JP4749938B2 - 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, there has been a strong market demand for energy saving and high speed 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 through 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-mentioned heat roller type fixing means, 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.

  Further, the fixing means of the electrophotographic image forming apparatus is required to have toner releasability (hereinafter also referred to as “offset resistance”) with respect to the heating member. Such offset resistance can be improved by the presence of a release agent on the toner surface, but the release agent present on the toner surface when a toner other than a predetermined toner is used or the toner is reused. May decrease and offset resistance may decrease.

  In addition, with the development of electrophotographic technology, a toner having excellent low-temperature fixing property, offset resistance, and storage stability (blocking resistance) is required. For example, a toner containing a linear polyester resin that defines physical properties such as molecular weight (see Patent Document 5), a toner containing a non-linear cross-linked polyester resin using a rosin as an acid component (see Patent Document 6), Toners using maleic acid-modified rosin and improved fixing properties (see Patent Document 7), toners using a blend of low molecular weight resin and high molecular weight resin (see Patent Document 8), etc. have been proposed. Yes.

However, due to the further increase in speed and energy saving of recent image forming apparatuses, it has been found that conventional binder resins for toner are insufficient for market demand. That is, it is very difficult to maintain sufficient fixability due to shortening of the fixing time in the fixing process and lowering of the heating temperature by the fixing means. In particular, when a low molecular weight resin is used as the binder resin, the glass transition temperature is inevitably lowered, so that there is a problem that the toner aggregates during storage and the storage stability is poor. In addition, due to the strong stress applied during image formation, image deterioration is particularly noticeable in high-speed continuous printing due to insufficient toner durability and the occurrence of filming due to poor dispersion of the internal additive.
Further, in the method of blending a low molecular weight resin and a high molecular weight resin, the presence of the high molecular weight resin is inferior in grindability in the resin production process and in grindability in the production process of the pulverized toner using the binder resin. There is a drawback.
Furthermore, although the rosins used in Patent Document 6 and Patent Document 7 are effective in improving the low-temperature fixability, there is a problem that odor is likely to be generated depending on the type of rosins.

  Accordingly, the image forming apparatus, the image forming method, and the low temperature fixability, the offset resistance, the durability, the pulverization property, and the storage stability are excellent, the generation of odor can be reduced, and a high-quality image can be formed over a long period of time. The present situation is that prompt provision of a process cartridge is desired.

JP-A-5-341617 JP-A-63-313182 Japanese Patent Laid-Open No. 1-263679 JP-A-8-22206 JP 2004-245854 A JP-A-4-70765 JP-A-4-307557 Japanese Patent Laid-Open No. 2-82267

  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 is excellent in all of low-temperature fixability, offset resistance, durability, grindability, and storage stability, can reduce the generation of odor, has no color tone change over a long period of use, and has a reduced density, An object of the present invention is to provide an image forming apparatus, an image forming method, and a process cartridge capable of forming an extremely high quality image in which an abnormal image such as a background stain is not seen.

Means for solving the above 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, and the binder resin contains a polyester resin (A) and a polyester resin (B) whose softening point is higher by 10 ° C. or more than the polyester resin (A). And
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. The image forming apparatus is characterized.
<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> Any one of <1> to <12>, wherein the alcohol component of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains an aliphatic alcohol. The image forming apparatus described in the above.
<14> The content of the (meth) acrylic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from the (meth) acrylic acid-modified rosin,
Any one of <1> to <13>, wherein the total content of the fumaric acid-modified rosin and the maleic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from fumaric acid / maleic acid modified rosin. The image forming apparatus described.
<15> The image forming apparatus according to any one of <1> to <14>, wherein at least one of a (meth) acrylic acid-modified rosin, a fumaric acid-modified rosin, and a maleic acid-modified rosin is obtained by modifying a purified rosin. is there.
<16> (meth) acrylic acid-modified rosin-derived resin and fumaric acid / maleic acid-modified rosin-derived resin at least one alcohol component contains a trivalent or higher alcohol,
At least any one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains a trivalent or higher carboxylic acid compound, or the alcohol component has a trivalent or higher valence. The image forming apparatus according to any one of <1> to <15>, wherein the image forming apparatus contains alcohol and the carboxylic acid component contains a trivalent or higher carboxylic acid compound.
<17> Any one of <1> to <16>, wherein the content of the low molecular weight component having a molecular weight of 500 or less in at least one of the polyester resin (A) and the polyester resin (B) is 12% or less. The image forming apparatus described in the above.
<18> Polycondensation of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin is a titanium compound and a tin (II) compound having no Sn-C bond. The image forming apparatus according to any one of <1> to <17>, which is performed in the presence of at least one of them.
<19> The above-mentioned <1> to <18>, wherein the total content of the resin derived from (meth) acrylic acid-modified rosin and the resin derived from fumaric acid / maleic acid-modified rosin is 70% by mass or more in the binder resin. The image forming apparatus according to any one of the above.
<20> At least one of (meth) acrylic acid-modified rosin (meth) acrylic acid-modified rosin, fumaric acid-modified rosin fumaric acid-modified rosin, and maleic acid-modified rosin maleic acid-modified rosin is 5 to 105 The image forming apparatus according to any one of <1> to <19>.
<21> The softening point of the polyester resin (A) is 80 to 120 ° C., and the softening point of the polyester resin (B) is 100 to 180 ° C. An image forming apparatus.
<22> 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, and the binder resin contains a polyester resin (A) and a polyester resin (B) whose softening point is higher by 10 ° C. or more than the polyester resin (A). And
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. This is a featured image forming method.
<23> The image forming method according to <22>, wherein the charging step is performed using a charging unit that charges the latent electrostatic image bearing member in a non-contact manner.
<24> The image forming method according to <22>, wherein the charging step is performed using a charging unit that contacts and charges the electrostatic latent image carrier.
<25> From the above <22>, wherein the developing step uses a developer carrier having a magnetic field generating means fixed therein and rotating on the surface carrying a two-component developer comprising a magnetic carrier and a toner The image forming method according to any one of <24>.
<26> The development process according to any one of <22> to <24>, 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.
<27> The image forming method according to any one of <22> to <26>, wherein the transfer step is a transfer step of transferring a visible image on the electrostatic latent image carrier to a recording medium.
<28> 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 are arranged,
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 <22> to <27>, wherein the image forming method is a transfer unit that transfers the visible image.
<29> The transfer step includes an intermediate transfer member on which a visible image formed on the electrostatic latent image carrier is primarily transferred, and a visible image carried on the intermediate transfer member is secondarily transferred to a recording medium. The image forming method according to any one of <22> to <26>, wherein the secondary transfer unit is used.
<30> The image forming method according to any one of <22> to <29>, including a cleaning step, wherein the cleaning step uses a cleaning blade that contacts the surface of the electrostatic latent image carrier.
<31> 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 <22> to <29>, wherein residual toner on the carrier is collected.
<32> The fixing step is a 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. The image forming method according to any one of <22> to <31>.
<33> 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 <31>.
<34> Any one of <22> to <33>, wherein the alcohol component of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains an aliphatic alcohol. The image forming method described in 1.
<35> The content of the (meth) acrylic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from the (meth) acrylic acid-modified rosin,
Any of <22> to <33>, wherein the total content of the fumaric acid-modified rosin and the maleic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from fumaric acid / maleic acid modified rosin. The image forming method described.
<36> The image forming method according to any one of <22> to <35>, wherein at least one of (meth) acrylic acid modified rosin, fumaric acid modified rosin and maleic acid modified rosin is obtained by modifying purified rosin. is there.
<37> A resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contain at least a trivalent alcohol,
At least any one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains a trivalent or higher carboxylic acid compound, or the alcohol component has a trivalent or higher valence. The image forming method according to any one of <22> to <36>, wherein the image contains an alcohol and the carboxylic acid component contains a trivalent or higher carboxylic acid compound.
<38> Any one of <22> to <37>, wherein the content of the low molecular weight component having a molecular weight of 500 or less in at least one of the polyester resin (A) and the polyester resin (B) is 12% or less. The image forming method described in 1.
<39> The condensation polymerization of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin is a titanium compound and a tin (II) compound having no Sn-C bond. The image forming method according to any one of <22> to <38>, wherein the image forming method is performed in the presence of at least one of them.
<40> From the above <22> to <39>, the total content of the resin derived from a (meth) acrylic acid modified rosin and the resin derived from a fumaric acid / maleic acid modified rosin is 70% by mass or more in the binder resin. The image forming method according to any one of the above.
<41> The aforementioned (meth) acrylic acid modified rosin has a (meth) acrylic acid modified degree, a fumaric acid modified rosin fumaric acid modified degree, and a maleic acid modified rosin maleic acid modified degree is at least 5 to 105 The image forming method according to any one of <22> to <40>.
<42> The softening point of the polyester resin (A) is 80 to 120 ° C., and the softening point of the polyester resin (B) is 100 to 180 ° C. An image forming method.
<43> 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, and the binder resin contains a polyester resin (A) and a polyester resin (B) whose softening point is higher by 10 ° C. or more than the polyester resin (A). And
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. This is a featured process cartridge.
<44> The process cartridge according to <43>, wherein the alcohol component of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains an aliphatic alcohol. .
<45> The content of the (meth) acrylic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from the (meth) acrylic acid-modified rosin,
Any of <43> to <44>, wherein the total content of the fumaric acid-modified rosin and the maleic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from fumaric acid / maleic acid modified rosin. It is a process cartridge of description.
<46> The process cartridge according to any one of <43> to <45>, wherein at least one of (meth) acrylic acid modified rosin, fumaric acid modified rosin and maleic acid modified rosin is obtained by modifying purified rosin. .
<47> (meth) acrylic acid-modified rosin-derived resin and fumaric acid / maleic acid-modified rosin-derived resin at least one alcohol component contains trivalent or higher alcohol,
At least any one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains a trivalent or higher carboxylic acid compound, or the alcohol component has a trivalent or higher valence. The process cartridge according to any one of <43> to <46>, wherein the process cartridge contains alcohol and the carboxylic acid component contains a trivalent or higher carboxylic acid compound.
<48> Any of the above <43> to <47>, wherein the content of the low molecular weight component having a molecular weight of 500 or less in at least one of the polyester resin (A) and the polyester resin (B) is 12% or less Is a process cartridge.
<49> A polycondensation of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin is a titanium compound and a tin (II) compound having no Sn-C bond. The process cartridge according to any one of <43> to <48>, which is performed in the presence of at least one of them.
<50> The above <43> to <49>, wherein the total content of the resin derived from (meth) acrylic acid-modified rosin and the resin derived from fumaric acid / maleic acid-modified rosin is 70% by mass or more in the binder resin. Any one of the process cartridges.
<51> The aforementioned (meth) acrylic acid modified rosin has a (meth) acrylic acid modified degree, a fumaric acid modified rosin fumaric acid modified degree, and a maleic acid modified rosin maleic acid modified degree is at least 5 to 105 The process cartridge according to any one of <43> to <50>.
<52> The polyester resin (A) has a softening point of 80 to 120 ° C, and the polyester resin (B) has a softening point of 100 to 180 ° C. Process cartridge.

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 And a fixing means for fixing the transferred image, wherein the toner contains at least a binder resin and a colorant, and the binder resin is made of a polyester resin (A) and the polyester resin (A). Containing a polyester resin (B) having a softening point higher by 10 ° C. or more,
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester-based resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. 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. At this time, the binder resin for the toner contains a polyester resin (A) and a polyester resin (B) whose softening point is 10 ° C. or higher higher than that of the polyester resin (A).
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) uses a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. Therefore, it has excellent low-temperature fixability, offset resistance, durability, grindability, and storage stability, can reduce odor generation, has no color tone change over a long period of use, and has a reduced density, background stains, etc. An extremely high quality image in which no abnormal image is seen can be formed.

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. The binder resin contains at least a polyester resin (A) and a polyester resin (B) having a softening point higher by 10 ° C. or more than the polyester resin (A),
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester-based resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. 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 for the toner contains a polyester resin (A) and a polyester resin (B) whose softening point is 10 ° C. or higher higher than that of the polyester resin (A).
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) uses a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. Therefore, it has excellent low-temperature fixability, offset resistance, durability, grindability, and storage stability, can reduce odor generation, has no color tone change over a long period of use, and has a reduced density, background stains, etc. An extremely high quality image in which no abnormal image is seen can be formed.

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. The toner can be attached to and detached from the image forming apparatus main body, and the toner contains at least a binder resin and a colorant, and the binder resin is softer than the polyester resin (A) and the polyester resin (A). It contains a polyester resin (B) whose point is 10 ° C. or higher,
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) uses a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. Therefore, it has excellent low-temperature fixability, offset resistance, durability, grindability, and storage stability, can reduce odor generation, has no color tone change over a long period of use, and has a reduced density, background stains, etc. An extremely high quality image in which no abnormal image is seen can be formed.

  According to the present invention, conventional problems can be solved, and low temperature fixability, offset resistance, durability, pulverization, and storability are all excellent, and the generation of odor can be reduced. It is possible to provide an image forming apparatus, an image forming method, and a process cartridge that can form an extremely high quality image that has no change in color tone and that does not show abnormal images such as density reduction and background stains.

(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 according to 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 to 50 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 a 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 divided 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 exposure 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 311 serving as a columnar conductive support, a resistance adjusting layer 312 formed on the outer peripheral surface of the cored bar 311, and a surface of the resistance adjusting layer 312. And a protective layer 313 for preventing leakage.
The resistance adjusting layer 312 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 311.
The resistivity value of the resistance adjustment layer 312 is preferably 10 ⁶ to 10 ⁹ Ω · cm. When 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 value is less than 10 ⁶ Ω · cm, there is a risk of leakage to the entire photosensitive drum.

  The thermoplastic resin used for the resistance adjusting layer 312 is not particularly limited and may be appropriately selected depending on the intended purpose. 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 set the resistance value of the resistance adjusting layer 312 to the above value, 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 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 ionic conductive agent is uniformly dispersed at the molecular level in the thermoplastic resin composition, the resistance adjusting layer 312 is poorly dispersed in the conductive material found in the resistance adjusting layer in which the conductive pigment is dispersed. The accompanying resistance value does not vary. Moreover, since the polymer type ionic conductive agent is a polymer compound, it is uniformly dispersed and fixed in the thermoplastic resin composition, and bleedout hardly occurs.

The protective layer 313 is formed such that its resistance value is larger than that of the resistance adjustment layer 312. As a result, leakage to the defective portion of the photosensitive drum is avoided. However, if the resistance value of the protective layer 313 is excessively increased, the charging efficiency is decreased. Therefore, the difference between the resistance value of the protective layer 313 and the resistance value of the resistance adjustment layer 312 is preferably 10 ³ Ω · cm or less. .

  As the material for the protective layer 313, 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 313 is formed of the resin material alone, the characteristics of the charging roller are not satisfied. Therefore, the resistance value of the protective layer 313 is adjusted by dispersing various conductive agents in the resin material. In order to improve the adhesion between the protective layer 303 and the resistance adjustment layer 302, 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 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 to 200 μm, more preferably 10 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, so that a certain minute gap H in the image area of the charging roller and the electrostatic latent image carrier can be obtained. 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 Sumitubes for 105 ° C. (trade name: F105 ° C., manufactured by Sumitomo Chemical Co., Ltd.).

<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 contains a polyester resin (A) and a polyester resin (B) having a softening point higher by 10 ° C. or more than the polyester resin (A), and further contains other components as necessary. Do it.

The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin.
The polyester resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin.

The resin derived from the (meth) acrylic acid-modified rosin and the resin derived from fumaric acid / maleic acid-modified rosin (sometimes referred to as “modified rosin-derived resin”) are fixed at an extremely low temperature. And storage stability is improved. Further, since the polyester resin (B) having a higher softening point is derived from (meth) acrylic acid-modified rosin, (meth) acrylic acid-modified rosin is part of the main chain of the polyester unit and the molecular weight of the resin. On the other hand, since low molecular weight components having a molecular weight of 500 or less, that is, residual monomer components and oligomer components are reduced, it is possible to satisfy both contradictory properties such as low-temperature fixability, offset resistance, and storage stability. . On the other hand, since the polyester resin (A) having a lower softening point is a resin derived from fumaric acid / maleic acid-modified rosin, fumaric acid-modified rosin and maleic acid-modified rosin having trifunctional groups are polyester units. The degree of cross-linking is increased, the glass transition temperature is increased, and durability is improved.
In this specification, for the sake of convenience, the resin in the present invention is indicated as a resin derived from (meth) acrylic acid-modified rosin and a resin derived from fumaric acid / maleic acid-modified rosin. This means that (meth) acrylic acid-modified rosin or at least one of fumaric acid-modified rosin and maleic acid-modified rosin is used.

-(Meth) acrylic acid modified rosin derived resin--
The (meth) acrylic acid-modified rosin in the resin derived from the (meth) acrylic acid-modified rosin is a rosin modified with (meth) acrylic acid and is abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid It is obtained by addition reaction of (meth) acrylic acid to rosin whose main component is sandaracopimaric acid, dehydroabietic acid, repopimaric acid, etc. Specifically, it is conjugated among the main components of rosin. It can be obtained through a Diels-Alder reaction under heating with (meth) acrylic acid and lepopimaric acid, abietic acid, neoabietic acid, and parastrinic acid having a double bond.

  In the present specification, “(meth) acryl” means acryl or methacryl. Therefore, (meth) acrylic acid means acrylic acid or methacrylic acid, and “(meth) acrylic acid-modified rosin” means rosin modified with acrylic acid or rosin modified with methacrylic acid. The (meth) acrylic acid-modified rosin in the present invention is preferably an acrylic acid-modified rosin modified with acrylic acid with little steric hindrance from the viewpoint of reaction activity in the Diels-Alder reaction.

The degree of modification of rosin with (meth) acrylic acid (degree of modification of (meth) acrylic acid) is preferably 5 to 105, more preferably 20 to 105, from the viewpoint of increasing the molecular weight of the polyester unit and reducing the low molecular weight oligomer component. 40 to 105 are more preferable, and 60 to 105 are particularly preferable.
Here, the (meth) acrylic acid modification degree can be calculated by the following mathematical formula (Aa).
However, in said numerical formula (Aa), _Xa1 represents SP value of the (meth) acrylic-acid modified rosin which calculates a modification degree. _Xa2 represents a saturated SP value of (meth) acrylic acid-modified rosin obtained by reacting 1 mol of (meth) acrylic acid and 1 mol of rosin. Y represents the SP value of rosin.
The SP value means a softening point measured by a ring and ball type automatic softening point tester as shown in Examples described later. The saturated SP value means the SP value when the reaction of (meth) acrylic acid and rosin is caused to react until the SP value of the obtained (meth) acrylic acid-modified rosin reaches a saturation value. The molecule (X _a1 -Y) in the formula (Aa) means an increase in the SP value of rosin modified with (meth) acrylic acid, and the degree of (meth) acrylic acid modification represented by the formula (Aa). A larger value indicates a higher degree of denaturation.

  The method for producing the (meth) acrylic acid-modified rosin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, rosin and (meth) acrylic acid are mixed and about 180 to 260 ° C., preferably Can be heated to 180-210 ° C., and (meth) acrylic acid-modified rosin can be obtained by adding (meth) acrylic acid to an acid having a conjugated double bond contained in rosin by Diels-Alder reaction. it can. The obtained (meth) acrylic acid-modified rosin may be used as it is, or may be used after purification through an operation such as distillation.

--Fumaric acid / maleic acid-modified rosin-derived resin--
The above-mentioned “resin derived from fumaric acid / maleic acid modified rosin” includes (i) a fumaric acid having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing fumaric acid modified rosin modified with fumaric acid. A resin derived from an acid-modified rosin, (ii) a resin derived from a maleic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a maleic acid-modified rosin modified with maleic acid, and ( iii) A resin derived from fumaric acid / maleic acid modified rosin having a polyester unit formed by condensation polymerization of an alcohol component and a carboxylic acid component containing fumaric acid modified rosin and maleic acid modified rosin is included in the present invention. From the viewpoint of storage stability, a resin derived from fumaric acid-modified rosin is particularly preferable.

  The fumaric acid-modified rosin is a rosin modified with fumaric acid and, like (meth) acrylic acid-modified rosin, abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, It is obtained by addition reaction of fumaric acid to rosin mainly composed of dehydroabietic acid, lepopimaric acid, etc. Specifically, lepopimatic acid having a conjugated double bond in the main component of rosin, abieticin It can be obtained through a Diels-Alder reaction under heating with acid, neoabietic acid and parastrinic acid, and fumaric acid.

The degree of modification of rosin with fumaric acid (fumaric acid modification degree) is preferably 5 to 105, more preferably 20 to 105, and still more preferably 40 to 105, from the viewpoint of increasing the molecular weight of the polyester resin and increasing the glass transition temperature. 60 to 105 are particularly preferable.
Here, the degree of modification with fumaric acid can be calculated by the following mathematical formula (Af).
However, the numerical expression _{(Af), X f1} represents the SP value of the fumaric acid-modified rosin for calculating the degree of modification. X _f2 represents the SP value of a fumaric acid-modified rosin obtained by reacting 1 mol of fumaric acid with 0.7 mol of rosin. Y represents the SP value of rosin.
The SP value means a softening point measured by a ring and ball type automatic softening point tester as shown in Examples described later. The numerator (X _f1 -Y) in the formula (Af) means the degree of increase in SP value of rosin modified with fumaric acid, and is similar to the degree of (meth) acrylic acid modification calculated by the formula (Aa). The larger the value of the degree of fumaric acid modification represented by the formula (Af), the higher the degree of modification.

  The method for producing the fumaric acid-modified rosin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, rosin and fumaric acid are mixed and about 180 to 260 ° C, preferably 180 to 210 ° C. By heating, fumaric acid-modified rosin can be obtained by adding fumaric acid to an acid having a conjugated double bond contained in rosin by Diels-Alder reaction.

Further, from the viewpoint of efficiently reacting rosin and fumaric acid, it is preferable to react rosin and fumaric acid in the presence of phenols. As the phenols, divalent phenols and phenolic compounds having a substituent at least in the ortho position relative to the hydroxyl group (hereinafter referred to as hindered phenols) are preferable, and among these, hindered phenols are particularly preferable.
The divalent phenol means a compound in which two OH groups are bonded to a benzene ring and does not have other substituents. Among them, hydroquinone is preferable.
The hindered phenol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, t-butylcatechol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, propyl garade, 4,4'-methylenebis (2,6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), butylhydroxyanisole, 2,6-di-t-butyl-p-cresol, 2, 6-di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol, octadecyl-3- (4 Hydroxy-3 ', 5'-di-t-butylphenyl) propionate, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, 6- (4-hydroxy-3,5-di -T-Butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 2,6-Difer-4-octadecanoxyphenol, 2,2'-methylenebis (4-methyl-6-t -Butyl fail), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-dihydroxy-3 , 3′-di- (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), tris [β- (3,5-di-t -Butyl 4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris (3,5-di-t- Butyl-4-hydroxyphenol) isocyanurate, 1,1,3′-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,6-bis (2′-hydroxy-3′-) t-butyl-5′-methylbenzyl) -4-methylphenol, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamate), hexamethyleneglycolbis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-5-methyl-4-hydride) Kishifeniru) propionate], tetrakis [methylene-3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] methane, and the like. Among these, t-butylcatechol is particularly preferable.

The amount of the phenols used is preferably 0.001 to 0.5 parts by weight, more preferably 0.003 to 0.1 parts by weight, with respect to 100 parts by weight of the raw material monomer of the fumaric acid-modified rosin, 0.005 -0.1 mass part is still more preferable.
The fumaric acid-modified rosin may be used as it is, or may be used after purification through an operation such as distillation.

  The maleic acid-modified rosin is a rosin modified with maleic acid or maleic anhydride, and in the same manner as the (meth) acrylic acid-modified rosin, abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopy It is obtained by addition reaction of maleic acid or maleic anhydride to rosin mainly composed of maric acid, dehydroabietic acid, repopimaric acid, etc. Specifically, among the main components of rosin, conjugated double It can be obtained through Diels-Alder reaction under heating with maleic acid or maleic anhydride with levopimaric acid, abietic acid, neoabietic acid and parastrinic acid having a bond.

The degree of modification of rosin with maleic acid or maleic anhydride (maleic acid modification degree) is preferably 5 to 105, more preferably 30 to 105, from the viewpoint of increasing the molecular weight of the polyester resin and reducing the low molecular weight oligomer component. 40-105 are more preferable, 50-105 are especially preferable, 60-105 are especially preferable, and 70-105 are the most preferable.
Here, the maleic acid modification degree can be calculated by the following mathematical formula (Am).
However, in the formula (Am), X _m1 represents the SP value of maleic acid-modified rosin for calculating the degree of modification. X _m2 represents a saturated SP value of maleic acid-modified rosin obtained by reacting 1 mol of maleic acid with 1 mol of rosin at 230 ° C. Y represents the SP value of rosin.
The SP value means a softening point measured by a ring and ball type automatic softening point tester as shown in Examples described later. The saturated SP value means the SP value when the reaction of maleic acid and rosin is allowed to react until the SP value of the resulting maleic acid-modified rosin reaches the saturation value. The molecule (X _m1 -Y) in the formula (Am) means the degree of increase in SP value of rosin modified with maleic acid or maleic anhydride, and is modified by (meth) acrylic acid modified by the formula (Aa). Similarly to the degree, the larger the maleic acid modification value represented by the formula (Am), the higher the degree of modification.

  The method for producing the maleic acid-modified rosin is not particularly limited. For example, the rosin and maleic acid or maleic anhydride are mixed and heated to about 180 to 260 ° C., preferably 180 to 210 ° C., so that the Diels-Alder reaction. Thus, maleic acid-modified rosin can be obtained by adding maleic acid or maleic anhydride to an acid having a conjugated double bond contained in rosin. The maleic acid-modified rosin may be used as it is, or may be used after purification through an operation such as distillation.

  Next, the rosin used in the (meth) acrylic acid-modified rosin, fumaric acid-modified rosin, and maleic acid-modified rosin (sometimes referred to as “modified rosin”) in the present invention is obtained from pine. Natural rosin, isomerized rosin, dimerized rosin, polymerized rosin, disproportionated rosin, etc., such as abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, lepopimaric acid, etc. From the viewpoint of color, tall rosin obtained from tall oil obtained as a by-product in the process of producing natural rosin pulp, gum rosin obtained from raw pine crab, pine Natural rosin such as wood rosin obtained from stumps of Emissions is more preferable.

  The modified rosin in the present invention is obtained through a Diels-Alder reaction under heating, so that the impurities causing odor are reduced and the odor is low, but the odor is further reduced and the storage stability is improved. From the viewpoint, (meth) acrylic acid-modified rosin is preferably obtained by modifying rosin (purified rosin) whose impurities have been reduced in the purification process with (meth) acrylic acid, and modified purified toll rosin with (meth) acrylic acid. What is obtained is more preferable. Similarly, the fumaric acid-modified rosin is preferably obtained by modifying rosin (purified rosin) whose impurities have been reduced in the purification step with fumaric acid, and more preferably obtained by modifying purified tall rosin with fumaric acid. Further, the maleic acid-modified rosin is preferably obtained by modifying rosin (purified rosin) whose impurities have been reduced in the purification step with maleic acid or maleic anhydride, and the purified tall rosin is modified with maleic acid or maleic anhydride. What is obtained is more preferable.

The purified rosin is a rosin whose impurities are reduced by a purification process. By purifying rosin in this manner, impurities contained in rosin are removed. Examples of main impurities include 2-methylpropane, acetaldehyde, 3-methyl-2-butanone, 2-methylpropanoic acid, butanoic acid, pentanoic acid, n-hexanal, octane, hexanoic acid, benzaldehyde, 2-pentylfuran, Examples include 2,6-dimethylcyclohexanone, 1-methyl-2- (1-methylethyl) benzene, 3,5-dimethyl-2-cyclohexene, 4- (1-methylethyl) benzaldehyde, and the like. In the present invention, among these, the peak intensity of three types of impurities, hexanoic acid, pentanoic acid, and benzaldehyde, detected as a volatile component by the headspace GC-MS method, can be used as an indicator of purified rosin. The reason why the volatile component, not the absolute amount of impurities, is used as an indicator is that the use of the purified rosin in the present invention makes the odor one of the problems of improvement over the conventional polyester using the rosin.
Specifically, the purified rosin means that the hexanoic acid peak intensity is 0.8 × 10 ⁷ or less and the pentanoic acid peak intensity is 0 under the measurement conditions of the headspace GC-MS method of Examples described later. .4 × is 10 ⁷ or less, a peak intensity of benzaldehyde refers to rosin is 0.4 × 10 ⁷ or less. Furthermore, from the viewpoint of storage stability and odor, the peak intensity of hexanoic acid is preferably 0.6 × 10 ⁷ or less, and more preferably 0.5 × 10 ⁷ or less. The peak intensity of pentanoic acid is preferably 0.3 × 10 ⁷ or less, and more preferably 0.2 × 10 ⁷ or less. The peak intensity of benzaldehyde is preferably 0.3 × 10 ⁷ or less, and more preferably 0.2 × 10 ⁷ or less.
Furthermore, from the viewpoint of storage stability and odor, it is preferable that n-hexanal and 2-pentylfuran are reduced in addition to the above three kinds of substances. The peak intensity of n-hexanal is preferably 1.7 × 10 ⁷ or less, more preferably 1.6 × 10 ⁷ or less, and even more preferably 1.5 × 10 ⁷ or less. Further, the peak intensity of 2-pentylfuran is preferably 1.0 × 10 ⁷ or less, more preferably 0.9 × 10 ⁷ or less, and further preferably 0.8 × 10 ⁷ or less.

  The method for purifying the rosin is not particularly limited, and a known method can be used. Examples thereof include distillation, recrystallization, extraction, and the like, and purification by distillation is preferable. As the distillation method, for example, the method described in JP-A-7-286139 can be used, and examples thereof include vacuum distillation, molecular distillation, steam distillation, etc., but purification by vacuum distillation is preferable. For example, distillation is usually carried out at a still temperature of 200 to 300 ° C. at a pressure of 6.67 kPa or less, and methods such as ordinary simple distillation, thin film distillation, rectification and the like are applied. Under normal distillation conditions, 2 to 10% by mass of a high molecular weight product is removed as a pitch component with respect to the charged rosin, and at the same time, 2 to 10% by mass of an initial fraction is simultaneously removed.

The softening point of the rosin before modification is preferably 50 to 100 ° C, more preferably 60 to 90 ° C, and still more preferably 65 to 85 ° C. The softening point of the rosin means a softening point measured after the rosin is once melted and naturally cooled in an environment of a temperature of 25 ° C. and a relative humidity of 50% for 1 hour by the method described in the examples described later. To do.
The acid value of rosin before modification is preferably 100 to 200 mgKOH / g, more preferably 130 to 180 mgKOH / g, and still more preferably 150 to 170 mgKOH / g.
The acid value of the rosin can be measured based on the method described in JIS K0070, for example.

The glass transition temperature of the fumaric acid-modified rosin is preferably 40 to 90 ° C, more preferably 45 to 85 ° C, and still more preferably 50 to 80 ° C, from the viewpoint of enhancing the storage stability of the resulting polyester resin. Further, in the fumaric acid-modified rosin, the glass transition temperature of the rosin before modification is preferably 10 to 50 ° C. and more preferably 15 to 50 ° C. in consideration of the glass transition temperature of the rosin after modification with fumaric acid.
In addition, the glass transition temperature of the maleic anhydride-modified rosin is preferably 35 to 90 ° C, more preferably 45 to 70 ° C, from the viewpoint of enhancing the storage stability of the resulting polyester resin. In addition, in the maleic anhydride-modified rosin, the glass transition temperature of the rosin before modification is preferably 10 to 50 ° C., more preferably 15 to 50 ° C. in consideration of the glass transition temperature of the rosin after modification with maleic anhydride. .

  Further, the content of the (meth) acrylic acid-modified rosin and the total content of the fumaric acid-modified rosin and the maleic acid-modified rosin are 15 masses from the viewpoint of low-temperature fixability in the carboxylic acid component of the resin derived from each modified rosin. % Or more is preferable, and 25 mass% or more is more preferable. Moreover, from a viewpoint of preservability, 85 mass% or less is preferable, 65 mass% or less is more preferable, and 50 mass% or less is still more preferable. From these viewpoints, the content of the (meth) acrylic acid-modified rosin and the total content of the fumaric acid-modified rosin and the maleic acid-modified rosin are 15 to 85% by mass in the carboxylic acid component of the resin derived from each modified rosin. Preferably, 25-65 mass% is more preferable, and 25-50 mass% is still more preferable.

  The carboxylic acid compound other than the modified rosin contained in the carboxylic acid component is not particularly limited and may be appropriately selected according to the purpose. For example, oxalic acid, malonic acid, maleic acid, fumaric acid, Aliphatic dicarboxylic acids such as citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid; aromatics such as phthalic acid, isophthalic acid and terephthalic acid Dicarboxylic acids; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyrrolemetic acid; or anhydrides of these acids, alkyl (C1 to C3) esters, etc. Can be mentioned. In this specification, the acids as described above, and anhydrides and alkyl esters of these acids are collectively referred to as carboxylic acid compounds.

--- Alcohol component--
The alcohol component preferably contains an aliphatic alcohol, particularly an aliphatic polyhydric alcohol. The aliphatic polyhydric alcohol is preferably a 2- to 6-valent aliphatic polyhydric alcohol, more preferably a 2- to 3-valent aliphatic polyhydric alcohol, from the viewpoint of reactivity with a carboxylic acid containing a modified rosin.
The aliphatic polyhydric alcohol preferably contains a C2-6 aliphatic polyhydric alcohol having a more compact molecular structure and high reactivity. Examples of the aliphatic polyhydric alcohol having 2 to 6 carbon atoms include ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Examples include 2,3-butanediol, pentaerythritol, trimethylolpropane, sorbitol, glycerin and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, 1,2-propanediol, 1,3-propanediol, and glycerin are particularly preferable.
The content of the aliphatic polyhydric alcohol having 2 to 6 carbon atoms in the aliphatic polyhydric alcohol is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, substantially. Particularly preferred is 100 mol%.

  There is no restriction | limiting in particular as alcohol other than the said aliphatic polyhydric alcohol contained in the said alcohol component, Although it can select suitably according to the objective, For example, polyoxypropylene-2,2-bis (4- Bisphenol A such as alkylene (carbon number 2 to 3) oxide (average number of added moles 1 to 16) adduct of bisphenol A such as hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane Alkylene oxide adduct, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, or their alkylene (2 to 4 carbon) oxide (average number of added moles 1 to 16) adduct.

  From the viewpoint of reactivity with the modified rosin, the content of the aliphatic polyhydric alcohol is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 85 mol% or more, substantially from the alcohol component. Particularly preferred is 100 mol%.

From the viewpoint of improving offset resistance, the polyester-based resin has at least one of a trihydric or higher polyhydric alcohol and a trivalent or higher polyvalent carboxylic acid compound as a trivalent or higher raw material monomer within a range not impairing storage stability. Either may be contained. The trihydric or higher polyhydric alcohol is preferably contained in the alcohol component, and the trihydric or higher polyvalent carboxylic acid compound is preferably contained in the carboxylic acid component. The trihydric or higher polyhydric alcohol is preferably contained in the alcohol component, and the trihydric or higher polyvalent carboxylic acid compound is preferably contained in the carboxylic acid component. From the viewpoint of preservability and residual monomer reduction, the content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.001 to 40 mol, and preferably 0.1 to 25 mol, per 100 mol of the alcohol component. More preferred. The content of the trihydric or higher polyhydric alcohol is preferably 0.001 to 40 mol%, more preferably 0.1 to 25 mol% in the alcohol component.
In the trivalent or higher starting monomer, the trivalent or higher polyvalent carboxylic acid compound is preferably trimellitic acid or a derivative thereof, and the trivalent or higher polyhydric alcohol is, for example, glycerin, pentaerythritol, tritriol. Examples include methylolpropane, sorbitol, or their alkylene (2 to 4 carbon atoms) oxide (average added mole number 1 to 16) adduct. Among these, glycerin, trimellitic acid, or a derivative thereof is particularly preferable because it is not only a branching site or acts as a crosslinking agent but is also 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 bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium tris 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 Preferred are myristyl titanate, tetraoctyl titanate, dioctyl dihydroxy octyl titanate, For example, the titanium halide may be obtained by reacting a corresponding alcohol, are also commercially available, such as Nisso Corporation.
0.01-1.0 mass part is preferable with respect to 100 mass parts of total amounts of the said alcohol component and the said carboxylic acid component, and, as for the abundance of the said titanium compound, 0.1-0.7 mass part is more preferable.

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 preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. More preferably, it is 1 to 0.7 parts by mass.

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 100% of the total amount of the alcohol component and the carboxylic acid component. 0.01-1.0 mass part is preferable with respect to mass part, and 0.1-0.7 mass part is more preferable.
The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 180 to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst.

  The difference between the softening points of the two polyester resins is 10 ° C. or more from the viewpoint of enhancing the dispersibility of the internal additive and enhancing the effect on the fixability and offset resistance, particularly high temperature offset resistance. In achromatic toners such as black toner, the temperature is preferably 10 to 60 ° C. and more preferably 20 to 50 ° C. from the viewpoint of suppressing gloss. In addition, in chromatic color toners such as yellow toner, magenta toner, and cyan toner, the temperature is preferably 10 to 30 ° C. and more preferably 15 to 30 ° C. from the viewpoint of improving glossiness. The softening point of the polyester resin (A) having a lower softening point is preferably from 80 to 120 ° C, more preferably from 90 to 110 ° C, from the viewpoint of fixability. On the other hand, the softening point of the polyester resin (B) having a higher softening point is preferably 100 to 180 ° C, more preferably 120 to 180 ° C, and still more preferably 120 to 160 ° C, from the viewpoint of high temperature offset resistance.

The glass transition temperature of the polyester resin (A) and the polyester resin (B) is preferably 45 to 75 ° C, more preferably 50 to 70 ° C, from the viewpoints of fixability, storage stability, and durability.
In addition, from the viewpoint of chargeability and environmental stability, the acid value of the polyester resin (A) and the polyester resin (B) is preferably 1 to 80 mgKOH / g, more preferably 5 to 60 mgKOH / g, More preferred is 50 mg KOH / g. Moreover, 1-80 mgKOH / g is preferable, as for the hydroxyl value of the said polyester-type resin (A) and polyester-type resin (B), 8-50 mgKOH / g is more preferable, and 8-40 mgKOH / g is still more preferable.

  In the polyester-based resin (A) and the polyester-based resin (B), from the viewpoint of low temperature fixability, offset resistance, and storage stability, The content in the polyester resin is preferably 12% or less, more preferably 10% or less, still more preferably 9% or less, and particularly preferably 8% or less. The content of the low molecular weight component can be reduced by a method such as increasing the degree of modification of rosin. In addition, content of a low molecular weight component is based on the area ratio of the molecular weight measured by the gel permeation chromatography (GPC) of the Example mentioned later.

  The polyester units in the polyester resins (A) and (B) are preferably amorphous different from crystallinity. In this specification, an amorphous resin refers to a resin having a difference between the softening point and the glass transition temperature (Tg) of 30 ° C. or more.

  The mass ratio (A / B) of the polyester resin (A) and the polyester resin (B) is preferably 10/90 to 90/10, and preferably 20/80 to 80 from the viewpoint of fixability and durability. / 20 is more preferable, and 30/70 to 70/30 is still more preferable.

  In the present invention, when the binder resin is composed of three or more kinds of polyester resins, any two kinds of resins whose total content in the binder resin is 50% by mass or more are polyester resins ( What is necessary is just to satisfy the relationship between the softening point of A) and a polyester-type resin (B). Therefore, the binder resin includes polyester resins not corresponding to the polyester resin (A) and the polyester resin (B) within a range not impairing the effects of the present invention, for example, known binder resins such as styrene- Other resins such as vinyl resins such as acrylic resins, epoxy resins, polycarbonates and polyurethanes may be used in combination, but the total content of polyester resins (A) and polyester resins (B) is the binder resin Among them, 70% by mass or more is preferable, 80% by mass or more is more preferable, 90% by mass or more is further preferable, and substantially 100% by mass is further preferable.

  Furthermore, from the viewpoint of low-temperature fixability, offset resistance, durability, and storage stability, the total content of the resin derived from (meth) acrylic acid-modified rosin and the resin derived from fumaric acid / maleic acid-modified rosin in the binder resin is 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 100% by mass.

  In the present invention, the polyester resin means a resin having a polyester unit. The polyester unit refers to a portion having a polyester structure, and the polyester resin includes not only the polyester resin but also a polyester resin modified to such an extent that the properties are not substantially impaired. It is preferable that both the system resins (A) and (B) are polyester resins. 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 composite resin is preferably a resin having a polyester unit and an addition polymerization resin unit such as a vinyl resin.
Examples of the raw material monomer for the polyester unit include the same alcohol component and carboxylic acid component as the raw material monomer for the polyester.
On the other hand, examples of the raw material monomer for the vinyl resin unit include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyls such as vinyl chloride. Vinyl esters such as vinyl acetate and vinyl propionate; alkyl (carbon number 1 to 18) esters of (meth) acrylic acid, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinylmethyl Vinyl ethers such as ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone and the like. Among these, styrene, 2-ethylhexyl acrylate, butyl acrylate, or a long-chain alkyl (carbon number 12 to 18) ester of acrylic acid is preferable, and from the viewpoint of chargeability, styrene is a viewpoint of fixing property and adjustment of glass transition temperature. Therefore, alkyl esters of (meth) acrylic acid are preferred.
The content of the styrene is preferably 50 to 90% by mass and more preferably 75 to 85% by mass in the raw material monomer of the vinyl resin. The monomer mass ratio of styrene to the alkyl ester of (meth) acrylic acid (styrene / (meth) acrylic acid alkyl ester) is preferably 50/50 to 95/5, more preferably 70/30 to 95/5.
In addition, you may use a polymerization initiator, a crosslinking agent, etc. for the addition polymerization of the raw material monomer of a vinyl-type resin unit as needed.

  In the present invention, the mass ratio of the raw material monomer of the polyester unit to the raw material monomer of the addition polymerization resin unit (raw material monomer of the polyester unit / raw material monomer of the addition polymerization resin unit) is such that the continuous phase is the polyester unit, Is preferably an addition polymerization resin unit, 50/50 to 95/5 is preferable, and 60/40 to 95/5 is more preferable.

In addition to the raw material monomer for the polyester unit and the raw material monomer for the addition polymerization resin unit, the composite resin is a compound that can react with both the raw material monomer for the polyester unit and the raw material monomer for the addition polymerization resin unit (both reactive monomers). It is preferable that it is a resin (hybrid resin) obtained by using (1).
The amphoteric monomer includes at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule, and ethylenically unsaturated. A compound having a bond is preferable, and by using such a bireactive monomer, the dispersibility of the resin to be a dispersed phase can be further improved. Specific examples of the both reactive monomers include, for example, acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, or carboxylic acids thereof. And anhydrides, alkyl (1 to 2 carbon atoms) derivatives and the like. Among these, acrylic acid, methacrylic acid, fumaric acid, maleic acid, or derivatives of these carboxylic acids are preferable from the viewpoint of reactivity. .

  Among the both reactive monomers, a monomer having two or more functional groups (polycarboxylic acid or the like) or a derivative thereof is a raw material monomer for a polyester unit, and a monomer having one functional group (monocarboxylic acid or the like) or a derivative thereof is Treated as a raw material monomer for addition polymerization resin units. The amount of the amphoteric monomer used is preferably 1 to 30 mol with respect to 100 mol of the raw material monomer of the polyester unit excluding the amphoteric monomer. In the production process of the resin, in the method of reacting at a high temperature after the addition polymerization reaction, 1.5 to 20 mol is more preferable, 2 to 10 mol is more preferable, and the reaction temperature is kept constant after the addition polymerization reaction. In the method using a large amount of both reactive monomers, 4 to 15 mol is more preferable, and 4 to 10 mol is more preferable.

  From the viewpoint of uniformity of the polyester unit and the addition polymerization resin unit, the composite resin is prepared by mixing the raw material monomer of the polyester unit and the raw material monomer of the addition polymerization resin unit in advance, and the condensation polymerization reaction and addition polymerization reaction are the same reaction It is preferably a resin obtained by carrying out in parallel in a container, and when the composite resin is a hybrid resin obtained by further using both reactive monomers, the raw material monomer and addition polymerization of the condensation polymerization resin unit It is preferable that the resin is obtained by previously mixing a mixture of monomers as raw materials of the resin-based resin unit and the both reactive monomers, and performing the condensation polymerization reaction and the addition polymerization reaction in parallel in the same reaction vessel.

  In the present invention, the progress and completion of the condensation polymerization reaction and the addition polymerization reaction do not need to be simultaneous in time, and the reaction temperature and time are appropriately selected according to each reaction mechanism to allow the reaction to proceed and complete. Just do it. For example, the raw material monomer of the polyester unit, the raw material monomer of the addition polymerization resin unit, the bireactive monomer, etc. are mixed, and first, condensation polymerization is carried out mainly by the addition polymerization reaction at a temperature condition suitable for the addition polymerization reaction, for example, 50 to 180 ° C. After forming an addition polymerization resin having a functional group capable of reaction, the reaction temperature is then increased to a temperature condition suitable for the condensation polymerization reaction, for example, 190 to 270 ° C., and then the condensation polymerization system is mainly formed by a condensation polymerization reaction. The method of forming resin is mentioned.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include 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 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, the coloring power decreases, and the electrical characteristics of the toner. May be reduced.

  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, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable. If the melting point is less than 40 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
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 to 1,000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 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, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

-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, hydrophobized titania fine particles, and hydrophobized alumina fine particles, the hydrophilic fine particles are converted into silane coupling agents such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. Can be obtained by processing.
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.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If 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. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, and more preferably 5 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. Moreover, it is preferable that the specific surface area by the BET method of the said inorganic fine particle is 20-500 m < ² > / g.
The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 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 to 5% by mass, and more preferably 0.1 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, and a fluoride can be used. 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 may be appropriately selected from conventionally known toner production methods according to the purpose. 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, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, a Kneader manufactured by Buss, etc. are suitable. 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 if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, the filming of the toner on the developing roller as the developer carrying member, and the thinning of the toner are performed. 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 maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. 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 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 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 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 the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the 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 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 on the surface carrying a two-component developer comprising a magnetic carrier and a toner. 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 by, for example, charging the visible image with the electrostatic latent image carrier using a transfer charger, 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 by 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. A sheet feeding device 6 must be disposed on the upstream side, and a fixing device 7 as a fixing unit must be disposed on the downstream side, which increases the size of the recording medium in the 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 systems 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 fixability may be insufficient.

  The temperature at which the image is fixed to the recording medium by the toner (that is, the surface temperature of the fixing member by the heating means) is not particularly limited and may be appropriately selected depending on the intended purpose. ° C is preferred, and 120 to 160 ° C is more preferred. When the fixing temperature is less than 120 ° C., the fixability may be insufficient, and when 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 recording medium S is prevented from being wound around the fixing belt 567. 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 a developing unit also serves as a 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 development 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 means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

-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, exposure 30 by an exposure device as an exposure unit, and a developing device 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 handleability, and can be suitably attached to the process cartridge, the image forming apparatus and the like of the present invention by being detachably attached thereto.

(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 contains a polyester resin (A) and a polyester resin (B) whose softening point is higher by 10 ° C. or more than the polyester resin (A). And
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester-based resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin.
As the polyester resins (A) and (B), the same resins as those described in the image forming apparatus and the image forming method described 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. In addition, a layer thickness regulating member for regulating the thickness of the toner layer carried on the developer carrying member may be provided. 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 removal 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.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples and comparative examples, various physical properties of the resin and rosin were measured as follows.

<Measurement of softening point of resin>
Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), as a sample, 1 g of each polyester-based binder resin was heated at a heating rate of 6 ° C./min. The sample was extruded from a nozzle having a length of 1 mm, the plunger drop amount of the flow tester was plotted against the temperature, and the temperature at which half the sample flowed out was defined as the softening point.

<Measurement of glass transition temperature (Tg) of resin and rosin>
Using a differential scanning calorimeter (DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of each sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature decreasing rate was 10 ° C./min. The sample was cooled to 0 ° C. at a heating rate of 10 ° C./min, and 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. The temperature at the intersection was taken as the glass transition temperature.

<Measurement of softening point of rosin>
(1) Preparation of sample 10 g of rosin is melted on a hot plate at 170 ° C. for 2 hours. Then, it was naturally cooled for 1 hour in an environment of a temperature of 25 ° C. and a relative humidity of 50% in an opened state, and ground for 10 seconds with a coffee mill (National MK-61M) to prepare a sample.
(2) Measurement Using a flow tester (manufactured by Shimadzu Corp., CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C./min. The sample was extruded from a 1 mm nozzle, and the plunger drop amount 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.

<Acid value of resin and rosin>
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)).

<Hydroxyl value of resin>
It measured based on the method of JISK0070.

<Content of low molecular weight component having a molecular weight of 500 or less>
The molecular weight distribution was measured by gel permeation chromatography (GPC). First, 10 mL of tetrahydrofuran was added to 30 mg of each resin, mixed for 1 hour with a ball mill, filtered through a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components, and a sample solution was prepared. Prepared.
Next, tetrahydrofuran was flowed as an eluent at a flow rate of 1 mL per minute, the column was stabilized in a constant temperature bath at 40 ° C., and 100 μL of the sample solution was injected for measurement. In addition, “GMHLX + G3000HXL” (manufactured by Tosoh Corporation) is used as the analytical column, and several types of monodisperse polystyrene (2.63 × 10 ³ , 2.06 × 10 ⁴ , manufactured by Tosoh Corporation) are used for the molecular weight calibration curve. 0.02 × 10 ⁵ , 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) manufactured by GL Sciences Inc. were prepared as standard samples.
Next, the content (%) of the low molecular weight component having a molecular weight of 500 or less is the ratio of the area of the corresponding area in the chart area obtained by the RI (refractive index) detector to the chart area (area / area of the corresponding area). Calculated as (total chart area).

<Measurement of SP value of rosin>
After pouring 2.1 g of the molten sample into a predetermined ring, the sample was cooled to room temperature and then measured under the following conditions based on JIS B7410.
-Measuring machine: Ring and ball type automatic softening point tester (ASP-MGK2, manufactured by Meitec Co., Ltd.)
・ Raising rate: 5 ° C / min
-Temperature rise start temperature: 40 ° C
・ Measurement solvent: Glycerin

<Measurement of degree of modification of rosin with (meth) acrylic acid>
The (meth) acrylic acid modification degree can be calculated by the following mathematical formula (Aa).
However, in said numerical formula (Aa), _Xa1 represents SP value of the (meth) acrylic-acid modified rosin which calculates a modification degree. _Xa2 represents a saturated SP value of (meth) acrylic acid-modified rosin obtained by reacting 1 mol of (meth) acrylic acid and 1 mol of rosin. Y represents the SP value of rosin.
The saturated SP value means the SP value when the reaction between (meth) acrylic acid and rosin is caused to react until the SP value of the obtained (meth) acrylic acid-modified rosin reaches a saturation value.

<Measurement of the degree of fumaric acid modification of rosin>
The fumaric acid modification degree can be calculated by the following mathematical formula (Af).
However, the numerical expression _{(Af), X f1} represents the SP value of the fumaric acid-modified rosin for calculating the degree of modification. X _f2 represents the SP value of a fumaric acid-modified rosin obtained by reacting 1 mol of fumaric acid with 0.7 mol of rosin. Y represents the SP value of rosin.
The SP value indicated by X _f2 is as follows: a mixture of 1 mol of fumaric acid, 0.7 mol of rosin and 0.4 g of t-butylcatechol was heated from 160 ° C. to 200 ° C. over 2 hours, and 2 at 200 ° C. It is SP value of the fumaric acid modification | denaturation rosin obtained by making it react under reduced pressure of 5.3 kPa after making it react for time.

<Measurement of degree of maleic acid modification of rosin>
The maleic acid modification degree can be calculated by the following mathematical formula (Am).
However, in the formula (Am), X _m1 represents the SP value of maleic acid-modified rosin for calculating the degree of modification. X _m2 represents a saturated SP value of maleic acid-modified rosin obtained by reacting 1 mol of maleic acid with 1 mol of rosin at 230 ° C. Y represents the SP value of rosin.
The saturated SP value means the SP value when the reaction of maleic acid and rosin is allowed to react until the SP value of the resulting maleic acid-modified rosin reaches the saturation value.

In the formula (Aa), formula (Af), and formula (Am), the molecular weight of 1 mol of rosin is potassium hydroxide (molecular weight: 56.000) with respect to 1 g of rosin, where the acid value is x (mg KOH / g). Since 1) is reacted by xmg (x × 10 ⁻³ g), it can be calculated by the following formula, molecular weight = (56100 ÷ x).

(Synthesis Example 1)
-Purification of rosin-
1,000 g of tall rosin (glass transition temperature (Tg) = 37.2 ° C.) was added to a 2,000 mL distillation flask equipped with a fractionating tube, a reflux condenser, and a receiver, and the pressure was reduced to 1 kPa. Distillation was performed, and a distillate at 195 ° C. to 250 ° C. was collected as a main distillate. Hereinafter, tall rosin subjected to purification is referred to as unpurified rosin, and rosin collected as a main fraction is referred to as purified rosin (glass transition temperature (Tg) = 39.2 ° C.).

  20 g of each rosin was pulverized with a coffee mill (National MK-61M) for 5 seconds, and 0.5 g was measured in a headspace vial (20 mL) through a sieve having an opening of 1 mm. The headspace gas was sampled, and impurities in the unpurified rosin and the purified rosin were analyzed by the headspace GC-MS method as follows. The results are shown in Table 1.

<Measurement conditions of the headspace GC-MS method>
A. Headspace sampler (manufactured by Agilent, HP7694)
Sample temperature: 200 ° C
・ Loop temperature: 200 ℃
・ Transfer line temperature: 200 ℃
・ Sample heating equilibrium time: 30 min
・ Vial pressurization gas: Helium (He)
・ Vial pressurization time: 0.3 min
・ Loop filling time: 0.03 min
-Loop equilibration time: 0.3 min
・ Injection time: 1 min

B. GC (gas chromatography) (manufactured by Agilent, HP6890)
Analytical column: DB-1 (60 m-320 μm-5 μm)
・ Carrier: Helium (He)
・ Flow conditions: 1 mL / min
・ Inlet temperature: 210 ° C
Column head pressure: 34.2 kPa
Injection mode: split
Split ratio: 10: 1
-Oven temperature conditions: 45 ° C (3min) -10 ° C / min-280 ° C (15min)

C. MS (mass spectrometry) (manufactured by Agilent, HP5973)
-Ionization method: EI (electron ionization) method-Interface temperature: 280 ° C
-Ion source temperature: 230 ° C
-Quadrupole temperature: 150 ° C
・ Detection mode: Scan 29-350m / s

<Measurement of saturation SP value of acrylic acid-modified rosin using unpurified rosin>
332 g (1 mol) of unpurified rosin (SP value = 77.0 ° C.) and 72 g (1 mol) of acrylic acid were added to a 1,000 mL flask equipped with a fractionation tube, a reflux condenser, and a receiver. The temperature was increased from 160 ° C. to 230 ° C. over 8 hours, and after confirming that the SP value did not increase at 230 ° C., unreacted acrylic acid and low-boiling substances at 230 ° C. under a reduced pressure of 5.3 kPa Then, acrylic acid-modified rosin was obtained.
The SP value of the obtained acrylic acid-modified rosin, that is, the saturated SP value of the acrylic acid-modified rosin using unpurified rosin was 110.1 ° C.

<Measurement of saturation SP value of acrylic acid-modified rosin using purified rosin>
Purified rosin (SP value = 76.8 ° C.) 338 g (1 mol) and acrylic acid 72 g (1 mol) were added into a 1,000 mL flask equipped with a fractionating tube, a reflux condenser, and a receiver. The temperature was increased from 160 ° C. to 230 ° C. over 8 hours, and after confirming that the SP value did not increase at 230 ° C., unreacted acrylic acid and low-boiling substances were reduced under reduced pressure of 230 ° C. and 5.3 kPa. Distillation was performed to obtain acrylic acid-modified rosin.
The SP value of the obtained acrylic acid-modified rosin, that is, the saturated SP value of the acrylic acid-modified rosin using purified rosin was 110.4 ° C.

(Synthesis Example 2)
-Synthesis of acrylic acid-modified rosin A-
Purified rosin (SP value = 76.8 ° C.) 6,084 g (18 mol) and acrylic acid 907.9 g (12.6 mol) in a 10 L flask equipped with a fractionation tube, reflux condenser and receiver ), Heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled at 220 ° C. under a reduced pressure of 5.3 kPa to obtain acrylic acid-modified rosin A Got. The obtained acrylic acid-modified rosin A had an SP value of 110.4 ° C., a glass transition temperature of 57.1 ° C., and an acrylic acid modification degree of 100.

(Synthesis Example 3)
-Synthesis of acrylic acid-modified rosin B-
In a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver, purified rosin (SP value = 76.8 ° C.) 6,084 g (18 mol) and acrylic acid 648.5 g (9.0 mol) ), Heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, further distilled at 220 ° C. under a reduced pressure of 5.3 kPa, and acrylic acid-modified rosin B Got.
The obtained acrylic acid-modified rosin B had an SP value of 99.1 ° C., a glass transition temperature of 53.2 ° C., and an acrylic acid modification degree of 66.

(Synthesis Example 4)
-Synthesis of acrylic acid-modified rosin C-
In a 10 L flask equipped with a fractionation tube, reflux condenser and receiver, unpurified rosin (S
P value = 77.0 ° C.) 5,976 g (18 mol), and acrylic acid 907.6 g (12.6 mol)
), Heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled at 220 ° C. under a reduced pressure of 5.3 kPa to obtain acrylic acid-modified rosin C. Obtained. The acrylic acid-modified rosin C obtained had an SP value of 110.1 ° C. and a glass transition temperature of 54.5.
The degree of acrylic acid modification was 100.

<Measurement of SP Value of Fumaric acid modified rosin using an unpurified rosin used as Xf ₂ Value>
In a 1,000 mL flask equipped with a fractionation tube, a reflux condenser, and a receiver, 332 g (1 mol) of unpurified rosin (SP value = 77.0 ° C.), 81 g (0.7 mol) of fumaric acid, And t-butylcatechol 0.4 g, heated from 160 ° C. to 200 ° C. over 2 hours, reacted at 200 ° C. for 2 hours, and further distilled at 200 ° C. under a reduced pressure of 5.3 kPa. Unreacted fumaric acid and low-boiling substances were distilled off to obtain fumaric acid-modified rosin.
The SP value of the obtained fumaric acid-modified rosin, that is, the SP value of the fumaric acid-modified rosin using unpurified rosin was 130.6 ° C.

<Measurement of SP Value of Fumaric acid modified rosin using purified rosin employed as Xf ₂ Value>
In a 1,000 mL flask equipped with a fractionation tube, reflux condenser and receiver, 388 g (1 mol) of purified rosin (SP value = 76.8 ° C.), 81 g (0.7 mol) of fumaric acid, and After adding 0.4 g of t-butylcatechol, the temperature was raised from 160 ° C. to 200 ° C. over 2 hours and reacted at 200 ° C. for 2 hours, and further distilled at 200 ° C. under a reduced pressure of 5.3 kPa. Unreacted fumaric acid and low-boiling substances were distilled off to obtain fumaric acid-modified rosin.
The SP value of the obtained fumaric acid-modified rosin, that is, the SP value of the fumaric acid-modified rosin using purified rosin was 130.9 ° C.

(Synthesis Example 5)
-Synthesis of fumaric acid-modified rosin A-
Purified rosin (SP value = 76.8 ° C.) 5,408 g (16 mol), fumaric acid 928 g (8 mol), and t − in a 10 L flask equipped with a fractionation tube, reflux condenser, and receiver 0.4 g of butylcatechol was added, the temperature was raised from 160 ° C. to 200 ° C. over 2 hours, reacted at 200 ° C. for 2 hours, and further distilled at 200 ° C. under a reduced pressure of 5.3 kPa. Acid-modified rosin A was obtained.
The obtained fumaric acid-modified rosin A had an SP value of 130.8 ° C., a glass transition temperature of 74.4 ° C., and a fumaric acid modification degree of 100.

(Synthesis Example 6)
-Synthesis of fumaric acid-modified rosin B-
In a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5,312 g (16 mol) of unpurified rosin (SP value = 77.0 ° C.), 928 g (8 mol) of fumaric acid, and t -0.4 g of butyl catechol was added, the temperature was raised from 160 ° C to 200 ° C over 2 hours, reacted at 200 ° C for 2 hours, and further distilled at 200 ° C under a reduced pressure of 5.3 kPa, Fumaric acid-modified rosin B was obtained.
The obtained fumaric acid-modified rosin B had an SP value of 130.4 ° C., a glass transition temperature of 72.1 ° C., and a fumaric acid modification degree of 100.

<Measurement of saturation SP value of maleic acid-modified rosin using unpurified rosin>
In a 1,000 mL flask equipped with a fractionation tube, a reflux condenser, and a receiver, 332 g (1 mol) of unpurified rosin (SP value = 77.0 ° C.) and 98 g (1 mol) of maleic anhydride were placed. In addition, the temperature was increased from 160 ° C. to 230 ° C. over 8 hours, and after confirming that the SP value did not increase at 230 ° C., unreacted maleic anhydride and low pressure were reduced at 230 ° C. under a reduced pressure of 5.3 kPa. Boiling substances were distilled off to obtain maleic acid-modified rosin.
The SP value of the obtained maleic acid-modified rosin, that is, the saturated SP value of maleic acid-modified rosin using unpurified rosin was 116 ° C.

<Measurement of saturation SP value of maleic acid-modified rosin using purified rosin>
Purified rosin (SP value = 76.8 ° C.) 338 g (1 mol) and maleic anhydride 98 g (1 mol) were added into a 1,000 mL flask equipped with a fractionating tube, a reflux condenser, and a receiver. The temperature was increased from 160 ° C. to 230 ° C. over 8 hours, and after confirming that the SP value did not increase at 230 ° C., unreacted maleic anhydride and low boiling point at 230 ° C. under a reduced pressure of 5.3 kPa. The product was distilled off to obtain maleic acid-modified rosin.
The SP value of the obtained maleic acid-modified rosin, that is, the saturated SP value of the maleic acid-modified rosin using purified rosin was 116 ° C.

(Synthesis Example 7)
-Synthesis of maleic acid-modified rosin A-
In a 10 L flask equipped with a fractionation tube, reflux condenser, and receiver, purified rosin (SP value = 76.8 ° C.) 6,084 g (18 mol) and maleic anhydride 1,323 g (13.5 g) Mol)), heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled at 220 ° C. under a reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin. A was obtained. The resulting maleic acid-modified rosin A had an SP value of 116.2 ° C., a glass transition temperature of 57.6 ° C., and a maleic acid modification degree of 101.

(Synthesis Example 8)
-Synthesis of maleic acid-modified rosin B-
Purified rosin (SP value = 76.8 ° C.) 6,084 g (18 mol) and maleic anhydride 529 g (5.4 mol) were placed in a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver. In addition, the temperature was raised from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled at 220 ° C. under a reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin B. It was.
The obtained maleic acid-modified rosin B had an SP value of 96.4 ° C. and a maleic acid modification degree of 50.

(Synthesis Example 9)
-Synthesis of maleic acid-modified rosin C-
In a 10 L flask equipped with a fractionation tube, a reflux condenser and a receiver, 5,976 g (18 mol) of crude rosin (SP value = 77.0 ° C.), 529 g (5.4 mol) of maleic anhydride The mixture was heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled at 220 ° C. under a reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin C. Obtained.
The obtained maleic acid-modified rosin C had an SP value of 96.4 ° C. and a maleic acid modification degree of 50.

(Synthesis Examples 10 to 21)
-Synthesis of resins 1-12-
A 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple for the alcohol component, the carboxylic acid component other than trimellitic anhydride, and the esterification catalyst shown in Tables 2 and 3 The mixture was subjected to a condensation polymerization reaction at 230 ° C. for 10 hours in a nitrogen atmosphere, and then reacted at 230 ° C. and 8 kPa for 1 hour. After cooling to 220 ° C., trimellitic anhydride shown in Table 2 and Table 3 is added, and after reacting at normal pressure (101.3 kPa) for 1 hour, the desired softening point is reached at 220 ° C. and 20 kPa. Reaction was performed and resin 1-12 was synthesize | combined.

* Unpurified rosin: unmodified rosin

* Unpurified rosin: unmodified rosin

(Production Example 1)
-Preparation of master batch 1-
The pigment having the following composition, the binder resin 2, 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 toner master batch 1 (TB-C1), magenta toner master batch 1 (TB-M1), and yellow toner master batch. 1 (TB-Y1) and black toner masterbatch 1 (TB-K1) were produced.

[Cyan toner masterbatch 1 (TB-C1) formulation]
-Binder resin 2 ... 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 (TB-M1) Formula]
-Binder resin 2 ... 100 parts by mass-Magenta pigment (CI Pigment red 122) ... 100 parts by mass-Pure water ... 50 parts by mass

[Yellow toner masterbatch 1 (TB-Y1) formulation]
-Binder resin 2 ... 100 parts by mass-Yellow pigment (CI Pigment yellow 180) ... 100 parts by mass-Pure water ... 50 parts by mass

[Black Toner Masterbatch 1 (TB-K1) prescription]
-Binder resin 2 ... 100 parts by mass-Black pigment (carbon black) ... 100 parts by mass-Pure water ... 50 parts by mass

(Production Example 2)
-Preparation of master batch 2-
In Production Example 1, except that the binder resin 2 was changed to the binder resin 3, the same procedure as in Production Example 1 was followed, except that cyan master batch 2 (TB-C2), magenta master batch 2 (TB-M2), yellow master batch 2 Master batch 2 consisting of (TB-Y2) and black master batch 2 (TB-K2) was produced.

(Production Example 3)
-Preparation of master batch 3-
In Production Example 1, except that the binder resin 2 was changed to the binder resin 5, the same procedure as in Production Example 1 was followed, cyan master batch 3 (TB-C3), magenta master batch 3 (TB-M3), yellow master batch 3 Master batch 3 consisting of (TB-Y3) and black master batch 3 (TB-K3) was produced.

(Production Example 4)
-Production of master batch 4-
In Production Example 1, except that binder resin 2 was changed to binder resin 7, cyan master batch 4 (TB-C4), magenta master batch 4 (TB-M4), yellow master batch 4 were the same as in Production Example 1. Master batch 4 consisting of (TB-Y4) and black master batch 4 (TB-K4) was produced.

(Production Example 5)
-Preparation of masterbatch 5-
In Production Example 1, except that binder resin 2 was changed to binder resin 9, cyan master batch 5 (TB-C5), magenta master batch 5 (TB-M5), yellow master batch 5 were the same as in Production Example 1. Master batch 5 consisting of (TB-Y5) and black master batch 5 (TB-K5) was produced.

(Production Example 6)
-Preparation of master batch 6-
In Production Example 1, except that the binder resin 2 was changed to the binder resin 10, the same procedure as in Production Example 1 was followed. Cyan masterbatch 6 (TB-C6), magenta masterbatch 6 (TB-M6), yellow masterbatch 6 Master batch 6 consisting of (TB-Y6) and black master batch 6 (TB-K6) was produced.

(Production Example 7)
-Preparation of master batch 7-
In Production Example 1, except that binder resin 2 was changed to binder resin 12, cyan master batch 7 (TB-C7), magenta master batch 7 (TB-M7), yellow master batch 7 were the same as in Production Example 1. A master batch 7 composed of (TB-Y7) and black master batch 7 (TB-K7) was produced.

(Production Example 8)
<Preparation of Toner 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 pulverizer (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). Toner base particles having a diameter of 7 μm were obtained.
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 2 as polyester resin (A): 42 parts by mass Resin 1 as polyester resin (B): 50 parts by mass Cyan toner masterbatch 1 (TB-C1): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 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]
Resin 2 as polyester resin (A): 41 parts by mass Resin 1 as polyester resin (B): 50 parts by mass Magenta toner masterbatch 1 (TB-M1): 18 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 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]
Resin 2 as polyester resin (A): 40 parts by mass Resin 1 as polyester resin (B): 50 parts by mass Yellow toner masterbatch 1 (TB-Y1): 20 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 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]
Resin 2 as polyester resin (A): 42 parts by mass Resin 1 as polyester resin (B): 50 parts by mass Black toner masterbatch 1 (TB-K1): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass

(Production Example 9)
-Production of Toner 2-
A toner 2 composed of a cyan toner 2, a yellow toner 2, a magenta toner 2, and a black toner 2 was produced in the same manner as in Production Example 8, except that the following toner formulations were used in Production Example 8.
[Cyan Toner Formula 2]
Resin 3 as polyester-based resin (A): 32 parts by mass Resin 1 as polyester-based resin (B): 60 parts by mass Cyan toner masterbatch 2 (TB-C2): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Industries, Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [magenta Toner Formula 2]
Resin 3 as polyester resin (A) 31 mass parts Resin 1 as polyester resin B 60 mass parts Magenta toner masterbatch 2 (TB-M2) 18 mass parts Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84): 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [yellow Toner Formula 2]
-Resin 3 as polyester-based resin (A) 30 mass parts-Resin 1 as polyester-based resin (B) 60 mass parts Yellow toner masterbatch 2 (TB-Y2) 20 mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Black Toner Formula 2]
-Resin 3 as polyester resin (A) ... 32 parts by mass-Resin 1 as polyester resin (B) ... 60 parts by mass-Black toner masterbatch 2 (TB-K2) ... 16 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass

(Production Example 10)
-Production of Toner 3-
A toner 3 composed of a cyan toner 3, a yellow toner 3, a magenta toner 3, and a black toner 3 was produced in the same manner as in Production Example 8, except that the following toner formulations were used in Production Example 8.
[Cyan Toner Formula 3]
Resin 5 as polyester resin (A): 32 parts by mass Resin 4 as polyester resin (B): 60 parts by mass Cyan toner masterbatch 3 (TB-C3) 16 mass Parts ・ Charge control agent (Orient Chemical Industries, Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [magenta Toner Formula 3]
Resin 5 as polyester resin (A): 31 parts by mass Resin 4 as polyester resin (B): 60 parts by mass Magenta toner masterbatch 3 (TB-M3) 18 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84): 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [yellow Toner Formula 3]
Resin 5 as polyester-based resin (A): 30 parts by mass Resin 4 as polyester-based resin (B): 60 parts by mass Yellow toner masterbatch 3 (TB-Y3) 20 mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Black Toner Formula 3]
Resin 5 as polyester resin (A): 32 parts by mass Resin 4 as polyester resin (B): 60 parts by mass Black toner masterbatch 3 (TB-K3): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass

(Production Example 11)
-Production of Toner 4-
In Production Example 8, a toner 4 composed of cyan toner 4, yellow toner 4, magenta toner 4 and black toner 4 was produced in the same manner as in Production Example 8, except that the following toner formulations were used.
[Cyan Toner Formula 4]
Resin 7 as a polyester resin (A): 22 parts by mass Resin 6 as a polyester resin (B): 70 parts by mass Cyan toner masterbatch 4 (TB-C4) 16 mass Parts ・ Charge control agent (Orient Chemical Industries, Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [magenta Toner Formula 4]
Resin 7 as polyester resin (A) 21 parts by mass 21 Resin 6 as polyester resin B 70 parts by mass Magenta toner masterbatch 4 (TB-M4) 18 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84): 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [yellow Toner Formula 4]
Resin 7 as polyester resin (A): 20 parts by mass Resin 6 as polyester resin (B): 70 parts by mass Yellow toner masterbatch 4 (TB-Y4) 20 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Black Toner Formula 4]
Resin 7 as a polyester-based resin (A): 22 parts by mass Resin 6 as a polyester-based resin (B) 70 mass parts Black toner masterbatch 4 (TB-K4) 16 mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass

(Production Example 12)
-Production of Toner 5-
A toner 5 composed of a cyan toner 5, a yellow toner 5, a magenta toner 5, and a black toner 5 was produced in the same manner as in Production Example 8, except that the following toner formulation was changed in Production Example 8.
[Cyan Toner Formula 5]
Resin 9 as polyester resin (A): 42 parts by mass Resin 8 as polyester resin (B): 50 parts by mass Cyan toner masterbatch 5 (TB-C5): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Industries, Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [magenta Toner Formula 5]
Resin 9 as polyester resin (A): 41 parts by mass Resin 8 as polyester resin (B): 50 parts by mass Magenta toner masterbatch 5 (TB-M5) 18 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84): 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [yellow Toner Formula 5]
Resin 9 as polyester resin (A): 40 parts by mass Resin 8 as polyester resin (B): 50 parts by mass Yellow toner masterbatch 5 (TB-Y5) 20 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Black Toner Formula 5]
Resin 9 as polyester resin (A): 42 parts by mass Resin 8 as polyester resin (B): 50 parts by mass Black toner masterbatch 5 (TB-K5): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ...

(Production Example 13)
-Production of Toner 6-
A toner 6 composed of a cyan toner 6, a yellow toner 6, a magenta toner 6, and a black toner 6 was produced in the same manner as in Production Example 8, except that the following toner formulations were used in Production Example 8.
[Cyan Toner Formula 6]
Resin 12 as polyester resin (A): 42 parts by mass Resin 11 as polyester resin (B): 50 parts by mass Cyan toner master batch 7 (TB-C7): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Industries, Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [magenta Toner Formula 6]
Resin 12 as polyester resin (A): 41 parts by mass Resin 11 as polyester resin (B): 50 parts by mass Magenta toner master batch 7 (TB-M7): 18 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84): 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [yellow Toner Formula 6]
Resin 12 as polyester resin (A): 40 parts by mass Resin 11 as polyester resin (B): 50 parts by mass Yellow toner master batch 7 (TB-Y7): 20 parts by mass Part ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Black Toner Formula 6]
Resin 12 as polyester resin (A): 42 parts by mass Resin 11 as polyester resin (B): 50 parts by mass Black toner master batch 7 (TB-K7): 16 parts by mass Parts ・ Charge control agent (Orient Chemical Co., Ltd., E-84) ・ ・ ・ 1 part by mass ・ Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass

(Production Example 14)
-Production of Toner 7-
A toner 7 composed of a cyan toner 7, a yellow toner 7, a magenta toner 7 and a black toner 7 was produced in the same manner as in Production Example 8, except that the following toner formulations were used in Production Example 8.
[Cyan toner prescription 7]
-Resin 10 as a polyester-based resin ... 92 parts by mass-Cyan toner master batch 6 (TB-C6) ... 16 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Industries, Ltd.) ... 1 part by mass-Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [magenta toner formulation 7]
-Resin 10 as a polyester-based resin ... 91 parts by mass-Magenta toner master batch 6 (TB-M6) ... 18 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Industries, Ltd.) ... 1 part by mass-Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Yellow Toner Formulation 7]
-Resin 10 as a polyester-based resin ... 90 parts by mass-Yellow toner master batch 6 (TB-Y6) ... 20 parts by mass-Charge control agent (E-84, manufactured by Orient Chemical Industries, Ltd.) ... 1 part by mass-Ester wax (acid value = 5 mg KOH / g, mass average molecular weight = 1,600) ... 5 parts by mass [Black toner formulation 7]
-Resin 10 as polyester resin ... 92 parts by mass-Black toner master batch 6 (TB-K6)-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

* In the table, () represents parts by mass.

-Evaluation of toner performance-
Next, the obtained toners 1 to 7 were evaluated for grindability, storage stability, and odor as follows. The results are shown in Table 6.

<Measurement of grindability>
Each kneaded resin of the combination shown in Table 5 used as a binder resin was coarsely crushed and sieved, passed through a 16 mesh (opening: 1 mm) sieve, and passed through a 22 mesh (opening: 710 μm) sieve. Not obtained resin powder. 10.00 g of this classified resin powder is precisely weighed, pulverized with a mill and mixer MM-I type (manufactured by Hitachi Living Supply Co., Ltd.) for 30 seconds, passed through a 30 mesh (aperture: 500 μm) sieve, and does not pass. The resin mass (A) g was precisely weighed, the residual ratio was obtained by the following formula, this operation was performed three times, and the average value was used as the grindability index, and grindability was evaluated according to the following evaluation criteria .
Residual rate = (A) / resin mass before grinding (10.00 g) × 100
〔Evaluation criteria〕
◎: Grindability index is less than 5 ○: Grindability index is 5 or more, less than 15 ×: Grindability index is 15 or more

<Evaluation method of toner storage stability>
Two samples were prepared by putting 4 g of each toner in an open cylindrical container having a diameter of 5 cm and a height of 2 cm. One was left in an environment at a temperature of 40 ° C. and a relative humidity of 60%, and the other was left in an environment at a temperature of 55 ° C. and a relative humidity of 60% for 72 hours. After leaving, the container containing the toner was shaken lightly to visually observe the presence or absence of toner aggregation, and the storage stability was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
A: No aggregation of toner is observed at any temperature of 40 ° C. and 55 ° C.
○: No aggregation of toner is observed in an environment of 40 ° C., but a slight amount of toner aggregation particles is observed in an environment of 55 ° C.
Δ: Toner agglomeration particles are slightly observed under an environment of 40 ° C., and aggregation is clearly observed under an environment of 55 ° C.
X: Aggregation is clearly observed in any environment of 40 ° C and 55 ° C.

<Evaluation method of toner odor>
20 g of each toner was weighed into an aluminum cup (manufactured by Terraoka Co., Ltd., FM-409 (main body)) and allowed to stand on a hot plate heated to 150 ° C. for 30 minutes, and the odor generated from the toner was measured according to the following evaluation criteria. evaluated.
〔Evaluation criteria〕
A: No odor is felt.
○: Almost no odor is felt.
Δ: Some odor is felt, but there is no practical problem.
X: Odor is felt strongly.

(Examples 1-5 and Comparative Examples 1-2)
-Image formation and evaluation-
The toners 1 to 7 produced as described above were loaded into the image forming apparatus A shown in FIG. 20, image formation was performed, and various performance evaluations were performed as follows. The results are shown in Table 6.

<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.

<Fixability>
-Minimum fixing temperature-
Using the image forming apparatus A, 1.0 ± 0.05 mg / cm ² of a solid image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) as a solid image. The toner was developed so that the toner was developed, and the temperature of the fixing unit was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured. The fixing lower limit temperature was defined as the fixing belt temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
〔Evaluation criteria〕
A: Lower limit fixing temperature is less than 135 ° C. O: Lower limit fixing temperature is 135 ° C. or more and less than 145 ° C. Δ: Lower limit fixing temperature is 145 ° C. or more and less than 155 ° C. ×: Lower limit fixing temperature is 155 ° C. or more −Hot offset occurrence temperature−
Fixing was evaluated in the same manner as the above-described minimum fixing temperature, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.
〔Evaluation criteria〕
◎: Hot offset generation temperature is 190 ° C or higher ○: Hot offset generation temperature is 180 ° C or higher and lower than 190 ° C △: Hot offset generation temperature is 170 ° C or higher and lower than 180 ° C ×: Hot offset generation temperature is lower than 170 ° C

<Image quality>
As for the image quality, a change in color tone (tone), background stain, image density, and blur in an image after output of 50,000 sheets were evaluated. The presence / absence of abnormality and the rank evaluation of image quality were visually observed and judged in the following four stages.
〔Evaluation criteria〕
◎: Image abnormality is not observed at all and is good ○: Compared with the original image, a slight difference in hue, image density, background stain, etc. is observed, but it is satisfactory without any practical problem △: Color tone A slight change is felt in (color tone), image density, background stain, etc. ×: Color tone change, image density, background stain, etc. are obvious and problematic

<Durability>
Using the image forming apparatus A, a running test was performed using a type 6000 paper manufactured by Ricoh Co., Ltd. with a printing ratio of 7% image occupancy, and a solid image at the initial printing (100 sheets) and after printing 50,000 sheets. The image density was measured, and the durability was evaluated according to the following evaluation criteria based on the difference in image density.
〔Evaluation criteria〕
◎: Less than 0.1 ○: 0.1 or more, less than 0.2 Δ: 0.2 or more, less than 0.3 ×: 0.3 or more

<Comprehensive evaluation>
The above various performance evaluation results were comprehensively judged and evaluated according to the following criteria.
○: Good △: Actually usable level ×: Unusable level

(Examples 6 to 10 and Comparative Examples 3 to 4)
-Carrier manufacturing-
A coating material having the following composition is dispersed with a stirrer for 10 minutes to prepare a coating solution, and 5,000 parts by mass of this coating solution and a core material (Cu—Zn ferrite particles, mass average particle size = 35 μm) are placed in a fluidized bed. The coating liquid was applied onto the core material by putting it in a coating apparatus for coating while forming a swirling flow provided with a rotating 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-
The produced toners 1 to 7 were each stirred for 5 minutes with a tumbler mixer (made by Willy A. Bachofen AG Maskinfabrik, T2F) with 95% by weight of the carrier thus prepared. 7 was prepared.

-Image formation and evaluation-
The two-component developers 1 to 7 produced as described above are loaded into the image forming apparatus B shown in FIG. 21 to perform image formation, and in the same manner as in Examples 1 to 5 and Comparative Example 2, fixability, durability, image quality And an overall evaluation. The results are shown in Table 7.

<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.
The image forming element 351 in the image forming apparatus B shown in FIG. 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.

  From the results of Table 6 and Table 7, Examples 1 to 10 are Comparative Examples 1 and 3 in which a resin using an unmodified rosin is used in combination, and Comparative Examples 2 and 4 in which a resin derived from a maleic acid modified rosin is used alone. As compared with the above, it is recognized that the low-temperature fixing property and the offset resistance are excellent, the durability and the pulverization property are excellent, and a high-quality image can be stably formed.

  The image forming apparatus, the image forming method, and the process cartridge of the present invention are excellent in all of low-temperature fixing property, offset resistance, durability, pulverization property, and storage property, can reduce odor generation, and can be used for a long time. It is possible to form extremely high quality images with no change in color tone and no abnormal images such as density reduction and background stains. For example, laser printers, direct digital plate-making machines, direct or indirect electrophotographic multicolor image development It can be used widely for full-color copiers, full-color laser printers, and full-color plain paper fax machines.

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 A used in the examples. FIG. 21 is a schematic diagram illustrating the image forming apparatus B used in the example.

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 311 Core metal 312 Resistance adjustment layer 313 Protective layer 310 Charging roller 321 Electrostatic latent image carrier 323 Exposure means 324 Development means 325 Transfer means 326 Recording medium 327 Fixing means 330 Cleaning means 331 Charger 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 (21)

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, and the binder resin contains a polyester resin (A) and a polyester resin (B) whose softening point is higher by 10 ° C. or more than the polyester resin (A). And
The polyester resin (A) is derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing at least one of fumaric acid modified rosin and maleic acid modified rosin. Resin,
The polyester resin (B) is a resin derived from a (meth) acrylic acid-modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. An image forming apparatus. 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. 3
The image forming apparatus according to any one of the above. 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 transfer means is a transfer means for transferring a visible image on the electrostatic latent image carrier to a recording medium.
6. The image forming apparatus according to any one of items 1 to 5. 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. 2. 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 toner.
To 10. The image forming apparatus according to any one of 10 to 10. The image forming apparatus according to claim 1, wherein the alcohol component of at least one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains an aliphatic alcohol. . The content of the (meth) acrylic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from the (meth) acrylic acid-modified rosin,
14. The image according to claim 1, wherein the total content of the fumaric acid-modified rosin and the maleic acid-modified rosin is 5 to 85% by mass in the carboxylic acid component of the resin derived from fumaric acid / maleic acid modified rosin. Forming equipment. The image forming apparatus according to claim 1, wherein at least one of a (meth) acrylic acid-modified rosin, a fumaric acid-modified rosin, and a maleic acid-modified rosin is obtained by modifying a purified rosin. (Meth) acrylic acid-modified rosin-derived resin and fumaric acid / maleic acid-modified rosin-derived resin at least one alcohol component contains a trivalent or higher alcohol,
At least any one of a resin derived from a (meth) acrylic acid-modified rosin and a resin derived from a fumaric acid / maleic acid-modified rosin contains a trivalent or higher carboxylic acid compound, or the alcohol component has a trivalent or higher valence. The image forming apparatus according to claim 1, wherein the image forming apparatus contains alcohol and the carboxylic acid component contains a trivalent or higher carboxylic acid compound. The image forming apparatus according to any one of claims 1 to 16, wherein the content of a low molecular weight component having a molecular weight of 500 or less in at least one of the polyester resin (A) and the polyester resin (B) is 12% or less. . Tin (II) in which the condensation polymerization of at least one of a resin derived from (meth) acrylic acid-modified rosin and a resin derived from fumaric acid / maleic acid-modified rosin has no titanium compound and Sn—C bond
The image forming apparatus according to claim 1, which is performed in the presence of at least one of compounds. The image according to any one of claims 1 to 18, wherein the total content of the resin derived from (meth) acrylic acid-modified rosin and the resin derived from fumaric acid / maleic acid-modified rosin is 70% by mass or more in the binder resin. Forming equipment. A charging step for charging the surface of the electrostatic latent image carrier, and exposing the surface of the charged electrostatic latent image carrier.
An exposure process for forming an electrostatic latent image, and developing the electrostatic latent image with toner to form a visible image
A developing step, a transfer step of transferring the visible image to a recording medium, and a transfer step of transferring the visible image to the recording medium.
An image forming method including at least a fixing step of fixing the transferred image.
  The toner contains at least a binder resin and a colorant, and the binder resin is polyester.
Polyester resin (A) and polyester resin having a softening point higher by 10 ° C. or more than polyester resin (A)
Containing resin (B),
  The polyester resin (A) comprises an alcohol component, fumaric acid-modified rosin and maleic acid.
A polyester obtained by polycondensation with a carboxylic acid component containing at least one of modified rosins.
It is a resin derived from fumaric acid / maleic acid modified rosin having a stealth unit,
  The polyester resin (B) contains an alcohol component and a (meth) acrylic acid-modified rosin.
(Meth) acrylic having a polyester unit formed by condensation polymerization of carboxylic acid component
An image forming method, which is a resin derived from an acid-modified rosin. The latent electrostatic image bearing member and the latent electrostatic image formed on the latent electrostatic image bearing member are developed with toner.
A process having at least a developing unit for forming a visible image and detachable from the main body of the image forming apparatus
A cartridge,
  The toner contains at least a binder resin and a colorant, and the binder resin is polyester.
Polyester resin (A) and polyester resin having a softening point higher by 10 ° C. or more than polyester resin (A)
Containing resin (B),
  The polyester resin (A) comprises an alcohol component, fumaric acid-modified rosin and maleic acid.
A polyester obtained by polycondensation with a carboxylic acid component containing at least one of modified rosins.
It is a resin derived from fumaric acid / maleic acid modified rosin having a stealth unit,
  The polyester resin (B) contains an alcohol component and a (meth) acrylic acid-modified rosin.
(Meth) acrylic having a polyester unit formed by condensation polymerization of carboxylic acid component
A process cartridge which is a resin derived from an acid-modified rosin.