of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image using toner. The image forming method includes at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium.
In the fixing step, a heating roller made of magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel with the heating roller, and stretched between the heating roller and the fixing roller, the heating roller And an endless belt-shaped toner heating medium rotated by these rollers, pressed against the fixing roller via the toner heating medium, and rotated in the forward direction with respect to the toner heating medium. A fixing device having a pressure roller that forms a nip portion is used.
In the first embodiment, the toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv). Of particles having a volume average particle diameter (Dv) and a number average particle diameter (Dn) (Dv / Dn) of 1.01 to 1.25 and a particle diameter of 0.6 to 2.0 μm. Including toner base particles having a content ratio of 20% by number or less and an average circularity of 0.93 to 0.99, and 0.3 to 5.0 parts by weight of an external additive with respect to 100 parts by weight of the toner base particles. Add it.
In the second embodiment, the toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein.
In the third aspect, the toner dissolves or dissolves a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, an organic acid compound, and an unmodified polyester resin in an organic solvent. After preparing a toner solution by dispersing, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound, the active hydrogen group-containing compound, It can be obtained by reacting with a reactive polymer to form an adhesive substrate in the form of particles and removing the organic solvent.
In a fourth aspect, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. After the preparation, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, obtained by removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of the component having a molecular weight of 500 or less is 4% by mass or less, and the molecular weight is 3000 to 3000. It has one peak in the 9000 region.
In the image forming methods according to the first to fourth embodiments of the present invention, the amount of adhesion to the cleaning roller is reduced by adopting the above configuration, and the toner collected by the cleaning roller is prevented from being melted again. Therefore, it is possible to provide a method of forming an image using an electromagnetic induction heating type fixing device that can prevent the backflow of toner and solve the problem of image smearing, is excellent in offset resistance, and is excellent in low-temperature fixability.

An image forming apparatus according to the first to fourth aspects of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; At least.
The fixing means is made of a magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel to the heating roller, and stretched between the heating roller and the fixing roller, and the heating roller An endless belt-shaped toner heating medium rotated by these rollers, and pressed against the fixing roller via the toner heating medium, and rotated in the forward direction with respect to the toner heating medium. And a pressure roller that forms a nip portion.
In the first embodiment, the toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv). Of particles having a volume average particle diameter (Dv) and a number average particle diameter (Dn) (Dv / Dn) of 1.01 to 1.25 and a particle diameter of 0.6 to 2.0 μm. Including toner base particles having a content ratio of 20% by number or less and an average circularity of 0.93 to 0.99, and 0.3 to 5.0 parts by weight of an external additive with respect to 100 parts by weight of the toner base particles. Add it.
In the second embodiment, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified polyester resin in an organic solvent. Then, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, obtained by removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein.
In the third aspect, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an organic acid compound in an organic solvent. After the preparation, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, and the organic solvent is removed.
In the fourth aspect, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified polyester resin in an organic solvent. Then, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, obtained by removing the organic solvent,
The unmodified polyester resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of a component having a molecular weight of 500 or less is 4% by mass or less and a molecular weight of 3000 It has one peak in the region of ~ 9000.
In the image forming apparatuses according to the first to fourth embodiments of the present invention, by adopting the above configuration, the amount of adhesion to the cleaning roller is reduced, and the toner collected by the cleaning roller is prevented from being melted again. In addition, it is possible to provide an image forming apparatus having an electromagnetic induction heating type fixing device that can prevent backflow of toner and solve the problem of image smearing, is excellent in offset resistance, and is excellent in low-temperature fixability.

  The toner of the present invention is used in the image forming method of the present invention. The toner of the present invention has excellent development stability, filming resistance, low-temperature fixability, excellent hot offset resistance, and excellent charging stability, and has a long life.

  The developer of the present invention contains the toner of the present invention. For this reason, when image formation is performed by electrophotography using the developer, the toner filling property in the toner image is high, a high-definition image can be obtained by reducing the image layer thickness, and stable over a long period of time. High image quality with cleanability and stable reproducibility can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when an image is formed by electrophotography using the toner contained in the toner-containing container, as a result, it has excellent cleaning properties, excellent characteristics such as chargeability and transferability, and high image quality. Is obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. As a result, the process cartridge has excellent cleaning properties and various characteristics such as chargeability and transferability. Excellent image quality.

  According to the present invention, conventional problems can be solved, development stability, filming resistance, low-temperature fixability are excellent, hot offset resistance is excellent, and charging stability is also excellent. By combining a long toner with a specific electromagnetic induction heating system fixing device, the amount of adhesion to the cleaning roller can be reduced, and the toner collected on the cleaning roller can be prevented from re-dissolving, preventing back flow of toner. Thus, an image forming method and an image forming apparatus excellent in offset resistance can be solved, and a toner, a developer, a container containing toner, and a process cartridge used in these can be provided.

  In addition, according to the present invention, it is possible to improve the anti-offset property and the low-temperature fixability by using a specific electromagnetic induction heating type fixing device and using a specific toner. Also, a charging device with reduced generation of ozone, a photoreceptor having high surface hardness, high sensitivity to long-wavelength light such as a semiconductor laser (770 to 800 nm), etc., and hardly deteriorated by repeated use, and It is possible to provide an image forming method and an image forming apparatus using a fixing device that can efficiently reduce the rise time, and a toner, a developer, a toner-containing container, and a process cartridge used in the image forming method.

  Further, according to the present invention, there is provided a fixing device and a fixing device using a specific electromagnetic induction heating method, which has strong filming, is compatible with a low-temperature fixing system, has good offset resistance, and does not contaminate an image. Charger with reduced ozone generation, high surface hardness, high sensitivity to long-wavelength light such as semiconductor laser (770-800 nm), etc., and almost no deterioration due to repeated use The present invention can provide an image forming method and an image forming apparatus using a fixing device capable of reducing the rise time and the body, and a toner, a developer, a container containing toner, and a process cartridge used in these.

(Image forming method and image forming apparatus)
The image forming methods according to the first to fourth embodiments of the present invention include at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other appropriate selections as necessary. The process includes, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like.

  The fixing step is composed of a magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel with the heating roller, and stretched between the heating roller and the fixing roller, and the heating roller And an endless belt-shaped toner heating medium rotated by these rollers, pressed against the fixing roller via the toner heating medium, and rotated in the forward direction with respect to the toner heating medium. A fixing device having a pressure roller that forms a nip portion is used.

In the first embodiment, the toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv). Of particles having a volume average particle diameter (Dv) and a number average particle diameter (Dn) (Dv / Dn) of 1.01 to 1.25 and a particle diameter of 0.6 to 2.0 μm. Including toner base particles having a content ratio of 20% by number or less and an average circularity of 0.93 to 0.99, and 0.3 to 5.0 parts by weight of an external additive with respect to 100 parts by weight of the toner base particles. Add it.
In the second embodiment, the toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein.
In the third aspect, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an organic acid compound in an organic solvent. After the preparation, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, and the organic solvent is removed.
In a fourth aspect, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. After the preparation, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, obtained by removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of the component having a molecular weight of 500 or less is 4% by mass or less, and the molecular weight is 3000 to 3000. It has one peak in the 9000 region.

  The image forming apparatus according to the first to fourth embodiments of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. In addition, other means appropriately selected as necessary, for example, a static elimination means, a cleaning means, a recycling means, a control means and the like are provided.

  The fixing means is made of a magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel to the heating roller, and stretched between the heating roller and the fixing roller, and the heating roller And an endless belt-shaped toner heating medium rotated by these rollers, pressed against the fixing roller via the toner heating medium, and rotated in the forward direction with respect to the toner heating medium. And a pressure roller that forms a nip portion.

In the first embodiment, the toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv). Of particles having a volume average particle diameter (Dv) and a number average particle diameter (Dn) (Dv / Dn) of 1.01 to 1.25 and a particle diameter of 0.6 to 2.0 μm. Including toner base particles having a content ratio of 20% by number or less and an average circularity of 0.93 to 0.99, and 0.3 to 5.0 parts by weight of an external additive with respect to 100 parts by weight of the toner base particles. Add it.
In the second embodiment, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified polyester resin in an organic solvent. Then, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, obtained by removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein.
In the third aspect, the toner dissolves or dissolves a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, an organic acid compound, and an unmodified polyester resin in an organic solvent. After preparing a toner solution by dispersing, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound, the active hydrogen group-containing compound, It can be obtained by reacting with a reactive polymer to form an adhesive substrate in the form of particles and removing the organic solvent.
In the fourth aspect, the toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified polyester resin in an organic solvent. Then, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive substrate in the form of particles, obtained by removing the organic solvent,
The unmodified polyester resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of a component having a molecular weight of 500 or less is 4% by mass or less and a molecular weight of 3000 It has one peak in the region of ~ 9000.

  The image forming methods according to the first to fourth aspects of the present invention can be preferably carried out by the image forming apparatus according to the first to fourth aspects of the present invention, and the electrostatic latent image forming step is the static image forming process. The latent image forming means can perform the developing process, the developing means can be performed, the transfer process can be performed by the transferring means, the fixing process can be performed by the fixing means, The other steps can be performed by the other means.

The image forming method and the image forming apparatus according to the first embodiment have the following characteristics.
The toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv) of 3 to 7 μm, The ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) (Dv / Dn) is 1.01 to 1.25, and the content of particles having a particle diameter of 0.6 to 2.0 μm is 20 % Of the toner base particles having an average circularity of 0.93 to 0.99, and 0.3 to 5.0 parts by weight of an external additive is added to 100 parts by weight of the toner base particles.

The volume average particle diameter (Dv) of the toner base particles is, for example, preferably 3 to 7 μm, more preferably 4 to 7 μm, and still more preferably 5 to 6 μm. Here, the volume average particle diameter is defined as Dv = [(Σ (nD ³ ) / Σn) ^1/3 (where n is the number of particles and D is the particle diameter).

  The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner base particles is preferably, for example, 1.01 to 1.25, and 1.01 to 1.20. Is more preferable, and 1.10 to 1.20 is more preferable.

Here, the volume average particle size and the volume average particle size / number average particle size (Dv / Dn) were measured using a measuring device for the particle size distribution of toner particles by a Coulter counter method. Specifically, a Coulter Multisizer (both manufactured by Coulter) is used, and 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted.

The content of particles having a particle size of 0.6 to 2.0 μm is 20% by number or less, and more preferably 3 to 12% by number.
In general, it is said that the smaller the toner particle size, the more advantageous is the fixing property, and it is said that it is advantageous for obtaining a high-resolution and high-quality image. It is disadvantageous for cleaning performance. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development is performed. When used as an agent, filming of toner on the developing roller and fusion of toner to a member such as a blade for thinning the toner are likely to occur. In particular, when more than 20% by weight of so-called ultrafine toner having a particle size of 2.0 μm or less, specifically 0.6 to 2.0 μm, is present, the toner is fused particularly on the surface of the carrier. The phenomenon tends to occur such as phenomenon, toner filming on the developing roller, and toner fusion to a member such as a blade for thinning the toner.
On the other hand, when the toner particle size is larger than the range of the present invention, the fixability is disadvantageous, and in particular, a cold offset (not fixed) occurs and it is difficult to obtain a high-resolution and high-quality image. . When the balance of the toner in the developer is performed, the toner particle size often varies greatly. Further, when the volume average particle diameter (Dv) / number average particle diameter (Dn) is larger than 1.25, the thermal efficiency of the toner particles varies greatly, so that the fixing property is deteriorated or the film is filled on the developing roller. It became clear that ming and fusion occurred.

  The content ratio of these particles having a particle size of 0.6 to 2.0 μm and Dv / Dn are not always correlated, and in order to achieve the object of the present invention, both characteristics are independent characteristics of the present invention. Must be in range (see Table 1 below). FIG. 3 shows the relationship between the toner Dv / Dn and the amount of fine powder of 2 μm or less. As is apparent from the graph of FIG. 3, it can be seen that the Dv / Dn and the fine powder amount of the toner are completely independent characteristics. Conventionally, Dv / Dn has been used as a characteristic indicating the particle size distribution of the toner. In the present invention, the amount of fine powder is also an important characteristic for achieving the object.

Here, the measurement of the content ratio of the particles having a particle size of 0.6 to 2.0 μm is measured using FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.), and analysis software (FPIA-2100 Data Processing Program for FPIA). Analysis was performed using version 00-10).
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, and each toner was added in an amount of 0.1%. 1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm, and the ratio of the number of particles in the range of 0.6 to 2.0 μm can be calculated.

The average circularity of the toner base particles is a value obtained by dividing the perimeter of an equivalent circle having the same projected area as the shape of the toner base particles by the perimeter of the actual particles, and is preferably 0.93 to 0.99, for example. 0.940 to 0.98 is more preferable.
Here, the said average circularity can be performed like the measurement of the content rate of the said particle diameter 0.6-2.0 micrometers.

  It is important from the viewpoint of developability and transferability that the external additive is added and mixed in a ratio of 0.3 to 5.0 parts by mass with respect to 100 parts by mass of toner base particles. 0 parts by mass is preferred. When the addition amount is less than 0.3 parts by mass, the toner fluidity is insufficient, the transfer efficiency of the toner from the photoreceptor to the transfer paper or the like is lowered, and the hot offset at the time of fixing becomes too weak, The fixing device may be stained with toner, and transfer paper or the like may be stained. On the other hand, since the additive is generally in the direction of inhibiting the fixing property, if the amount exceeds 5.0 parts by mass, the toner fixing property is inferior. .

As the external additive, inorganic fine particles can be preferably used for the purpose of improving fluidity and chargeability.
The primary particle size of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. Specific examples of the inorganic fine particles include, for example, silica, titanium oxide, alumina, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, methacrylic acid ester, acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Examples thereof include polymer particles made of a resin.

Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Among these, as the inorganic fine particles, silica, titanium oxide, alumina and the like are preferable, and silica subjected to hydrophobic treatment is particularly preferable.

The image forming method and the image forming apparatus according to the second embodiment have the following characteristics.
After the toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified polyester resin in an organic solvent, The toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium. It is obtained by generating an adhesive substrate in the form of particles and removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound preferably has an average of 1.5 to 3 functional groups per molecule and preferably an average of 2.1 to 2.8. If the average number of functional groups is less than 1.5, low-temperature fixability is excellent, but there may be no room for melting from the cleaning roller. Although it is excellent for melting out from a roller, it may cause adverse effects on low-temperature fixability.

The toner contains at least one inorganic fine particle therein. When the inorganic fine particles are contained inside the toner, the charging characteristics of the toner base can be stabilized, and a decrease in charging ability due to long-term toner stirring in the developing machine can be suppressed.
The inorganic fine particles exposed on the surface of the toner base not only prevent the external additive from being buried but also function as a lubricant and exhibit excellent fluidity.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

Further, the inorganic fine particles may be those that have been surface-treated with a hydrophobizing agent. Examples of the hydrophobic treatment agent include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, and the like. A sufficient effect can be obtained even when silicone oil is used as a hydrophobizing agent.
The inorganic fine particles can be easily contained in the toner by being added to the toner composition solution or dispersion during the production process of the present invention.
Further, even if it is added to the aqueous medium containing the resin fine particles in the production process of the present invention, it can be contained in the toner, but in this case, the inorganic fine particles subjected to the hydrophobic treatment as described above are used. preferable.

The content of the inorganic fine particles is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the toner base particles. When the addition amount is within this range, the toner base can have good charging characteristics, and there is an effect of preventing the charging ability from being lowered due to burying or liberation of the external additive at the time of toner strong stirring deterioration. Further, the inorganic fine particles exposed on the toner surface can sufficiently exhibit the effect as a lubricant and can have excellent fluidity.
If it is smaller than this range, it will be difficult to exhibit sufficient charging ability and fluidity, and if it is larger than this range, the amount of inorganic fine particles exposed on the toner surface will increase, not only deteriorating the circularity of the toner particles. Inorganic fine particles act as a fixing inhibitor, and the minimum fixing temperature is increased, so that the low-temperature fixing property is impaired.

Here, the content of inorganic fine particles in the toner base particles is determined by fluorescent X-ray analysis. A calibration curve is prepared by fluorescent X-ray analysis using toner base particles in which the content of inorganic fine particles is clear in advance, and the content of inorganic fine particles in the toner base particles is determined by fluorescent X-ray analysis using the calibration curve. . For example, ZSX-100E manufactured by Rigaku Corporation can be used as the fluorescent X-ray apparatus. Further, when two or more kinds of inorganic fine particles were used, the total of the analysis values of the inorganic fine particle content was used as the inorganic fine particle content in the toner base particles.
The presence of a certain amount of inorganic fine particles in the vicinity of the surface of the toner base particles can give a better effect to the charging stability and fluidity of the toner, and can prevent the burying of the external additive. it can. The amount of inorganic fine particles present on the surface of the toner base particles is measured as follows.
For the measurement, XPS (X-ray photoelectron spectroscopy) method is used. Here, it is a region of the extreme surface with a toner surface number of about several nm. The measurement method, apparatus type, conditions, and the like are not particularly limited as long as similar results can be obtained, but the following conditions are preferable.
Apparatus: 1600S type X-ray photoelectron spectrometer manufactured by PHI X-ray source: MgKα (400 W)
Analysis area: 0.8 × 2.0mm
Pretreatment: The sample was packed in an aluminum pan and measured by adhering to a sample holder with a carbon sheet.
Surface atom concentration calculation: Relative sensitivity factor provided by PHI was used.
The obtained result is atomic% (number of atoms%).
Further, when two or more kinds of inorganic fine particles were used, the total of the element concentrations derived from the inorganic fine particles was used as the calculated analysis value.
According to the analysis results obtained by the above method, the concentration of elements derived from inorganic fine particles obtained by the XPS method in the toner base particles is preferably 0.1 to 15 atomic% (atom number%), and 0.5 to 5 atomic%. More preferred. If it is less than this range, it will be difficult to exert an effect on toner charging stability, fluidity, and external additive embedding, and if it is more than this range, the minimum fixing temperature will rise and the low-temperature fixability will be impaired. It is not preferable.

Moreover, 5-200 nm is preferable and, as for the average particle diameter of the primary particle of an inorganic fine particle, 10-180 nm is more preferable. By setting the particle size within this range, the spacer effect for preventing the aggregation of the toners is sufficiently exerted, and the effect of preventing the burying of the external additive when the toner is stored at a high temperature or when the toner is strongly stirred and deteriorated is excellent.
If it is smaller than this range, toner agglomeration and external additives are liable to occur, and if it is larger than this range, not only the circularity of the toner particles is deteriorated, but also the fixing minimum temperature is increased and the low temperature fixing property is increased. Is unfavorable because it is damaged.
These inorganic fine particles may be used alone or in admixture of two or more when used as an electrostatic charge image developing toner.
The average particle size here is the number average particle size. The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring device using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary aggregation of the particles after the silicone oil treatment, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

The image forming method and the image forming apparatus according to the third embodiment have the following characteristics.
The toner is obtained by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, an organic acid compound, and an unmodified polyester resin in an organic solvent. Then, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive base material in the form of particles and remove the organic solvent.

The organic acid compound can be used for the purpose of stabilizing the particle size distribution of the toner. The organic acid compound is not particularly limited and may be appropriately selected depending on the intended purpose. When granulating in an aqueous solvent, in addition to the above, emulsified particles are used to affect emulsification or dispersion. Oxidation can be adjusted so as not to affect the emulsification or dispersion even if the amount of the unmodified polyester is varied.
As the organic acid compound, at least one of a carboxylic acid compound and a carboxylic acid anhydride is preferable, and acetic acid and polycarboxylic acid which are hydrolysates of methyl acetate and ethyl acetate are more preferable. These are preferably contained in the emulsified particles.
The number average molecular weight of the organic acid compound is preferably 15 to 1500. When the number average molecular weight is less than 15, the effect as an acid may be lost, and when it exceeds 1500, it may be difficult to be contained in the particles.
The content of the organic acid compound in the toner material is preferably 1 to 10000 ppm, and more preferably 10 to 1000 ppm.

The image forming method and the image forming apparatus according to the fourth embodiment have the following characteristics.
The toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of the component having a molecular weight of 500 or less is 4% by mass or less, and the molecular weight is 3000 to 3000. It has one peak in the 9000 region.

The unmodified resin may be a resin having a content ratio of a component having a molecular weight of 500 or less in a molecular weight distribution in gel permeation chromatography (GPC) of 4% by mass or less and a peak in a region having a molecular weight of 3000 to 9000. There is no particular limitation as long as it can be appropriately selected according to the purpose, and examples thereof include unmodified polyester resins and unmodified polyol resins.
The components having a molecular weight of 500 or less are fragile portions having a low molecular weight even in the resin, and therefore are easily dissolved again by heat after adhering to the cleaning roller.
In addition, these portions are liable to cause fusing or the like even with a small amount of heat and the like, which causes contamination of the developing sleeve, the photoconductor and the like. For this reason, by setting the content ratio of the component having a molecular weight of 500 or less to 4% by mass or less, these problems are solved and a stable image can be provided.

  As a binder resin for a full-color toner, a polyester resin suitable from the viewpoint of color development and image strength is used. In a color image, several types of toner layers are stacked several times, so that the toner layer becomes thick, and cracks and defects of the image due to insufficient strength of the toner layer occur, or an appropriate gloss is lost. For this reason, a polyester resin or a polyol resin is used to maintain an appropriate gloss and excellent strength.

The unmodified polyester resin can be generally obtained by an esterification reaction of a polyhydric alcohol and a polyvalent carboxylic acid. Among the monomers constituting the polyester resin in the present invention, examples of the alcohol monomer include trifunctional or higher polyfunctional monomers such as ethylene glycol, diethylene glycol triethylene glycol, 1,2-propylene glycol, and 1,3-propylene. Diols such as glycol, 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxypropylene Bisphenol A alkylene oxide adducts such as bisphenol A, other dihydric alcohols, or sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol , Tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane , Trimethylolpropane, 1,3,5-trihydroxybenzene, and other trihydric or higher polyhydric alcohols.
Among these monomers, those using a bisphenol A alkylene oxide adduct as a main component monomer are preferably used.
When a bisphenol A alkylene oxide adduct is used as a constituent monomer, a polyester having a relatively high glass transition point is obtained due to the nature of the bisphenol A skeleton, and the copy blocking resistance and heat resistant storage stability are good. In addition, the presence of alkyl groups on both sides of the bisphenol A skeleton acts as a soft segment in the polymer, and the color developability and image strength during toner fixing are improved. In particular, among bisphenol A alkylene oxide adducts, those having an ethylene group or a propylene group are preferably used.

Among the monomers constituting the polyester resin, examples of acid monomers include trifunctional or higher polyfunctional monomers such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid. Acids, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, anhydrides of these acids, alkyl Esters, other divalent carboxylic acids, and 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid Acid, 1,2,4-butanetricarboxylic acid, 1,2,5- Xanthricarboxylic acid, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empor trimer acid, and anhydrides thereof , Alkyl esters, alkenyl esters, aryl esters, and other trivalent or higher carboxylic acids.
Specific examples of the alkyl group, alkenyl group or aryl ester described here include 1,2,4-benzenetricarboxylic acid, trimethyl 1,2,4-benzenetricarboxylate, and triethyl 1,2,4-benzenetricarboxylate. 1,2,4-benzenetricarboxylic acid tri-n-butyl, 1,2,4-benzenetricarboxylic acid isobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri 2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl, 1,2,4-benzenetricarboxylic acid tris (4-isopropylbenzyl) and the like.
The relationship between the chargeability of the polyester resin and the acid value is almost proportional, and it is known that the higher the acid value, the greater the negative chargeability of the resin. At the same time, it affects the environmental stability of the charge. . That is, when the acid value is high, the charge amount is high under low temperature and low humidity, and the charge amount is low under high temperature and high humidity, resulting in large changes in background stains, image density, and color reproducibility, and it is difficult to maintain high image quality. . Therefore, the acid value of the polyester resin is preferably 30 mgKOH / g or less, and more preferably 5 mgKOH / g or less.
Here, the said acid value can be performed using the following measuring devices, for example.
Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
Working electrode: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No
Next, measurement is performed under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows. Titrate with a pre-standardized N / 10 caustic potassium to alcohol solution, and the acid value is determined by the following calculation from the consumption of the alcohol potassium solution.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (photosensitive member) are not particularly limited, and can be appropriately selected from known ones. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the latent electrostatic image bearing member charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using a toner or the developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, toner or the developer, and can be appropriately selected from known ones. Preferable examples include those having at least a developing unit capable of applying the toner or the developer to the electrostatic latent image in a contact or non-contact manner.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.

The fixing device is not particularly limited and may be appropriately selected according to the purpose. However, the fixing device can be in contact with each other to form a nip portion, and a recording medium on which an image of toner is transferred to the nip portion It is preferable to have at least two fixing members capable of fixing the image onto the recording medium by passing through, and further including other members appropriately selected as necessary.
Specifically, the fixing device is composed of a magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel to the heating roller, and the heating roller and the fixing roller. And is heated by the heating roller, and is rotated by the endless belt-like toner heating medium, and is pressed against the fixing roller via the toner heating medium, and is also against the toner heating medium. A fixing device having a pressure roller that rotates in the forward direction to form a nip portion is particularly preferable.

The nip portion is formed by bringing at least two fixing members into contact with each other.
There is no restriction | limiting in particular as the surface pressure of the said nip part, Although it can select suitably according to the objective, 7-50 N / cm < ² > is preferable.

  An intermediate region located between the introduction side end and the discharge side end of the recording medium in the nip portion may be positioned substantially on the same straight line as the introduction side end and the discharge side end. You may be located in the image contact side fixing member side located in a contact side. When the intermediate region is located on the image contact side fixing member side, the discharge of the recording medium from the nip portion is in a direction to separate the image surface from the fixing member, so that the fixing of the recording medium is performed. Winding around the member can be prevented.

The fixing member is not particularly limited as long as it can abut against each other to form a nip portion, and can be appropriately selected according to the purpose. For example, a combination of an endless belt and a roller, a roller and a roller, The heating method from the surface of the fixing member by a combination of an endless belt and a roller or induction heating can be used in order to reduce the warm-up time and realize energy saving. It is preferable to use it.
Examples of the fixing member include known heating and pressing means (combination of heating means and pressing means). In the case of a combination of the endless belt and the roller, for example, a combination of a heating roller, a pressure roller, and an endless belt may be used as the heating and pressing unit, and the combination of the roller and the roller may be used. In this case, for example, a combination of a heating roller and a pressure roller can be used.

  When the fixing member is an endless belt, the endless belt is preferably formed of a material having a small heat capacity. For example, an embodiment in which an offset prevention layer is provided on a substrate may be used. Examples of the material for forming the base include nickel and polyimide, and examples of the material for forming the offset prevention layer include silicone rubber and fluorine-based resin.

  When the fixing member is a roller, the cored bar of the roller is preferably formed of an inelastic member to prevent deformation (deflection) due to high pressure. There is no restriction | limiting in particular as this inelastic member, Although it can select suitably according to the objective, For example, high thermal conductivity bodies, such as aluminum, iron, stainless steel, brass, are mentioned suitably. Moreover, it is preferable that the surface of the roller is covered with an offset prevention layer. The material for forming the offset prevention layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include RTV silicone rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA), and polytetrafluoroethylene. (PTFE) etc. are mentioned suitably.

  The fixing member itself has a heating unit and may function as a heating member, but at least a part of the surface of at least one of the fixing members is heated by the heating unit. preferable. There is no restriction | limiting in particular as such a heating means, According to the objective, it can select suitably, For example, an electromagnetic induction heating means etc. are mentioned.

The electromagnetic induction heating means is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an induction coil disposed close to the fixing member (for example, a heating roller) and this induction It is preferable to comprise a shielding layer provided with a coil and an insulating layer provided on the opposite side of the surface of the shielding layer on which the induction coil is provided. In this case, it is preferable that the heating roller is formed of a magnetic material, a heat pipe, or the like.
The induction coil is disposed in a state of wrapping at least a semi-cylindrical portion on the opposite side of the contact portion between the heating roller and the fixing member (for example, a pressure roller, an endless belt). Is preferred.

The temperature for fixing the image on the recording medium with the toner, that is, the surface temperature of the fixing member by the heating means is not particularly limited and may be appropriately selected depending on the intended purpose. 170 degreeC is preferable and 120-160 degreeC is more preferable. If the fixing temperature is less than 120 ° C, the fixability may be insufficient, and if it exceeds 170 ° C, it is not preferable in terms of realizing energy saving.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

Here, the fixing device shown in FIG. 2 includes a heating roller 1 that is heated by electromagnetic induction of the induction heating unit 6, a fixing roller 2 that is arranged in parallel with the heating roller 1, and the heating roller 1 and the fixing roller 2. An endless belt-like heat-resistant belt (toner heating medium) 3 that is stretched and heated by the heating roller 1 and rotated in the direction of arrow A by at least one of these rollers, and a fixing roller 2 via the belt 3 And a pressure roller 4 that rotates in the forward direction with respect to the belt 3.
The heating roller 1 is made of, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals. The outer diameter is 20 mm, the wall thickness is 0.1 mm, for example, and the temperature rises quickly with a low heat capacity. It has a configuration.

  The fixing roller 2 includes a metal core 2a made of, for example, stainless steel, and an elastic member 2b covered with the core 2a in a solid or foamed heat-resistant silicone rubber. In order to form a contact portion having a predetermined width between the pressure roller 4 and the fixing roller 2 by the pressing force from the pressure roller 4, the outer diameter is set to about 40 mm and larger than the heating roller 1. The elastic member 2b has a thickness of about 3 to 6 mm and a hardness of about 40 to 60 ° (Asker hardness). With this configuration, the heat capacity of the heating roller 1 is smaller than the heat capacity of the fixing roller 2, so that the heating roller 1 is rapidly heated and the warm-up time is shortened.

The belt 3 stretched between the heating roller 1 and the fixing roller 2 is heated at a contact portion W1 with the heating roller 1 heated by the induction heating means 6. The inner surface of the belt 3 is continuously heated by the rotation of the rollers 1 and 2, and as a result, the entire belt is heated.
The thickness of the release layer that is the surface layer portion of the belt 3 is preferably about 50 μm to 500 μm, and more preferably about 200 μm. By doing so, the toner image T formed on the recording medium 111 is sufficiently wrapped by the surface layer portion of the belt 3, so that the toner image T can be uniformly heated and melted.

When the thickness of the release layer is smaller than 100 μm, the heat capacity of the belt 3 becomes small and the belt surface temperature rapidly decreases in the toner fixing process, so that the fixing performance cannot be sufficiently ensured. Further, when the thickness of the release layer is larger than 500 μm, the heat capacity of the belt 3 is increased and the time required for warm-up is increased. In addition, in the toner fixing step, the surface temperature of the belt is difficult to decrease, and the effect of aggregating the melted toner at the fixing portion outlet cannot be obtained, so that the releasability of the belt is reduced and the toner adheres to the belt. Hot offset occurs.
In addition, as a base material of the belt 3, heat-resistant materials such as fluorine resin, polyimide resin, polyamide resin, polyamideimide resin, PEEK resin, PES resin, and PPS resin are used instead of the heat generating layer inside the belt 3 made of the metal. A resin layer having properties may be used.

The pressure roller 4 includes a cored bar 4a made of a cylindrical member made of a metal having a high thermal conductivity such as copper or aluminum, and an elastic member having a high heat resistance and toner releasability provided on the surface of the cored bar 4a. 4b. In addition to the above metal, SUS may be used for the core metal 4a.
The pressure roller 4 presses the fixing roller 2 via the belt 3 to form the nip portion N. In this embodiment, the pressure roller 4 is made harder than the fixing roller 2. The pressure roller 4 bites into the fixing roller 2 (and the belt 3), and the recording medium 111 follows the circumferential shape of the surface of the pressure roller 4 by this biting, so that the recording medium 111 is easily separated from the belt 3 surface. Has the effect of becoming. The outer diameter of the pressure roller 4 is about 40 mm, which is the same as that of the fixing roller 2, but the wall pressure is about 1 to 3 mm, thinner than the fixing roller 2, and the hardness is about 50 to 70 ° (Asker hardness) as described above. It is configured to be harder than the fixing roller 2.

As shown in FIGS. 2, 3A, and 3B, the induction heating means 6 that heats the heating roller 1 by electromagnetic induction includes an exciting coil 7 that is a magnetic field generating means, and the exciting coil 7 is wound. And a coil guide plate 8. The coil guide plate 8 has a semi-cylindrical shape that is disposed close to the outer peripheral surface of the heating roller 1, and as shown in FIG. 3B, the excitation coil 7 is composed of a single long excitation coil wire. 8 is alternately wound in the axial direction of the heating roller 1. The exciting coil 7 is connected to a driving power source (not shown) whose oscillation circuit has a variable frequency.
Outside the excitation coil 7, a semi-cylindrical excitation coil core 9 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 10 and is disposed close to the excitation coil 7. In the present embodiment, the exciting coil core 9 has a relative permeability of 2500.

A high frequency alternating current of 10 kHz to 1 MHz, preferably a high frequency alternating current of 20 kHz to 800 kHz is supplied to the exciting coil 7 from a driving power source, thereby generating an alternating magnetic field. The alternating magnetic field acts on the heat generation layer of the heating roller 1 and the belt 3 in the contact area W1 between the heating roller 1 and the heat-resistant belt 3 and in the vicinity thereof, and the vortices are formed in the direction in which the change of the alternating magnetic field is prevented. Current I flows.
This eddy current I generates Joule heat according to the resistance of the heating roller 1 and the heat generating layer, and the belt 3 having the heating roller 1 and the heat generating layer mainly in the contact area between the heating roller 1 and the belt 3 and its vicinity. Induction heating.
The belt 3 heated in this way is detected by a temperature detecting means 5 comprising a thermosensitive element such as a thermistor disposed in contact with the inner surface side of the belt 3 in the vicinity of the inlet side of the nip portion N. The belt inner surface temperature is detected.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 5 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and also for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final recording medium. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 5, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 6 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 5, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is directly opposed, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 6, the same components as those in FIG. 5 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 7 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 7. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 220 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 220. On the opposite side of the intermediate transfer member 50 from the side where the tandem developing device 220 is disposed, the secondary transfer device 22 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 8), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, even when a specific binder resin and a large amount of charge control agent are used, stable chargeability is obtained, and there is no occurrence of background stains, white stripes, filming, etc. Since the toner of the present invention having sufficient durability is used, a clear high-quality image can be formed.

<Toner>
The toner of the present invention is used in the image forming method and the image forming apparatus of the present invention, and the production method and materials are not particularly limited and can be appropriately selected from known ones according to the purpose. It contains a toner material containing a hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and further contains other components as necessary.

  Examples of the toner production method include a pulverization classification method, a suspension polymerization method, an emulsion polymerization method, and a polymer suspension method in which an oil phase is emulsified, suspended, or aggregated in an aqueous medium to form toner base particles.

In the pulverization method, toner materials such as a toner binder resin, a charge control agent, and a pigment are mechanically mixed. This mixing step may be performed under normal conditions using a normal mixer with rotating wings, and is not particularly limited.
When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used.
It is important that this melt-kneading is performed under appropriate conditions that do not cause the molecular chains of the toner binder resin to be broken. Specifically, the melt kneading temperature should be performed with reference to the softening point of the toner binder resin. If the temperature is lower than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.
When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream or pulverizing with a narrow gap between a rotor and a stator that rotate mechanically is preferably used.

After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner having a predetermined particle diameter, for example, an average particle diameter of 5 to 20 μm.
Further, when preparing the toner, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the hydrophobic silica fine powder and the like mentioned above are further added to the toner manufactured as described above. Add and mix inorganic fine particles. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, and then a relatively weak load, or vice versa.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.
In order to spheroidize the obtained toner, a toner material composed of a toner binder resin and a colorant is melt-kneaded and then finely pulverized and then mechanically spheronized using a hybridizer, mechano-fusion, etc. A method of obtaining a spherical toner by dissolving and dispersing a toner material called a dry method in a solvent in which a toner binder is soluble, and then removing the solvent using a spray drying device, or a method of making a sphere by heating in an aqueous medium, etc. However, it is not limited to this.

The suspension polymerization method is an oil-soluble polymerization initiator, emulsification described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersant are contained. Emulsified and dispersed by the method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, By using a part of acrylate or methacrylate having amino groups such as methacrylamide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate, etc. on the toner particle surface. Functional groups can be introduced.
Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

  As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

  In the present invention, among these, since the selectivity of the resin is high, the low-temperature fixability is high, the granulation property is excellent, and the particle size, the particle size distribution, and the shape can be easily controlled. The toner is preferably obtained by emulsifying or dispersing a toner material dissolved or dispersed in an aqueous medium and granulating the toner.

The toner material solution is obtained by dissolving the toner material in a solvent, and the toner material dispersion liquid is obtained by dispersing the toner material in a solvent.
Examples of the toner material include an adhesive base obtained by reacting an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a binder resin, a release agent, and a colorant. Etc., and further contains other components such as resin fine particles and a charge control agent as necessary.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a mass mean molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the mass average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

The storage elastic modulus of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² , Usually, it is 100 ° C. or higher, and preferably 110 to 200 ° C. When the (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
The viscosity of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (Tη) at which a measurement frequency of 20 Hz is 1,000 poise is usually 180 ° C. or lower. Yes, 90-160 degreeC is preferable. When the (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
Therefore, from the viewpoint of achieving both hot offset resistance and low-temperature fixability, the (TG ′) is preferably higher than the (Tη). That is, the difference (TG′−Tη) between (TG ′) and (Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The larger the difference, the better.
Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the (TG′−Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20 to 80 ° C.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin will be low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and the like are preferable. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
As said aromatic polycarboxylic acid, a C9-C20 thing is preferable, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing group are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The mass average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. When the mass average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

Measurement of molecular weight distribution by gel permeation chromatography (GPC) was performed as follows.
Gel permeation chromatography (GPC) measuring apparatus: GPC-8220 GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation) is used to stabilize the column in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ were used, and at least about 10 standard polystyrene samples were used. An RI (refractive index) detector was used as the detector. The presence or absence of THF-insoluble matter in the binder resin is determined at the time of preparing a THF sample solution for molecular weight distribution measurement. That is, when a 0.45 μm filter unit is attached to the tip of the syringe and the liquid is pushed out from the syringe, it is determined that there is no THF-insoluble matter unless the filter is clogged.

--Binder resin--
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

The mass average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferred. When the mass average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Is required to be 8 to 28% by mass. On the other hand, when the mass average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 70 ° C, still more preferably 35 to 50 ° C, and particularly preferably 35 to 45 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
Here, the glass transition temperature can be measured using, for example, a differential scanning calorimeter. Specifically, it is determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
<Measurement conditions>
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50ml / min)
(Temperature conditions)
Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement results were analyzed using the data analysis software (Ta-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve which is the DSC differential curve of the second temperature rise, and the peak temperature is determined using the peak analysis function of the analysis software. Ask. Next, the maximum endothermic temperature of the DSC curve is obtained using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition temperature (Tg) of the toner.

The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, more preferably 1.0 to 45.0 mgKOH / g, and still more preferably 15.0 to 45.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner material, a mixing mass ratio of a polymer (for example, a urea bond-forming group-containing polyester resin) capable of reacting with an active hydrogen group-containing compound and the unmodified polyester resin ( The polymer / unmodified polyester resin) is preferably 5/95 to 80/20, more preferably 10/90 to 25/75.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
As content of the said non-modified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, 70-95 mass% is more preferable, 80-90 mass% is still more preferable. When the content is less than 50% by mass, the low-temperature fixability and the glossiness of the image may be deteriorated.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a release agent, a charge control agent, resin fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal Soap and the like.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
It is preferable that the waxes are finely dispersed in the toner and more in the vicinity of the surface than in the central part of the toner.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added when directly dissolving or dispersing in the organic solvent together with the components of the toner, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Among these, vinyl resins are particularly preferable.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Further, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

  Next, examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, and the like. The active hydrogen group-containing compound, the active hydrogen group-containing compound, The toner material containing a reactive polymer is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion liquid. Preferable examples include a toner obtained by reacting a hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in the form of particles and removing the organic solvent.

-Toner solution-
The toner solution can be prepared by dissolving the toner material in the organic solvent.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

The toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and may be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch system, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

As an example of the method for producing the toner, a method for producing the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive base material in the form of particles, for example, the preparation of an aqueous medium phase, the preparation of the toner solution, the preparation of the dispersion, the addition of the aqueous medium, etc. Synthesis of a polymer (prepolymer) capable of reacting with an active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as addition amount in this aqueous medium of this resin microparticles | fine-particles, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, the charge control agent, the unmodified, in the organic solvent. A toner material such as a polyester resin can be dissolved or dispersed. In order to form an inorganic oxide particle-containing layer within 1 μm from the toner surface, inorganic oxide particles such as silica, titania and alumina are added.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the preparation of the aqueous medium phase. The toner solution may be added and mixed in the aqueous medium, or may be added to the aqueous medium phase together with the toner solution when the toner solution is added to the aqueous medium phase.

The dispersion liquid can be prepared by emulsifying or dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. When the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an elongation reaction or a crosslinking reaction during the emulsification or dispersion, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A toner solution is emulsified or dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The toner solution is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and in the aqueous medium phase Or (3) the active hydrogen group after the toner solution is added and mixed in the aqueous medium. The organic compound is added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, the unmodified Examples thereof include a method in which the toner solution prepared by dissolving or dispersing the toner material such as polyester resin in the organic solvent is added and dispersed by shearing force. The details of the dispersion method are as described above.

In the preparation of the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets made of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate ester and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florad FC-135 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-202 (manufactured by Daikin Industries, Ltd.), MegaFuck F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, a hybridization system (manufactured by Nara Machinery Co., Ltd.) ), Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  The toner has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), content ratio of particles having a particle diameter of 0.6 to 2.0 μm, and average circularity. It is preferable to have a degree, a shape factor SF-1, a volumetric shrinkage ratio, a T1 / 2 melting temperature, and the like in an aqueous medium.

The volume average particle diameter (Dv) of the toner is, for example, preferably 3 to 8 μm, more preferably 4 to 7 μm, and still more preferably 5 to 6 μm. Here, the volume average particle diameter is defined as Dv = [(Σ (nD ³ ) / Σn) ^1/3 (where n is the number of particles and D is the particle diameter).
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned, and if it exceeds 8 μm, the resolution is high and the resolution is high. It becomes difficult to obtain an image having an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.00 to 1.25, more preferably 1.00 to 1.20. Preferably, 1.10 to 1.20 is more preferable.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.25 or less, the particle size distribution of the toner is relatively sharp and the fixability is improved. If it is less than the above, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be deteriorated or the cleaning property may be deteriorated. In the case of the agent, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner layer is thinned. It becomes difficult to obtain a high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase.

Here, the volume average particle diameter and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured using a measuring device for the particle size distribution of toner particles by a Coulter counter method. Specifically, a Coulter Multisizer (both manufactured by Coulter) is used, and 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the mass average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles, and is preferably 0.900 to 0.98, for example, 0.940 to 0 .98 is more preferred.
When the average circularity is less than 0.900, the toner becomes an irregular shape separated from the spherical shape, and a satisfactory transfer property and a high-quality image free from dust may not be obtained, and exceeds 0.98. In an image forming system that employs blade cleaning or the like, defective cleaning occurs on the photosensitive member and the transfer belt, and in the case of image formation with high image area ratio such as dirt on the image, for example, a photographic image. The toner on which an untransferred image is formed due to a paper feed failure or the like may become a transfer residual toner on the photosensitive member, resulting in background smearing of the image, or the charging roller for contact charging the photosensitive member Etc., and the original charging ability may not be exhibited.

Here, the average circularity was measured using, for example, FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10).
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner is treated with 0.1. 1-0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

The shape factor SF-1 is obtained by, for example, randomly sampling 300 SEM images of toner obtained by FE-SEM (S-4200) manufactured by Hitachi, Ltd. Analysis was performed by introducing the image into an image analysis apparatus (Luzex AP) manufactured by a company, and a value obtained by the following mathematical formula 1 was defined as a shape factor SF-1. The value of SF-1 is preferably a value obtained by Luzex, but is not particularly limited to the FE-SEM device and the image analysis device as long as the same analysis result can be obtained.
In Equation 1, MXLNG represents the maximum length of a shape that can be formed by projecting toner onto a two-dimensional plane. AREA represents the area of a figure formed by projecting toner onto a two-dimensional plane.

  Therefore, SF-1 represents the shape of the whole toner (ellipse, sphere, etc.). If the toner is a true sphere, the value is 100, and the value becomes larger than 100, and the sphere becomes indefinite. In the toner, SF-1 is preferably 105 to 170, more preferably 120 to 155.

In the toner, in order to give an appropriate toner shape, it is important to use a solid fine particle dispersant in a production method having a volume shrinkage step of 10 to 90% in volumetric shrinkage in an aqueous medium. Here, the volume shrinkage ratio is Vo, the volume of the oil phase (dispersed phase) in which the toner material before being emulsified and dispersed in the aqueous medium is dispersed, and the volume of the dispersed phase after emulsifying and dispersing to remove volatile components. Vt is expressed as volume shrinkage rate = (1−Vt / Vo) × 100, and the change in characteristics before emulsification and after being emulsified and dispersed is measured.
Specifically, it can be determined by the method exemplified below.
(1) A method of measuring the mass and true specific gravity of the oil phase before emulsification and the obtained toner.
(2) A method of measuring the average particle diameter of the particles after emulsification and dispersion in an aqueous medium and the particles from which volatile components have been removed, and converting the volume into a volume.
Therefore, the volume shrinkage is preferably 10 to 90%, more preferably 30 to 70%. If the volume shrinkage is outside the range of 10 to 90%, the toner particle shape becomes indefinite, which is not preferable.

  The T1 / 2 melting temperature of the toner by a flow tester is preferably 140 to 180 ° C, more preferably 145 to 165 ° C. This is because toner having a high outflow start temperature and a T1 / 2 outflow temperature is difficult to melt, and thus the toner collected by the cleaning roller does not melt again. If the temperature is less than 140 ° C., the toner accumulated on the cleaning roller may be melted again by the heat generated by the heating of the fixing roller, causing reverse transfer to the fixing roller and smearing the image. It is not preferable because it affects the

  Here, the T1 / 2 melting temperature can be determined as follows. The softening point of the toner is a flow tester (CFT-500, manufactured by Shimadzu Corporation), and the measurement is performed under the conditions of a load of 30 kg, a temperature rising rate: 3 ° C./min, a die diameter of 0.5 mm, and a die length of 1.0 mm. The T1 / 2 melting temperature can be calculated from the measured curve.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle size of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, and butyl acetate.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
The mixing ratio of the toner and the carrier of the two-component developer is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, a high-definition image can be obtained and the cleaning property is stable over a long period of time.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. A developing means for forming the image forming apparatus, and further having other means such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a discharging means, which are appropriately selected as necessary. .
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 9, the process cartridge includes a photosensitive member 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other members as necessary. It has. In FIG. 9, reference numeral 103 denotes exposure by an exposure means, and a light source capable of writing with high resolution is used. Reference numeral 105 denotes a recording medium.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 102.
Next, the image forming process using the process cartridge shown in FIG. 9 will be described. The photoconductor 101 is charged on the surface by charging by the charging means 102 and exposure 103 by the exposure means (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the exposure image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention is constructed by integrally combining the electrostatic latent image carrier and the components such as a developing device and a cleaning device as a process cartridge, and this unit can be attached to and detached from the apparatus main body. It may be configured. Further, at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be detachable using guide means such as a rail of the apparatus main body.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the following examples, “part” means “part by mass”, and “%” means “% by mass”.

(Production Example A-1)
-Production of Toner 1-
<Synthesis of toner binder resin>
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe and reacted at 230 ° C. for 8 hours under normal pressure. The mixture was further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours, then cooled to 160 ° C., 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained. Subsequently, 267 parts of prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester resin (1) having a mass average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. An unfinished polyester resin (a) was synthesized.
200 parts of the urea-modified polyester resin (1) and 800 parts of the unmodified polyester resin (a) are dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent to mix the toner binder resin (1). An ethyl acetate / MEK solution was obtained. Part of the mixture was dried under reduced pressure to isolate the toner binder resin (1). The glass transition temperature (Tg) was 62 ° C., and the acid value was 10 mgKOH / g.

<Method for measuring acid value>
About the measuring method of the said acid value, it carried out using the following measuring devices.
Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
Working electrode: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No
Next, measurement is performed under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows. Titrate with a pre-standardized N / 10 caustic potassium to alcohol solution, and the acid value is determined by the following calculation from the consumption of the alcohol potassium solution.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

<Measurement of glass transition temperature>
The glass transition temperature can be measured using a differential scanning calorimeter. Specifically, it is determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50ml / min)
(Temperature conditions)
Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement results were analyzed using the data analysis software (Ta-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve which is the DSC differential curve of the second temperature rise, and the peak temperature is determined using the peak analysis function of the analysis software. Ask. Next, the maximum endothermic temperature of the DSC curve is obtained using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition temperature (Tg) of the toner.

-Preparation of toner-
In a beaker, 240 parts of the ethyl acetate / MEK solution of the toner binder resin (1), 20 parts of pentaerythritol tetrabehenate (melting point: 81 ° C., melt viscosity: 25 cps), and 10 parts of carbon black were placed, and TK type at 60 ° C. The mixture was stirred at 12000 rpm using a homomixer and uniformly dissolved and dispersed.
Next, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite suspension (Nippon Chemical Industry Co., Ltd., Superite 10) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved in a beaker. Next, the temperature was raised to 60 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer.
Next, the obtained mixed liquid is transferred to a Kolben equipped with a stirring bar and a thermometer, heated to 98 ° C. to partially remove the solvent, and returned to room temperature, and then stirred at 12000 rpm using the same homomixer. The shape of the toner was changed from a spherical shape, and the solvent was completely removed. Next, after filtering, washing and drying, air classification was performed to obtain toner base particles. Toner 1 was prepared by mixing 100 parts of the obtained toner base particles with 1.0 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer. Other conditions are as shown in Table 3.

(Production Example A-2)
-Production of Toner 2-
Toner 2 was produced in the same manner as in Production Example A-1, except that in Production Example A-1, 10 parts of carbon black were replaced with 12 parts of magenta colorant (CI pigment Yellow 180).

(Production Example A-3)
-Production of Toner 3-
Toner 3 was produced in the same manner as in Production Example A-1, except that in Production Example A-1, 10 parts of carbon black were changed to 7 parts of magenta colorant (CI pigment Red 184).

(Production Example A-4)
-Production of Toner 4-
Toner 4 was produced in the same manner as in Production Example A-1, except that in Production Example A-1, 10 parts of carbon black were changed to 5 parts of magenta colorant (CI pigment Blue 15: 3).

(Production Example A-5)
-Production of Toner 5-
<Synthesis of toner binder resin>
In the same manner as in Production Example A-3, after polycondensing 334 parts of bisphenol A ethylene oxide 2 mol adduct, 334 parts of bisphenol A propylene oxide 2 mol adduct, 274 parts of isophthalic acid, and 20 parts of trimellitic anhydride, The prepolymer (2) was synthesized by reacting 154 parts of isophorone diisocyanate. Next, 213 parts of the obtained prepolymer (2), 9.5 parts of isophoronediamine and 0.5 part of dibutylamine were reacted in the same manner as in Production Example A-3 to give a urea-modified polyester resin (2 ) Was synthesized.
Next, 200 parts of the resulting urea-modified polyester resin (2) and 800 parts of the unmodified polyester resin (a) were dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent, An ethyl acetate solution of toner binder resin (2) was obtained. This was partially dried under reduced pressure to isolate the toner binder resin (2). The peak molecular weight was 5000, the glass transition temperature (Tg) was 62 ° C., and the acid value was 10 mgKOH / g.

<Production of toner>
In the same manner as in Production Example A-3, except that the toner binder resin (1) was changed to the toner binder resin (2) and the dissolution temperature and the dispersion temperature were changed to 50 ° C. in Production Example A-3 Particles (2) were obtained. To 100 parts of the obtained toner base particles (2), 1.0 part of a zinc salt of a salicylic acid derivative as a charge control agent was mixed and stirred in a heated atmosphere to fix the charge control agent on the surface of the toner. . Next, 0.5 part of hydrophobic silica was mixed with 100 parts of toner particles with a Henschel mixer to prepare toner 5. Other detailed conditions are shown in Table 3.

(Production Example A-6)
-Production of Toner 6-
<Production of toner binder resin>
30 parts of the urea-modified polyester resin (1) and 970 parts of the unmodified polyester resin (a) are dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent, and the toner binder resin (3). Of ethyl acetate / MEK was obtained. A part of this was dried under reduced pressure to isolate the toner binder resin (3). The peak molecular weight was 5000, the glass transition temperature (Tg) was 62 ° C., and the acid value was 10 mgKOH / g.

<Production of toner>
In Production Example A-5, Toner 6 was prepared in the same manner as in Production Example A-5 except that toner binder resin (2) was changed to toner binder resin (3) and the colorant was changed to 8 parts of carbon black. Produced. Other conditions are shown in Table 3.

(Production Example A-7)
-Production of Toner 7-
<Synthesis of toner binder resin>
500 parts of urea-modified polyester resin (1) and 500 parts of unmodified polyester resin (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and acetic acid of toner binder resin (4) is mixed. An ethyl / MEK solution was obtained. A part of this was dried under reduced pressure to isolate the toner binder resin (4). The peak molecular weight was 5000, the glass transition temperature (Tg) was 62 ° C., and the acid value was 10 mgKOH / g.

<Production of toner>
In Production Example A-3, the toner binder resin (1) was changed to the toner binder resin (4), and C.I. I. Toner 7 was produced in the same manner as in Production Example A-3, except that 8 parts of Pigment Red 184 were used. Other conditions are shown in Table 3.

(Production Example A-8)
-Production of Toner 8-
<Synthesis of toner binder resin>
750 parts of the urea-modified polyester resin (1) and 250 parts of the unmodified polyester resin (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and the toner binder resin (5). An ethyl acetate / MEK solution was obtained. A part of this was dried under reduced pressure to isolate the toner binder resin (5). The peak molecular weight was 5000, the glass transition temperature (Tg) was 62 ° C., and the acid value was 10 mgKOH / g.

<Production of toner>
Toner 8 was produced in the same manner as in Production Example A-3, except that in Production Example A-3, the toner binder resin (1) was changed to the toner binder resin (5). Other conditions are shown in Table 3.

(Production Example A-9)
-Production of Toner 9-
<Synthesis of toner binder resin>
850 parts of urea-modified polyester resin (1) and 150 parts of unmodified polyester resin (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and acetic acid of toner binder resin (6) is mixed. An ethyl / MEK solution was obtained. A part of this was dried under reduced pressure to isolate the toner binder resin (6). The peak molecular weight was 5000, the Tg was 62 ° C., and the acid value was 10 mgKOH / g.

<Production of toner>
A toner 9 was produced in the same manner as in Production Example A-3, except that the toner binder resin (1) was changed to the toner binder resin (6) in Production Example A-3. Other conditions are shown in Table 3.

(Production Example A-10)
-Production of Toner 10-
<Synthesis of toner binder resin>
724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were subjected to polycondensation at 230 ° C. for 2 hours under normal pressure. Next, the reaction was performed at a reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester resin (b) having a peak molecular weight of 800.
Next, 200 parts of urea-modified polyester resin (1) and 800 parts of the unmodified polyester resin (b) are dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent, and a toner binder resin ( An ethyl acetate / MEK solution of 7) was obtained. A part of this was dried under reduced pressure to isolate the toner binder resin (7). The glass transition temperature (Tg) was 45 ° C.

<Production of toner>
A toner 10 was produced in the same manner as in Production Example A-3, except that in Production Example A-3, the toner binder resin (1) was changed to the toner binder resin (7). Other conditions are shown in Table 3.

(Production Example A-11)
-Production of Toner 11-
210 parts of the toner binder solution obtained in Production Example A-1 was diluted with 210 parts of ethyl acetate, and 210 parts of this diluted dispersion was treated in the same manner as in Production Example A-1 to form particles after emulsification. Next, a toner 11 was produced in the same manner as in Production Example A-1. Other conditions are shown in Table 3.

(Production Example A-12)
-Production of Toner 12-
350 parts of the toner composition obtained in Production Example A-3 was concentrated to 175 parts by an evaporator, and 210 parts of this concentrated dispersion was treated in the same manner as in Production Example A-3 to form particles after emulsification. Next, a toner 12 was produced in the same manner as in Production Example A-3. Other conditions are shown in Table 3.

(Production Example A-13)
-Production of Toner 13-
210 parts of the toner composition obtained in Production Example A-3 was diluted with 965 parts of ethyl acetate, and 210 parts of this diluted dispersion was treated in the same manner as in Production Example A-3 to form particles after emulsification. Next, a toner 13 was produced in the same manner as in Production Example A-3. Other conditions are shown in Table 3.

(Production Example A-14)
-Production of Toner 14)-
350 parts of the toner composition obtained in Production Example A-3 was concentrated to 125 parts by an evaporator, and 210 parts of this concentrated dispersion was treated in the same manner as in Production Example A-3 to be emulsified and then granulated. Next, a toner 14 was produced in the same manner as in Production Example A-3. Other conditions are shown in Table 3.

(Production Example A-15)
-Production of Toner 15-
<Synthesis of toner binder resin>
343 parts of bisphenol A ethylene oxide 2-mole adduct, 166 parts of isophthalic acid, and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 230 ° C. for 8 hours under normal pressure. Reacted. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 80 ° C., 14 parts of toluene diisocyanate was added in toluene, and the reaction was performed at 110 ° C. for 5 hours. Thereafter, the solvent was removed to synthesize a urethane-modified polyester resin having a mass average molecular weight of 98,000.
Next, 363 parts of the obtained bisphenol A ethylene oxide 2-mol adduct and 166 parts of isophthalic acid were polycondensed in the same manner as in Production Example A-1, and an unmodified polyester resin having a peak molecular weight of 3800 and an acid value of 7 was obtained. Obtained. 350 parts of the resulting urethane-modified polyester resin and 650 parts of the unmodified polyester resin were dissolved in toluene, mixed, and then the solvent was removed to prepare a comparative toner binder resin (2). The comparative toner binder resin (2) obtained had a glass transition temperature (Tg) of 58 ° C.

<Production of toner>
100 parts of the comparative toner binder resin (2), C.I. I. 7 parts of Pigment Red 184 were converted into toner by the following method. First, after preliminary mixing using a Henschel mixer, the mixture was kneaded with a continuous kneader. Next, after finely pulverizing with a jet pulverizer, it was classified with an airflow classifier to produce toner particles. Next, the toner was rounded using a rotary kiln. Toner 15 was prepared by mixing 100 parts of the obtained toner particles with 1.0 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer. Other conditions are shown in Table 3.

(Production Example A-16)
-Production of Toner 16-
<Synthesis of toner binder resin>
724 parts of bisphenol A ethylene oxide 2-mole adduct, 184 parts of terephthalic acid, and 55 parts of fumaric acid were polycondensed at 230 ° C. for 2 hours under normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester resin (c) having a peak molecular weight of 1000. 200 parts of urea-modified polyester resin (1) and 800 parts of unmodified polyester resin (c) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and acetic acid in toner binder resin (8). An ethyl / MEK solution was obtained. A part of this was dried under reduced pressure to isolate the toner binder resin (8). The glass transition temperature (Tg) was 45 ° C.

<Production of toner>
A toner 16 was produced in the same manner as in Production Example A-3, except that the toner binder resin (1) was changed to the toner binder resin (8) in Production Example A-3. Other conditions are shown in Table 3.

(Production Example A-17)
-Production of Toner 17-
<Synthesis of toner binder resin>
724 parts of bisphenol A ethylene oxide 2-mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 1.5 hours under normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester resin (d) having a peak molecular weight of 600. 200 parts of the obtained urea-modified polyester resin (1) and 800 parts of the unmodified polyester resin (d) are dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent, and the toner binder resin (9 ) In ethyl acetate / MEK. A part of this was dried under reduced pressure to isolate the toner binder resin (9). The glass transition temperature (Tg) was 45 ° C.

<Production of toner>
A toner 17 was produced in the same manner as in Production Example A-3, except that in Production Example A-3, the toner binder resin (1) was changed to the toner binder resin (9). Other conditions are shown in Table 3.

(Production Example A-18)
-Production of Toner 18-
<Synthesis of toner binder resin>
A comparative toner binder resin (1) having a peak molecular weight of 4,000 was synthesized by polycondensation of 354 parts of bisphenol A ethylene oxide 2-mole adduct and 166 parts of isophthalic acid using 2 parts of dibutyltin oxide as a catalyst. The comparative toner binder resin (1) obtained had a glass transition temperature (Tg) of 57 ° C.

<Production of toner>
In a beaker, 100 parts of the comparative toner binder resin (1), 200 parts of ethyl acetate solution, and C.I. I. 7 parts of Pigment Red 184 was added and stirred at 12000 rpm using a TK homomixer at 50 ° C. to uniformly dissolve and disperse. Next, the toner was produced in the same manner as in Production Example A-1, and toner 18 was produced. Other conditions are shown in Table 3.

(Production Example A-19)
-Production of Toner 19-
In Production Example A-15, Toner 19 was produced in the same manner as in Production Example A-15, except that the toner was not rounded with a rotary kiln. Other conditions are shown in Table 3.

(Production Example A-20)
-Production of Toner 20-
<Synthesis of toner binder resin>
A comparative toner binder resin (3) having a peak molecular weight of 12,000 was synthesized by polycondensation of 354 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of terephthalic acid using 2 parts of dibutyltin oxide as a catalyst. The glass transition temperature (Tg) was 62 ° C. and the acid value was 10.

<Manufacture of toner>
In a beaker, put 100 parts of the comparative toner binder resin (3), 200 parts of ethyl acetate, and 4 parts of copper phthalocyanine blue pigment, stir at 12,000 rpm with a TK homomixer at 50 ° C., and uniformly dissolve and disperse. A comparative toner material solution was prepared. Next, toner 20 was produced in the same manner as in Production Example A-11. Table 3 shows other conditions.

(Production Example A-21)
-Production of Toner 21-
In the step of atyping with the toner base particles produced in Production Example A-3, after partly removing the solvent and returning to room temperature, the mixture is stirred at 18000 rpm using a TK homomixer to change the toner shape from spherical A toner 21 was produced in the same manner as in Production Example A-3 except for the deformation. Other conditions are shown in Table 3.

(Production Example A-22)
-Production of Toner 22-
Toner 22 was produced in the same manner as in Production Example A-1, except that 100 parts of the toner base particles produced in Production Example A-1 were mixed with 0.2 part of hydrophobic silica using a Henschel mixer. Other conditions are shown in Table 3.

(Production Example A-23)
-Production of Toner 23-
<Synthesis of toner binder resin>
724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 1 hour under normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester resin (f) having a peak molecular weight of 400. 200 parts of the resulting urea-modified polyester resin (1) and 800 parts of the unmodified polyester resin (f) are dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent, and the toner binder resin (9 ) In ethyl acetate / MEK. A part of this was dried under reduced pressure to isolate the toner binder resin (9). The glass transition temperature (Tg) was 45 ° C.

<Production of toner>
A toner 23 was produced in the same manner as in Production Example A-3, except that the toner binder resin (1) was changed to the toner binder resin (9) in Production Example A-3. Other conditions are shown in Table 3.

(Production Example A-24 to Production Example A-27)
-Production of toners 24-27-
In Production Example A-3, toners 24 to 27 were produced in the same manner as in Production Example A-3 except that the additive conditions were changed as shown in Table 3.

  Next, various physical properties of each of the obtained toners 1 to 27 were measured as follows. The results are shown in Table 2.

<Toner particle size (volume average particle size (Dv), number average particle size (Dn))>
The volume average particle diameter and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured using a toner particle size distribution measuring apparatus by a Coulter counter method. Specifically, a Coulter Multisizer (both manufactured by Coulter) is used, and 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted.

<Measuring method of average circularity>
The average circularity was measured using FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10).
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, and each toner was added in an amount of 0.1%. 1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

<Content of particles having a particle size of 0.6 to 2.0 μm>
The measurement of the content rate of particles having a particle size of 0.6 to 2.0 μm was measured using FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.), and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). The analysis was performed using.
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, and each toner was added in an amount of 0.1%. 1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm, and the ratio of the number of particles in the range of 0.6 to 2.0 μm can be calculated.

<Shape factor SF-1>
Using a FE-SEM (S-800) manufactured by Hitachi, Ltd., 100 toner particle images of 2 μm or larger magnified 1000 times are sampled randomly, and the image information is sent via an interface, for example, an image analysis device manufactured by Nicole (Luzex III) was introduced and analyzed.

<T1 / 2 outflow temperature>
For the softening point of the toner, a flow tester (CFT-500, manufactured by Shimadzu Corporation) was used, and the measurement was performed under the conditions of a load of 30 kg, a heating rate: 3 ° C./min, a die diameter of 0.5 mm, and a die length of 1.0 mm. The T1 / 2 melting temperature was calculated from the obtained curve.

( Examples A-1 to A-13, Reference Examples A-1 to A-9, and Comparative Examples A-1 to A-6)
Next, the toners 1 to 27, the fixing device A (FIG. 2), and the fixing device B (FIG. 1) were combined as shown in Table 4, and various characteristics were evaluated as follows. The results are shown in Table 4.

<Filming>
An experiment was carried out with a remodeling machine of an image forming apparatus (Ricoh Co., Ltd., Ipsio color 8100) to rotate the toner equivalent to 10,000 sheets (blank paper passing), and toner filming occurred on the surface of the developing roller. Was visually observed.
〔Evaluation criteria〕
○: No occurrence ×: Occurrence

<Dissolving and fixing cleaning roller adhesion amount>
A 5% image of 100,000 sheets of toner was formed with a modified machine of an image forming apparatus (Ricoh Co., Ltd., Ipsio color 8100), and reverse transfer due to melting on transfer paper was confirmed according to the following criteria. At the same time, the weight of the cleaning roller for fixing was measured, and the increase in mass was measured as the toner adhesion amount.
〔Evaluation criteria〕
○: No occurrence ×: Occurrence

<Fixability (fixing lower limit temperature)>
A solid image and 1.0 ± 0.05 mg / cm ² of toner are developed on a plain paper and a thick paper transfer paper (manufactured by Ricoh Co., Ltd., type 6200 and NBS Ricoh, copy-printed paper <135>) with a solid image. Adjustments were made so that the temperature of the fixing belt was variable, and the temperature at which no offset occurred on plain paper and the lower limit fixing temperature on thick paper were measured. The minimum fixing temperature was determined as the fixing belt temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

<Hot offset generation temperature (HOT)>
Fixing was evaluated in the same manner as the above-described minimum fixing temperature, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.

(Example B-1)
Hereinafter, the “organic solvent phase in which at least the functional group-containing polyester resin is dissolved, the active hydrogen-containing compound, and the colorant are dispersed in an aqueous medium phase in which resin fine particles are dispersed. An electrostatic charge image developing toner that causes an elongation reaction and / or a crosslinking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, and forms particles from the resulting dispersion. The average number of functional groups contained in one molecule of the functional group-containing polyester resin is 1.5 to 3, more preferably 2.1 to 2.8 on average. This will be explained step by step.

-Production of inorganic fine particles-
Blowing liquid SiCl ₄ ingredients core at a flow rate of Ar gas as a carrier gas using a liquid material supply system 300 SCCM (min standard volume flow (CC)), the SiCl ₄ vapor flow rate 250 SCCM, _{H 2} gas 20 SLM (per Minute standard volume flow rate (L)) and O ₂ gas 20SLM were sent to a core burner for flame hydrolysis and fusion to produce SiO ₂ fine particles. The obtained fine particles were grown to a predetermined primary particle size, and the obtained fine particles were subjected to a hydrophobic treatment with hexamethyldisilazane to produce [Inorganic fine particles 1] having an average primary particle size of 5 nm.

-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid Parts, 110 parts of butyl acrylate, 12 parts of butyl thioglycolate, and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to obtain an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1].
The volume average particle diameter of the obtained [fine particle dispersion 1] measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation) was 120 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 42 ° C., and the mass average molecular weight was 30,000.

-Preparation of aqueous phase-
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, Then, 2 parts of dibutyltin oxide was added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after 5 hours of reaction at a reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. under normal pressure for 2 hours to obtain [Low molecular weight polyester 1].
The obtained [Low molecular weight polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1].
The obtained [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51.

-Synthesis of a modified polyester resin (referred to as prepolymer 1) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts of the [intermediate polyester 1], 125 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added, and reacted at 100 ° C. for 5 hours. Prepolymer 1] was obtained.
The average number of isocyanate groups contained per molecule of the obtained [Prepolymer 1] was 2.15.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 418.

-Synthesis of master batch-
1200 parts of water, 40 parts of carbon black (Cabot, Regal 400R), 60 parts of polyester resin (manufactured by Sanyo Chemical Industries, RS801) and 30 parts of water are mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.) Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

-Preparation of toner composition containing oil phase, that is, inorganic fine particles-
In a reaction vessel equipped with a stir bar and a thermometer, 400 parts of the above [low molecular weight polyester 1], 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After being kept for 5 hours, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain [Raw material solution 1].
Next, 1324 parts of the obtained [Raw Material Solution 1] was transferred to a reaction vessel, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.001. Filling with 80% by volume of 5 mm zirconia beads, the wax was dispersed under the condition of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] and 34 parts of the above [inorganic fine particles 1] were added, followed by one pass with a bead mill under the above conditions to obtain [Pigment and wax dispersion 1]. The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
648 parts of [Pigment and Wax Dispersion 1], 154 parts of [Prepolymer 1], and 8.5 parts of [Ketimine Compound 1] are put in a container and 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika). After mixing for 1 minute, 1200 parts of [Aqueous phase 1] was added to the container and mixed with a TK homomixer at a rotational speed of 10,000 rpm for 20 minutes to obtain [Emulsion slurry 1]. That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

-Solvent removal-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 45 ° C for 4 hours to obtain [Dispersion slurry 1].

-Cleaning and drying-
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a cake. . This is designated as [filter cake 1].
The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain toner base particles. This is designated as [toner base particle 1].

-External additive treatment-
To 100 parts of the obtained [toner base particle 1], 0.7 parts of hydrophobic silica as an external additive and 0.3 parts of hydrophobic titanium oxide were mixed with a Henschel mixer to obtain a toner. This is referred to as [Toner 1].

(Example B-2)
-Production of Toner 2-
In Example B-1, Toner 2 was produced in the same manner as in Example B-1, except that [Prepolymer 2] produced as follows was used.
-Synthesis of intermediate polyester-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 264 parts of terephthalic acid, 41 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10-15 mmHg for 5 hours to obtain [Intermediate Polyester 2]. [Intermediate Polyester 2] had a number average molecular weight of 2400, a weight average molecular weight of 11400, a glass transition temperature (Tg) of 59 ° C., an acid value of 0.9 mgKOH / g, and a hydroxyl value of 94.

-Synthesis of a modified polyester resin (referred to as prepolymer 2) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 2], 160 parts of isophorone diisocyanate and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. 2] was obtained. The average number of isocyanate groups contained per molecule of [Prepolymer 2] was 2.75.

(Example B-3)
-Production of Toner 3-
In Example B-1, Toner 3 was prepared in the same manner as in Example B-1, except that [Prepolymer 3] prepared as follows was used.
-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 264 parts of terephthalic acid, and 41% trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 3]. [Intermediate Polyester 3] had a number average molecular weight of 2400, a weight average molecular weight of 11400, a glass transition temperature (Tg) of 59 ° C., an acid value of 0.9 mgKOH / g, and a hydroxyl value of 94.

-Synthesis of a modified polyester resin (referred to as prepolymer 3) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 3], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were reacted at 100 ° C. for 5 hours. Prepolymer 3] was obtained. The average number of isocyanate groups contained per molecule of the obtained [Prepolymer 3] was 1.53.

(Example B-4)
-Production of Toner 4-
Toner 4 was produced in the same manner as in Example B-1, except that [Prepolymer 4] produced in the following manner was used in Example B-1.
-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 264 parts of terephthalic acid, and 41% trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 4]. [Intermediate Polyester 4] had a number average molecular weight of 2400, a weight average molecular weight of 11400, a glass transition temperature (Tg) of 59 ° C., an acid value of 0.9 mgKOH / g, and a hydroxyl value of 94.

-Synthesis of a modified polyester resin (referred to as prepolymer 4) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 410 parts of the above [intermediate polyester 4], 170 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. 4] was obtained. The average number of isocyanate groups contained per molecule of [Prepolymer 4] was 2.92.

(Comparative Example B-1)
-Production of Toner 5-
In Example B-1, Toner 5 was produced in the same manner as in Example B-1, except that [Prepolymer 5] produced as follows was used.
-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 253 parts of terephthalic acid, trimellitic anhydride 52 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 5]. [Intermediate Polyester 5] had a number average molecular weight of 2,800, a weight average molecular weight of 12,300, a glass transition temperature (Tg) of 62 ° C., an acid value of 1.1 mgKOH / g, and a hydroxyl value of 118.

-Synthesis of a modified polyester resin (referred to as prepolymer 5) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 5], 72 parts of isophorone diisocyanate and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. 5] was obtained. The average number of isocyanate groups contained per molecule of [Prepolymer 5] was 1.23.

(Comparative Example B-2)
-Production of Toner 6-
In Example B-1, Toner 6 was produced in the same manner as in Example B-1, except that [Prepolymer 6] produced as follows was used.
-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 680 parts of bisphenol A ethylene oxide 2-mole adduct, 79 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 6 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 6]. [Intermediate Polyester 6] had a number average molecular weight of 1800, a weight average molecular weight of 5800, a glass transition temperature (Tg) of 52 ° C., an acid value of 0.2 mgKOH / g, and a hydroxyl value of 38.

-Synthesis of a modified polyester resin (prepolymer 6) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts of the [intermediate polyester 6], 186 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. Polymer 6] was obtained. The average number of isocyanate groups contained per molecule of the obtained [Prepolymer 6] was 3.20.

  Next, various physical properties of each obtained toner were measured as follows. The results are shown in Table 5.

<Measurement of Volume Average Particle Size (Dv) and (Dv / Dn)>
The volume average particle diameter and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured using a toner particle size distribution measuring apparatus by a Coulter counter method. Specifically, a Coulter Multisizer (both manufactured by Coulter) is used, and 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted.

<Average circularity>
The average circularity was measured using FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10).
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, and each toner was added in an amount of 0.1%. 1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

-Preparation of developer-
A two-component developer was prepared by a conventional method from 5% by mass of each toner and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin.
Remodeling machine (fixing device A (FIG. 2) or fixing device B) of an image forming apparatus (Ricoh Co., Ltd., Ipsio color 8100) capable of printing 45 sheets of A4 size paper per minute using each developer thus obtained. (FIG. 1)), various characteristics were evaluated as follows. The results are shown in Tables 6 and 7.

<Charge amount>
6 g of each developer is weighed, charged into a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 4.5 to 5.5% by mass.

<Cleanability>
Using the fixing device A (FIG. 2), the transfer residual toner on the photosensitive member that has passed through the cleaning process after outputting 100 sheets is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Limited), and this is transferred to a Macbeth reflection densitometer RD514 type. The difference between the blank and the blank is less than 0.005: ◎, 0.005-0.010: ○, 0.011-0.02: Δ, 0.02 As evaluated.

<Image density>
Using the fixing device A (FIG. 2), after running 150,000 sheets of an image chart having a 50% image area in a single color mode, a solid image was output to 6000 paper manufactured by Ricoh, and the image density was changed to X-Rite ( Measurement was performed by X-Rite). This was performed for four colors alone, and an average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

<Image graininess, sharpness>
The fixing device B (FIG. 1) was used to output a photographic image in a single color, and the degree of graininess and sharpness was visually evaluated. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.

<Skin dirt>
Using the fixing device A (FIG. 1), after running 30,000 image charts with 50% image area in the monochrome mode, the blank image is stopped during development, and the developer on the photoconductor after development is taped. The difference from the image density of the transferred and untransferred tape was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background stains, and the better the rank in the order of x, Δ, ○, ◎.

<White spots inside character images>
Using the fixing device A (FIG. 2), after running 30,000 50% image area image charts in single color mode, the character image is overlaid on a Ricoh type DX OHP sheet and output. The toner non-transfer frequency at which the inside of the line image of the character part is lost was compared with a step sample. Rank 1 is the lowest and rank 5 is the highest. Rank 1 or 2 was rated as x, Rank 3 was rated as △, Rank 4 was rated as ◯, and Rank 5 was rated as ◎.

<Toner fluidity>
A powder tester (PT-N type, manufactured by Hosokawa Micron) was loaded with meshes of 75 μm, 45 μm, and 22 μm openings in order from the top, and 2 g of the toner base was placed on the uppermost 75 μm mesh and 1 mm in the vertical direction. Vibration was applied for 10 seconds, and the fluidity (cohesion degree) of the toner base was calculated from the residual amount of toner on each mesh.
<Formula 2>
Aggregation degree (%) = (5 × (residual toner amount (g) on 75 μm mesh) + 3 × (residual toner amount (g) on 45 μm mesh) + (residual toner amount (g) on 22 μm mesh)) × 10
When the degree of aggregation was 8% or less, ◎, when it was 8 to 16%, ◯, when it was 16 to 25%, Δ, and when it was 25% or more, ×.

<Fixability>
Using the fixing device A (FIG. 2) and the fixing device B (FIG. 1), a plain image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) are solid images. Fixing evaluation was performed with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² . The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The upper limit fixing temperature was ◎ for 190 ° C or higher, ○ for 190-180 ° C, △ for 180-170 ° C, and x for 170 ° C or lower. The lower limit fixing temperature was ◎ for 135 ° C. or less, ◯ for 135 to 145 ° C., Δ for 145 to 155 ° C., and × for 155 ° C. or more.

<Comprehensive evaluation>
From the evaluation results of the above characteristics, comprehensive evaluation was performed according to the following criteria.
○: Good ×: Bad

(Example C-1)
Hereinafter, the “organic solvent phase in which at least the functional group-containing polyester resin is dissolved, the active hydrogen-containing compound, and the colorant are dispersed in an aqueous medium phase in which resin fine particles are dispersed. An electrostatic charge image developing toner which causes an elongation reaction and / or a cross-linking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, and forms particles from the resulting dispersion. The specific production of the toner containing an organic acid compound in the organic solvent phase will be described step by step.

-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid Parts, butyl acrylate 110 parts, thioglycolate butyl 12 parts, and ammonium persulfate 1 part were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to obtain an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1].
The volume average particle diameter of the obtained [fine particle dispersion 1] measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation) was 120 nm. A portion of this [fine particle dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 42 ° C., and the mass average molecular weight was 30,000.

-Preparation of aqueous phase-
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, Then, 2 parts of dibutyltin oxide was added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after 5 hours of reaction at a reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. under normal pressure for 2 hours to obtain [Low molecular weight polyester 1].
The obtained [Low molecular weight polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 24 mgKOH / g.

-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1].
The obtained [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51.

-Synthesis of a modified polyester resin (referred to as prepolymer 1) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 410 parts of the above [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. 1] was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 418.

-Synthesis of master batch-
1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Regal 400R), 60 parts of polyester resin (manufactured by Sanyo Chemical Industries, RS801) and 30 parts of water were added and mixed with a Henschel mixer (manufactured by Mitsui Mining). . Next, the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

-Preparation of toner composition containing oil phase, that is, inorganic fine particles-
In a container equipped with a stirrer and a thermometer, 400 parts of the above [low molecular weight polyester 1], 110 parts of carnauba wax and 947 parts of ethyl acetate are charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. After that, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80 vol%. The wax was dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] and 34 parts of the above [inorganic fine particles 1] were added, followed by one pass with a bead mill under the above conditions to obtain [Pigment and wax dispersion 1]. [Pigment and wax dispersion 1] had a solid content (130 ° C., 30 minutes) of 50%.

-Emulsification-
[Pigment and wax dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine compound 1] 8.5 parts, and organic acid compound (acetic acid) 0.01 part are put in a container, and a TK homomixer ( After mixing at 5,000 rpm for 1 minute using a special machine, 1200 parts of [Aqueous phase 1] was added to the container and mixed with a TK homomixer at a rotational speed of 10,000 rpm for 20 minutes to obtain [Emulsion slurry 1]. That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

-Solvent removal-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 45 ° C for 4 hours to obtain [Dispersion slurry 1].

-Cleaning and drying-
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a cake-like product. . This is designated as [filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This is designated as [toner base particle 1].

-External additive treatment-
To 100 parts of [Mother toner particles 1] obtained above, 0.7 parts of hydrophobic silica as an external additive and 0.3 parts of hydrophobized titanium oxide were mixed with a Henschel mixer to obtain a toner. It was. This is referred to as [Toner 1].

(Example C-2)
-Production of Toner 2-
Toner 2 was produced in the same manner as in Example C-1, except that the amount of organic acid compound (acetic acid) added was changed from 0.01 part to 0.03 part in the emulsification of Example C-1.

(Example C-3)
-Production of Toner 3-
In the emulsification of Example C-1, except that 0.01 part of the organic acid compound (acetic acid) was changed to 0.01 part of the organic acid compound (trimellitic anhydride), the same as in Example C-1, Toner 3 was produced.

(Example C-4)
-Production of Toner 4-
In the emulsification of Example C-1, except that 0.01 part of the organic acid compound (acetic acid) was changed to 0.03 part of the organic acid compound (trimellitic anhydride), the same as in Example C-1, Toner 4 was produced.

(Comparative Example C-1)
-Production of Toner 5-
Toner 5 was produced in the same manner as in Example C-1, except that no organic acid compound was added in the emulsification of Example C-1.

  Next, various physical properties of each toner were measured as follows. The results are shown in Table 8.

<Measurement of volume average particle diameter and (Dv / Dn)>
The volume average particle diameter and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured using a toner particle size distribution measuring apparatus by a Coulter counter method. Specifically, a Coulter Multisizer (both manufactured by Coulter) is used, and 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and number average particle diameter of the toner can be determined.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted.

<Average circularity>
The average circularity was measured using FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10).
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, and each toner was added in an amount of 0.1%. 1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

-Preparation of developer-
A two-component developer was prepared by a conventional method from 5% by mass of each toner and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin.
Remodeling machine (fixing device A (FIG. 2) or fixing device B) of an image forming apparatus (Ricoh Co., Ltd., Ipsio color 8100) capable of printing 45 sheets of A4 size paper per minute using each developer thus obtained. (FIG. 1)), various characteristics were evaluated as follows. The results are shown in Table 9 and Table 10.

<Charge amount>
6 g of each developer is weighed, charged into a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 4.5 to 5.5% by mass.

<Cleanability>
Using the fixing device A (FIG. 2), the transfer residual toner on the photosensitive member that has passed through the cleaning process after outputting 100 sheets is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Limited), and then transferred to a Macbeth reflection densitometer RD514 The difference between the blank and the blank is less than 0.005: ◎, 0.005-0.010: ○, 0.011-0.02: Δ, 0.02 As evaluated.

<Image density>
Using the fixing device A (FIG. 2), after running 150,000 sheets of an image chart having a 50% image area in a single color mode, a solid image was output to 6000 paper manufactured by Ricoh, and the image density was changed to X-Rite ( Measurement was performed by X-Rite). This was performed for four colors alone, and an average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

<Image graininess, sharpness>
The fixing device B (FIG. 1) was used to output a photographic image in a single color, and the degree of graininess and sharpness was visually evaluated. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.

<Skin dirt>
Using the fixing device A (FIG. 1), after running 30,000 image charts with 50% image area in the monochrome mode, the blank image is stopped during development, and the developer on the photoconductor after development is taped. The difference from the image density of the transferred and untransferred tape was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background stains, and the better the rank in the order of x, Δ, ○, ◎.

<White spots inside character images>
Using the fixing device A (FIG. 2), after running 30,000 50% image area image charts in single color mode, the character image is overlaid on a Ricoh type DX OHP sheet and output. The toner non-transfer frequency at which the inside of the line image of the character part is lost was compared with a step sample. Rank 1 is the lowest and rank 5 is the highest. Rank 1 or 2 was rated as x, Rank 3 was rated as △, Rank 4 was rated as ◯, and Rank 5 was rated as ◎.

<Toner fluidity>
A powder tester (PT-N type, manufactured by Hosokawa Micron Corporation) is loaded with a mesh of 75 μm, 45 μm, and 22 μm openings in order from the top, and 2 g of the toner base is placed on the uppermost 75 μm mesh and 1 mm in the vertical direction. Was applied for 10 seconds, and the fluidity (cohesion degree) of the toner base was calculated from the residual amount of toner on each mesh.
<Formula 2>
Aggregation degree (%) = (5 × (residual toner amount (g) on 75 μm mesh) + 3 × (residual toner amount (g) on 45 μm mesh) + (residual toner amount (g) on 22 μm mesh)) × 10
When the degree of aggregation was 8% or less, ◎, when it was 8 to 16%, ◯, when it was 16 to 25%, Δ, and when it was 25% or more, ×.

<Fixability>
Using the fixing device A (FIG. 2) and the fixing device B (FIG. 1), a plain image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) are solid images. Fixing evaluation was performed with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² . The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The upper limit fixing temperature was ◎ for 190 ° C or higher, ○ for 190-180 ° C, △ for 180-170 ° C, and x for 170 ° C or lower. The lower limit fixing temperature was ◎ for 135 ° C. or less, ◯ for 135 to 145 ° C., Δ for 145 to 155 ° C., and × for 155 ° C. or more.

<Comprehensive evaluation>
From the evaluation results of the above characteristics, comprehensive evaluation was performed according to the following criteria.
○: Good ×: Bad

(Synthesis Example D-1)
-Synthesis of unmodified polyester resin (A)-
In a 4-neck separable flask with a stirrer, thermometer, nitrogen inlet, flow-down condenser, and condenser, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, poly Oxyethylene (2,2) -2.2-bis (4-hydroxyphenyl) propane 300 g, dimethyl terephthalate 466 g, isododecenyl succinic anhydride 80 g, 1,2,4-benzenetricarboxylic acid tri-n-butyl 114 g Added with catalyst. Under a nitrogen atmosphere, the temperature was raised to normal pressure up to 210 ° C in the first half, and the reaction was allowed to proceed to 210 ° C in the second half with stirring under reduced pressure. Thereby, an unmodified polyester resin (A) having a molecular weight of 500 or less and a content of 3.5% and a molecular weight peak of 7500 was synthesized. The obtained unmodified polyester resin (A) did not contain a tetrahydrofuran (THF) insoluble component.

(Synthesis Example D-2)
-Synthesis of unmodified polyester resin (B)-
Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 1225 g Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 165 g, terephthalic acid 500 g, isododecenyl 130 g of succinic anhydride and 170 g of triisopropyl 1,2,4-benzenetricarboxylate were added to the flask along with the esterification catalyst. These were reacted in the same apparatus and conditions as in Synthesis Example D-1 to synthesize an unmodified polyester resin (B) having a molecular weight of 500 or less and a content of 3.0% and a molecular weight peak of 8000. The obtained unmodified polyester resin (B) did not contain a tetrahydrofuran (THF) insoluble component.

(Synthesis Example D-3)
-Synthesis of unmodified polyol resin (C)-
378.4 g of epoxy resin (number average molecular weight: about 360) with low molecular weight bisphenol A in a separable flask equipped with a stirrer, thermometer, nitrogen inlet, and cooling tube, glycidyl of high molecular weight bisphenol A type propylene oxide adduct 191.0 g of a compound, 274.5 g of bisphenol F, 70.1 g of p-cumylphenol, and 200 g of xylene were added. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, and 0.1839 g of lithium chloride was added. Next, the temperature was raised to 160 ° C., xylene was removed under reduced pressure, and polymerization was carried out at a reaction temperature of 180 ° C. for 5 hours. By the above. A polyol resin having a molecular weight of 500 or less and a content of 3.7% and a molecular weight peak of 4000 was synthesized. This was pulverized with a simple pulverizer to prepare an unmodified polyol resin (C) having a mass average particle diameter of 0.42 mm. The obtained unmodified polyester resin (C) did not contain a tetrahydrofuran (THF) insoluble component.

(Synthesis Example D-4)
-Synthesis of unmodified polyester resin (D)-
714 g polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 663 g polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 648 g isophthalic acid, iso 150 g octenyl succinic acid, 120 g 1,2,4-benzenetricarboxylic acid was added to the flask along with the esterification catalyst. These were reacted in the same apparatus and conditions as in Synthesis Example 1 to synthesize an unmodified polyester resin (D) having a molecular weight of 500 or less and a molecular weight of 4.8% and a molecular weight peak of 8000. The obtained unmodified polyester resin (D) did not contain a tetrahydrofuran (THF) insoluble component.

(Synthesis Example D-5)
-Synthesis of unmodified polyol resin (E)-
In a separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube, 378.4 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360), a glycidylated product of a high molecular weight bisphenol A type propylene oxide adduct 191.0 g, bisphenol F 274.5 g, p-cumylphenol 70.1 g, and xylene 200 g were added. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, and 0.1839 g of lithium chloride was added. Next, the temperature was raised to 160 ° C., xylene was removed under reduced pressure, and polymerization was carried out at a reaction temperature of 180 ° C. for 9 hours. As described above, a polyol resin having a molecular weight of 500 or less and a content of 2.0% and a molecular weight peak of 9500 was synthesized. This was pulverized with a simple pulverizer to prepare an unmodified polyol resin (E) having a mass average particle diameter of 0.42 mm. The obtained unmodified polyester resin (E) did not contain a tetrahydrofuran (THF) insoluble component.

(Production Example D-1)
-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid Parts, 110 parts of butyl acrylate, 12 parts of butyl thioglycolate, and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate). A dispersion was obtained. This is designated as [fine particle dispersion 1].
The volume average particle size of the obtained [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation) was 120 nm. A portion of this [fine particle dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 42 ° C., and the mass average molecular weight was 30,000.

-Preparation of aqueous phase-
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours at normal pressure. Next, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1].
The obtained [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51.

-Synthesis of a modified polyester resin (referred to as prepolymer 1) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. Prepolymer 1] was obtained. [Prepolymer 1] obtained had a free isocyanate mass% of 1.53%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 418.

-Synthesis of master batch-
Add 1200 parts of water, 40 parts of carbon black (Cabot Corp., Regal 400R), 60 parts of the unmodified polyester resin (A) and 30 parts of water, and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). This roll was kneaded at 150 ° C. for 30 minutes, then cooled by rolling and pulverized with a pulverizer to obtain [Masterbatch 1].

-Preparation of toner composition containing oil phase, that is, inorganic fine particles-
In a reaction vessel in which a stir bar and a thermometer were set, 400 parts of the unmodified polyester resin (A), 110 parts of carnauba wax, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After being kept for 5 hours, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain [Raw material solution 1].
Next, 1324 parts of the obtained [Raw Material Solution 1] was transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm. The wax was dispersed under the condition of 80% by volume of zirconia beads and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] and 34 parts of [inorganic fine particles 1] were added, followed by one pass using a bead mill under the above conditions to obtain [Pigment and wax dispersion 1]. The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
648 parts of [Pigment and Wax Dispersion 1], 154 parts of [Prepolymer 1], and 8.5 parts of [Ketimine Compound 1] are put in a container and 5,000 rpm with a TK homomixer (made by Tokushu Kika Co., Ltd.). After mixing for 1 minute, 1200 parts of [Aqueous phase 1] was added to the container and mixed with a TK homomixer at a rotational speed of 10,000 rpm for 20 minutes to obtain [Emulsion slurry 1].
That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

-Solvent removal-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was performed at 45 ° C for 4 hours to obtain [Dispersion slurry 1].

-Cleaning and drying-
After filtering 100 parts of [Dispersion Slurry 1] under reduced pressure,
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4) After adding 300 parts of ion-exchanged water to the filter cake of (3) and mixing with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), filtration was performed twice to obtain a cake. . This is designated as [filter cake 1].
The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain toner base particles. This is designated as [toner base particle 1].

-External additive treatment-
To 100 parts of the obtained [toner base particle 1], 0.7 parts of hydrophobic silica as an external additive and 0.3 parts of hydrophobic titanium oxide were mixed with a Henschel mixer to obtain a toner. This is referred to as [Toner 1].

(Production Example D-2)
-Production of Toner 2-
Toner 2 was produced in the same manner as in Production Example D-1, except that the unmodified polyester resin (A) was changed to the unmodified polyester resin (B) in the emulsification of Production Example D-1.

(Production Example D-3)
-Production of Toner 3-
Toner 3 was produced in the same manner as in Production Example D-1, except that the unmodified polyester resin (A) was changed to the unmodified polyester resin (C) in the emulsification of Production Example D-1.

(Production Example D-4)
-Production of Toner 4-
Toner 4 was produced in the same manner as in Production Example D-1, except that the unmodified polyester resin (A) was changed to the unmodified polyester resin (D) in the emulsification of Production Example D-1.

(Production Example D-5)
-Production of Toner 5-
Toner 5 was produced in the same manner as in Production Example D-1, except that the unmodified polyester resin (A) was changed to the unmodified polyol resin (E) in the emulsification of Production Example D-1.

(Production Example D-6)
-Production of Toner 6-
After warming the _0.1M-Na 2 PO ₄ aqueous solution 451g to put to 60 ° C. in deionized water 709 g, and stirred at 12,000rpm using a TK homomixer. To this, 68 g of 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing CaPO ₄ .
Next, 170 g of styrene, 30 g of 2-ethylhexyl acrylate, 10 g of carbon black (manufactured by Cabot, Regal 400R), 60 g of paraffin wax (sp. 70 ° C.), 5 g of a metal compound of di-tert-butylsalicylate, and styrene-methacryl 10 g of an acid copolymer (Mw 50,000, acid value 20 mgKOH / g) was put in a TK homomixer, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm. In this, 10 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer system.
Next, the polymerizable monomer system was put into the aqueous medium, and stirred at 10,000 rpm for 20 minutes in a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer system. .
Next, after stirring for 3 hours at 60 ° C. while stirring with a paddle stirring blade, the liquid temperature was set to 80 ° C. and the reaction was performed for 10 hours. After the completion of the polymerization reaction, the mixture is cooled, hydrochloric acid is added to dissolve calcium phosphate, and the mixture is filtered, washed with water, dried, and the additives are mixed and mixed in the same manner as in Production Example D-1. Obtained.

(Production Example D-7)
-Preparation of wax particle aqueous dispersion 1-
A 1000 ml stirring device, a temperature sensor, a nitrogen inlet tube, and 500 ml of distilled water deaerated in a four-headed Kolben with a cooling tube were added to 28.5 g of New Coal 565C (manufactured by Nippon Emulsifier Co., Ltd.) 1 (made by Noda Wax Co., Ltd.) 185.5 g was added, and the temperature was raised while stirring under a nitrogen stream. When the internal temperature was 85 ° C., a 5N aqueous sodium hydroxide solution was added and the temperature was raised to 75 ° C. as it was, followed by continuing heating and stirring as it was for 1 hour and cooling to room temperature to obtain [Wax Particle Aqueous Dispersion 1].

-Preparation of Colorant Aqueous Dispersion 1-
Carbon black (trade name: Mogal L, manufactured by Cabot) 100 g, sodium dodecyl sulfate 25 g was added to 540 ml of distilled water, and after sufficient stirring, a pressure disperser (MINI-LAB, manufactured by Lani) was used. Dispersion was performed to obtain [Colorant aqueous dispersion 1].

-Synthesis of aqueous dispersion of binder fine particles-
1 L 4-head Kolben equipped with a stirrer, a cooling tube, a temperature sensor, and a nitrogen inlet tube is 480 ml of distilled water, 0.6 g of sodium dodecyl sulfate, 106.4 g of styrene, 43.2 g of n-butyl acrylate, 10. While adding 4 g and stirring, the temperature was raised to 70 ° C. under a nitrogen stream. Here, an initiator aqueous solution in which 2.1 g of potassium persulfate was dissolved in 120 ml of distilled water was added, and the mixture was stirred at 70 ° C. for 3 hours under a nitrogen stream to complete the polymerization, and then cooled to room temperature. Resin fine particle dispersion 1] was obtained.
Next, 5 L 4-head Kolben equipped with a stirrer, a cooling pipe, a temperature sensor, and a nitrogen introducing pipe, 2400 ml of distilled water, 2.8 g of sodium dodecyl sulfate, 620 g of styrene, 128 g of n-butyl acrylate, 52 g of methacrylic acid, and While adding 27.4 g of tert-dodecyl mercaptan and stirring, the temperature was raised to 70 ° C. under a nitrogen stream. Here, an initiator aqueous solution in which 11.2 g of potassium persulfate was dissolved in 600 ml of distilled water was added, and the mixture was stirred at 70 ° C. for 3 hours under a nitrogen stream to complete the polymerization, and then cooled to room temperature. Resin fine particle dispersion 2] was obtained.

-Preparation of toner-
In a 1 L separable flask equipped with a stirrer, a cooling tube, and a temperature sensor, 47.6 g of [High molecular weight binder fine particle dispersion 1], 190.5 g of [Low molecular weight binder fine particle dispersion 2], [Aqueous dispersion of wax particles] 1] 7.7 g, [Colorant Dispersion Liquid 1] 26.7 g and distilled water 252.5 ml were added and mixed and stirred, and then adjusted to pH = 9.5 using 5N aqueous sodium hydroxide solution. Then, under stirring, an aqueous solution in which 50 g of sodium chloride was dissolved in 600 ml of distilled water, 77 ml of isopropanol, and fluorad FC-170C (manufactured by Sumitomo 3M: fluorinated nonionic surfactant) 10 mg were dissolved in 10 ml of distilled water. An aqueous activator solution was sequentially added, the internal temperature was raised to 85 ° C., the reaction was performed for 6 hours, and then cooled to room temperature. The reaction solution was adjusted to pH = 13 using 5N aqueous sodium hydroxide solution and then filtered.
Next, re-suspension was performed in distilled water, filtration and re-suspension were repeated, and after washing, drying was performed, and in the same manner as in Production Example D-1, toner 7 was produced by mixing external additives.

  Next, various properties of each obtained toner were measured as follows. The results are shown in Table 11.

<Measurement of volume average particle diameter and (Dv / Dn)>
The volume average particle diameter and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured using a toner particle size distribution measuring apparatus by a Coulter counter method. Specifically, a Coulter Multisizer (both manufactured by Coulter) is used, and 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted.

<Average circularity>
The average circularity was measured using FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10).
Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, and each toner was added in an amount of 0.1%. 1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. Subsequently, the dispersion process was performed for 1 minute with an ultrasonic disperser (manufactured by STM, UH-50) under the conditions of 20 kHz and 50 W / 10 cm ³ . Furthermore, a dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 pieces / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range) is 0.60 μm or more. The particle size distribution and shape of particles having an equivalent circle diameter of less than 159.21 μm were measured.
The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

-Preparation of developer-
A two-component developer was prepared by a conventional method from 5% by mass of each toner and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin.
Using each developer thus obtained, a modified machine (fixing device A (FIG. 2) or fixing device B (FIG. 1) capable of printing 45 sheets of A4 size paper per minute (manufactured by Ricoh Co., Ltd., imagio Neo450). ) And various properties were evaluated as follows. The results are shown in Table 12 and Table 13.

<Cleanability>
Using fixing device A, the untransferred toner on the photosensitive member that passed through the cleaning process after outputting 100 sheets was transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Limited), and measured with a Macbeth reflection densitometer RD514 type. The difference between the blank and the blank was less than 0.005, the 0.005 to 0.010 was evaluated as ○, the 0.011 to 0.02 was evaluated as Δ, and the one exceeding 0.02 was evaluated as ×. .

<Contamination status>
Using the fixing device A, after running 100,000 sheets of an image chart having a 5% image area, the state of contamination on the developing roller, the layer regulating member, and the photosensitive member was observed. ○ is good, Δ is confirmed but cannot be clearly confirmed in the image, × is contaminated and can be confirmed in the image.

<Image density>
After completion of the evaluation of the contamination state, the solid image was output on a recording paper (Ricoh Co., Ltd., type 6000), and the image density was measured by X-Rite (manufactured by X-Rite). This was performed for four colors alone, and an average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

<Fixability>
Using the fixing device A (FIG. 2) and the fixing device B (FIG. 1), a plain image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) are solid images. Fixing evaluation was performed with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² . The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The upper limit fixing temperature was ◎ for 190 ° C or higher, ○ for 190-180 ° C, △ for 180-170 ° C, and x for 170 ° C or lower. The lower limit fixing temperature was ◎ for 135 ° C. or less, ◯ for 135 to 145 ° C., Δ for 145 to 155 ° C., and × for 155 ° C. or more.

<Comprehensive evaluation>
From the evaluation results of the above characteristics, comprehensive evaluation was performed according to the following criteria.
○: Good ×: Bad

  The image forming method and the image forming apparatus of the present invention can reduce the adhesion amount to the cleaning roller, prevent the toner collected by the cleaning roller from being melted again, and prevent the backflow of the toner, thereby preventing the problem of image smearing. In addition to being excellent in offset resistance and excellent in low-temperature fixability, it is particularly suitable for an image forming method and an image forming apparatus using an electromagnetic induction heating type fixing device.

FIG. 1 is a schematic diagram showing a conventional fixing device using an electromagnetic induction heating method. FIG. 2 is an explanatory diagram showing a fixing device according to an embodiment of the present invention. FIG. 3A is a cross-sectional view showing the arrangement of the excitation coils of the induction heating means in the fixing device of the present invention. FIG. 3B is a side view showing the arrangement of the exciting coils of the induction heating means in the fixing device of the present invention. FIG. 4 is a diagram showing the relationship between Dv / Dn of toner and the amount of fine powder (number%) of 2 μm or less. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 6 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 7 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention (tandem color image forming apparatus). FIG. 8 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 9 is a schematic configuration diagram showing an example of the process cartridge of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heating roller 2 Fixing roller 3 Belt 4 Pressure roller 5 Temperature detection means 6 Induction heating means 7 Excitation coil 8 Coil guide plate 9 Excitation coil core 10 Photoconductor (photosensitive drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 static eliminator 70 static elimination lamp 71 cleaning blade 72 support member 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming apparatus 101 photoconductor DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure 104 Developing means 105 Recording medium 108 Transfer means 107 Cleaning means 110 Excitation coil core support member 111 Recording medium 220 Tandem developer 130 Original Table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (35)

An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction , and a fixing roller arranged in parallel with the heating roller; stretched in the heating roller and the fixing roller, while being heated by the heating roller is rotated by these rollers, an endless belt-like toner heating that having a release layer having a thickness of 200μm~500μm the surface portion A fixing device having a medium and a pressure roller that is pressed against the fixing roller via the toner heating medium and rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv) of 3 μm to 7 μm . The ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) (Dv / Dn) is 1.01 to 1.25, and the content ratio of particles having a particle diameter of 0.6 μm to 2.0 μm is The toner base particles having 20% by number or less and an average circularity of 0.93 to 0.99 are included, and 0.3 parts by weight to 5.0 parts by weight of an external additive is added to 100 parts by weight of the toner base particles. and Ri Na, the external additive is, an image forming method characterized by comprising a particle size different hydrophobized silica and hydrophobized titanium oxide.   The image forming method according to claim 1, wherein the toner is granulated by emulsifying or dispersing a solution or dispersion of the toner material in an aqueous medium.   The image forming method according to claim 2, wherein the toner material is dissolved or dispersed in an organic solvent, and the organic solvent is removed during or after granulation.   By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The image forming method according to claim 2, wherein the image forming method is performed. The external additive comprises hydrophobized silica or hydrophobized titanium oxide having an average primary particle size of less than 20 nm and hydrophobized silica having an average primary particle size of 20 nm or more. Any one of the image forming methods. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A fixing device having a pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner prepares a toner solution by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. A dispersion is prepared by emulsifying or dispersing therein, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form particles of the adhesive substrate. Obtained by removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein. An image forming method. The image forming method according to claim 6, wherein the polymer capable of reacting with the active hydrogen group-containing compound has an average of 2.1 to 2.8 functional groups per molecule. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A fixing device having a pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner includes an active hydrogen group-containing compound, a polymer that can react with the active hydrogen group-containing compound, and an organic acid compound that is at least one of a carboxylic acid compound and a carboxylic acid anhydride as an organic solvent. A toner solution is prepared by dissolving or dispersing in an aqueous medium, and then the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound and the active hydrogen group are prepared. An image forming method, which is obtained by reacting a containing compound with a polymer capable of reacting to form an adhesive substrate in the form of particles and removing the organic solvent. The image forming method according to claim 8, wherein the organic acid compound has a number average molecular weight of 15 to 1,500. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
In the fixing step, a heating roller made of magnetic metal, having an outer diameter of 20 mm, a wall thickness of 0.1 mm, heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A fixing device having a pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion;
The toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of a component having a molecular weight of 500 or less is 4% by mass or less, and a molecular weight of 3, An image forming method having one peak in an area of 000 to 9,000. The image forming method according to claim 10, wherein the unmodified resin contains an unmodified polyester resin. The toner material further comprises an unmodified polyester resin, and the mass ratio of the polymer capable of reacting with the active hydrogen group-containing compound and the unmodified polyester resin (polymer capable of reacting with the active hydrogen group-containing compound / unmodified polyester resin) The image forming method according to claim 1, wherein the image forming method is 5/95 to 80/20. The image forming method according to claim 1, wherein the polymer capable of reacting with the active hydrogen group-containing compound contains a functional group-containing polyester resin. The image forming method according to claim 13, wherein the functional group-containing polyester resin is a polyester resin having a urea group. The image forming method according to claim 11, wherein the unmodified polyester resin has a peak molecular weight of 1,000 to 20,000. The image forming method according to claim 11, wherein the acid value of the unmodified polyester resin is 10 mgKOH / g to 30 mgKOH / g. The image forming method according to any one of claims 11 to 16, wherein the glass transition temperature (Tg) of the unmodified polyester resin is 35 ° C to 55 ° C. The image forming method according to claim 1, wherein the toner contains a wax, the wax is finely dispersed in the toner, and is present in the vicinity of the surface more than the central portion of the toner. The image forming method according to claim 1, wherein the toner contains a charge control agent. The image forming method according to claim 6, wherein the toner has a volume average particle diameter of 3 μm to 8 μm. 21. The image forming method according to claim 6, wherein a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is 1.00 to 1.25. The image forming method according to claim 6, wherein the toner has an average circularity of 0.900 to 0.980. The image forming method according to any one of claims 1 to 22, wherein a T1 / 2 melting temperature of the toner by a flow tester is 140 ° C to 180 ° C. The image forming method according to any one of claims 1 to 23, wherein a shape factor SF-1 of the toner represented by the following formula 1 is 105 to 170.
In Equation 1, MXLNG represents the maximum length of a shape that can be formed by projecting toner onto a two-dimensional plane. AREA represents the area of a figure formed by projecting toner onto a two-dimensional plane. The image forming method according to any one of claims 2 to 24, wherein the toner is obtained with a volume shrinkage of 10% to 90% in an aqueous medium using a solid fine particle dispersant. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion.
The toner includes a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the toner has a volume average particle diameter (Dv) of 3 μm to 7 μm, The ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) (Dv / Dn) is 1.01 to 1.25, and the content ratio of particles having a particle diameter of 0.6 μm to 2.0 μm is 20 % Of the toner base particles having an average circularity of 0.93 to 0.99, and 0.3 parts by weight to 5.0 parts by weight of an external additive is added to 100 parts by weight of the toner base particles. The image forming apparatus is characterized in that the external additive is composed of hydrophobized silica having different particle diameters and hydrophobized titanium oxide. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion.
The toner prepares a toner solution by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. A dispersion is prepared by emulsifying or dispersing therein, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form particles of the adhesive substrate. Obtained by removing the organic solvent,
The polymer capable of reacting with the active hydrogen group-containing compound has an average of 1.5 to 3 functional groups per molecule, and the toner contains at least one inorganic fine particle therein. An image forming apparatus. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion.
The toner includes an active hydrogen group-containing compound, a polymer that can react with the active hydrogen group-containing compound, and an organic acid compound that is at least one of a carboxylic acid compound and a carboxylic acid anhydride as an organic solvent. A toner solution is prepared by dissolving or dispersing in an aqueous medium, and then the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound and the active hydrogen group are prepared. An image forming apparatus obtained by reacting a containing compound with a polymer capable of reacting to form an adhesive substrate in the form of particles and removing the organic solvent. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The fixing means is made of magnetic metal, has an outer diameter of 20 mm, a wall thickness of 0.1 mm, a heating roller heated by electromagnetic induction, and a fixing roller arranged in parallel with the heating roller; An endless belt-like toner heating medium stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers, and having a release layer having a thickness of 200 μm to 500 μm on the surface layer portion; A pressure roller that is pressed against the fixing roller via the toner heating medium and that rotates in the forward direction with respect to the toner heating medium to form a nip portion.
The toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an unmodified resin in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. Produced in the form of particles, removing the organic solvent,
The unmodified resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of a component having a molecular weight of 500 or less is 4% by mass or less, and a molecular weight of 3, An image forming apparatus having one peak in an area of 000 to 9,000. 30. The image forming apparatus according to claim 26, wherein the electrostatic latent image carrier includes amorphous silicon . 31. The apparatus according to claim 26, further comprising a charger, wherein the electrostatic latent image carrier is charged by bringing the charger into contact with the electrostatic latent image carrier and applying a voltage to the charger. The image forming apparatus described. 26. A toner used in the image forming method according to claim 1. A developer comprising the toner according to claim 32. A toner-filled container filled with the toner according to claim 32. An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 32 to form a visible image. Feature process cartridge.