JP2005265887A - Image forming method, image forming apparatus, process cartridge and electrostatic image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method using a fixing device due to an electromagnetic induction heating system which has an excellent offset resistance and also has an excellent low temperature fixing property. <P>SOLUTION: The toner is produced as follows; an organic solvent phase in which at least functional group-containing polyester resin is dissolved, an active hydrogen-containing compound and a colorant are dispersed into an aqueous medium phase in which resin fine particles are dispersed, thereby, extension reaction and/or crosslinking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound is allowed to occur and, from dispersion liquid obtained through the reaction, particles are formed. The image forming method comprises a developing process of using an electrostatic image developing toner produced by adding a tertiary amine compound into the organic solvent phase as a developer and a fixing process of using a fixing means of the electromagnetic induction heating system. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic image forming method such as a printer, a copying machine, and a facsimile. More specifically, the present invention relates to a method for forming a toner image using an electromagnetic induction heating method.

In recent years, market demands for energy saving and high speed have been increasing for image forming apparatuses such as printers, copying machines, and facsimiles. In order to achieve these required 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 transferred to a recording material sheet, printing paper, photosensitive paper, electrostatic recording paper, etc. by an image transfer method or a direct method by an image forming process such as electrophotographic recording, electrostatic recording, and magnetic recording. Formed on recording material. As a fixing device for fixing an unfixed toner image, a contact heating method fixing device such as a heat roller method, a film heating method, and an electromagnetic induction heating method is widely used.

The heat roller type fixing device has a basic configuration of 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. A recording material is introduced into a contact portion of the pair of rotating rollers, a so-called fixing nip portion, and conveyed, and an unfixed toner image is melted and fixed by heat and pressure from the fixing roller and the pressure roller.
In addition, the fixing device of the film heating method is such that a recording material is brought into close contact with a heating body fixedly supported by a support member via a thin fixing film having heat resistance, and the fixing film is slid with respect to the heating body. The heat of the heating body is supplied to the recording material through the film material (see, for example, Patent Documents 1 and 2). In this fixing device, for example, a ceramic heater including 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 as a heating body. Since this fixing device can use a thin film with a low heat capacity as the fixing film, it has higher heat transfer efficiency than the heat roller type fixing device, can shorten the warm-up time, and can achieve quick start and energy saving. It becomes possible.

As an electromagnetic induction heating type fixing device, for example, as disclosed in Patent Document 3, 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 is heated by electromagnetic induction. There is technology to let you. Hereinafter, the configuration of the electromagnetic induction heating type fixing device will be described.
FIG. 6 is a schematic view showing a conventional fixing device using an electromagnetic induction heating method.
As shown in FIG. 6, the conventional fixing device has a film inner surface guide 702 on which a heating body 701 composed of an exciting coil unit 701a and a magnetic metal member 701b as a heating unit is mounted, and a magnetic metal member 701b against the inner wall. A fixing nip portion N is formed between the heat-resistant cylindrical film 703 that wraps the film inner surface guide 702 in contact with the film 703 at the position of the magnetic metal member 701b and the film 703. The pressure roller 704 rotates the film 703.
The film 703 has a film thickness of 100 μm or less, preferably 50 μm or less and 20 μm or more. A composite layer film coated with PTFE, PFA, FEP or the like is used.
The film inner surface guide 702 is made of a member having rigidity and heat resistance formed of a resin such as PEEK or PPS, and the heating body 701 is fitted in a substantially central portion of the film inner surface guide 702 in the longitudinal direction. .
The pressure roller 704 includes a core 704a and a heat-resistant rubber layer 704b having good releasability such as silicone rubber provided around the core 704a, and a predetermined pressing force is applied by a bearing or an urging means (none of which is shown). Holding the film 703, the magnetic metal member 701b of the heating body 701 is disposed in pressure contact with the film 703. The pressure roller 704 is rotated counterclockwise by a driving means (not shown).
By the rotational driving of the pressure roller 704, a frictional force is generated between the pressure roller 704 and the film 703, and the rotational force acts on the film 703. The film 703 is in close contact with the magnetic metal member 701b of the heating body 701. Slide and rotate.
A recording having an unfixed toner image T formed by an image forming unit (not shown) between the film 703 and the pressure roller 704 in the fixing nip N when the heating body 701 reaches a predetermined temperature. The material P is introduced. The recording material P is sandwiched between the pressure roller 704 and the film 703 and conveyed through the fixing nip N, whereby the heat of the magnetic metal member 701b is applied to the recording material P via the film 703, and the unfixed toner image T Is melt-fixed on the recording material P. At the exit of the fixing nip portion N, the recording material P that has passed is separated from the surface of the film 703 and conveyed to a paper discharge tray (not shown).
As described above, in the electromagnetic induction heating type fixing device, the magnetic metal member 701b as the induction heating means is disposed close to the toner image T of the recording material P through the film 703 by utilizing the generation of eddy current. Therefore, the heating efficiency is further improved as compared with the fixing device of the film heating type.

  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, the electromagnetic induction heating type fixing device needs a rubber elastic layer of a certain thickness on the surface of the film in order to sufficiently enclose the toner image and uniformly heat and melt it. 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. Was.

  The toner used for electrostatic image development is generally colored particles in which a binder, a charge control agent, and other additives are contained in a binder resin. A conventionally used toner production method is a pulverization method. In this method, a colorant, a charge control agent, an anti-offset agent, etc. are melt-mixed in a thermoplastic resin and uniformly dispersed. The toner is manufactured by pulverizing and classifying the obtained composition. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. Therefore, when the above composition is actually 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 particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield. Further, 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. In addition, the pulverization method has a limit on the particle size 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 by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method. However, the toner particles obtained by the suspension polymerization method are spherical and have a drawback of poor cleaning properties. Development / transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not pose a problem. However, images with a high image area ratio, such as photographic images, and untransferred images formed due to poor paper feed, etc. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. Further, since the toner has a spherical shape, the contact area between the toners decreases and the adhesion force decreases, so that the margin for fixing tends to decrease, and the stability at the lower limit of fixing cannot be obtained.

  For this reason, a method is disclosed in which resin fine particles obtained by an emulsion polymerization method are associated to obtain amorphous toner particles (see, for example, Patent Document 4). However, the toner particles obtained by the emulsion polymerization method have a large amount of surfactant remaining not only on the surface but also inside the particles even after the water washing step, impairing the environmental stability of toner charging, and the charge amount distribution. The background of the obtained image becomes poor. 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, the release property of the toner particles with respect to the heating member (hereinafter referred to as “offset resistance”) is required. Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface.
However, the method of obtaining irregular toner particles by associating resin fine particles obtained by the emulsion polymerization method causes the following problems. That is, when releasing agent fine particles are associated with each other in order to improve offset resistance, the releasing agent fine particles are taken into the toner particles, and as a result, offset resistance can be sufficiently improved. I can't. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system that requires low-temperature fixing, fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface, and a fixing temperature range cannot be secured.
In addition, the suspension polymerization method, emulsion polymerization method, and dissolution suspension method generally use a styrene / acrylic resin, and the polyester resin has difficulty in particle formation, and the particle size, particle size distribution, Shape control was difficult. In addition, there was a limit to fixability when aiming at lower temperature fixing.

On the other hand, it is also known to use a polyester modified with a urea bond for the purpose of heat-resistant storage and low-temperature fixing (see, for example, Patent Document 5). Therefore, it was not sufficient in terms of environmental charge stability under severe conditions.
Also, in the field of electrophotography, high image quality has been studied from various angles, and among them, the recognition that reducing the diameter of toner is extremely effective is increasing. However, as the diameter of the toner is reduced, the transferability and the fixing property are lowered, and a tendency to become a poor image is observed.

JP-A-63-313182 Japanese Patent Laid-Open No. 1-263679 JP-A-8-22206 Japanese Patent No. 2537503 Japanese Patent Laid-Open No. 11-133667

  In view of the above problems, it is an object of the present invention to provide an image forming method using a fixing device using an electromagnetic induction heating method that is excellent in offset resistance and excellent in low-temperature fixability.

  In order to solve the above-described problems, the present inventors have found that it is effective to use a specific toner by using a specific electromagnetic induction heating type fixing device. That is, the present invention is characterized by the following.

1. The present invention includes a step of forming an electrostatic latent image on an image carrier, a step of developing the electrostatic latent image with a developer containing toner for developing an electrostatic image, and a toner image. In the image forming method including the step of transferring onto the transfer body and the step of fixing the toner image on the transfer body, the fixing step is made of a magnetic metal and heated by electromagnetic induction, A fixing roller arranged in parallel with the heating roller, an endless belt-like toner heating medium that is stretched between the heating roller and the fixing roller, heated by the heating roller, and rotated by these rollers; and the toner A fixing device having a pressure roller that is pressed against the fixing roller via a heating medium and rotates in the forward direction with respect to the toner heating medium to form a fixing nip portion; The toner for developing an electrostatic charge image used in the development step has a resin fine particle dispersed in an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant. For electrostatic charge image development that is dispersed in an aqueous medium phase to cause elongation reaction and / or cross-linking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, thereby forming particles from the resulting dispersion. This is a toner, and an image forming method produced by adding a tertiary amine compound to the organic solvent phase.

2. The toner for developing an electrostatic charge image is characterized in that the tertiary amine compound added in the production process is represented by the following structural formula (I).

3. The electrostatic image developing toner is produced by dissolving a non-reactive polyester resin together with a functional group-containing polyester resin in the organic solvent phase, and the non-reactive with the functional group-containing polyester resin. The weight ratio to the conductive polyester resin is 5/95 to 75/25.
4). The electrostatic image developing toner has a volume average particle diameter of 3 to 8 μm.
5). The toner for developing an electrostatic charge image has a ratio (Dv / Dn) of a volume average particle diameter (Dv) to a number average particle diameter (Dn) of 1.00 to 1.25.
6). The toner for developing an electrostatic charge image has an average circularity of 0.900 to 0.980.

7). The present invention also provides an image carrier on which an electrostatic latent image is formed, a charging means for uniformly charging the surface of the image carrier, and exposing the charged image carrier surface based on image data to An exposure unit for writing a latent image; a developing unit for developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner for developing an electrostatic image; and a toner image on the surface of the image carrier. An image forming apparatus comprising: a transfer unit that transfers a toner image to a transfer member; and a fixing unit that fixes a toner image on the transfer member. The fixing unit is made of a magnetic metal and is heated by electromagnetic induction. A heating roller, a fixing roller arranged in parallel with the heating roller, an endless belt-like toner heating stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by these rollers Medium 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 fixing nip portion; The toner for developing an electrostatic image used in 1 is an aqueous medium phase in which resin fine particles are dispersed in an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant. A toner for developing an electrostatic image, which is dispersed in the toner to cause elongation reaction and / or crosslinking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, thereby forming particles from the resulting dispersion. An image forming apparatus manufactured by adding a tertiary amine compound to the organic solvent phase.
8). One of the image forming methods described above is further applied to the image forming apparatus.

9. In the image forming apparatus, the latent image carrier is a photoconductor having a photoconductive layer made of amorphous silicon.
10. In the image forming apparatus, the charging unit performs charging by bringing a charging member into contact with the latent image carrier and applying a voltage to the charging member.

11. The present invention also forms an image carrier on which an electrostatic latent image is formed and a toner image by developing the electrostatic latent image formed on the surface of the image carrier with a developer containing an electrostatic image developing toner. A process cartridge that is integrally supported including at least a developing unit and is detachably formed on the main body of the image forming apparatus, wherein the toner for developing an electrostatic image used in the developing unit is at least a functional group-containing polyester system An organic solvent phase in which a resin is dissolved, an active hydrogen-containing compound, and a colorant are dispersed in an aqueous medium phase in which resin fine particles are dispersed to obtain a functional group-containing polyester resin and an active hydrogen-containing compound. An electrostatic charge image developing toner that causes particles to form an elongation reaction and / or a cross-linking reaction of the resulting dispersion, and a tertiary amine compound is added to the organic solvent phase. A heating roller manufactured and 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, and heated by the heating roller And 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 fixing nip portion The process cartridge is used in an image forming apparatus including a fixing device having a pressure roller for forming the toner.

12 Furthermore, the present invention provides an image bearing member on which an electrostatic latent image is formed, a charging means for uniformly charging the surface of the image bearing member, and exposing the charged image bearing member surface based on image data to electrostatically charge the image bearing member. An exposure unit for writing a latent image; a developing unit for developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner for developing an electrostatic image; and a toner image on the surface of the image carrier. And a fixing unit for fixing the toner image on the transfer medium, the fixing unit being made of a magnetic metal and heated by electromagnetic induction, and the heating A fixing roller disposed in parallel with the roller, an endless belt-like toner heating medium that is stretched between the heating roller and the fixing roller, heated by the heating roller, and rotated by these rollers, and the toner heating Medium And is used in developing means of an image forming apparatus comprising a fixing roller having a pressure roller that rotates in the forward direction with respect to the toner heating medium to form a fixing nip portion. An electrostatic charge image developing toner, wherein the electrostatic charge image developing toner comprises an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, a colorant, and resin fine particles. The dispersion is dispersed in an aqueous medium phase to cause an elongation reaction and / or a crosslinking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, thereby forming particles from the resulting dispersion. A toner for developing a charge image, which is a toner for developing an electrostatic image produced by adding a tertiary amine compound to the organic solvent phase.

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 method fixing device and using a specific toner.
Even if a process cartridge using electrostatic charge image developing toner is mounted, the same excellent effect can be obtained.
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 being hardly deteriorated by repeated use, and It is possible to provide an image forming apparatus using a fixing device that is efficient and can shorten the rise time.

  The best mode for carrying out the present invention will be described below with reference to the drawings. The following description is an example of the best mode of the present invention, and it is easy for those skilled in the art to make other embodiments within the scope of the claims by making changes and modifications within the scope of the claims. However, this does not limit the scope of the claims.

FIG. 1 is a schematic configuration diagram of an image forming apparatus for carrying out an image forming method according to the present invention. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon.
The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having various units for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided. Above the tandem image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoconductor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.
A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22. The configuration of the fixing device 25 will be described in detail later.
The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .

The operation of the image forming apparatus is as follows.
First, a document is set on the document table 30 of the automatic document feeder 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Hold it down.
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 other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and reflects by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer belt 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer belt 10, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, 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.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer belt 10, the sheet is fed between the intermediate transfer belt 10 and the secondary transfer device 22, and is transferred by the secondary transfer device 22. A color image is recorded on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer belt 10 after the image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for the image formation again.

In the image forming apparatus, the photoconductor 40 can be a photoconductor having a photoconductive layer made of amorphous silicon (a-Si) (hereinafter referred to as “a-Si-based photoconductor”). The a-Si photoconductor exhibits high sensitivity to long-wavelength light such as a semiconductor laser, has high surface hardness, and is excellent in durability so that deterioration due to repeated use is hardly observed.
The a-Si photosensitive member is heated at 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. The photoconductive layer made of a-Si is formed by a film forming method. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferably used.

  FIG. 2 is a schematic configuration diagram for explaining a layer configuration of the a-Si photosensitive member. A photoreceptor 500 shown in FIG. 2A has an amorphous material (hereinafter referred to as “a-Si (H, X), which contains a silicon atom as a base and further contains hydrogen atoms and / or halogen atoms” on a support 501. The photoconductive layer 502 having photoconductivity is provided. 2B includes a photoconductive layer 502 made of a-Si (H, X) and having photoconductivity on a support 501 and an a-Si based surface layer 503. Has been. A photoconductor 500 shown in FIG. 2C has a photoconductive layer 502 made of a-Si (H, X) and having photoconductivity on a support 501, an a-Si based surface layer 503, a -Si based charge injection blocking layer 504. In the photoconductor 500 shown in FIG. 2D, a photoconductive layer 502 is provided on a support 501. The photoconductive layer 502 includes a charge generation layer 505 and a charge transport layer 506 made of a-Si (H, X), and an a-Si based surface layer 503 is provided thereon.

The support for the photoreceptor 500 may be conductive or electrically insulating. Examples of the conductive support include metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Also, at least the surface on the side where the photosensitive layer is to be formed of an electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide or other synthetic resin film or sheet, glass or ceramic. A conductively treated support can also be used.
The shape of the support can be a cylindrical or plate-like or endless belt with a smooth or uneven surface, and the thickness thereof is appropriately determined so that a desired photoreceptor for an image forming apparatus can be formed. When flexibility as a photoreceptor for an image forming apparatus is required, it can be made as thin as possible within a range where the function as a support can be sufficiently exhibited. However, the support is usually 10 μm or more from the viewpoints of manufacturing and handling, such as mechanical strength.

In the a-Si type photosensitive member that can be used in the present invention, a charge injection functioning to prevent charge injection from the conductive support side between the conductive support and the photoconductive layer, if necessary. It is more effective to provide a blocking layer (FIG. 2 (c)). That is, the charge injection blocking layer has a function of blocking charge injection from the support side to the photoconductive layer side when the photosensitive layer is subjected to a charging process with a certain polarity on its free surface. When charged, it has a so-called polarity dependency that does not exhibit such a function. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.
The layer thickness of the charge injection blocking layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 μm, and most preferably from 0.5 to 0.5 in view of obtaining desired electrophotographic characteristics and economic effects. It is desirable to be 3 μm.

  The photoconductive layer is formed on the undercoat layer as necessary, and the layer thickness of the photoconductive layer 502 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, preferably It is desirable that the thickness is 1 to 100 μm, more preferably 20 to 50 μm, and most preferably 23 to 45 μm.

The charge transport layer is a layer mainly having a function of transporting charges when the photoconductive layer is functionally separated. The charge transport layer includes at least silicon atoms, carbon atoms, and fluorine atoms as constituent elements, and is formed of a-SiC (H, F, O) including hydrogen atoms and oxygen atoms as required. It has conductive properties, particularly charge retention properties, charge generation properties, and charge transport properties. In the present invention, it is particularly preferable to contain an oxygen atom.
The layer thickness of the charge transport layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. The charge transport layer is preferably 5 to 50 μm, more preferably 10 to 40 μm, Optimally, the thickness is desirably 20 to 30 μm.

The charge generation layer is a layer mainly having a function of generating charges when the photoconductive layer is functionally separated. This charge generation layer is composed of a-Si (H) containing at least silicon atoms as components and substantially not containing carbon atoms and, if necessary, containing hydrogen atoms, and has desired photoconductive properties, particularly charge generation. Characteristics and charge transport properties.
The layer thickness of the charge generation layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, etc., preferably 0.5 to 15 μm, more preferably 1 to 10 μm, optimally 1 ˜5 μm.

The a-Si type photoreceptor that can be used in the present invention can be further provided with a surface layer on the photoconductive layer formed on the support as described above, if necessary. It is preferable to form a -Si based surface layer. This surface layer has a free surface, and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.
The thickness of the surface layer is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to wear or the like during use of the photoreceptor, and if it exceeds 3 μm, electrophotographic characteristics such as an increase in residual potential are observed.

In the image forming apparatus, the charging unit may be a contact charging type charging device in which a charging member is brought into contact with the photoreceptor 40 and charging is performed by applying a voltage to the charging member. Ozone generation can be reduced by providing a contact-type charging device.
FIG. 3 is a diagram illustrating a schematic configuration of a contact-type charging device. The photosensitive member 40 as a member to be charged is rotationally driven in the direction of the arrow at a predetermined speed (process speed). The charging roller 60 as a charging member brought into contact with the photoreceptor 40 is basically composed of a core metal 60a and a conductive rubber layer 60b formed on the roller concentrically on the outer periphery of the core metal 60a, and both ends of the core metal 60a. Is rotatably held by a bearing member (not shown) and the like, and is pressed against the photosensitive member 40 by a pressing means (not shown) with a predetermined pressure. It rotates following the rotation drive. Here, the charging roller 60 is formed to have a diameter of 16 mm by coating a medium resistance rubber layer of about 10 ⁵ Ω · cm on a core metal having a diameter of 9 mm.
The metal core 60a of the charging roller 60 and the power source 60c are electrically connected, and a predetermined bias is applied to the charging roller 60 by the power source 60c. As a result, the peripheral surface of the photoconductor 40 is uniformly charged to a predetermined polarity and potential.

  The shape of the charging member used in the contact-type charging device is not limited to the charging roller, and may take any form such as a magnetic brush or a fur brush, and can be selected according to the specifications and form of the image forming apparatus. is there. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. In addition, when using a fur brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal, and metal oxide is used, and this is wound around a metal or other conductive core metal. By charging or pasting, it becomes a charging member.

The fixing device 25 will be described in detail.
FIG. 4 is an enlarged view showing the fixing device according to the present invention. The fixing device 25 is stretched between a heating roller 251 heated by electromagnetic induction of the induction heating unit 256, a fixing roller 252 disposed in parallel with the heating roller 251, and the heating roller 251 and the fixing roller 252. An endless belt-like heat-resistant belt (toner heating medium) 253 that is heated by 251 and rotated in the direction of arrow A by at least one of the rollers rotating, and is pressed against the fixing roller 252 via the belt 253 and the belt The pressure roller 254 rotates in the forward direction with respect to H.253.

The heating roller 251 is made of, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals, and has an outer diameter of 20 mm and a wall thickness of, for example, 0.1 mm. It has a fast configuration.
The fixing roller 252 includes a metal core 252a made of, for example, stainless steel, and an elastic member 252b covered with a core metal 252a in a solid or foamed heat-resistant silicone rubber. In order to form a contact portion having a predetermined width between the pressure roller 254 and the fixing roller 252 by the pressing force from the pressure roller 254, the outer diameter is set to about 40 mm, which is larger than the heating roller 251. The elastic member 252b has a thickness of about 3 to 6 mm and a hardness of about 40 to 60 ° (Asker hardness).
With this configuration, since the heat capacity of the heating roller 251 is smaller than the heat capacity of the fixing roller 252, the heating roller 251 is rapidly heated and the warm-up time is shortened.

The belt 253 stretched between the heating roller 251 and the fixing roller 252 is heated at a contact portion W1 with the heating roller 251 heated by the induction heating unit 256. Then, the inner surface of the belt 253 is continuously heated by the rotation of the heating roller 251 and the fixing roller 252, and as a result, the entire belt is heated.
The belt 253 is provided with a release layer on a heat generating layer made of metal. The thickness of the release layer is preferably about 50 μm to 500 μm, particularly about 200 μm. By doing so, the toner image T formed on the recording material P is sufficiently wrapped by the surface layer portion of the belt 253, so that the toner image T can be uniformly heated and melted.
When the thickness of the release layer is less than 50 μm, the heat capacity of the belt 253 becomes small, and the belt surface temperature rapidly decreases in the toner fixing process, so that sufficient fixing performance cannot be ensured. Further, when the thickness of the release layer is larger than 500 μm, the heat capacity of the belt 253 is increased and the time required for warm-up is increased. In addition, in the toner fixing process, the belt surface temperature is difficult to decrease, the agglomeration effect of the melted toner at the fixing portion outlet cannot be obtained, the belt releasability is reduced, and the toner adheres to the belt. Hot offset occurs. As a base material for the belt 253, a heat-resistant resin layer such as a fluorine resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a PEEK resin, a PES resin, or a PPS resin is used instead of the heat generating layer made of the metal. It may be used.

The pressure roller 254 includes a cored bar 254a made of a metal cylindrical member having a high thermal conductivity, such as copper or aluminum, and an elastic member having high heat resistance and toner releasability provided on the surface of the cored bar 254a. 254b. In addition to the above metal, SUS may be used for the core metal 254a.
The pressure roller 254 presses the fixing roller 252 via the belt 253 to form the fixing nip portion N. In this embodiment, the pressure roller 254 is harder than the fixing roller 252. As a result, the pressure roller 254 bites into the fixing roller 252 (and the belt 253), and the recording material P follows the circumferential shape of the surface of the pressure roller 254 due to this biting, so that the recording material P moves away from the surface of the belt 253. Has the effect of facilitating. The outer diameter of the pressure roller 254 is about 40 mm, which is the same as that of the fixing roller 252, but the wall pressure is about 1 to 3 mm, thinner than the fixing roller 252, and the hardness is about 50 to 70 ° (Asker hardness) as described above. The fixing roller 252 is harder.

As shown in FIG. 4 and FIGS. 5A and 5B, the induction heating means 256 that heats the heating roller 251 by electromagnetic induction includes an exciting coil 257 that is a magnetic field generating means, and the exciting coil 257 is wound. The coil guide plate 258 is provided. The coil guide plate 258 has a semi-cylindrical shape arranged close to the outer peripheral surface of the heating roller 251. As shown in FIG. 5B, the excitation coil 257 is composed of one long excitation coil wire. It is alternately wound along the axial direction of the heating roller 251 along the line 268.
The exciting coil 257 is connected to a driving power source (not shown) whose frequency is variable.

  Outside the excitation coil 257, a semi-cylindrical excitation coil core 259 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 260 and is disposed close to the excitation coil 257. In the present embodiment, the exciting coil core 259 having a relative permeability of 2500 is used.

The excitation coil 257 is supplied with a high frequency alternating current of 10 kHz to 1 MHz, preferably a high frequency alternating current of 20 kHz to 800 kHz from the drive power source, thereby generating an alternating magnetic field. The alternating magnetic field acts on the heat generating layer of the heating roller 251 and the belt 253 in the contact area W1 between the heating roller 251 and the heat-resistant belt 253 and the vicinity thereof, and in the direction in which the change of the alternating magnetic field is prevented. Eddy current flows.
This eddy current generates Joule heat corresponding to the resistance of the heat generating layer of the heating roller 251 and the belt 253, and the belt having the heating roller 251 and the heat generating layer mainly in the contact area between the heating roller 251 and the belt 253 and in the vicinity thereof. 253 is heated by electromagnetic induction.
The belt 253 heated in this way is in the vicinity of the inlet side of the fixing nip portion N, and a temperature detecting means 255 comprising a thermosensitive element such as a thermistor disposed in contact with the inner surface side of the belt 253. Thus, the belt inner surface temperature is detected.

  By the fixing device 25 described above, the heating roller 251 and the belt 253 can be heated instantaneously, and the warm-up time of the device can be shortened. Further, the temperature detecting means 255 provided in the vicinity of the entrance of the fixing nip portion N detects the temperature change of the fixing nip portion N in a timely manner, and when a temperature drop is detected, the heating roller 251 instantaneously moves to the belt 253. Since the heating is performed, the toner image T on the recording material P can be fixed satisfactorily without causing a cold offset. Further, the developer used in the developing device 4 is excellent in low-temperature fixability, which will be described later, and includes an electrostatic charge image developing toner having a sufficient fixing temperature range, so that an image with better fixability can be output. Can do.

Next, the electrostatic image developing toner used in the developing device 4 will be described in detail.
The electrostatic image developing toner used in the image forming method of the present invention has an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, a colorant, and resin fine particles dispersed therein. It is obtained by dispersing particles in an aqueous medium phase, causing an elongation reaction and / or a crosslinking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, and forming particles from the resulting dispersion. .

[Organic solvent phase]
<Organic solvent>
In the present invention, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving and / or dispersing the toner composition. As a preferable thing, it is preferable from the point that removal is easy that the boiling point of a solvent is less than 150 degreeC. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone, Tetrahydrofuran or the like can be used alone or in combination of two or more. Of these, methyl acetate and ethyl acetate are preferred because they are particularly volatile to toner. The amount of the solvent used relative to 100 parts of the toner solid component is usually 40 to 300 parts, preferably 60 to 140 parts, and more preferably 80 to 120 parts.

<Functional group-containing polyester resin>
In the present invention, a polyester prepolymer having an isocyanate group can be used as the modified polyester resin. Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol And alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  In order to prepare a polyester having an alcoholic hydroxyl group at the terminal by polycondensation reaction, the ratio of the polyol (1) to the polycarboxylic acid (2) is equivalent to the equivalent ratio [OH] / [hydroxyl group [OH] and carboxyl group [COOH]. COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) used for preparing the polyester prepolymer by reacting with the alcoholic hydroxyl group of the polyester include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl carbonate). Proate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); Xylylene diisocyanate); isocyanurates; the polyisocyanate blocked with a phenol derivative, oxime, caprolactam, etc .; and These two or more combination thereof.

  The use ratio of the polyisocyanate is usually 5/1 to 1/1, preferably 4/1 as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

<Combination of non-reactive low molecular weight polyester>
In the present invention, it is important not only to use the modified polyester (A) alone, but also to contain an unmodified polyester (C) that is not modified as a toner binder component together with the modified polyester (A). By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (C). (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, a urethane bond. It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The peak molecular weight measured by GPC (gel permeation chromatography) of the polyester (C) is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate.
The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. If the acid value is too high, it tends to be negatively charged, which is not preferable. Those exceeding this range are susceptible to environmental influences under high temperature and high humidity and low temperature and low humidity environments, and are liable to cause image deterioration.

[Active hydrogen-containing compounds]
As will be described later, the above-mentioned polyester prepolymer (A) having an isocyanate group is made to have a higher molecular weight by being subjected to elongation and / or crosslinking reaction with an active hydrogen compound.
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for the elongation and / or crosslinking reaction. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

[Tertiary amine compound]
In the present invention, a tertiary amine compound is used as an accelerator for elongation and / or crosslinking reaction. Any tertiary amine compound can be used and is not particularly limited. Examples of the tertiary amine compound include amines, amino alcohols, amino mercaptans, and amidines. Examples of amines include aromatic amines (such as triphenylamine and triallylamine), alicyclic amines (such as N-methylpiperidine); and aliphatic amines (such as triethylamine and trimethylamine). Examples of amino alcohols include triethanolamine and dihydroxyethylaniline. Examples of amino mercaptans include triethanethiolamine and trimethanethiolamine. Examples of amidine include DBU (1,8-diaza-bicyclo [5.4.0] undecene-7) and DBN (1,5-diaza-bicyclo [4.3.0] nonene-5). It is done. Among these tertiary amine compounds, the compound of the structural formula (I) is more preferable.

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.

<Features of toner binder>
In the present invention, as described above, the polyester prepolymer (A) is characterized by using, as a toner binder, a urea-modified polyester resin obtained by a reaction between an amine (B) and a non-reactive polyester or the like. Other components (including the resin used for the colorant master batch) are also used. In the present invention, the glass transition point (Tg) of the toner binder is usually 40 to 70 ° C., preferably 45 to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the stretched and / or cross-linked polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low as compared with known polyester-based toners.
As the storage elastic modulus of the toner, the temperature (TG ′) at which the measurement frequency is 20 Hz becomes 1000 Pa is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner, the temperature (Tη) at 100 Pa · s at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

[Aqueous medium phase]
<Aqueous medium>
In the present invention, the aqueous medium in which the resin fine particles described later are dispersed to form the aqueous medium phase may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones (acetone, methyl ethyl ketone, etc.). These can be used singly or in combination of two or more.

<Resin fine particles>
The resin fine particles in the toner of the present invention are added in the production process in order to control the toner shape (circularity, particle size distribution, etc.) described later. As will be described later, the fine particles are considered to be bonded to the surface portion when the organic solvent phase and the active hydrogen-containing compound (amines) are dispersed in an aqueous medium to form organic dispersed particles. Thus, it is considered that the toner base particles obtained are unevenly distributed mainly on the surface portion as in the case of the external additive described later. In the present invention, it is necessary and important that the amount of resin fine particles contained in the obtained toner particles after the external additive treatment is 0.5 to 5.0% by weight. When the content is less than 0.5% by weight, the storability of the toner is deteriorated, blocking occurs during storage and in the developing machine, and when the content exceeds 5.0% by weight, The resin fine particles inhibit the exudation of the wax, the effect of releasing the wax cannot be obtained, and the occurrence of offset is observed.
The content of the resin fine particles in the toner particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

  Further, it is important that the glass transition point (Tg) of the resin fine particles is 40 to 100 ° C. and the weight average molecular weight is 9000 to 200,000. If the Tg of the resin fine particles is less than 40 ° C. and / or the weight average molecular weight is less than 9,000, the storage stability of the toner deteriorates, and blocking occurs during storage and in the developing machine. Is 80 ° C. or higher and / or the weight average molecular weight is 200,000 or higher, the resin fine particles inhibit the adhesion to the recording material, and an increase in the minimum fixing temperature is observed.

The dispersion / blending amount of the resin fine particles in the aqueous medium may be set so as to satisfy the above-mentioned conditions relating to the content, but is usually in the range of about 0.5 to 10% by weight.
The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

[Other ingredients]
<Colorant>
As the colorant, all known dyes and pigments can be used. 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, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, parachlor ortho nitro Nirin Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Tolujing 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, Thio Indigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, Riazo Red, Chrome Vermillion, 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, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalo Cyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight as the content in the toner base of the present invention.

  The colorant used in the present invention can also be used as a master batch combined with a resin. Examples of the binder resin kneaded together with the production of the master batch or the master batch include, for example, the above-mentioned urea-modified polyester resin and non-reactive polyester resin, as well as the weight of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and their substitutes. Copolymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene- α-Chlormeta Methyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid Styrene copolymers such as copolymers, styrene-maleic acid ester copolymers; 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 or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Alternatively, they can be used in combination.

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method called an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used. The colorant or masterbatch can be dissolved or dispersed in the organic solvent phase, but is not limited thereto.

<Release agent>
A wax as a release agent may be included together with the toner binder and the colorant. Known waxes can be used, and examples thereof include polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

  The melting point of the wax is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax 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. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The amount of the wax used is usually 0 to 40% by weight, preferably 3 to 30% by weight as the content in the toner base. The wax can be dissolved or dispersed in the organic solvent phase, but is not limited thereto.

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copyable-PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts.

  The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, but is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.

  These charge control agents can be dissolved and dispersed after being melt-kneaded with the masterbatch and resin, or of course, it may be added when directly dissolving and dispersing in an organic solvent. It is preferable to make it.

[Preparation of toner particles]
The dry toner of the present invention can be produced by the following method, but is not limited thereto.
<Toner production method in aqueous medium>
The aqueous medium phase is used by adding resin fine particles in advance. The water used in the aqueous medium phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

<Dispersion and reaction of organic solvent phase>
As described above, the toner particles are obtained by dispersing the organic solvent phase containing the polyester prepolymer (A) in the aqueous medium phase together with the amines (B) and the tertiary amine, It is formed through a step of forming a urea-modified polyester by cross-linking reaction.
As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous medium phase, a composition of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent in an aqueous medium phase And a method of dispersing by shearing force. Polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), colorant masterbatch, release agent, charge control agent, non-reactive polyester May be mixed when the dispersion is formed in the aqueous medium phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture is added to the aqueous medium phase and dispersed. Is more preferable.
Further, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily need to be mixed when forming particles in the aqueous medium phase, and may be added after the particles are formed. Good. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easily dispersed.

  The usage-amount of the aqueous medium with respect to 100 parts of solid components contained in the organic solvent phase of a polyester prepolymer (A) is 50-2000 weight part normally, Preferably it is 100-1000 weight part. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  As a dispersant for emulsifying and dispersing the organic solvent phase containing the polyester prepolymer (A), an anionic surfactant such as alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, alkylamine salt, Amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and quaternary alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl -N, amphoteric surfactants such as N- dimethyl ammonium betaine.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. , DS-102 (manufactured by Taikin Kogyo Co., Ltd.), MegaFuck F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a perfluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, Benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.) ), Megafuck F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant that is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the above classification operation.

Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

[Application of external additives]
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and 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. It is done.

  On the other hand, examples of the cleaning property improver for removing the developer after transfer remaining on the photosensitive member or the primary transfer medium include fatty acid metal salts such as zinc stearate and calcium stearate, such as polymethyl methacrylate fine particles and polystyrene fine particles. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

[Toner shape, etc.]
<Circularity and circularity distribution>
It is important that the toner in the present invention has a specific shape and shape distribution. An toner having an average circularity of less than 0.90 and an irregular shape that is too far from a spherical shape exhibits satisfactory transferability and dust. A high-quality image with no image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. A toner having an average circularity of 0.980 to 0.900, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has high reproducibility with an appropriate density. It was proved effective for forming a fine image. More preferably, particles having an average circularity of 0.970 to 0.950 and a circularity of less than 0.94 are 15% or less. When the average circularity is 0.980 or more, in a system that employs blade cleaning or the like, a cleaning failure occurs on the photosensitive member or the transfer belt, causing stains on the image. For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not become a problem. The image-formed toner may be generated as a transfer residual toner on the photosensitive member, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. This value was measured as an average circularity by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). A specific measurement method will be described later.

<Volume average particle diameter, number average particle diameter>
The toner of the present invention preferably has a volume average particle diameter (Dv) of 3 to 8 μm, and more preferably 4 to 7 μm. The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.25 or less, preferably 1.10 to 1.20. Here, the volume average particle diameter (Dv) is defined as Dv = [Σ (nD ³ ) / Σn] ^1/3 (where n is the number of particles and D is the particle diameter). In the present invention, by setting the value of (Dv / Dn) within the above range, it is excellent in all of heat resistant storage stability, low temperature fixability and hot offset resistance, and particularly when used in a full-color copying machine or the like. Excellent two-component developer, even with long-term toner balance, fluctuations in toner particle diameter in the developer are reduced, and even with long-term agitation in the developing device, it is stable and stable. Developability is obtained. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner layer are made thin. The toner is not fused to a member such as a blade, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle size is smaller than the range of the present invention, in the case of a 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 one-component development is performed. When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.
On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large.

  The volume average particle diameter / number average particle diameter (Dv / Dn) is measured using a volume average particle diameter (Dv) measured with an aperture diameter of 100 μm using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics. It is automatically measured by the number average particle diameter (Dn).

[Carrier for two-component developer]
When the toner of the present invention is used as a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. Is preferable, and it is more preferable to set it as the range of 3-9 weight part. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene-acrylic copolymer resins, Halogenated olefin resins such as vinyl chloride, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene Resins, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl Fluoro terpolymers, and silicone resins terpolymers etc. of vinylidene fluoride and non-fluorinated monomer. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  For the developing device 4 of the image forming unit 18, a developer containing the toner for developing an electrostatic image is used. In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.

  Further, the developing device 4 can be a process cartridge that is integrally supported together with the photoreceptor 40 and is detachably formed on the main body of the image forming apparatus. In addition, the process cartridge may include a charging unit and a cleaning unit. Thereby, exchangeability and convenience can be achieved, and maintenance of the image forming apparatus can be facilitated.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “parts” means parts by weight, and “%” means percent by weight.

(Example 1)
<Synthesis of resin 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, When 110 parts of butyl acrylate, 12 parts of butyl thioglycolate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. 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 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 size of the [fine particle dispersion 1] measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 120 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin component was 42 ° C., and the weight average molecular weight was 30,000.

<Preparation of aqueous medium phase>
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of a 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 to give a milky white liquid. 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 inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours at 10-15 mmHg reduced pressure, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a 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, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was 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 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

<Synthesis of polyester prepolymer>
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. ] Was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine>
In a reaction vessel equipped with a stirrer 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 [ketimine compound 1] was 418.

<Synthesis of master batch>
1200 parts of water, 40 parts of carbon black (Regal 400R, manufactured by Cabot Corp.), 60 parts of polyester resin (RS801, manufactured by Sanyo Chemical Co., Ltd.), 30 parts of water are further added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) 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 oil phase>
In a container equipped with a stir bar and a thermometer, 400 parts of [Low molecular weight polyester 1], 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. in 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 are 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 are 80% by volume. 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] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Emulsification>
[Pigment / Wax Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 8.5 parts, and tertiary amine compound represented by Structural Formula (I) 1.0 part The mixture was mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), then 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 [emulsification Slurry 1] was obtained.
That is, it is dispersed in an aqueous medium containing resin fine particles, and elongation and / or crosslinking reaction is performed.

<Desolvent>
[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].

<Washing 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 (10 minutes at 12,000 rpm), 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): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to obtain a cake. . 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 [Toner Base Particle 1] obtained above, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide as external additives were mixed with a Henschel mixer, and [Toner 1 ] Was obtained.

(Example 2)
In [Emulsification] of Example 1, [Toner 2] was obtained in the same manner as in Example 1 except that the tertiary amine compound represented by the structural formula (I) was changed to 0.6 part.

(Example 3)
[Toner 3] was obtained in the same manner as in Example 1 except that in Example 1 <Emulsification>, the tertiary amine compound represented by the structural formula (I) was changed to 0.3 part.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that triethanolamine was changed to 0.9 part as the tertiary amine compound in <Emulsification> in Example 1.

(Comparative Example 1)
[Toner 5] was obtained in the same manner as in Example 1 except that the tertiary amine compound was changed to 0 part in <Emulsification> in Example 1.

Table 1 shows the characteristics of [Toner 1] to [Toner 5].

  To the toner 5% by weight of [Toner 1] to [Toner 5], 95% by weight of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 μm was mixed to prepare a two-component developer. Using these developers, continuous evaluation was performed using an evaluation machine capable of printing 45 sheets of A4 size paper per minute (modified based on Ricoh's Ipsio color 8100) and evaluated as follows. The method was evaluated.

<Evaluation method>
(Evaluation item)
(1) Measurement of Volume Average Particle Size and (Dv / Dn) The particle size of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument. (Dv / Dn) was automatically calculated from the above values.
(2) Average circularity The average circularity can be measured by a flow particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measurement method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(3) Charge amount 6 g of developer is weighed, charged into a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration is adjusted to 4.5 to 5.5 wt%.
(4) Cleanability Using an evaluator, the transfer residual toner on the photoconductor that has passed the cleaning process after outputting 100 sheets is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and it is transferred to a Macbeth reflection densitometer RD514. Measured with a mold, “◎” indicates that the difference from the blank is less than 0.005, “◯” indicates 0.005-0.010, “Δ” indicates 0.011-0.02, 0 Those exceeding .02 were evaluated as “x”.
(5) Image Density Using an evaluator, after running 150,000 sheets of an image chart with a 50% image area in a single color mode, the 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. When this value is less than 1.2, “x”, when it is 1.2 or more and less than 1.4, “△”, when it is 1.4 or more and less than 1.8, “◯”, 1.8 or more and 2 If less than 2, “◎” was assigned.

(6) Image granularity and sharpness Using an evaluator, a photographic image was output in a single color, and the degree of granularity and sharpness was visually evaluated. In order from the best, “◎” is equivalent to offset printing, “○” is slightly worse than offset printing, “△” is much worse than offset printing, “×” is about the same as conventional electrophotographic images (very much Bad).
(7) Background stain After running 30,000 image charts with a 50% image area in monochrome mode using an evaluation machine, the blank image is stopped during development, and the developer on the photoreceptor 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 stain, and the better ones were ranked in the order of “◎”, “◯”, “Δ”, “×”.
(8) White spots inside character images Using an evaluator, 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 in four colors. The toner untransferred frequency at which the inside of the line image of the character portion is lost is compared with the step sample. Rank 1 is the lowest and rank 5 is the highest. In the case of rank 1 or 2, “X” was assigned, “△” was assigned in rank 3, “◯” was given in rank 4, and “◎” was given in rank 5.

(9) Toner fluidity A powder tester (PT-N type, manufactured by Hosokawa Micron Co., Ltd.) is loaded with meshes of 75 μm, 45 μm, and 22 μm openings in order from the top, and 2 g of the toner base is put on the uppermost 75 μm mesh. Then, a vibration of 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.
Aggregation degree (%) = (5 × (remaining toner amount (g) on 75 μm mesh))
+ 3 × (residual toner amount on 45 μm mesh (g))
+ (Residual toner amount on 22 μm mesh (g))) × 10
When the degree of aggregation was 8% or less, “◎”, when it was 8-16%, “◯”, when it was 16-25%, “Δ”, when it was 25% or more, “×”.
(10) Fixability (fixing lower limit temperature)
Using the fixing device illustrated in FIG. 4 (apparatus A) or FIG. 6 (apparatus B), a solid image and a thick paper transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>) are printed as solid images. 1. Adjustment is made so that 0 ± 0.05 mg / cm ² of toner is developed, and the temperature of the fixing belt is adjusted to be variable. Was measured. The lower limit fixing temperature was defined 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. The fixing lower limit temperature is “◎” when the temperature is 135 ° C. or less, “◯” when the temperature is 135 to 145 ° C., “Δ” when the temperature is 145 to 155 ° C., and “X” when the temperature is 155 ° C. or higher.
(Hot offset generation temperature)
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. The hot offset occurrence temperature was “◎” when it was 190 ° C. or higher, “◯” when it was 190 to 180 ° C., “Δ” when it was 180 to 170 ° C., and “X” when it was 170 ° C. or lower.

  The image evaluation results are shown in Table 2, and the fixing characteristic evaluation results are shown in Table 3.

  As can be seen with reference to Tables 2 and 3, in Examples 1 to 4 in which the image forming method of the present invention was performed, the toner chargeability was stably obtained, and sufficient image density and good image granularity were obtained. The sharpness was obtained and the fixing property was excellent.

1 is a schematic configuration diagram of an image forming apparatus for carrying out an image forming method according to the present invention. It is a typical block diagram for demonstrating the layer structure of an a-Si type photoreceptor. It is a figure which shows schematic structure of the charging device of a contact system. FIG. 2 is an enlarged view showing a fixing device according to the present invention. It is a figure for demonstrating the structure of an induction heating means. It is a schematic diagram which shows the fixing device by the conventional electromagnetic induction heating system.

Explanation of symbols

4 Developing device 10 Intermediate transfer belt (intermediate transfer member)
18 Image forming means 21 Exposure device 25 Fixing device 251 Heating roller 252 Fixing roller 253 Belt (toner heating member)
254 Pressure roller 40 Photosensitive member (latent image carrier)
22 Secondary transfer device 62 Primary transfer means 100 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (17)

A step of forming an electrostatic latent image on the image carrier, a step of developing the electrostatic latent image with a developer containing a toner for developing an electrostatic image, and forming a toner image; In an image forming method including a step of transferring, and a step of fixing a toner image on a transfer target,
The fixing step is made of a magnetic metal and is stretched between a heating roller heated by electromagnetic induction, a fixing roller arranged in parallel to the heating roller, the heating roller and the fixing roller, and the heating roller An endless belt-shaped toner heating medium heated by the roller and 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 for fixing. A fixing device having a pressure roller for forming a nip portion is used,
The toner for developing an electrostatic charge image used in the developing step has resin fine particles dispersed in an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant. For electrostatic charge image development that is dispersed in an aqueous medium phase to cause elongation reaction and / or cross-linking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, thereby forming particles from the resulting dispersion. An image forming method, which is a toner and is produced by adding a tertiary amine compound to the organic solvent phase. 2. The image forming method according to claim 1, wherein the tertiary amine compound added to the production process of the electrostatic image developing toner is represented by the following structural formula (I):

  The toner for developing an electrostatic image is produced by dissolving a non-reactive polyester resin together with a functional group-containing polyester resin in the organic solvent phase, and the non-reactive with the functional group-containing polyester resin. The image forming method according to claim 1, wherein the weight ratio to the conductive polyester resin is 5/95 to 75/25.   The image forming method according to claim 1, wherein the electrostatic image developing toner has a volume average particle diameter of 3 to 8 μm.   The toner for developing an electrostatic charge image has a ratio (Dv / Dn) of a volume average particle diameter (Dv) to a number average particle diameter (Dn) of 1.00 to 1.25. 5. The image forming method according to any one of 4 to 4.   The image forming method according to claim 1, wherein the toner for developing an electrostatic charge image has an average circularity of 0.900 to 0.980. An image carrier on which an electrostatic latent image is formed, a charging unit that uniformly charges the surface of the image carrier, and an exposure unit that exposes the charged image carrier surface based on image data and writes the electrostatic latent image And developing means for developing the electrostatic latent image formed on the surface of the image carrier with a developer containing an electrostatic charge image developing toner to form a toner image, and transferring the toner image on the surface of the image carrier to the transfer target An image forming apparatus comprising: a transfer unit that fixes the toner image on the transfer target;
The fixing unit is made of a magnetic metal, and is stretched between a heating roller heated by electromagnetic induction, a fixing roller arranged in parallel to the heating roller, the heating roller and the fixing roller, and the heating roller An endless belt-shaped toner heating medium heated by the roller and 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 for fixing. A fixing device having a pressure roller that forms a nip portion;
In the toner for developing an electrostatic charge image used in the developing means, resin fine particles are dispersed in an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant. For electrostatic charge image development that is dispersed in an aqueous medium phase to cause elongation reaction and / or cross-linking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, thereby forming particles from the resulting dispersion. An image forming apparatus which is a toner and is produced by adding a tertiary amine compound to the organic solvent phase.   7. The image forming apparatus according to claim 2, wherein the image forming method according to claim 2 is further applied to the image forming apparatus.   The image forming apparatus according to claim 7, wherein the latent image carrier is a photoconductor having a photoconductive layer made of amorphous silicon.   The image forming apparatus according to claim 7, wherein the charging unit performs charging by bringing a charging member into contact with the latent image carrier and applying a voltage to the charging member. Image forming apparatus. At least an image carrier on which an electrostatic latent image is formed, and developing means for developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner for developing an electrostatic image to form a toner image. A process cartridge that is integrally supported by the image forming apparatus and detachably formed on the image forming apparatus main body,
In the toner for developing an electrostatic charge image used in the developing means, resin fine particles are dispersed in an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant. For electrostatic charge image development that is dispersed in an aqueous medium phase to cause elongation reaction and / or cross-linking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, thereby forming particles from the resulting dispersion. A toner, which is produced by adding a tertiary amine compound to the organic solvent phase;
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, and heated by the heating roller An endless belt-like toner heating medium rotated by these rollers and the fixing roller via the toner heating medium are pressed against the fixing roller and rotated in the forward direction with respect to the toner heating medium to form a fixing nip portion. A process cartridge for use in an image forming apparatus including a fixing device having a pressure roller. An image carrier on which an electrostatic latent image is formed, a charging unit that uniformly charges the surface of the image carrier, and an exposure unit that exposes the charged image carrier surface based on image data and writes the electrostatic latent image And developing means for developing the electrostatic latent image formed on the surface of the image carrier with a developer containing an electrostatic charge image developing toner to form a toner image, and transferring the toner image on the surface of the image carrier to the transfer target Transfer means, and fixing means for fixing the toner image on the transfer object,
The fixing means is made 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 An endless belt-shaped toner heating medium heated by the roller and 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 for fixing. An electrostatic charge image developing toner used for developing means of an image forming apparatus comprising a fixing device having a pressure roller that forms a nip portion,
The electrostatic charge image developing toner has an organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant 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 cross-linking reaction between the functional group-containing polyester resin and the active hydrogen-containing compound, and forms particles from the resulting dispersion. A toner for developing an electrostatic image, wherein the toner is produced by adding a tertiary amine compound to an organic solvent phase. The electrostatic charge image developing toner according to claim 12, wherein the tertiary amine compound added to the production process of the electrostatic charge image developing toner is represented by the following structural formula (I): toner.

  The toner for developing an electrostatic image is produced by dissolving a non-reactive polyester resin together with a functional group-containing polyester resin in the organic solvent phase, and the non-reactive with the functional group-containing polyester resin. 14. The electrostatic charge image developing toner according to claim 12, wherein a weight ratio to the conductive polyester resin is 5/95 to 75/25.   The electrostatic image developing toner according to claim 12, wherein the electrostatic image developing toner has a volume average particle diameter of 3 to 8 μm.   The toner for developing an electrostatic charge image has a ratio (Dv / Dn) of a volume average particle diameter (Dv) to a number average particle diameter (Dn) of 1.00 to 1.25. The toner for developing an electrostatic charge image according to any one of Items 15 to 15.   The electrostatic image developing toner according to claim 12, wherein the electrostatic image developing toner has an average circularity of 0.900 to 0.980.

Images