JP4909233B2 - Image forming apparatus, image forming method, and process cartridge - Google Patents

Description

  The present invention relates to an electrophotographic image forming apparatus such as a copying machine, electrostatic printing, a printer, a facsimile, and electrostatic recording, an image forming method, and a process cartridge.

  2. Description of the Related Art Conventionally, various methods are known for electrophotographic image formation, and are generally referred to as an electrostatic latent image carrier (hereinafter referred to as “photoreceptor”, “electrophotographic photoreceptor”, “image carrier”). In some cases, the surface is charged, and the surface of the charged electrostatic latent image carrier is exposed to form an electrostatic latent image. Next, the electrostatic latent image is developed with toner to form a visible image on the electrostatic latent image carrier. The visible image is transferred directly or via an intermediate transfer member onto a recording medium, and the transferred image is fixed by heating, pressing, or a combination thereof, whereby an image is formed on the recording medium. Record is obtained. The toner remaining on the latent electrostatic image bearing member after the transfer of the visible image is cleaned by a known method such as a blade, a brush, or a roller.

  As a full-color image forming apparatus using such an electrophotographic system, two systems are generally known. One is called a single method (or a single drum method), and an electrostatic latent image carrier is mounted in the image forming apparatus, and four images corresponding to four colors of cyan, magenta, yellow, and black are provided. The developing means is mounted. In such a single method, visible images of four colors are formed on an electrostatic latent image carrier or a recording medium. In this single method, the charging unit, the exposure unit, the transfer unit, the cleaning unit, and the like arranged around the electrostatic latent image carrier can be shared, and are smaller and lower than the tandem method described later. It is possible to design at cost.

  On the other hand, the other is called a tandem system (or tandem drum system), in which a plurality of electrostatic latent image carriers are mounted in an image forming apparatus (see Patent Document 1). In general, one charging unit, one developing unit, one transfer unit, and one cleaning unit are arranged on one electrostatic latent image carrier to form one image forming element. (Generally four) are mounted. In this tandem method, a single color visible image is formed by one image forming element, and the visible image is sequentially transferred onto a recording medium to form a full color image. In this tandem method, visible images of each color can be created by parallel processing, so high-speed image formation is possible. In other words, the tandem method requires about one-fourth the time required for image formation compared to the single method, and can correspond to four times higher speed printing. Further, the durability of each means in the image forming element including the electrostatic latent image carrier can be substantially increased. In the single method, one electrostatic latent image carrier carries out the charging, exposure, development, and transfer processes four times to form one full-color image, whereas in the tandem method, the above-mentioned This is because the operation of each process needs to be performed only once with one electrostatic latent image carrier.

However, the tandem method has a demerit that the entire image forming apparatus becomes large and costs increase because a plurality of image forming elements are arranged.
In order to solve the above problems, the diameter of the electrostatic latent image carrier is reduced, each means installed around the electrostatic latent image carrier is reduced in size, and one image forming element is reduced in size. As a result, not only the image forming apparatus is reduced in size but also the effect of reducing the material cost is produced, and the overall cost reduction is somewhat advanced. However, with the downsizing and miniaturization of such an image forming apparatus, a new problem has arisen in that each means mounted on the image forming element has to be improved in performance and greatly improved in stability. Yes.

In recent years, market demands for energy saving and high speed have been increasing for image forming apparatuses such as printers, copiers, and facsimiles. In order to achieve such performance, it is important to improve the thermal efficiency of the fixing unit in the image forming apparatus.
In general, in an image forming apparatus, an unfixed toner image is formed on a recording sheet, printing paper, photosensitive paper, electrostatic recording by an indirect transfer method or a direct transfer method by an image forming process such as electrophotographic recording, electrostatic recording, or magnetic recording. It is formed on a recording medium such as paper. As fixing means for fixing such an unfixed toner image, for example, a contact heating method such as a heat roller method, a film heating method, and an electromagnetic induction heating method is widely adopted.

  The heat roller type fixing means has a heat source such as a halogen lamp inside, and has a basic configuration of a rotating roller pair of a fixing roller temperature-controlled at a predetermined temperature and a pressure roller pressed against the fixing roller. It is said. A recording medium is inserted into a contact portion (so-called nip portion) of the pair of rotating rollers, conveyed, and the unfixed toner image is melted and fixed by heat and pressure from the fixing roller and the pressure roller.

As the film heating type fixing means, for example, Patent Document 2 and Patent Document 3 are proposed. Such a film heating type fixing means is such that a recording medium 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 against the heating body. The heat of the heating body is supplied to the recording medium through the fixing film while being moved.
As the heating body, for example, a ceramic heater provided with a resistance layer on a ceramic substrate such as alumina or aluminum nitride having characteristics such as heat resistance, insulation, and good thermal conductivity is used. In such a fixing means, a thin film having a low heat capacity can be used as a fixing film, heat transfer efficiency is higher than that of the above heat roller type fixing means, a warm-up time can be shortened, quick start and energy saving can be achieved. Is possible.

As the electromagnetic induction heating type fixing means, for example, a technique has been proposed in which Joule heat is generated by an eddy current generated in a magnetic metal member by an AC magnetic field, and a heating body including the metal member is heated by electromagnetic induction (Patent). Reference 4).
In such electromagnetic induction heating type fixing means, a film having a rubber elastic layer on the surface is disposed between the heating body and the recording medium in order to sufficiently wrap the visible image and uniformly heat and melt it. . If this rubber elastic layer is formed of silicone rubber or the like, the thermal conductivity is low, resulting in poor thermal response, and the temperature difference between the inner surface of the film heated from the heating body and the outer surface of the film in contact with the toner becomes very large. End up. When the toner adhesion amount is large, the belt surface temperature is rapidly lowered, so that sufficient fixing performance cannot be ensured, and so-called cold offset may occur.

  In the fixing step, toner releasability with respect to the heating member (hereinafter also referred to as “offset resistance”) is required. Such offset resistance can be improved by the presence of a release agent on the toner surface, but reusing a non-predetermined toner only reduces the release agent present on the toner surface. In addition, since the particles designed as a core-shell structure of two or more layers are unevenly distributed on the surface of the toner, the minimum fixing temperature increases, and the low-temperature fixing property, that is, the energy-saving fixing property is not sufficient. In a low-temperature fixing system that requires low-temperature fixing, there is a problem that the fixing temperature range cannot be secured because of inhibition of fixing due to inorganic fine particles unevenly distributed on the toner surface.

  While a toner excellent in low-temperature fixability is required, a toner having characteristics contrary to low-temperature fixability such as offset resistance and storage stability (blocking resistance) is required. As a toner satisfying these requirements, a toner containing a polyester resin using a rosin as an acid component has been proposed (see Patent Documents 5 and 6).

On the other hand, in a so-called capsule toner comprising a core material and an outer shell, it is reported that the chargeability and developability are improved by treating the colorant in the core material with rosins such as natural rosin and abietic acid derivatives. (See Patent Document 7). In addition, it has been reported that a color toner containing a colorant surface-treated with abietic acid is excellent in transferability, cleaning properties, and charging stability, and a good full-color image can be obtained (see Patent Document 8).
In these techniques, a rosin derivative such as abietic acid having a heteroaromatic ring is added, and by adding these rosin derivatives, the dispersion of the colorant is good, and initially good. Transferability and charging stability are exhibited. However, these rosin derivatives are low molecular weight substances and are not chemically bonded to the binder resin. Toners containing a large amount of low molecular weight rosin derivatives at the time of abrasion resistance are used in two-component development systems. In addition, in the one-component development system, it tends to adhere to the charging roller, and it is difficult to maintain the transferability and charging property obtained in the initial stage. Further, with the recent increase in development speed, the toner is required to have a high charge rising property, but the toner does not have a sufficient charge rising property.

  Accordingly, there is a demand for prompt provision of an image forming apparatus, an image forming method, and a process cartridge that are excellent in chargeability, spent resistance, and transferability, and that can form a high-quality image with no deterioration in image quality over a long period of time. The current situation is.

JP-A-5-341617 JP-A-63-313182 Japanese Patent Laid-Open No. 1-263679 JP-A-8-22206 JP-A-4-70765 Japanese Patent Laid-Open No. 2007-139813 JP-A-8-54755 JP-A-7-128911

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides an image forming apparatus, an image forming method, and a process cartridge that can form a high-quality image that is excellent in chargeability, spent resistance, and transferability and that does not deteriorate image quality over a long period of time. For the purpose.

Means for solving the problems are as follows. That is,
<1> An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit,
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
In the image forming apparatus, the content of abietic acid in the toner is 1% by mass or less.
<2> The image forming apparatus according to <1>, wherein the charging unit is a charging unit that charges the electrostatic latent image carrier in a non-contact manner.
<3> The image forming apparatus according to <1>, wherein the charging unit is a charging unit that contacts and charges the electrostatic latent image carrier.
<4> The developing unit has a magnetic field generating unit fixed inside, and a developer carrier that can rotate by carrying a two-component developer composed of a magnetic carrier and a toner on the surface. The image forming apparatus according to any one of <1> to <3>.
<5> The developing device according to any one of <1> to <3>, wherein the developing unit includes a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier. The image forming apparatus described.
<6> The image forming apparatus according to any one of <1> to <5>, wherein the transfer unit is a transfer unit that transfers a visible image on the electrostatic latent image carrier to a recording medium.
<7> A plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit are arranged,
The transfer means sequentially applies the recording medium whose surface moves so as to pass through a transfer position, which is a region facing the electrostatic latent image carrier of the plurality of image forming elements, onto each electrostatic latent image carrier. The image forming apparatus according to any one of <1> to <6>, wherein the image forming apparatus is a transfer unit that transfers a visible image formed on the surface.
<8> An intermediate transfer member on which a visible image formed on the electrostatic latent image carrier is primarily transferred, and a transfer unit that secondary-transfers the visible image carried on the intermediate transfer member to a recording medium. The image forming apparatus according to any one of <1> to <5>, further including a secondary transfer unit.
<9> The image forming apparatus according to any one of <1> to <8>, including a cleaning unit, and the cleaning unit including a cleaning blade that contacts the surface of the electrostatic latent image carrier.
<10> The developing unit has a developer carrier that is brought into contact with the surface of the electrostatic latent image carrier, and develops the electrostatic latent image formed on the electrostatic latent image carrier and The image forming apparatus according to any one of <1> to <8>, wherein residual toner on the latent image carrier is collected.
<11> The fixing unit includes at least one of a roller and a belt, and is a fixing unit that heats and presses a transfer image transferred onto a recording medium by heating from a surface that is not in contact with the toner. > To <10>.
<12> The fixing unit according to <1>, wherein the fixing unit includes at least one of a roller and a belt and is heated from a surface in contact with the toner to fix the transfer image transferred onto the recording medium by heating and pressing. To <10>.
<13> The image forming apparatus according to any one of <1> to <12>, wherein the alcohol component in the polyester resin contains an aliphatic diol in an amount of 65 mol% or more in the divalent alcohol component.
<14> The image forming apparatus according to <13>, wherein the aliphatic diol contains 65 mol% or more of 1,2-propanediol.
<15> The image forming apparatus according to any one of <1> to <14>, wherein the carboxylic acid component further contains an aromatic dicarboxylic acid compound.
<16> A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image with toner. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium Because
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
The image forming method according to claim 1, wherein the content of abietic acid in the toner is 1% by mass or less.
<17> The image forming method according to <16>, wherein the charging step is performed using a charging unit that charges the latent electrostatic image bearing member in a non-contact manner.
<18> The image forming method according to <16>, wherein the charging step is performed using a charging unit that contacts and charges the electrostatic latent image carrier.
<19> From the above <16>, wherein the developing step uses a developer carrying member that has a magnetic field generating means fixed inside and that rotates on the surface carrying a two-component developer comprising a magnetic carrier and a toner. The image forming method according to any one of <18>.
<20> The development process according to any one of <16> to <18>, wherein the developing step uses a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier. The image forming method described.
<21> The image forming method according to any one of <16> to <20>, wherein the transfer step is a transfer step of transferring a visible image on the electrostatic latent image carrier to a recording medium.
<22> A plurality of image forming elements including at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, and a transfer unit,
The transfer means is arranged on each electrostatic latent image carrier in sequence on a recording medium whose surface moves so as to pass through a transfer position that is a region facing the electrostatic latent image carrier of the plurality of image forming elements. The image forming method according to any one of <16> to <21>, wherein the image forming method is a transfer unit that transfers the visible image.
<23> The transfer process includes an intermediate transfer body on which a visible image formed on the electrostatic latent image carrier is primarily transferred, and a secondary transfer of the visible image carried on the intermediate transfer body to a recording medium. The image forming method according to any one of <16> to <20>, wherein the secondary transfer unit is used.
<24> The image forming method according to any one of <16> to <23>, including a cleaning step, wherein the cleaning step uses a cleaning blade that contacts the surface of the electrostatic latent image carrier.
<25> The developing step includes a developer carrier that is brought into contact with the electrostatic latent image carrier, develops the electrostatic latent image formed on the electrostatic latent image carrier, and develops the electrostatic latent image. The image forming method according to any one of <16> to <23>, wherein residual toner on the carrier is collected.
<26> The fixing step in which the fixing step includes at least one of a roller and a belt, is heated from a surface side not in contact with the toner, and is fixed by heating and pressurizing the transferred image transferred onto the recording medium. 16> to <25>.
<27> The fixing step in which the fixing step includes at least one of a roller and a belt, is heated from the side in contact with the toner, and the transfer image transferred onto the recording medium is fixed by heating and pressing. > To <25>.
<28> The image forming method according to any one of <16> to <27>, wherein the alcohol component in the polyester resin contains an aliphatic diol in an amount of 65 mol% or more in the divalent alcohol component.
<29> The image forming method according to <28>, wherein the aliphatic diol contains 65 mol% or more of 1,2-propanediol.
<30> The image forming method according to any one of <16> to <29>, wherein the carboxylic acid component further contains an aromatic dicarboxylic acid compound.
<31> An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forming an image A process cartridge that is detachable from the apparatus body,
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
The process cartridge is characterized in that the content of abietic acid in the toner is 1% by mass or less.
<32> The process cartridge according to <31>, wherein the alcohol component in the polyester resin contains an aliphatic diol in an amount of 65 mol% or more in the divalent alcohol component.
<33> The process cartridge according to <32>, wherein the aliphatic diol contains 65 mol% or more of 1,2-propanediol.
<34> The process cartridge according to any one of <31> to <33>, wherein the carboxylic acid component further contains an aromatic dicarboxylic acid compound.

An image forming apparatus according to the present invention includes an electrostatic latent image carrier, a charging unit that charges the surface of the electrostatic latent image carrier, and an electrostatic latent image formed by exposing the charged electrostatic latent image carrier surface. An exposure unit for forming, a developing unit for developing the electrostatic latent image with toner to form a visible image, a transfer unit for transferring the visible image to a recording medium, and the image transferred to the recording medium A fixing means for fixing the transferred image, and the toner contains at least a binder resin and a colorant,
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
The content of abietic acid in the toner is 1% by mass or less.
In the image forming apparatus of the present invention, the charging unit uniformly charges the surface of the electrostatic latent image carrier. The exposure means exposes the surface of the electrostatic latent image carrier to form an electrostatic latent image. The developing means develops the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. In this case, the toner binder resin is a polyester resin obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid-modified rosin, acrylic acid-modified rosin and itaconic acid-modified rosin. A toner in which the content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component, and the content of abietic acid in the toner is 1% by mass or less. Therefore, it is possible to form a high-quality image that is excellent in chargeability and transferability and has no deterioration in image quality over a long period of time.

The image forming method of the present invention comprises a charging step of charging the surface of the electrostatic latent image carrier, an exposure step of exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic A developing process for developing a latent image with toner to form a visible image, a transfer process for transferring the visible image to a recording medium, and a fixing process for fixing the transferred image transferred to the recording medium. Including at least
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
The content of abietic acid in the toner is 1% by mass or less.
In the image forming method of the present invention, the surface of the electrostatic latent image carrier is uniformly charged in the charging step. In the exposure step, the surface of the electrostatic latent image carrier is exposed to form an electrostatic latent image. In the developing step, the electrostatic latent image formed on the electrostatic latent image carrier is developed with toner to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. At this time, the binder resin of the toner contains a polyester resin formed by condensation polymerization of an alcohol component and at least one carboxylic acid component of fumaric acid-modified rosin, acrylic acid-modified rosin and itaconic acid-modified rosin, Since a toner in which the content of the rosin compound is 5% by mass or more with respect to the total mass of the alcohol component and the carboxylic acid component and the content of abietic acid in the toner is 1% by mass or less is used. In addition, it is excellent in chargeability, spent resistance and transferability, and can form a high-quality image with no deterioration in image quality over a long period of time.

The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. And the binder resin as the toner includes an alcohol component, and a carboxylic acid component containing at least one of fumaric acid-modified rosin, acrylic acid-modified rosin, and itaconic acid-modified rosin. A rosin compound content is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component, and the content of abietic acid in the toner is Uses 1% by weight or less of toner, so it is excellent in chargeability, spent resistance and transferability, and can form high-quality images with no deterioration in image quality over a long period of time. That.

  According to the present invention, an image forming apparatus capable of solving conventional problems, forming a high-quality image with excellent chargeability, spent resistance, transferability, and no deterioration in image quality over a long period of time. A forming method and a process cartridge can be provided.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit, and a cleaning unit, and further if necessary. Other means appropriately selected, for example, static elimination means, recycling means, control means, etc. are provided. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit.
The image forming method of the present invention includes at least a charging step, an exposure step, a development step, a transfer step, and a fixing step, and includes a cleaning step and other steps appropriately selected as necessary, for example, It includes a static elimination process, a recycling process, a control process, and the like. The charging process and the exposure process may be collectively referred to as an electrostatic latent image forming process.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, the fixing step can be performed by the fixing unit, and the cleaning step can be performed by the cleaning unit. The other steps can be performed by the other means.

<Electrostatic latent image carrier>
The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape include a drum shape and a sheet. And endless belts. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.

  For example, the amorphous silicon 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. A photosensitive layer made of a-Si is formed by the film forming method. Among these, the plasma CVD method is particularly preferable, and specifically, a method in which the source gas is decomposed by direct current, high frequency, or microwave glow discharge to form a photosensitive layer made of a-Si on the support is preferable. .

The organic photoreceptor (OPC) has (1) optical characteristics such as a wide light absorption wavelength range and a large amount of light absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, (3) In general, it is widely applied because of the wide selection range of materials, (4) ease of production, (5) low cost, and (6) non-toxicity. The layer structure of such an organic photoreceptor is roughly classified into a single layer structure and a laminated structure.
The single-layered photoreceptor has a support and a single-layer type photosensitive layer provided on the support, and further includes a protective layer, an intermediate layer, and other layers as necessary.
The laminated structure of the photoreceptor comprises a support, and a laminate type photosensitive layer having at least a charge generation layer and a charge transport layer in this order on the support, and further includes a protective layer and an intermediate layer as necessary. And other layers.

<Charging step and charging means>
The charging step is a step of charging the surface of the electrostatic latent image carrier, and is performed by the charging unit.
The charging means is not particularly limited as long as it can apply a voltage to the surface of the latent electrostatic image bearing member to be uniformly charged, and can be appropriately selected according to the purpose. (1) Contact type charging means for charging in contact with the electrostatic latent image carrier and (2) Non-contact type charging means for charging in a non-contact manner with the electrostatic latent image carrier.

-Contact charging means-
Examples of the contact type charging means (1) include a conductive or semiconductive charging roller, a magnetic brush, a fur brush, a film, and a rubber blade. Among these, the charging roller can significantly reduce the amount of ozone generated compared to corona discharge, and is excellent in stability during repeated use of the electrostatic latent image carrier, and effective in preventing image quality deterioration. It is.
The magnetic brush includes a non-magnetic conductive sleeve that supports various ferrite particles such as Zn-Cu ferrite and a magnet roll included in the sleeve. The fur brush is formed by, for example, winding or pasting a fur treated with carbon, copper sulfide, metal, metal oxide, or the like around a metal or a treated metal core.

Here, FIG. 1 is a sectional view showing an example of the charging roller. The charging roller 310 includes a cored bar 312 serving as a cylindrical conductive support, a resistance adjusting layer 313 formed on the outer peripheral surface of the cored bar 312, and a surface of the resistance adjusting layer 313. A protective layer 314 which prevents leakage.
The resistance adjusting layer 313 is formed by extruding or injection-molding a thermoplastic resin composition containing at least a thermoplastic resin and a polymer type ionic conductive agent on the peripheral surface of the core metal 312.
The resistivity value of the resistance adjusting layer 313 is preferably 10 ⁶ to 10 ⁹ Ω · cm. If the volume resistivity value exceeds 10 ⁹ Ω · cm, the charge amount is insufficient, and the photosensitive drum may not be able to obtain a sufficient charging potential to obtain a uniform image. If the resistance value is less than 10 ⁶ Ω · cm, there is a risk of leakage to the entire photosensitive drum.

  There is no restriction | limiting in particular as a thermoplastic resin used for the said resistance adjustment layer 313, Although it can select suitably according to the objective, For example, polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), Examples thereof include polystyrene (PS) and copolymers thereof (AS, ABS, etc.).

As the polymer-type ion conductive agent, one having a resistance value of about 10 ⁶ to 10 ¹⁰ Ω · cm as a single substance and easily reducing the resistance of the resin is used. One example is a compound containing a polyether ester amide component. In order to make the resistance value of the resistance adjusting layer 313 as described above, the blending amount is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
In addition, a quaternary ammonium base-containing polymer compound can also be used as the polymer type ion conductive agent. Examples of the quaternary ammonium base-containing polymer compound include quaternary ammonium base-containing polyolefin. In order to set the resistance value of the resistance adjusting layer 312 to the above value, the blending amount is preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

  The polymer type ionic conductive agent can be dispersed in the thermoplastic resin by a biaxial kneader, a kneader or the like. Since the polymer type ion conductive agent is uniformly dispersed in the thermoplastic resin composition at the molecular level, the resistance adjustment layer 313 has a poor dispersion of the conductive material found in the resistance adjustment layer in which the conductive pigment is dispersed. The accompanying resistance value does not vary. In addition, since the polymer type ion conductive agent is a polymer compound, it is uniformly dispersed and fixed in the thermoplastic resin composition, and bleedout hardly occurs.

The protective layer 314 is formed such that its resistance value is larger than the resistance value of the resistance adjustment layer 313. As a result, leakage to the defective portion of the photosensitive drum is avoided. However, if the resistance value of the protective layer 314 is excessively increased, the charging efficiency is lowered. Therefore, the difference between the resistance value of the protective layer 314 and the resistance value of the resistance adjustment layer 313 is preferably 10 ³ Ω · cm or less. .

  As the material for the protective layer 314, a resin material is preferable because of its good film formability. As the resin material, for example, a fluororesin, a polyamide resin, a polyester resin, a polyvinyl acetal resin and the like are preferable from the viewpoint of excellent non-adhesiveness and preventing toner adhesion. In addition, since the resin material generally has electrical insulation, if the protective layer 314 is formed of the resin material alone, the characteristics of the charging roller are not satisfied. Therefore, the resistance value of the protective layer 314 is adjusted by dispersing various conductive agents in the resin material. In order to improve the adhesion between the protective layer 314 and the resistance adjustment layer 313, a reactive curing agent such as isocyanate may be dispersed in the resin material.

  The charging roller 310 is connected to a power source and is applied with a predetermined voltage. The voltage may be only a direct current (DC) voltage, but is preferably a voltage obtained by superimposing an alternating current (AC) voltage on a DC voltage. By thus applying the AC voltage, the surface of the photosensitive drum can be more uniformly charged.

  Here, FIG. 2 is a schematic view showing an example in which a contact-type charging roller 310 as shown in FIG. 1 is applied to an image forming apparatus as a charging unit. In FIG. 2, around the photosensitive drum 321 as an electrostatic latent image carrier, a charging means 310 for charging the surface of the photosensitive drum, and an exposure means for forming an electrostatic latent image on the charging processing surface. 323, a developing unit 324 that forms a visible image by attaching toner to the electrostatic latent image on the surface of the photosensitive drum, and a transfer unit 325 that transfers the visible image formed on the photosensitive drum onto the recording medium 326. The fixing unit 327 for fixing the transfer image on the recording medium, the cleaning unit 330 for removing and collecting the residual toner on the photosensitive drum, and the static eliminating device 331 for removing the residual potential on the photosensitive drum are sequentially provided. It is arranged. As the charging unit 310, a contact type charging roller 310 shown in FIG. 1 is provided, and the surface of the photosensitive drum 321 is uniformly charged by the charging roller 310.

-Non-contact charging means-
The non-contact charging means (2) includes, for example, a non-contact charger using a corona discharge, a needle electrode device, a solid discharge element; a conductive material disposed with a minute gap with respect to the electrostatic latent image carrier. Or a semiconductive charging roller.

The corona discharge is a non-contact charging method that gives positive or negative ions generated by corona discharge in the air to the surface of the electrostatic latent image carrier, and gives a constant amount of charge to the electrostatic latent image carrier. There are a coroton charger having characteristics and a scorotron charger having characteristics that give a constant potential.
The coroton charger is composed of a casing electrode that occupies a half space around the discharge wire, and a discharge wire placed almost at the center thereof.
The scorotron charger is obtained by adding a grid electrode to the corotron charger, and the grid electrode is provided at a position 1.0 mm to 2.0 mm away from the surface of the electrostatic latent image carrier.

Here, FIG. 3 is a schematic diagram showing an example in which a non-contact type corona charger is applied to an image forming apparatus as a charging unit. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.
As the charging means, a non-contact type corona charger 311 is provided, and the surface of the photosensitive drum 321 is uniformly charged by the corona charger 311.

  As the charging roller disposed with a small gap with respect to the electrostatic latent image carrier, the charging roller is improved so as to have a small gap with respect to the electrostatic latent image carrier. The fine gap is preferably 10 μm to 200 μm, and more preferably 10 μm to 100 μm.

Here, FIG. 4 is a schematic view showing an example of a non-contact charging roller. In FIG. 4, the charging roller 310 is disposed with a minute gap H with respect to the photosensitive drum 321. The minute gap H is set by causing the spacer member surface to contact the surface of the photosensitive drum 321 by, for example, winding a spacer member having a certain thickness around the non-image forming regions at both ends of the charging roller 310. be able to. In FIG. 4, 304 is a power source.
In FIG. 4, as a method for maintaining the minute gap H, a film 302 is wound around both ends of the charging roller 310 to form a spacer member. The spacer 302 is brought into contact with the photosensitive surface of the electrostatic latent image carrier to obtain a certain minute gap H in the image area of the charging roller and the electrostatic latent image carrier. The applied bias applies an AC superposition type voltage to charge the electrostatic latent image carrier by a discharge generated in a minute gap H between the charging roller and the electrostatic latent image carrier. As shown in FIG. 4, the accuracy of maintaining the minute gap H is improved by pressing the shaft 311 of the charging roller with the spring 303.

The spacer member may be integrally formed with the charging roller. At this time, at least the surface of the gap portion is an insulator. As a result, the discharge at the gap portion is eliminated, and the discharge product is deposited on the gap portion, and the adhesion of the discharge product prevents the toner from adhering to the gap portion and spreading the gap.
Moreover, as the spacer member, a heat shrinkable tube may be used. Examples of such heat-shrinkable tubes include Sumitube (trade name: F105, manufactured by Sumitomo Chemical Co., Ltd.) for 105 ° C.

<Exposure process and exposure means>
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure unit.
The optical system in the exposure is roughly classified into an analog optical system and a digital optical system. The analog optical system is an optical system that projects an original directly onto an electrostatic latent image carrier by an optical system, and the digital optical system receives image information as an electrical signal and converts it into an optical signal. It is an optical system that exposes an electrostatic latent image carrier to form an image.
The exposure means is not particularly limited as long as the surface of the latent electrostatic image bearing member charged by the charging means can be exposed like an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, and an LED optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

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

〔toner〕
The toner contains at least a binder resin and a colorant, preferably contains a release agent, a charge control agent, and an external additive, and further contains other components as necessary.

-Binder resin-
The binder resin includes a polyester resin obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound, and is characterized in that the content of abietic acid in the toner is controlled.

In the present invention, the rosin compound as the carboxylic acid component contains abietic acid as a main component. When abietic acid derived from the rosin compound remains in the toner, the toner adheres to the carrier, the charging roller, or the like. Cheap. However, in the present invention, the dispersibility of the colorant is improved by introducing the rosin skeleton into the polyester, and further, the amount of abietic acid remaining in the toner is reduced, so that the toner carrier, the charging roller, etc. It is considered that high transferability and chargeability can be maintained even during printing, and high quality images can be obtained.
From the above viewpoint, in the present invention, the content of abietic acid in the toner is 1.0% by mass or less, preferably 0.9% by mass or less, more preferably 0.5% by mass or less, and 0.3% by mass. % Or less is more preferable.

The rosin compound contained in the carboxylic acid component contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin. As described above, the rosin compound contains abietic acid as a main component, and the amount of abietic acid was controlled within a predetermined range only by reducing the rosin compound used within the range where the effects of the present invention were exhibited. No toner can be obtained. Therefore, in the present invention, for example, as a method of reducing the content of abietic acid in the toner, for example, (1) using an aliphatic diol having excellent reactivity as the alcohol component, the reaction rate of the rosin compound is increased. (2) A method of using a modified rosin modified with an unsaturated fatty acid and pre-reducing the amount of abietic acid, (3) In the production of a polyester resin, the reaction time, reaction temperature and degree of vacuum are adjusted to adjust the rosin compound (4) A method of removing low molecular weight components contained in the polyester resin by performing steam distillation or water dropping after the reaction of the raw material monomers, (5) Two hydroxyl groups in the alcohol component And a method using an aliphatic diol, each of which is a primary hydroxyl group.

-Alcohol component-
As described above, the alcohol component of the polyester resin is preferably an aliphatic diol. By using an aliphatic diol, which is more reactive than an aromatic alcohol, as an alcohol component, the rosin compound is easily taken into the polyester resin, and the abietic acid content can be reduced. Further, the rosin compound is first easily added to the polyester resin by adding the rosin compound together with the aliphatic alcohol to the reaction system to react the rosin compound and the aliphatic alcohol.

  There is no restriction | limiting in particular as said aliphatic diol, According to the objective, it can select suitably, For example, a C2-C6 aliphatic alcohol is suitable, These may be used individually by 1 type. Two or more kinds may be used in combination. Among these, ethylene glycol, 1,2-propanediol, and 1,3-propanediol are more preferable. From the viewpoint of keeping the glass transition temperature of the resin high and ensuring the storage stability of the toner, 1,2-propanediol is preferred. Is particularly preferred. 1,2-propanediol, which is an alcohol having a secondary hydroxyl group having 3 carbon atoms, has a lower glass transition temperature of the resin and toner storage stability than an alcohol having a secondary hydroxyl group having 4 or more carbon atoms. The effect of preventing the reduction is great. The 1,2-propanediol content in the aliphatic diol is preferably 65 mol% or more, more preferably 70 mol% or more, and still more preferably 80 to 100 mol%.

The aliphatic diol is preferably 65 mol% or more, more preferably 80 to 100 mol% in the divalent alcohol component.
Examples of the divalent alcohol component other than the aliphatic diol include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. Aromatic alcohols such as alkylene oxide adducts of bisphenol A; hydrogenated bisphenol A or its alkylene (2 to 4 carbon atoms) oxide (average number of added moles 1 to 16) adduct, and the like.

  The content of the divalent alcohol component is preferably 60 mol% to 100 mol%, more preferably 60 mol% to 95 mol%, still more preferably 65 mol% to 90 mol% in the alcohol component.

-Carboxylic acid component-
As described above, the carboxylic acid component contains at least one of fumaric acid-modified rosin, acrylic acid-modified rosin, and itaconic acid-modified rosin.
In the present invention, rosin is a natural resin obtained from pine, and the main components thereof are abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, lepopimaric acid A resin acid or a mixture thereof.
The modified rosin in the present invention is preferably a modified rosin modified with an unsaturated fatty acid in which the content of abietic acid has been reduced in advance.
A modified rosin modified with an unsaturated fatty acid is obtained by addition reaction of an unsaturated fatty acid to rosin, and specifically, repopimaric acid, abietic acid, neodymium having a conjugated double bond among the main components of rosin. It can be obtained via a Diels-Alder reaction or an ene reaction under heating with abietic acid and parastrinic acid and an unsaturated fatty acid.
As the rosin to be modified, the above-mentioned known rosin can be used, but natural rosin is preferable from the viewpoint of color, and tall rosin is more preferable from the viewpoint of low-temperature fixability.
Examples of unsaturated fatty acids that modify rosin include (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, and the like.
In the present specification, “(meth) acryl” means acryl or methacryl. Therefore, (meth) acrylic acid means acrylic acid or methacrylic acid, and as a modified rosin modified with (meth) acrylic acid, a viewpoint of reaction activity in Diels-Alder reaction or ene reaction. Therefore, acrylic acid-modified rosin modified with acrylic acid having little steric hindrance is preferable.

  There is no restriction | limiting in particular as a manufacturing method of the modified | denatured rosin by an unsaturated fatty acid, According to the objective, it can select suitably, For example, a rosin and an unsaturated fatty acid are mixed and Diels are heated by heating to 180 to 260 degreeC. -A modified rosin can be obtained by adding an unsaturated fatty acid to an acid having a conjugated double bond contained in rosin by an alder reaction or an ene reaction. The obtained modified rosin may be used as it is, or may be used after purification through an operation such as distillation.

The content of the rosin compound is preferably 5% by mass or more, more preferably 5% by mass to 40% by mass, still more preferably 10% by mass to 40% by mass, and more preferably 15% by mass in the total mass of the alcohol component and the carboxylic acid component. % To 40% by weight is particularly preferable, and 25% to 40% by weight is most preferable.
As the carboxylic acid component other than the rosin compound, aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of obtaining a resin having a high glass transition temperature.
The content of the aromatic dicarboxylic acid compound is preferably 40 mol to 95 mol, more preferably 50 mol to 90 mol, and still more preferably 60 mol to 80 mol with respect to 100 mol of the alcohol component.
In the present invention, carboxylic acid, anhydride of carboxylic acid, and alkyl ester of carboxylic acid are collectively referred to as a carboxylic acid compound in this specification.

  At least one of the alcohol component and the carboxylic acid component may contain a trivalent or higher raw material monomer. The content of trivalent or higher raw material monomers is preferably 40 mol or less, more preferably 5 mol to 30 mol, per 100 mol of the divalent alcohol component.

  In the trivalent or higher raw material monomer, the trivalent or higher polyvalent carboxylic acid compound is preferably trimellitic acid or a derivative thereof. Examples of the trivalent or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane and sorbitol. Or an alkylene (2 to 4 carbon) oxide adduct (average number of added moles 1 to 16) thereof, or the like. Among these, glycerin, trimellitic acid, or a derivative thereof is particularly preferable because it not only serves as a branching site or acts as a crosslinking agent but is effective in improving low-temperature fixability.

-Esterification catalyst-
The condensation polymerization of the alcohol component and the carboxylic acid component is preferably performed in the presence of an esterification catalyst. Examples of the esterification catalyst include Lewis acids such as p-toluenesulfonic acid, titanium compounds, and tin (II) compounds having no Sn-C bond, and these are used alone or in combination. . Among these, a titanium compound and a tin (II) compound having no Sn—C bond are particularly preferable.

As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group, or an acyloxy group is more preferable.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diethylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) _2], titanium distearate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 18 H 37 O) 2 ], Chitanto Isopropylate triethanolaminate _{[Ti (C 6 H 14 O 3} N) 1 (C 3 H 7 O) 3 ], titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) ₃ (C ₃ H ₇ O) ₁ ] and the like. Among these, titanium diisopropylate bistriethanolaminate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate are particularly preferred, and these are also available as, for example, commercial products manufactured by Matsumoto Kosho Co., Ltd. It is.

Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) _4], tetra myristyl titanate _{[Ti (C 14 H 29 O)} 4 ], tetraoctyl titanate _{[Ti (C 8 H 17 O)} 4 ], dioctyl-dihydroxy-octyl titanate [Ti _(C 8 _{H 17} O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetra Myristyl titanate, tetraoctyl titanate, dioctyl dihydroxy octyl titanate are preferred, For example, the titanium halide may be obtained by reacting a corresponding alcohol, are also commercially available, such as Nisso Corporation.
The abundance of the titanium compound is preferably 0.01 parts by mass to 1.0 part by mass, and 0.1 parts by mass to 0.7 parts by mass with respect to 100 parts by mass of the total mass of the alcohol component and the carboxylic acid component. Part is more preferred.

Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, and a tin (II) having a Sn—X bond (where X represents a halogen atom). A compound etc. are preferable and the tin (II) compound which has a Sn-O bond is more preferable.
Examples of the tin (II) compound having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) dilaurate, and tin (II) distearate. Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms, such as tin (II) dioleate; dioctyloxytin (II), dilauroxytin (II), distearoxytin (II), dioleoxytin (II) Dialkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as tin oxide (II) and tin sulfate (II).
Examples of the compound having the Sn-X (wherein X represents a halogen atom) bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, among these. And fatty acid tin (II) represented by (R ¹ COO) ₂ Sn (wherein R ¹ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R 1 ² O) ₂ Sn (provided that, ^{R 2} is dialkoxy tin represented by an alkyl group or alkenyl group having 6 to 20 carbon atoms) (II), tin oxide represented by SnO (II) are preferred, ( Fatty acid tin (II) and tin (II) oxide represented by R ¹ COO) ₂ Sn are more preferable, and tin (II) dioctanoate, tin (II) distearate, and tin (II) oxide are more preferable.
The abundance of the tin (II) compound having no Sn-C bond is 0.01 parts by mass to 1.0 part by mass with respect to 100 parts by mass of the total mass of the alcohol component and the carboxylic acid component. Preferably, 0.1 mass part-0.5 mass part is more preferable.

  When the titanium compound and the tin (II) compound having no Sn-C bond are used in combination, the total amount of the titanium compound and the tin (II) compound is the total mass of the alcohol component and the carboxylic acid component. 0.01 mass part-1.0 mass part is preferable with respect to 100 mass parts, and 0.1 mass part-0.5 mass part is more preferable.

  The condensation polymerization of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 180 ° C. to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst.

As described above, steam distillation may be performed as a means for reducing the amount of abietic acid by reducing unreacted rosin.
In the steam distillation, water mixed with the resin may be liquid or gaseous (steam), and the amount of water mixed is obtained from the viewpoint of controlling the influence on the physical properties of the resin. 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of resin obtained, 0.5-40 mass parts is more preferable, and 1-30 mass parts is still more preferable.
The mixing of the resin and water is preferably 100 ° C. to 300 ° C., more preferably 130 ° C. to 250 ° C., particularly 150 ° C. to 240 ° C. It is preferable.
In the mixing of the resin and water, the water addition rate is preferably 0.002 to 0.5 parts by mass / min with respect to 100 parts by mass of the resin obtained from the viewpoint of the share given to the release agent, and is 0.008. -0.3 mass part / min is more preferable, and 0.008-0.2 mass part / min is still more preferable.
The mixing of the resin and water is not particularly limited as long as it is from the addition of rosin to the time when the reaction product is withdrawn from the reaction vessel after the completion of the entire reaction. In addition, it is preferable to be in a mixed state with water until just before the resin is extracted.

  There is no restriction | limiting in particular as a method of mixing resin and water, According to the objective, it can select suitably, 100 to 260 degreeC is preferable, Especially the method of blowing in water vapor | steam of 120 to 180 degreeC in resin. preferable. In the method of bubbling by blowing air and nitrogen or the like, if the resin viscosity is high, each of the bubbles increases and there is no interaction between the bubbles and the resin, so that a sufficient effect cannot be obtained. On the other hand, when water vapor is blown in, water becomes fine water vapor bubbles and uniformly diffuses over a wide area in the resin, so it is estimated that unreacted rosin compounds can be released from the resin. Is done.

The softening point of the polyester resin is preferably 80 ° C. or higher and lower than 160 ° C., more preferably 90 ° C. to 150 ° C., and still more preferably 95 ° C. to 150 ° C., from the viewpoint of reducing adhesion of the toner to the carrier and the charging roller. . The softening point can be easily adjusted by, for example, the polymerization time.
In addition, the glass transition temperature of the polyester resin is preferably 45 ° C to 75 ° C, more preferably 50 ° C to 65 ° C, from the viewpoints of fixability, storage stability, and durability. The acid value of the polyester resin is preferably 1 to 90 mgKOH / g, more preferably 10 to 50 mgKOH / g, from the viewpoints of chargeability and environmental stability.

  In the present invention, the polyester resin may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of the modified polyester resin include grafting or blocking with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more types of resin units including a polyester unit.

The content of the polyester resin obtained by using a predetermined amount of the rosin compound is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, substantially 100% in the binder resin. Mass% is particularly preferred.
As the binder resin, a known binder resin, for example, a vinyl resin such as styrene-acrylic resin; other resins such as an epoxy resin, a polycarbonate resin, and a polyurethane resin may be used in combination as long as the effects of the present invention are not impaired. It may be.

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

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black material include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).
Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

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

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

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

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

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes, such as carbonyl group containing wax, polyolefin wax, and long-chain hydrocarbon, are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.

Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40 to 160 degreeC is preferable, 50 to 120 degreeC is more preferable, and 60 to 90 degreeC is especially preferable. preferable. When the melting point is less than 40 ° C., the heat resistant storage stability may be adversely affected. When the melting point exceeds 160 ° C., cold offset may easily occur during fixing at low temperatures.
The melting point of the release agent is, for example, a sample that is heated up to 200 ° C. using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), and cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. And the maximum peak temperature of the heat of fusion can be determined as the melting point.
The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as measured at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

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

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.

Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (all manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (all manufactured by Hodogaya Chemical Co., Ltd.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (Nippon Carlit Co., Ltd.); quinacridone, azo pigment; sulfone Group, a carboxyl group, and the like and polymeric compounds having a functional group such as a quaternary ammonium salt.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or the toner. You may fix to the toner surface after particle manufacture.

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

-External additive-
The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, And aluminum oxide stearate); metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Japan) Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT -150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like. Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both made by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T ( All are Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both are Teika Co., Ltd.), IT-S (Ishihara Sangyo Co., Ltd.) and the like.

In order to obtain the hydrophobized silica fine particles, the hydrophobized titania fine particles, and the hydrophobized alumina fine particles, the hydrophilic fine particles are made of silane cups such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with a ring agent.
Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

Further, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

The average particle size of primary particles of the inorganic fine particles is preferably 1 nm to 100 nm, and more preferably 3 nm to 70 nm. When the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. When the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier is damaged unevenly. May end up. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and more preferably 5 nm to 70 nm. More preferably, the primary particles subjected to the hydrophobization treatment include at least two types of inorganic fine particles having an average particle diameter of 20 nm or less and at least one type of inorganic fine particles of 30 nm or more. Further, BET specific surface area of the inorganic fine particles ^is preferably 20m ² / g~500m 2 / g.
The amount of the external additive added is preferably 0.1% by mass to 5% by mass and more preferably 0.3% by mass to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01% by mass to 5% by mass and more preferably 0.1% by mass to 2% by mass with respect to the toner.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, etc. are mentioned.

The fluidity improver can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils.
The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Metal salts; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

-Toner production method-
The method for producing the toner is not particularly limited and can be appropriately selected according to the purpose from conventionally known toner production methods. For example, a kneading / pulverizing method, a polymerization method, a dissolution suspension method, The spray granulation method etc. are mentioned.

--Kneading and grinding method--
The kneading and pulverizing method is, for example, a method of manufacturing the toner base particles by melt-kneading a toner material containing at least a binder resin and a colorant, pulverizing and classifying the obtained kneaded material. is there.
In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  Next, the external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

--- Polymerization method--
As a method for producing a toner by the polymerization method, for example, a toner material containing a modified polyester resin capable of at least urea or urethane bonding and a colorant is dissolved or dispersed in an organic solvent. Then, the solution or dispersion is dispersed in an aqueous medium, subjected to a polyaddition reaction, the solvent of this dispersion is removed and washed.

  Examples of the modified polyester resin capable of being bonded with urea or urethane include, for example, polyester prepolymer having an isocyanate group obtained by reacting a carboxyl group or a hydroxyl group at a terminal of a polyester with a polyvalent isocyanate compound (PIC). Can be mentioned. The modified polyester resin obtained by crosslinking and / or extending the molecular chain by the reaction of this polyester prepolymer and amines can improve the hot offset property while maintaining the low temperature fixability.

Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane). Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; And those blocked with oxime, caprolactam, and the like. These may be used individually by 1 type and may use 2 or more types together.
The ratio of the polyvalent isocyanate compound (PIC) is preferably 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group, 4/1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable.

  The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having the isocyanate group is preferably 1 or more, more preferably 1.5 to 3 on average, and 1.8 to 2.5 on average. Is more preferable.

Examples of amines (B) to be reacted with the polyester prepolymer include a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4), an amino acid (B5). ), B1 to B5 amino groups blocked (B6), and the like.
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-). Dimethyl dicyclohexyl methane, diamine cyclohexane, isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the blocked B1-B5 amino group (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). . Among these amines (B), B1 and a mixture of B1 and a small amount of B2 are particularly preferable.

  The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the polyester prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and still more preferably 1.2 / 1 to 1 / 1.2.

  According to the method for producing a toner by the polymerization method as described above, a toner having a small particle diameter and a spherical shape can be produced at low cost with little environmental load.

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

The mass average particle diameter of the toner is not particularly limited and can be appropriately selected according to the purpose. Here, the mass average particle diameter of the toner can be determined as follows.
[Mass average particle diameter of toner]
Measuring instrument: Coulter Multisizer II (Beckman Coulter, Inc.)
・ Aperture diameter: 100μm
・ Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (Beckman Coulter)
-Dispersion liquid: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB = 13.6) 5% by weight electrolytic solution-Dispersion condition: 10 mg of a measurement sample is added to 5 ml of the dispersion liquid, and an ultrasonic disperser is used. Disperse for 1 minute, then add 25 ml of electrolyte and further disperse for 1 minute with an ultrasonic disperser.
Measurement conditions: Add 100 ml of electrolyte and dispersion into a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and calculate the mass average particle size from the particle size distribution. Ask.

(Developer)
The developer contains at least the toner and contains other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even when the toner balance is performed, the toner particle diameter does not fluctuate so much that the toner filming on the developing roller as the developer carrier or the toner is thinned. There is no fusion of toner to a layer thickness regulating member such as a blade for layering, and good and stable developability and images can be obtained even when the developing means is used for a long time (stirring). Further, in the case of the two-component developer using the toner, even if the toner balance is performed over a long period of time, there is little fluctuation in the toner particle diameter in the developer, and it is good and stable even with long-term stirring in the developing means. Developability is obtained.

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

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

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

  The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyesters Resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and Copolymers with vinyl fluoride, fluoroterpolymers (triple fluoride (multiple) copolymer) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. . These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

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

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

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

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

  The developing means may be of a dry development type or a wet development type. Further, it may be a monochromatic developing unit or a multi-color developing unit. For example, a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller are provided. Preferred examples include those possessed.

In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.
The developer accommodated in the developing unit is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

[One-component developer]
As the one-component developing means, for example, a one-component developing device having a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier is preferably used. .

  FIG. 5 is a schematic diagram illustrating an example of a one-component developing device. This one-component developing device uses a one-component developer made of toner, forms a toner layer on a developing roller 402 as a developer carrying member, and uses the toner layer on the developing roller 402 as an electrostatic latent image carrying member. The photosensitive drum 1 is conveyed so as to be in contact with the photosensitive drum 1 to perform contact one-component development for developing the electrostatic latent image on the photosensitive drum 1.

  In FIG. 5, the toner in the casing 401 is agitated by the rotation of an agitator 411 as agitation means and mechanically supplied to a supply roller 412 as a toner supply member. The supply roller 412 is made of foamed polyurethane or the like, has flexibility, and has a structure in which toner is easily held by a cell having a diameter of 50 to 500 μm. Further, the supply roller has a relatively low JIS-A hardness of 10 to 30 °, and can be brought into contact with the developing roller 402 uniformly.

  The supply roller 412 is driven to rotate in the same direction as the developing roller 402, that is, the surface of the supply roller 412 moves in the opposite direction at the opposing portion of both rollers. The linear speed ratio (supply roller / developing roller) of both rollers is preferably 0.5 to 1.5. Further, the supply roller 412 may be rotated so that the surfaces of the supply roller 412 move in the same direction as the developing roller 402, that is, at the opposite portions of the two rollers. In this embodiment, the supply roller 412 rotates in the same direction as the developing roller 402, and the linear speed ratio is set to 0.9. The biting amount of the supply roller 412 with respect to the developing roller 402 is set to 0.5 to 1.5 mm. In the present embodiment, when the unit effective width is 240 mm (A4 size vertical), the required torque is 14.7 to 24.5 N · cm.

The developing roller 402 has a surface layer made of a rubber material on a conductive substrate, has a diameter of 10 to 30 mm, and appropriately roughens the surface to have a surface roughness Rz of 1 to 4 μm. The value of the surface roughness Rz is preferably 13 to 80% with respect to the average particle diameter of the toner. As a result, the toner is conveyed without being buried in the surface of the developing roller 402. In particular, the surface roughness Rz of the developing roller 402 is preferably in the range of 20 to 30% of the average particle size of the toner so as not to retain a remarkably low charged toner.
Examples of the rubber material include silicone rubber, butadiene rubber, NBR rubber, hydrin rubber, EPDM rubber, and the like. Further, it is preferable to coat the surface of the developing roller 402 with a coating layer in order to stabilize the quality with time. Examples of the material for the coating layer include silicone materials and Teflon (registered trademark) materials. The silicone material is excellent in toner chargeability, and the Teflon (registered trademark) material is excellent in releasability. In order to obtain conductivity, a conductive material such as carbon black can be appropriately contained. The thickness of the coat layer is preferably 5 to 50 μm. If it is out of this range, problems such as easy cracking may occur.

Toner having a predetermined polarity (negative polarity in the case of the present embodiment) existing on or inside the supply roller 412 is pinched by the developing roller 402 that rotates in the opposite direction at the contact point due to the rotation. A negatively charged charge is obtained by the charging effect and is held on the developing roller 402 by an electrostatic force and by a conveying effect by the surface roughness of the developing roller 402. However, the toner layer on the developing roller 402 at this time is not uniform and is considerably excessively attached (1 to 3 mg / cm ² ). Accordingly, a toner thin layer having a uniform layer thickness is formed on the developing roller 402 by bringing a regulating blade 413 as a layer thickness regulating member into contact with the developing roller 402. The restriction blade 413 is a so-called belly contact where the tip is directed downstream with respect to the rotation direction of the developing roller 402 and the central portion of the restriction blade 413 comes into contact, but it can also be set in the reverse direction. It is also possible to realize edge contact.
As the material of the regulating blade, a metal such as SUS304 is preferable, and the thickness is 0.1 to 0.15 mm. In addition to the metal, a rubber material such as polyurethane rubber having a thickness of 1 to 2 mm or a resin material having a relatively high hardness such as a silicone resin can be used. In addition, since the resistance can be reduced by mixing carbon black or the like other than metal, it is possible to form an electric field between the developing roller 402 by connecting a bias power source.

The regulating blade 413 as the layer thickness regulating member is preferably 10 to 15 mm as a free end length from the holder. If the free end length exceeds 15 mm, the developing means becomes large and cannot be stored compactly in the image forming apparatus. If it is less than 10 mm, vibration occurs when the regulating blade comes into contact with the surface of the developing roller 402. In some cases, an abnormal image such as unevenness in the horizontal direction is likely to occur on the image.
The contact pressure of the regulating blade 413 is preferably in the range of 0.049 to 2.45 N / cm. If the contact pressure exceeds 2.45 N / cm, the toner adhesion amount on the developing roller 402 decreases and the toner charge amount increases excessively, so the development amount may decrease and the image density may decrease. If it is less than 0.049 N / cm, a thin layer may not be formed uniformly, and the toner mass may pass through the regulating blade, and the image quality may be significantly lowered. In this embodiment, the developing roller 402 has a JIS-A hardness of 30 °, the regulating blade 413 is a SUS plate having a thickness of 0.1 mm, and the contact pressure is set to 60 gf / cm. At this time, the target toner adhesion amount on the developing roller could be obtained.

Further, the contact angle of the regulating blade 413 as the layer thickness regulating member is preferably 10 to 45 ° with respect to the tangent line of the developing roller 402 in the direction in which the tip faces the downstream side of the developing roller 402. A portion unnecessary for forming a thin layer of toner sandwiched between the regulating blade 413 and the developing roller 402 is peeled off from the developing roller 402 and is 0.4 to 0.8 mg / cm ² per unit area which is a target range. A thin layer having a uniform thickness is formed. The toner charge at this time is finally in the range of −10 to −30 μC / g in this embodiment, and is developed to face the electrostatic latent image on the photosensitive drum 1.

  Therefore, according to the one-component developing device of this embodiment, the distance between the surface of the photosensitive drum 1 and the surface of the developing roller 402 is further narrower than that in the case of the conventional two-component developing unit, the developing ability is increased, and the further low potential is achieved. But development is possible.

[Two-component developing means]
The two-component developing means has a magnetic field generating means fixed inside, and a two-component development having a rotatable developer carrier carrying a two-component developer comprising a magnetic carrier and toner on the surface. A device is preferred.

  Here, FIG. 6 is a schematic view showing an example of a two-component developing device using a two-component developer composed of toner and a magnetic carrier. In the two-component developing device of FIG. 6, the two-component developer is stirred and conveyed by a screw 441 and supplied to a developing sleeve 442 as a developer carrier. The two-component developer supplied to the developing sleeve 442 is regulated by a doctor blade 443 as a layer thickness regulating member, and the amount of developer supplied is controlled by a doctor gap which is a distance between the doctor blade 443 and the developing sleeve 442. The If the doctor gap is too small, the developer amount is too small and the image density is insufficient. Conversely, if the doctor gap is too large, the developer amount is excessively supplied and the photosensitive drum as an electrostatic latent image carrier. There arises a problem that carrier adhesion occurs on 1. Therefore, the developing sleeve 442 is provided with a magnet as a magnetic field generating means for generating a magnetic field so that the developer is sprinkled on the peripheral surface thereof, so as to follow a normal magnetic field line generated from the magnet. Then, the developer is spiked in a chain shape on the developing sleeve 442 to form a magnetic brush.

The developing sleeve 442 and the photosensitive drum 1 are disposed so as to be close to each other with a certain gap (developing gap) therebetween, and a developing region is formed in a portion facing both. The developing sleeve 442 is formed of a non-magnetic material such as aluminum, brass, stainless steel, or conductive resin in a cylindrical shape, and is rotated by a rotation drive mechanism (not shown). The magnetic brush is transferred to the developing area by the rotation of the developing sleeve 442. A developing voltage is applied to the developing sleeve 442 from a developing power source (not shown), and the toner on the magnetic brush is separated from the carrier by the developing electric field formed between the developing sleeve 442 and the photosensitive drum 1, and the photosensitive drum 1. It is developed on the upper electrostatic latent image. An alternating current may be superimposed on the development voltage.
The development gap is preferably about 5 to 30 times the particle size of the developer, and is preferably set to 0.5 to 1.5 mm if the developer particle size is 50 μm. If the development gap is wider than this, the desired image density may be difficult to achieve.
The doctor gap is preferably the same as or slightly larger than the development gap. The drum diameter and drum linear speed of the photosensitive drum 1 and the sleeve diameter and sleeve linear speed of the developing sleeve 442 are determined by restrictions such as the copying speed and the size of the apparatus. The ratio of the sleeve linear velocity to the drum linear velocity is preferably 1.1 or more in order to obtain a necessary image density. It is also possible to control the process conditions by installing a sensor at a position after development and detecting the toner adhesion amount from the optical reflectance.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image to a recording medium, and is performed using a transfer unit. As the transfer means. Using a transfer unit that directly transfers a visible image on the electrostatic latent image carrier to a recording medium, or an intermediate transfer member, after the primary transfer of the visible image onto the intermediate transfer member, the visible image is It is roughly divided into secondary transfer means for secondary transfer onto a recording medium.
The transfer can be performed, for example, by charging the visible latent image using a transfer charger and charging the electrostatic latent image carrier, and can be performed by the transfer unit. The transfer unit preferably includes a primary transfer unit that forms a composite transfer image by transferring a visible image onto an intermediate transfer member, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. .

-Intermediate transfer member-
There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably from well-known transfer bodies, For example, a transfer belt, a transfer roller, etc. are mentioned suitably.
The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably several Ωcm or more and 10 ³ Ωcm or less. Thus, by setting the volume resistance of the intermediate transfer member to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Therefore, transfer unevenness during secondary transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

There is no restriction | limiting in particular as a material of the said intermediate transfer body, Although it can select suitably according to the objective from well-known materials, the following are suitable.
(1) A material having a high Young's modulus (tensile modulus) is used as a single layer belt. For example, PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) and PAT (Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) and PC blend material, ETFE and PAT blend material, PC and PAT blend material, thermosetting of carbon black dispersion Examples thereof include polyimide. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and rib displacement is unlikely to occur particularly during color image formation.
(2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus (1) is used as a base layer and a surface layer or an intermediate layer is formed on the outer periphery thereof. It has a performance capable of preventing the line image from being lost due to the hardness of the single layer belt.
(3) An elastic belt having a relatively low Young's modulus using resin, rubber, or elastomer, and such an elastic belt has an advantage that almost no void in a line image occurs due to its softness. In addition, the elastic belt is wider than the drive roll and tension roll, and the elasticity of the belt ears protruding from the roll can be used to prevent meandering, thus reducing costs without requiring ribs or meandering prevention devices. it can.
Among these, the elastic belt (3) is particularly preferable.
The elastic belt is deformed corresponding to a toner layer and a recording medium having poor smoothness in the transfer portion. In other words, since the elastic belt deforms following the local unevenness, good adhesion can be obtained without excessively increasing the transfer pressure with respect to the toner layer, there is no void in characters, and flatness is poor. A transfer image with excellent uniformity can be obtained even on a recording medium.

  There is no restriction | limiting in particular as resin used for the said elastic belt, Although it can select suitably according to the objective, For example, polycarbonate resin, fluororesin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-alpha -Methylstyrene resin, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-acrylic) Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer Polymer (eg, styrene-methyl methacrylate copolymer) Styrene resins such as styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate copolymer, etc. Or a styrene-substituted monopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified) Acrylic resin, acrylic-urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyethylene resin, polypropylene Resin, polybutadiene Emissions, polyvinylidene chloride resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as rubber | gum used for the said elastic belt, According to the objective, it can select suitably, For example, natural rubber, butyl rubber, fluorine-type rubber, acrylic rubber, EPDM rubber, NBR rubber, acrylonitrile-butadiene-styrene rubber , Isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydride Examples thereof include phosphorus rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as an elastomer used for the said elastic belt, According to the objective, it can select suitably, For example, a polystyrene-type thermoplastic elastomer, a polyolefin-type thermoplastic elastomer, a polyvinyl chloride-type thermoplastic elastomer, a polyurethane-type thermoplasticity Examples thereof include elastomers, polyamide-based thermoplastic elastomers, polyurea thermoplastic elastomers, polyester-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers. These may be used individually by 1 type and may use 2 or more types together.

  The conductive agent for adjusting the resistance value used in the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal powder such as carbon black, graphite, aluminum, nickel; tin oxide, titanium oxide And conductive metal oxides such as antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), and indium oxide-tin oxide composite oxide (ITO). The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  In addition, the surface layer of the elastic belt prevents contamination of the electrostatic latent image carrier by the elastic material, reduces the frictional resistance of the belt surface, reduces the adhesion of the toner, and improves the cleaning property and the secondary transfer property. What can do is preferable. The surface layer is made of, for example, a binder resin such as a polyurethane resin, a polyester resin, or an epoxy resin, and a material capable of increasing the lubricity by reducing the surface energy, such as a fluororesin, a fluorine compound, a fluorocarbon, titanium dioxide, a silicon car It is preferable to contain powder or particles such as bites. Further, it is possible to use a material having a reduced surface energy by forming a fluorine-rich surface layer by heat treatment, such as a fluorine-based rubber material.

  There is no restriction | limiting in particular as a manufacturing method of the said elastic belt, Although it can select suitably according to the objective, For example, (1) Centrifugal molding method which pours material into a rotating cylindrical type | mold and forms a belt, ( 2) Spray coating method to form a film by spraying a liquid paint, (3) Dipping method in which a cylindrical mold is dipped in a solution of the material, and (4) Casting to be injected into an inner mold or an outer mold And (5) a method in which a compound is wound around a cylindrical mold and vulcanized and polished.

The method for preventing the elastic belt from stretching is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a method of adding a material for preventing elongation to the core layer, 2) A method of forming a rubber layer on a core layer with little elongation, and the like.
There is no restriction | limiting in particular as a material which prevents the said elongation, Although it can select suitably according to the objective, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol Synthetic fibers such as fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers; inorganic fibers such as carbon fibers, glass fibers, boron fibers; iron fibers, copper fibers, etc. A metal fiber etc. are mentioned, What made these materials into the shape of a woven fabric or a thread form is used suitably.

The method for forming the core layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a woven fabric woven in a cylindrical shape is covered with a mold or the like and coated thereon (2) A method of providing a coating layer on one or both sides of the core layer by immersing a woven fabric woven in a cylindrical shape into liquid rubber, etc. For example, a method of winding in a spiral shape and providing a coating layer thereon may be used.
The thickness of the coating layer depends on the hardness of the coating layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur on the surface layer. Further, since the amount of expansion / contraction increases and the expansion and contraction of the image increase, it is not preferable that the thickness is too large (about 1 mm or more).

The transfer unit (the primary transfer unit and the secondary transfer unit) has at least a transfer unit that peels and charges the visible image formed on the electrostatic latent image carrier to the recording medium side. Is preferred. There may be one transfer unit or two or more transfer units. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as an unfixed image after development can be transferred, and can be appropriately selected according to the purpose. Etc. can also be used.

-Transfer means of tandem type image forming apparatus-
The tandem type image forming apparatus has a plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit. In this tandem type image forming apparatus, four image forming elements for yellow, magenta, cyan, and black are mounted, and each visible image is created in parallel with the four image forming elements, and is recorded on a recording medium or an intermediate transfer member. Therefore, a full color image can be formed at a higher speed.

  As the tandem type image forming apparatus, (1) as shown in FIG. 7, the surface moves so as to pass through a transfer position which is a region facing each electrostatic latent image carrier 1 of a plurality of image forming elements. A direct transfer system in which the visible image formed on each electrostatic latent image carrier 1 is sequentially transferred to the recording medium S by the transfer means 2, and (2) a plurality of images as shown in FIG. The visible image on each electrostatic latent image carrier 1 of the forming element is once transferred sequentially to the intermediate transfer body 4 by the transfer means (primary transfer means) 2, and then the image on the intermediate transfer body 4 is transferred to the secondary transfer means 5. There is an indirect transfer method in which the image is transferred to the recording medium S at once. In FIG. 8, a transfer conveyance belt is used as the secondary transfer unit, but a roller shape may be used.

Comparing the direct transfer method (1) and the indirect transfer method (2), the direct transfer method (1) is a tandem type image forming unit T in which the electrostatic latent image carriers 1 are arranged. The sheet feeding device 6 must be disposed on the upstream side, and the fixing device 7 as a fixing unit must be disposed on the downstream side, which increases the size in the recording medium conveyance direction. On the other hand, in the indirect transfer method (2), the secondary transfer position can be set relatively freely, and the paper feeding device 6 and the fixing device 7 are arranged so as to overlap the tandem type image forming unit T. There is an advantage that downsizing is possible.
In the direct transfer method (1), the fixing device 7 is disposed close to the tandem image forming unit T in order not to increase the size in the recording medium conveyance direction. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the recording medium S can bend, and an impact when the leading end of the recording medium S enters the fixing device 7 (particularly with a thick recording medium). In addition, the fixing device 7 tends to affect upstream image formation due to the speed difference between the recording medium conveyance speed when passing through the fixing device 7 and the recording medium conveyance speed by the transfer conveyance belt. On the other hand, in the indirect transfer method (2), the fixing device 7 can be disposed with a sufficient margin that the recording medium S can bend, so that the fixing device 7 hardly affects image formation.
In view of the above, in recent years, indirect transfer methods have attracted attention. In such a color image forming apparatus, as shown in FIG. 8, the transfer residual toner remaining on the electrostatic latent image carrier 1 after the primary transfer is removed by a cleaning device 8 as a cleaning unit, and the electrostatic latent image is thus removed. The surface of the carrier 1 is cleaned to prepare for the image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. A fixing device having a fixing member and a heat source for heating the fixing member is preferably used.
The fixing member is not particularly limited as long as it can contact each other to form a nip portion, and can be appropriately selected according to the purpose. For example, a combination of an endless belt and a roller, a roller and a roller, The heating method from the surface of the fixing member by a combination of an endless belt and a roller or induction heating can be used in order to reduce the warm-up time and realize energy saving. It is preferable to use it.
Examples of the fixing member include known heating and pressing means (combination of heating means and pressing means). In the case of a combination of the endless belt and the roller, for example, a combination of a heating roller, a pressure roller, and an endless belt may be used as the heating and pressing unit, and the combination of the roller and the roller may be used. In this case, for example, a combination of a heating roller and a pressure roller can be used.

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

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

In the fixing step, the image by the toner may be transferred to the recording medium, and the recording medium on which the image has been transferred may be passed through the nip portion to fix the image to the recording medium. The image may be transferred and fixed to the recording medium at the nip portion at the same time.
The fixing step may be performed each time the toner of each color is transferred to the recording medium, or may be performed at the same time in a state where the toner of each color is stacked.

The nip portion is formed by bringing at least two fixing members into contact with each other.
The surface pressure of the nip portion is not particularly limited and may be appropriately selected depending on the intended purpose, 5N / cm ² or more, more preferably ^{7~100N / cm 2, 10~60N / cm} 2 Is more preferable. If the surface pressure of the nip portion is too high, the durability of the roller may decrease. On the other hand, if the surface pressure of the nip portion is less than 5 N / cm ² , the offset prevention property may be insufficient.

  The temperature for fixing the image on the recording medium with the toner (that is, the surface temperature of the fixing member by the heating unit) is not particularly limited and may be appropriately selected depending on the intended purpose. 170 degreeC is preferable and 120 to 160 degreeC is more preferable. If the fixing temperature is less than 120 ° C., the fixability may be insufficient, and if it exceeds 170 ° C., it is not preferable in terms of realizing energy saving.

As the fixing means, (1) an aspect in which the fixing means has at least one of a roller and a belt, is heated from a surface not in contact with the toner, and the transferred image transferred onto the recording medium is fixed by heating and pressing. (Internal heating system) and (2) A fixing unit has at least one of a roller and a belt, and heats and presses a transfer image transferred onto a recording medium by heating from the surface in contact with the toner. (External heating method). It is also possible to use a combination of both.
As the internal heating type fixing means (1), for example, the fixing member itself has a heating means inside. Examples of such heating means include a heat source such as a heater and a halogen lamp.

As the (2) external heating type fixing means, for example, at least a part of the surface of at least one of the fixing members is preferably heated by the heating means. There is no restriction | limiting in particular as such a heating means, According to the objective, it can select suitably, For example, an electromagnetic induction heating means etc. are mentioned.
There is no restriction | limiting in particular as said electromagnetic induction heating means, Although it can select suitably according to the objective, What has a means to generate | occur | produce a magnetic field and a means to generate | occur | produce heat | fever by electromagnetic induction, etc. are suitable.
The electromagnetic induction heating means includes, for example, an induction coil disposed so as to be close to the fixing member (for example, a heating roller), a shielding layer provided with the induction coil, and an induction coil of the shielding layer. What consists of an insulating layer provided in the other side of the provided surface is preferable. In this case, it is preferable that the heating roller is formed of a magnetic material or a heat pipe.
The induction coil is arranged in a state of wrapping at least a semi-cylindrical portion on the opposite side of the contact portion between the heating roller and the fixing member (for example, a pressure roller, an endless belt, etc.) of the heating roller. Is preferred.

-Internal heating type fixing means-
FIG. 9 is a belt-type fixing device showing an example of an internal heating type fixing means. The belt-type fixing device 510 in FIG. 9 includes a heating roller 511, a fixing roller 512, a fixing belt 513, and a pressure roller 514.
The fixing belt 513 is stretched by a heating roller 511 and a fixing roller 512 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 511. The heating roller 511 has a built-in heating source 515 and is designed so that the temperature can be adjusted by a temperature sensor 517 attached in the vicinity of the heating roller 511. The fixing roller 512 is rotatably disposed inside the fixing belt 513 and in contact with the inner surface of the fixing belt 513. The pressure roller 514 is in contact with the outer side of the fixing belt 513 and the outer surface of the fixing belt 513 so as to press the fixing roller 512 and is rotatably arranged. Further, the surface hardness of the fixing belt 513 is lower than the surface hardness of the pressure roller 514, and the nip portion N formed between the fixing roller 512 and the pressure roller 514 has an introduction side end and a discharge side of the recording medium S. An intermediate region located between the ends is located closer to the fixing roller 512 than the introduction side end and the discharge side end.

In the belt-type fixing device 510 shown in FIG. 9, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the heating roller 511. The toner image T on the recording medium S is heated and melted by the heating roller 511 and the fixing belt 513 heated to a predetermined temperature by the action of the built-in heating source 515. In this state, the recording medium S is inserted into a nip portion N formed between the fixing roller 512 and the pressure roller 514. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 513 that rotates in conjunction with the rotation of the fixing roller 512 and the pressure roller 514 and is pressed when passing through the nip N. The toner image T is fixed on the recording medium S.
Next, the recording medium S on which the toner image T is fixed passes between the fixing roller 512 and the pressure roller 514, is peeled off from the fixing belt 513, and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 514, and the winding of the recording medium S around the fixing belt 513 is prevented. The fixing belt 513 is cleaned by the cleaning roller 516.

Further, the heat roll type fixing device 515 shown in FIG. 10 includes a heating roller 520 as the fixing member and a pressure roller 530 disposed in contact therewith.
The heating roller 520 has a hollow metal cylinder 521, the surface of which is covered with an offset prevention layer 522, and a heating lamp 523 is disposed therein. The pressure roller 530 includes a metal cylinder 531 and the surface thereof is covered with an offset prevention layer 532. In the pressure roller 530, the metal cylinder 531 may have a hollow shape, and a heating lamp 533 may be disposed therein.
The heating roller 520 and the pressure roller 530 are urged by a spring (not shown), and are rotatably provided in a pressure-contacted state to form a nip portion N. Further, the surface hardness of the offset prevention layer 522 in the heating roller 520 is lower than the surface hardness of the offset prevention layer 532 in the pressure roller 530, and in the nip portion N formed between the heating roller 520 and the pressure roller 530, An intermediate region located between the introduction side end and the discharge side end of the recording medium S is located closer to the heating roller 520 than the introduction side end and the discharge side end.

In the heat roll type fixing device 515 shown in FIG. 10, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the nip portion N between the heating roller 520 and the pressure roller 530. The toner T on the recording medium S is heated and melted by the heating roller 520 heated to a predetermined temperature by the action of the built-in heating lamp 523, and at the same time, when passing through the nip portion N, the toner T is heated. The toner image T is fixed on the recording medium S by being pressed by the pressing force of the pressure roller 530.
Next, the recording medium S on which the toner image T is fixed passes between the heating roller 520 and the pressure roller 530 and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 530, and the recording medium S is prevented from being wound around the pressure roller 530. The heating roller 520 is cleaned by a cleaning roller (not shown).

-External heating type fixing means-
FIG. 11 shows an electromagnetic induction heating type fixing device 570 showing an example of an external heating type fixing unit. The electromagnetic induction heating type fixing device 570 includes a heating roller 566, a fixing roller 580, a fixing belt 567, a pressure roller 590, and an electromagnetic induction heating unit 560.
The fixing belt 567 is stretched by a heating roller 566 and a fixing roller 580 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 566.
The heating roller 566 has, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals. For example, the outer diameter is 20 to 40 mm and the wall thickness is 0.3 to 1.0 mm. It has a low heat capacity and quick temperature rise.
The fixing roller 580 has, for example, a metal core 581 made of stainless steel or the like, and the surface thereof is formed by covering a heat-resistant silicone rubber with a solid or foamed elastic layer 582. It is disposed inside the fixing belt 567 and rotatably while being in contact with the inner surface of the fixing belt 567. The fixing roller 580 is provided with an outer diameter of about 20 to 40 mm in order to form a nip portion N having a predetermined width between the pressure roller 590 and the fixing roller 580 by the pressing force from the pressure roller 590, and is heated. It is larger than the roller 566. The elastic layer 582 has a thickness of about 4 to 6 mm, and is formed so that the heat capacity of the heating roller 566 is smaller than the heat capacity of the fixing roller 580, thereby shortening the warm-up time of the heating roller 566.
The pressure roller 590 has a metal core 591 made of a cylindrical member made of a metal having high thermal conductivity such as copper or aluminum, and the surface thereof is covered with an elastic layer 592 having high heat resistance and high toner releasability. The fixing roller 580 is in contact with the outer surface of the fixing belt 567 and the outer surface of the fixing belt 567 so as to be in pressure contact with the fixing belt 567, and is rotatably disposed. In addition to the above metal, SUS may be used for the metal core 591.
The electromagnetic induction heating unit 560 is disposed in the vicinity of the heating roller 566 and in the axial direction of the heating roller 566. The electromagnetic induction heating unit 560 includes an excitation coil 561 that is a magnetic field generation unit, and a coil guide plate 562 around which the excitation coil 561 is wound. The coil guide plate 562 has a semi-cylindrical shape disposed close to the outer peripheral surface of the heating roller 566, and the exciting coil 561 is formed by passing a long exciting coil wire along the coil guide plate 562 in the axial direction of the heating roller 566. It is one that is wound around alternately. The exciting coil 561 is connected to a driving power source (not shown) whose frequency is variable. On the outside of the excitation coil 561, a semi-cylindrical excitation coil core 563 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 564 and is disposed close to the excitation coil 561.

In the electromagnetic induction heating type fixing device 570 shown in FIG. 11, when the excitation coil 561 of the electromagnetic induction heating unit 560 is energized, an alternating magnetic field is formed around the electromagnetic induction heating unit 560, close to the excitation coil 561, and The heating roller 566 surrounded by the excitation coil 561 is preheated uniformly and efficiently by excitation of overcurrent. The recording medium S on which the toner image T to be fixed is formed is conveyed to the nip N between the fixing roller 580 and the pressure roller 590. The toner image T on the recording medium S is then heated by the fixing belt 567 heated at the contact portion W1 with the heating roller 566 by the heating roller 566 heated to a predetermined temperature by the action of the electromagnetic induction heating unit 560. It is heated and becomes a molten state. In this state, the recording medium S is inserted into a nip portion N formed between the fixing roller 580 and the pressure roller 590. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 567 that rotates in conjunction with the rotation of the fixing roller 580 and the pressure roller 590 and is pressed when passing through the nip N. The toner image T is fixed on the recording medium S.
Next, the recording medium S on which the toner image T is fixed passes between the fixing roller 580 and the pressure roller 590, is peeled off from the fixing belt 567, and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 590 and the winding of the recording medium S around the fixing belt 567 is prevented. The fixing belt 567 is cleaned by a cleaning roller (not shown).

12 includes a fixing roller 520 serving as the fixing member, a pressure roller 530 disposed in contact with the fixing roller 520, a fixing roller 520, and a pressure roller. The fixing unit includes an electromagnetic induction heating source 540 that heats from the outside.
The fixing roller 520 includes a cored bar 521, and the surface thereof is formed by covering a heat insulating elastic layer 522, a heat generating layer 523, and a release layer 524 in this order. The pressure roller 530 has a metal core 531, and the surface thereof is formed by covering a heat insulating elastic layer 532, a heat generating layer 533, and a release layer 534 in this order. Note that the release layer 524 and the release layer 534 are formed of tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA).
The fixing roller 520 and the pressure roller 530 are urged by a spring (not shown), and are rotatably provided in a pressure-contacted state to form a nip portion N.
The electromagnetic induction heating source 540 is disposed in the vicinity of the fixing roller 520 and the pressure roller 530, respectively, and heats the heat generation layer 523 and the heat generation layer 533 by electromagnetic induction.
In the fixing device shown in FIG. 12, the fixing roller 520 and the pressure roller 530 are uniformly and efficiently preheated by the electromagnetic induction heating source 540. In addition, since the combination of the roller and the roller, a high surface pressure of the nip portion N can be easily realized.

<Cleaning process and cleaning means>
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
Further, the developing means has a developer carrier that abuts on the surface of the electrostatic latent image carrier, and develops the electrostatic latent image formed on the electrostatic latent image carrier and By collecting the residual toner on the latent image carrier, cleaning can be performed without providing a cleaning means (cleaning-less method).

The cleaning means is not particularly limited, and may be selected from known cleaners as long as it can remove the toner remaining on the electrostatic latent image carrier. For example, a magnetic brush cleaner, Examples thereof include an electrostatic brush cleaner, a magnetic roller cleaner, a cleaning blade, a brush cleaner, and a web cleaner. Among these, a cleaning blade having a high toner removing ability, a small size and an inexpensive price is particularly preferable.
Examples of the material of the rubber blade used for the cleaning blade include urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, and the like. Among these, urethane rubber is particularly preferable.

  Here, FIG. 13 is an explanatory view showing, in an enlarged manner, the vicinity of the contact portion 615 of the cleaning blade 613 with the electrostatic latent image carrier. The cleaning blade 613 is provided with a toner blocking surface 617 that forms a space S that expands from the contact portion 615 toward the upstream side in the rotation direction of the electrostatic latent image carrier with the surface of the photosensitive drum 1. Yes. In the present embodiment, the toner blocking surface 617 extends from the contact portion 615 to the upstream side in the rotation direction of the photosensitive drum 1 so that the space S has an acute angle.

  As shown in FIG. 13, the toner blocking surface 617 is provided with a coating portion 618 as a high friction portion having a higher friction coefficient than the cleaning blade 613. The coating portion 618 is formed of a material (high friction material) having a higher friction coefficient than the material forming the cleaning blade 613. Examples of such a high friction material include DLC (diamond-like carbon). The high friction material is not limited to DLC. The coating unit 618 is provided in a range where the toner blocking surface 617 does not contact the surface of the photosensitive drum 1.

  Although not shown, the cleaning unit includes a toner collection blade that collects the residual toner scraped by the cleaning blade, a toner collection coil that conveys the residual toner collected by the toner collection blade to the collection unit, and the like. ing.

-Cleaning-less image forming device-
FIG. 14 is a schematic diagram illustrating an example of a cleaningless type image forming apparatus in which the developing unit also serves as the cleaning unit.
In FIG. 14, 1 is a photosensitive drum as an electrostatic latent image carrier, 620 is a brush charging device as contact charging means, 603 is an exposure device as exposure means, 604 is a developing device as developing means, and 640 is a supply. A paper cassette, 650 is a roller transfer means, and P is a recording medium.

In this cleaningless type image forming apparatus, the transfer residual toner on the surface of the photosensitive drum 1 reaches the position of the contact charging device 620 in contact with the photosensitive drum 1 by the subsequent rotation of the photosensitive drum 1, and the photosensitive drum. 1 is temporarily collected by a magnetic brush portion (not shown) of the brush charging member 621 that is in contact with the toner 1, and the collected toner is again discharged onto the surface of the photosensitive drum 1 to finally enter the developing device 604. The toner is collected together with the developer by the developer carrier 631, and the photosensitive drum 1 is repeatedly used for image formation.
Here, the developing means 604 also serves as a cleaning means that the toner slightly remaining on the photosensitive drum 1 after the transfer is developed bias (between the DC voltage applied to the developer carrier 631 and the surface potential of the photosensitive drum 1). It means a method of recovery by potential difference.
In such a cleaningless type image forming apparatus in which the developing unit also serves as a cleaning unit, the transfer residual toner is collected by the developing unit 604 and is used after the next step, so that waste toner is eliminated, maintenance-free, and cleaner-less. Since it becomes a system, the advantage in terms of space is remarkably large, and the image forming apparatus can be greatly downsized.

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

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

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

-Image forming apparatus and image forming method-
Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 15 includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure 30 by an exposure unit as an exposure unit, and a developing unit as a developing unit. 40, an intermediate transfer member 50, a cleaning blade 60 as a cleaning means, and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.

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

  In the image forming apparatus 100 shown in FIG. 15, first, the charging roller 20 uniformly charges the photosensitive drum 10. An exposure device (not shown) performs image-wise exposure 30 on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image. The visible image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the recording medium 95. As a result, a transfer image is formed on the recording medium 95. The residual toner on the electrostatic latent image carrier 10 is removed by the cleaning blade 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination lamp 70.

  Next, another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 16 does not include the developing belt 41 as the developer carrying member in the image forming apparatus 100 shown in FIG. 15, and the black developing unit 45 </ b> K is disposed around the electrostatic latent image carrying member 10. The yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are configured in the same manner as the image forming apparatus 100 shown in FIG. Show. In FIG. 16, the same components as those in FIG. 15 are denoted by the same reference numerals.

-Tandem type image forming apparatus and image forming method-
Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem type image forming apparatus shown in FIG. 17 is a tandem type color image forming apparatus. The tandem color image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 17. In the vicinity of the support roller 15, an intermediate transfer member cleaning unit 17 for removing residual toner on the intermediate transfer member 50 is disposed. A tandem in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 along the conveyance direction. A mold developing means 120 is arranged. An exposure device 21 is disposed in the vicinity of the tandem developing unit 120. A secondary transfer unit 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing unit 120 is disposed. In the secondary transfer unit 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer unit 22.
In addition, a reversing device 28 for reversing the recording medium in order to form an image on both sides of the recording medium is disposed in the vicinity of the secondary transfer unit 22 and the fixing device 25.

  Next, formation of a full-color image (color copy) using the tandem developing unit 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

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

  The image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing unit 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing means 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier 10 is uniformly charged, and the electrostatic latent image carrier is exposed like an image corresponding to each color image based on each color image information (L in FIG. 18). An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Using The image forming apparatus includes a developing device 61 configured to form a toner image using each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64. Each single-color image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the recording roller 142 is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording medium. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and the recording medium is sent between the intermediate transfer member 50 and the secondary transfer unit 22. Then, by transferring (secondary transfer) the composite color image (color transfer image) onto the recording medium by the secondary transfer means 22, a color image is transferred and formed on the recording medium. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording medium on which the color image has been transferred is conveyed by the secondary transfer means 22 and sent to the fixing device 25, where the combined color image (color transfer image) is generated by heat and pressure. ) Is fixed on the recording medium. After that, the recording medium is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57. Alternatively, the recording medium is switched by the switching claw 55 and reversed by the reversing device 28 and led again to the transfer position. After the image is also recorded on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

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

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using toner to produce a visible image. A developing unit to be formed, and other units such as a charging unit, an exposure unit, a transfer unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary.
The toner contains at least a binder resin and a colorant, and the binder resin includes a polyester resin (A) and a polyester resin (B) having a softening point higher by 10 ° C. or more than the polyester resin (A). Containing
A polyester unit in which at least one of the polyester resins (A) and (B) is obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid-modified rosin and acrylic acid-modified rosin. It is a resin derived from fumaric acid / acrylic acid modified rosin.
About the detail of the said polyester resin (A) and (B), the thing similar to what was demonstrated with the image forming apparatus and image forming method mentioned above can be used.

The developing means includes at least a developer container that contains the toner or the developer, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer carried on the developer carrying member. Specifically, any one of the one-component developing unit and the two-component developing unit described in the image forming apparatus and the image forming method can be preferably used.
Further, as the charging unit, the exposure unit, the transfer unit, the cleaning unit, and the charge eliminating unit, the same ones as those of the above-described image forming apparatus can be appropriately selected and used.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, facsimile machines, and printers, and it is particularly preferable that the process cartridge is detachably provided in the image forming apparatus of the present invention.

Here, for example, as shown in FIG. 19, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further if necessary. And other means. In FIG. 19, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 19 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

In the image forming apparatus, the image forming method, and the process cartridge of the present invention, the toner binder resin contains an alcohol component and at least one of a fumaric acid-modified rosin, an acrylic acid-modified rosin, and an itaconic acid-modified rosin. A polyester resin obtained by condensation polymerization with a carboxylic acid component, wherein the content of the carboxylic acid component is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component, and abietic acid in the toner Since the toner having a content of 1% by mass or less is used, it is possible to form a high-quality image that is excellent in chargeability, spent resistance, and transferability and that does not deteriorate image quality over a long period of time. .

Examples of the present invention will be described below, but the present invention is not limited to these examples.
The characteristic values of the polyester resin and rosin compound and the weight average particle diameter of the toner in the following synthesis examples, production examples, examples, and comparative examples were measured as follows.

<Softening point of resin>
(1) Preparation of sample 10 g of resin was melted on a hot plate at 170 ° C. for 2 hours. Then, it was naturally cooled for 1 hour under an environment of a temperature of 25 ° C. and a relative humidity of 50% in an opened state, and pulverized for 10 seconds with a coffee mill (National MK-61M).
(2) Measurement Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. Extruded from the nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

<Measurement of glass transition temperature (Tg) of resin>
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), 0.01 to 0.02 g of sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature was lowered at a rate of 10 ° C./min. The sample cooled to 0 ° C is heated at a heating rate of 10 ° C / min, and the intersection of the baseline extension line below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rise to the peak apex Was defined as the glass transition temperature.

<Resin acid value>
It measured based on the method of JISK0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

<Weight average particle diameter of toner>
Measuring instrument: Coulter Multisizer III (Beckman Coulter, Inc.)
・ Aperture diameter: 100μm
・ Analysis software: Beckman Coulter Multisizer 3 Version 3.51 (Beckman Coulter)
・ Electrolyte: Isoton III (Beckman Coulter, Inc.)
-Dispersion: 10% by mass surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
-Dispersion condition: 10 mg of a measurement sample was added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 mL of an electrolyte was added, and further dispersed for 1 minute with an ultrasonic disperser.
・ Measurement conditions: Add 100 mL of electrolyte and dispersion into a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and calculate the weight average particle size from the particle size distribution. Asked.

<Content of abietic acid in rosin or toner>
The sample was dissolved in acetone, adjusted to be a 0.3 mass% solution, methyl esterified with diazomethane, and then GC (gas chromatography, Agilent, HP6890) under the following measurement conditions. Analysis was carried out.
-GC measurement conditions-
Analytical column: HP-5 (30 m-250 μm-0.25 μm)
・ Carrier: Helium (He)
・ Flow rate conditions: 1 ml / min
・ Inlet temperature: 250 ° C
Column head pressure: 126.8 kPa
Injection mode: split
-Oven temperature condition: after holding at 180 ° C. for 5 min, increase to 200 ° C. at a rate of 2 ° C./min and hold at 200 ° C. for 5 min

(Synthesis Example 1)
-Synthesis of acrylic acid-modified rosin-
To a 10-liter flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5630 g of unpurified tall rosin and 610 g of acrylic acid are added, and the temperature is raised from 160 ° C. to 210 ° C. over 2 hours. After reacting for 3 hours, distillation was carried out at 210 ° C. under a reduced pressure of 4 kPa to synthesize modified rosin modified with acrylic acid (acrylic acid modified rosin).
The content of abietic acid in the unpurified tall rosin used to produce the acrylic acid-modified rosin was 35.9% by mass, and the content of abietic acid in the acrylic acid-modified rosin was 14.2% by mass. It was.

(Synthesis Example 2)
-Synthesis of itaconic acid-modified rosin-
In a 10-liter flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5630 g of unpurified tall rosin used for the production of acrylic acid-modified rosin and 1130 g of itaconic acid were added, and the temperature was increased from 160 ° C. to 210 ° C. for 2 hours. Then, the mixture was reacted at 210 ° C. for 3 hours, and then distilled at 210 ° C. under a reduced pressure of 4 kPa, thereby synthesizing a modified rosin modified with itaconic acid (itaconic acid-modified rosin).
The content of abietic acid in the obtained itaconic acid-modified rosin was 4.1% by mass.

(Synthesis Example 3)
-Synthesis of fumaric acid-modified rosin-
In a 10-liter flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5630 g of unpurified tall rosin and 950 g of fumaric acid used for the production of acrylic acid-modified rosin were added, and the temperature was increased from 160 ° C. to 210 ° C. for 2 hours. Then, the mixture was reacted at 210 ° C. for 3 hours, and then distilled at 210 ° C. under a reduced pressure of 4 kPa to synthesize a modified rosin modified with fumaric acid (fumaric acid-modified rosin).
The content of abietic acid in the obtained fumaric acid-modified rosin was 2.6% by mass.

(Synthesis Example 4)
-Synthesis of Resins 1-3 and Resins 10-12-
The alcohol component, carboxylic acid component other than trimellitic anhydride, and esterification catalyst shown in Table 1-1 and Table 1-2 below, and a 5 L capacity equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple After putting into a four-necked flask and subjecting it to a condensation polymerization reaction at 235 ° C. for 15 hours in a nitrogen atmosphere, the reaction was carried out at 235 ° C. for 1 hour under 8.0 kPa. After cooling to 210 ° C., trimellitic anhydride shown in Table 1-1 and Table 1-2 was added, and the reaction was performed at 210 ° C. for 1 hour under normal pressure (101.3 kPa). Then, the reaction was performed to a desired softening point to synthesize polyester resins (resins 1 to 3 and resins 10 to 12).

(Synthesis Example 5)
-Synthesis of Resins 4-6-
The alcohol component, the carboxylic acid component other than trimellitic anhydride, and the esterification catalyst shown in Table 1-1 below were mixed in a 5 L volume equipped with a nitrogen introduction tube, a dehydration tube, a rectifying column, a stirrer, and a thermocouple. The mixture was placed in a necked flask and subjected to a condensation polymerization reaction at 235 ° C. for 15 hours in a nitrogen atmosphere, and then reacted at 235 ° C. for 2 hours under 8.0 kPa. After cooling to 210 ° C., trimellitic anhydride shown in Table 1-1 was added, the reaction was performed at 210 ° C. for 2 hours under normal pressure (101.3 kPa), and the desired softening point at 210 ° C. and 10 kPa. The polyester resin (resins 4 to 6) was synthesized.

(Synthesis Example 6)
-Synthesis of Resins 7-9-
The alcohol component, the carboxylic acid component other than the modified rosin, and the esterification catalyst shown in Table 1-2 below are placed in a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. Then, after performing a condensation polymerization reaction at 230 ° C. for 15 hours in a nitrogen atmosphere, the reaction was performed at 230 ° C. for 1 hour under 8.0 kPa. After cooling to 180 ° C., the modified rosin shown in Table 1-2 was added, the temperature was raised to 210 ° C. over 3 hours under normal pressure (101.3 kPa), and 10 hours at normal pressure (101.3 kPa). After making it react, it reacted to 210 degreeC and 20 kPa to a desired softening point, and synthesize | combined the polyester resin (resins 7-9).

(* 1): Content in the total mass of alcohol component and carboxylic acid component

(Master batch production example 1)
-Preparation of master batch 1-
The pigment having the following composition, the resin 1, and pure water were mixed at a ratio of 1: 1: 0.5 (mass ratio) and kneaded by two rolls. Kneading is performed at 70 ° C., and then the roll temperature is increased to 120 ° C. to evaporate water, and cyan master batch 1 (TB-C1), magenta master batch 1 (TB-M1), yellow master batch 1 (TB -Y1), and master batch 1 consisting of black master batch 1 (TB-K1) was produced.
[Cyan toner masterbatch 1 formulation: (TB-C1)]
-Resin 1 ... 100 parts by mass-Cyan pigment (CI Pigment blue 15: 3) ... 100 parts by mass-Pure water ... 50 parts by mass [Magenta Toner Masterbatch 1 Formula: (TB-M1) )]
-Resin 1 ... 100 parts by mass-Magenta pigment (CI Pigment red 122) ... 100 parts by mass-Pure water ... 50 parts by mass [Yellow Toner Masterbatch 1 Formula: (TB-Y1)]
-Resin 1 ... 100 parts by mass-Yellow pigment (CI Pigment yellow 180) ... 100 parts by mass-Pure water ... 50 parts by mass [Black toner masterbatch 1 formulation: (TB-K1)]
-Resin 1 ... 100 parts by mass-Black pigment (carbon black) ... 100 parts by mass-Pure water ... 50 parts by mass

(Master batch production example 2)
-Preparation of master batches 2-12-
In master batch production example 1, except that resin 1 was changed to resins 2 to 12, cyan master batches 2 to 12 (TB-C2 to TB-C12), magenta master batch 2 were the same as in master batch production example 1. Master batch 2 consisting of -12 (TB-M2-TB-M12), yellow master batch 2-12 (TB-Y2-TB-Y12), and black master batch 2-12 (TB-K2-TB-K12). 12 were prepared.

(Toner Production Example 1)
Toner 1 composed of cyan toner 1, magenta toner 1, yellow toner 1, and black toner 1 was produced as follows.
-Preparation of cyan toner 1-
Cyan toner formulation 1 having the following composition was premixed using a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.), and then kneaded using a biaxial kneader (PCM-30, manufactured by Ikegai Co., Ltd.). Next, the mixture was finely pulverized using a supersonic jet crusher lab jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), and then classified by an airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Produced toner base particles having a particle size of 7 μm.
Next, 1.0 part by mass of colloidal silica (H-2000, manufactured by Clariant Co., Ltd.) was mixed with 100 parts by mass of toner base particles using a sample mill to prepare cyan toner 1.
[Cyan Toner Formula 1]
-Resin 1 ... 92 parts by mass-Cyan masterbatch 1 (TB-C1) ... 16 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) ... 1 part by mass-Ester wax (Acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass

-Preparation of magenta toner 1-
A magenta toner 1 was produced in the same manner as the cyan toner 1 except that the cyan toner formulation 1 was changed to the magenta toner formulation 1 having the following composition in the cyan toner 1 production method.
[Magenta Toner Formula 1]
-Binder resin 1 ... 92 parts by mass-Magenta masterbatch 1 (TB-M1) ... 16 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) ... 1 part by mass-Ester Wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600)... 5 parts by mass

-Preparation of Yellow Toner 1-
A yellow toner 1 was produced in the same manner as the cyan toner 1 except that the cyan toner formulation 1 was changed to a yellow toner formulation 1 having the following composition in the cyan toner 1 production method.
[Yellow Toner Formula 1]
-Binder resin 1 ... 92 parts by mass-Yellow masterbatch 1 (TB-Y1) ... 16 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) ... 1 part by mass-Ester Wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600)... 5 parts by mass

-Preparation of black toner 1-
A black toner 1 was produced in the same manner as the cyan toner 1 except that the cyan toner formulation 1 was changed to the black toner formulation 1 having the following composition in the cyan toner 1 production method.
[Black Toner Formula 1]
-Binder resin 1 ... 92 parts by mass-Black masterbatch 1 (TB-K1) ... 16 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) ... 1 part by mass-Ester Wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600)... 5 parts by mass

(Toner Production Examples 2 to 12)
-Production of toners 2-12-
In the toner production example 1, except that the resin 1 is changed to the resins 2 to 12, the same as the toner production example 1, the cyan toner 2 to 12, the yellow toner 2 to 12, the magenta toner 2 to the toner production example 2 to 12, No. 12 and black toners 2 to 12 were produced.

* Numbers in parentheses indicate parts by mass

(Examples 1-6, 13-14 and Comparative Examples 1-3, 7)
The produced toners 1 to 12 were loaded into the image forming apparatus A shown in FIG. 20 to perform image formation, and various performance evaluations were performed as follows. The results are shown in Table 3.
<Image forming apparatus A>
An image forming apparatus A shown in FIG. 20 is a tandem type image forming apparatus of a direct transfer method adopting a contact charging method, a one-component developing method, a direct transfer method, a cleanerless method, and an internal heating belt fixing method.
In the image forming apparatus A shown in FIG. 20, a charging roller of a contact type as shown in FIG. As the developing means 324, a one-component developing device as shown in FIG. 5 is used, and this developing device adopts a cleaner-less system capable of collecting residual toner. A belt-type fixing device as shown in FIG. 9 is adopted as the fixing means 327, and this fixing device uses a halogen lamp as a heat source of the heating roller. In FIG. 20, 330 is a conveyor belt.
The image forming element 341 in the image forming apparatus A shown in FIG. 20 is provided with a charging unit 310, an exposure unit 323, a developing unit 324, and a transfer unit 325 around the photosensitive drum 321. As the photosensitive drum 321 in the image forming element 341 rotates, an electrostatic latent image corresponding to the exposure image is formed on the surface by charging by the charging unit 310 and exposure by the exposure unit 323. This electrostatic latent image is developed with yellow toner by the developing means 324, and a visible image with yellow toner is formed on the photosensitive drum 321. This visible image is transferred onto the recording medium 326 by the transfer unit 325, and then the toner remaining on the photosensitive drum 321 is collected by the developing unit 324. Similarly, the image forming elements 342, 343, and 344 superimpose visible images of magenta toner, cyan toner, and black toner on the recording medium 326, and the color image formed on the recording medium 326 is fixed by the fixing unit. 327 is fixed.

(Examples 7-12, 15-16 and Comparative Examples 4-6, 8)
-Carrier manufacturing-
A coating material having the following composition is dispersed with a stirrer for 10 minutes to prepare a coating solution, and this coating solution and 5,000 parts by mass of a core material (Cu—Zn ferrite particles, mass average diameter = 35 μm) are rotated into a fluidized bed. The coating liquid was applied to the core material by applying it to a coating apparatus for coating while forming a swirling flow provided with a type bottom plate disk and stirring blades. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to prepare a carrier.
[Coating material composition]
-Toluene: 450 parts by mass-Silicone resin (SR2400, manufactured by Toray Dow Corning Silicone Co., Ltd., nonvolatile content 50 mass%): 450 parts by mass-Aminosilane (SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.) ) ... 10 parts by massCarbon black ... 10 parts by mass

-Preparation of two-component developer-
A two-component developer composed of 5% by mass of each of the produced toners 1 to 12 and 95% by mass of the produced carrier was prepared by a conventional method.

-Image formation and evaluation-
The image forming apparatus B shown in FIG. 21 was loaded to form an image, and the carrier spent, chargeability and image quality were evaluated in the same manner as in Example 1 above. The results are shown in Table 3.
<Image forming apparatus B>
An image forming apparatus B shown in FIG. 21 is a tandem type image forming apparatus of an indirect transfer method adopting a non-contact charging method, a two-component developing method, a secondary transfer method, a blade cleaning method, and an external heating roller fixing method. .
In the image forming apparatus B shown in FIG. 21, a non-contact corona charger as shown in FIG. As the developing unit 324, a two-component developing device as shown in FIG. As the cleaning means 330, a cleaning blade as shown in FIG. As the fixing means 327, an electromagnetic induction heating type roller fixing device as shown in FIG. 12 is adopted.
An image forming element 351 in the image forming apparatus B shown in FIG. 21 is provided with a charging unit 311, an exposing unit 323, a developing unit 324, a primary transfer unit 325, and a cleaning unit 330 around the photosensitive drum 321. As the photosensitive drum 321 in the image forming element 351 rotates, charging by the charging unit 310 and exposure by the exposure unit 323 form an electrostatic latent image corresponding to the exposure image on the surface. This electrostatic latent image is developed with yellow toner by the developing means 324, and a visible image with yellow toner is formed on the photosensitive drum 321. The visible image is transferred onto the intermediate transfer belt 355 by the primary transfer unit 325, and the yellow toner remaining on the photosensitive drum 321 is removed by the cleaning unit 330. Similarly, visible images of magenta toner, cyan toner, and black toner are formed on the intermediate transfer belt 355 by the image forming elements 352, 353, and 354. The color image on the intermediate transfer belt 355 is transferred onto the recording medium 326 by the transfer device 356, and the toner remaining on the intermediate transfer belt 355 is removed by the intermediate transfer belt cleaning unit 358. The color image formed on the recording medium 326 is fixed by the fixing unit 327.

<Charge amount distribution>
The distribution of the charge amount is determined by developing the unit after a continuous 50,000-sheet output durability test using a predetermined image forming apparatus and a 7% image area ratio chart in an environment of a temperature of 35 ° C. and a relative humidity of 95%. Q / d distribution (fC / μm) was measured with respect to the developer collected from the sleeve by a charge amount distribution measuring device (Espert Analyzer, manufactured by Hosokawa Micron Corporation), and the half-value width was obtained from this measured value. In addition, as a measurement condition of the Espert Analyzer (E-SPART ANALYZER), the nitrogen gas flow rate was 0.3 NL / min and the gas pressure was 0.3 atm. As an index indicating the distribution of the charge amount, it is expressed by the mode (peak value) [q / d] and the distribution width (half width) at the half height position of the most frequent. It was evaluated with.
〔Evaluation criteria〕
○: Mode value 0.25 fC / μm or more and less than half value width 0.2 Δ: Mode value 0.15 fC / μm or more and less than 0.25 fC / μm or half value width 0.2 or more and less than 0.3 ×: most Frequencies less than 0.15 fC / μm or half width 0.3 or more

<Career spent>
The carrier spent property is determined by using a predetermined image forming apparatus, extracting the developer after performing a continuous 50,000 sheet output durability test with a 7% image area ratio chart using each toner, and the developer is covered with a mesh having a mesh size of 32 μm. An appropriate amount was put in the gauge and air blown to separate the toner and the carrier. 1.0 g of the obtained carrier was put in a 50 ml glass bottle, 10 ml of chloroform was added, and the mixture was shaken 50 times and allowed to stand for 10 minutes. Thereafter, the supernatant chloroform solution was put into a glass cell, and the transmittance of the chloroform solution was measured using a turbidimeter, and measured according to the following criteria.
〔Evaluation criteria〕
A: Transmission 95% or more B: Transmission 90% -94%
Δ: Transmittance 80% to 89%
X: transmittance 79% or less

<Image quality>
The image quality was evaluated by using a predetermined image forming apparatus for the presence or absence of color tone (hue) change, background stain, image density, blurring, and the like due to an output image of 50,000 sheets. The presence / absence of abnormality and the rank evaluation of image quality were visually evaluated and judged in the following four stages.
〔Evaluation criteria〕
◎: Image abnormality is not observed at all, and it is good ○: Compared with the original image, a slight difference in hue, image density, background stain, etc. are observed, but it is good without any practical problem △: Color tone ( Slight changes in color tone), image density, background stain, etc. x: Color change, density change, background stain, etc. are obvious and problematic <Comprehensive evaluation>
○: Good ×: Unusable level

From the results shown in Table 3, no carrier spent was generated and no reduction in charge amount was observed when the toner and developer with controlled abietic acid content were used. Further, it was found that even after image formation for a long time, no image abnormality such as transfer failure was observed and a good image was obtained (Examples 1 to 16). On the other hand, when the content of abietic acid is not controlled and the toner has a large amount of residual toner, the carrier spent and chargeability deteriorate with time, and good image quality over a long period of time cannot be obtained (Comparative Examples 1 to 6). . In addition, when the content of the rosin compound is low, the dispersion of the colorant is poor, the image quality is not good even in the initial stage, and since the glass transition temperature of the resin is low, the change over time such as the carrier spent is extreme. It was difficult to form an image over a long period of time (Comparative Examples 7 and 8).

  The image forming apparatus, the image forming method, and the process cartridge of the present invention can form an extremely high-quality image that does not change color tone over a long period of time and does not show abnormal images such as density reduction and background stains. Therefore, it can be widely used in, for example, a laser printer, a direct digital plate making machine, a full color copier using a direct or indirect electrophotographic multicolor image developing system, a full color laser printer, and a full color plain paper fax machine.

FIG. 1 is a schematic sectional view showing an example of a charging roller in the image forming apparatus of the present invention. FIG. 2 is a schematic view showing an example in which the contact-type charging roller in the image forming apparatus of the present invention is applied to the image forming apparatus. FIG. 3 is a schematic view showing an example in which the non-contact type corona charger in the image forming apparatus of the present invention is applied to the image forming apparatus. FIG. 4 is a schematic view showing an example of a non-contact charging roller in the image forming apparatus of the present invention. FIG. 5 is a schematic view showing an example of a one-component developing unit in the image forming apparatus of the present invention. FIG. 6 is a schematic view showing an example of a two-component developing unit in the image forming apparatus of the present invention. FIG. 7 is a schematic view showing an example of a direct transfer system of the tandem type image forming apparatus of the present invention. FIG. 8 is a schematic view showing an example of an indirect transfer method of the tandem type image forming apparatus of the present invention. FIG. 9 is a schematic view showing an example of a belt-type fixing unit in the image forming apparatus of the present invention. FIG. 10 is a schematic view showing an example of a heat roller type fixing unit in the image forming apparatus of the present invention. FIG. 11 is a schematic view showing an example of an electromagnetic induction heating type fixing unit in the image forming apparatus of the present invention. FIG. 12 is a schematic view showing another example of the electromagnetic induction heating type fixing means in the image forming apparatus of the present invention. FIG. 13 is a schematic view showing an example of a cleaning blade in the image forming apparatus of the present invention. FIG. 14 is a schematic view showing an example of a cleaningless type image forming apparatus in the image forming apparatus of the present invention. FIG. 15 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 16 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 17 is a schematic view showing an example of the tandem type image forming apparatus of the present invention. FIG. 18 is an enlarged view of each image forming element of FIG. FIG. 19 is a schematic view showing an example of the process cartridge of the present invention. FIG. 20 is a schematic diagram illustrating the image forming apparatus (evaluator A) used in the examples. FIG. 21 is a schematic diagram illustrating the image forming apparatus (evaluator B) used in the examples.

Explanation of symbols

1 Electrostatic latent image carrier (photosensitive drum)
2 Transfer means (primary transfer means)
DESCRIPTION OF SYMBOLS 3 Conveying belt 4 Intermediate transfer body 5 Secondary transfer means 6 Paper feeding device 7 Fixing device 8 Cleaning device 9 Intermediate transfer body cleaning device 10 Electrostatic latent image carrier (photosensitive drum)
10K black electrostatic latent image carrier 10Y yellow electrostatic latent image carrier 10M magenta electrostatic latent image carrier 10C cyan electrostatic latent image carrier 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning means DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer means 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Reversing apparatus 30 Exposure apparatus 32 Contact glass 33 First traveling body 34 Second traveling Body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller 4 4Y developing roller 44M developing roller 44C developing roller 45K black developing unit 45Y yellow developing unit 45M magenta developing unit 45C cyan developing unit 49 registration roller 50 intermediate transfer member 51 roller 52 separation roller 53 manual feed path 54 manual tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 60 Cleaning means 61 Developing device 62 Transfer charger 63 Cleaning device 64 Discharge device 70 Discharge lamp 80 Transfer roller 90 Cleaning device 95 Recording medium 100 Image forming device 101 Electrostatic latent image carrier Body 102 Charging means 103 Exposure means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developing means 130 Document table 142 Feed roller 143 Paper Link 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed table 220 Heating roller 230 Pressure roller 300 Scanner 302 Film 303 Spring 310 Charging roller 311 Corona charger 312 Core metal 313 Resistance adjustment layer 314 Protective layer 321 Electrostatic latent image carrier 323 Exposure means 324 Development means 325 Transfer means 326 Recording medium 327 Fixing means 330 Cleaning means 331 Static elimination device 400 Automatic document feeder (ADF)
401 casing 402 developing roller 411 agitator 412 supply roller 413 regulating blade 510 belt type fixing device 511 heating roller 512 fixing roller 513 fixing belt 514 pressure roller 515 heat roll type fixing device 525 roll type fixing device 570 electromagnetic induction heating type fixing device 613 Cleaning blade S Recording medium P Recording medium

Claims (17)

An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus having at least
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound contains at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
An image forming apparatus, wherein the content of abietic acid in the toner is 1% by mass or less.   The image forming apparatus according to claim 1, wherein the charging unit is a charging unit that charges the electrostatic latent image carrier in a non-contact manner.   The image forming apparatus according to claim 1, wherein the charging unit is a charging unit that contacts and charges the electrostatic latent image carrier.   2. The developing means has a magnetic field generating means fixed inside, and a developer carrying member that can rotate by carrying a two-component developer comprising a magnetic carrier and a toner on the surface. The image forming apparatus according to claim 3.   The image forming apparatus according to claim 1, wherein the developing unit includes a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier.   The image forming apparatus according to claim 1, wherein the transfer unit is a transfer unit that transfers a visible image on the electrostatic latent image carrier to a recording medium. A plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit are arranged,
The transfer means sequentially applies the recording medium whose surface moves so as to pass through a transfer position, which is a region facing the electrostatic latent image carrier of the plurality of image forming elements, onto each electrostatic latent image carrier. The image forming apparatus according to claim 1, wherein the image forming apparatus is a transfer unit that transfers a visible image formed on the image forming apparatus.   An intermediate transfer member on which a visible image formed on the electrostatic latent image carrier is primarily transferred, and a secondary for secondary transfer of the visible image carried on the intermediate transfer member to a recording medium. 6. The image forming apparatus according to claim 1, further comprising a transfer unit.   The image forming apparatus according to claim 1, further comprising a cleaning unit, wherein the cleaning unit includes a cleaning blade that contacts the surface of the electrostatic latent image carrier.   The developing means has a developer carrier that is brought into contact with the surface of the electrostatic latent image carrier, and develops the electrostatic latent image formed on the electrostatic latent image carrier and also carries the electrostatic latent image carrier. The image forming apparatus according to claim 1, wherein residual toner on the body is collected.   11. The fixing unit according to claim 1, wherein the fixing unit includes at least one of a roller and a belt, and heats and presses a transfer image transferred onto a recording medium by heating from a surface not in contact with the toner. The image forming apparatus according to any one of the above.   11. The fixing unit according to claim 1, wherein the fixing unit includes at least one of a roller and a belt, and is a fixing unit that heats and presses a transfer image transferred onto a recording medium by heating from a surface in contact with the toner. An image forming apparatus according to claim 1.   The image forming apparatus according to claim 1, wherein the alcohol component in the polyester resin contains an aliphatic diol in an amount of 65 mol% or more in the divalent alcohol component.   The image forming apparatus according to claim 13, wherein the aliphatic diol contains 65 mol% or more of 1,2-propanediol.   The image forming apparatus according to claim 1, wherein the carboxylic acid component further contains an aromatic dicarboxylic acid compound. A charging process for charging the surface of the electrostatic latent image carrier, an exposure process for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method including at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. ,
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound is at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
An image forming method, wherein the content of abietic acid in the toner is 1% by mass or less. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A removable process cartridge,
The toner contains at least a binder resin and a colorant;
The binder resin contains a polyester resin formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The rosin compound is at least one of fumaric acid modified rosin, acrylic acid modified rosin and itaconic acid modified rosin,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
A process cartridge, wherein the content of abietic acid in the toner is 1% by mass or less.