JP2014178665A - Image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress a reduction in primary transfer ratio of a toner image in a high-temperature and high-humidity environment, while suppressing the occurrence of unevenness in concentration and color tone on a recording sheet having a rough surface nature stably for a long period.SOLUTION: An image forming apparatus comprises: photoreceptors 3Y, M, C, K for forming Y, M, C, K toner images; and a transfer unit 60 that intermediately transfers the toner images on the photoreceptors onto the surface of an intermediate transfer belt 61. A toner contains a crystalline resin including a urethane bond and a urea bond in a main chain; when an integrated intensity of a spectrum derived from a crystalline structure of the crystalline resin in an X-ray diffraction spectrum of the toner is denoted as C, and an integrated intensity of a spectrum derived from an amorphous structure of an amorphous resin is denoted as A, a solution for C/(C+A) is 0.15 or more; and a surface friction coefficient of the photoreceptors is a value lower than a value of a surface friction coefficient of the intermediate transfer belt 61.

Description

  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus such as a copying machine, a facsimile machine, and a printer that includes an image carrier that carries a toner image and intermediate transfer means that intermediately transfers a toner image on the image carrier onto the surface of an intermediate transfer member. It is.

  Conventionally, as this type of image forming apparatus, the one described in Patent Document 1 is known. This image forming apparatus forms a toner image on the surface of a drum-shaped photoconductor as an image carrier by a known electrophotographic process. Then, the toner image is transferred onto the surface of the intermediate transfer belt that moves endlessly, and then secondarily transferred onto the recording sheet.

  In such a configuration, if an intermediate transfer belt made of a material having low hardness is used, the belt is stretched in a relatively short period of time, and image deterioration is caused by a belt speed variation caused by the elongation. In addition, when a large-diameter intermediate transfer roller is used instead of the intermediate transfer belt, if the intermediate transfer roller is made of a material with low hardness, the roller will crack in a relatively short period of time. It will cause deterioration. For this reason, as an intermediate transfer body such as an intermediate transfer belt or an intermediate transfer roller, a material made of a material having high strength such as polyimide resin or polyamideimide resin is used to suppress the occurrence of image deterioration due to elongation or cracks. It is desirable to do so.

  However, in general, a high strength material has a high hardness. For this reason, if an intermediate transfer member made of a high-strength material is used, it becomes difficult to flexibly deform the surface of the intermediate transfer member by following subtle irregularities on the surface of the recording sheet in the secondary transfer step. It becomes easy to cause pressure unevenness. In particular, when recording sheets with rough surface properties such as Japanese paper, embossed paper, kraft paper, etc. are used, uneven transfer pressure becomes prominent and it becomes easy to generate unevenness in color and unevenness in color tone. .

  Accordingly, the present inventors conducted various experiments for suppressing shading unevenness and color tone unevenness using a printer testing machine in which an intermediate transfer belt having a belt layer made of polyimide resin as a base material is set. Then, by using a toner containing a crystalline resin having a urethane bond or a urea bond in the main chain in the following proportion as a toner, even for a recording sheet with rough surface properties such as Japanese paper, uneven density It was found that an image having no color unevenness can be formed. That is, the ratio is such that the solution of the calculation formula “C / (C + A)” is 0.15 or more. C in this calculation formula indicates the integral intensity of the spectrum derived from the crystal structure of the crystalline resin in the X-ray diffraction spectrum of the toner. A represents the integrated intensity of the spectrum derived from the amorphous structure of the amorphous resin in the X-ray diffraction spectrum of the toner.

  However, it has also been found that when such toner is used, the primary transfer rate of the toner image from the photoconductor to the intermediate transfer belt is greatly reduced in a high-temperature and high-humidity environment, and the image density tends to be insufficient. .

  The present invention has been made in view of the above background, and an object thereof is to provide the following image forming apparatus. That is, an image capable of suppressing a decrease in the primary transfer rate of a toner image in a high-temperature and high-humidity environment while stably suppressing the occurrence of shading unevenness and color tone unevenness in a recording sheet with rough surface properties over a long period of time. Forming device.

  In order to achieve the above object, the present invention provides an image forming apparatus comprising: an image carrier; and an intermediate transfer unit that intermediately transfers a toner image on the image carrier to a surface of an intermediate transfer member. Which contains a crystalline resin having at least one of a urethane bond and a urea bond in the main chain, and integration of a spectrum derived from the crystal structure of the crystalline resin in the X-ray diffraction spectrum of the toner When the intensity is represented by C and the integral intensity of the spectrum derived from the amorphous structure of the amorphous resin in the X-ray diffraction spectrum is represented by A, the solution of “C / (C + A)” is 0.15 or more. In addition, the surface friction coefficient of the image carrier is lower than the surface friction coefficient of the intermediate transfer member.

  In the present invention, the toner includes a crystalline resin having at least one of a urethane bond and a urea bond in the main chain at a ratio of setting the solution of “C / (C + A)” to 0.15 or more. Therefore, as revealed by the inventors in experiments described later, it is possible to stably suppress the occurrence of shading unevenness and color tone unevenness in a recording sheet with rough surface properties over a long period of time.

  In the present invention, the surface friction coefficient of the image bearing member is made lower than the surface friction coefficient of the intermediate transfer member, so that the present inventors have made it clear in an experiment described later in an environment of high temperature and high humidity. It is possible to suppress a decrease in the primary transfer rate of the toner image.

1 is a schematic configuration diagram showing a copier according to an embodiment. FIG. 3 is a partially enlarged configuration diagram illustrating a part of an internal configuration of a printer unit in the copier. FIG. 3 is an enlarged configuration diagram showing a process unit for Y of the printer unit. The expansion block diagram which shows the modification of the lubricant coating device in a process unit. FIG. 3 is an enlarged configuration diagram illustrating the periphery of a secondary transfer nip of the printer unit. 6 is a graph showing an example of a diffraction spectrum obtained by an X-ray diffraction apparatus for toner. The graph which shows the characteristic of the fitting function of the same example. The figure which shows a 13C-NMR spectrum.

Hereinafter, as an image forming apparatus to which the present invention is applied, an embodiment of a copying machine that forms an image by an electrophotographic method will be described.
First, a basic configuration of the copying machine according to the embodiment will be described. FIG. 1 is a schematic configuration diagram illustrating a copying machine according to an embodiment. The copying machine includes a printer unit 1, a blank paper supply device 100, and a document conveyance reading unit 150. The document conveyance reading unit 150 includes a scanner 160 as a document reading device fixed on the printer unit 1 and an ADF 170 as a document conveyance device supported by the scanner 160.

  The blank paper supply apparatus 100 includes four paper supply units 107, paper supply paths 108, a plurality of conveyance roller pairs 109, and the like that are arranged in multiple stages in the paper bank 101. Each of the four paper feed units 107 includes a paper feed cassette 104, a paper feed roller 105, a separation roller pair 106, and the like.

  The paper feed unit 107 is housed in the paper feed cassette 104 in a state of a bundle of sheets in which a plurality of recording sheets P are stacked. Then, based on a control signal from the printer unit 1, the paper feed roller 105 is driven to rotate, and the uppermost recording sheet P in the paper bundle is sent out toward the paper feed path 108. The fed recording sheet P is separated into one sheet by the separation roller pair 106 and then reaches the inside of the sheet feeding path 108. Then, the sheet is sent to the first receiving branch path 30 of the printer unit 1 through the conveyance nips of the plurality of conveyance roller pairs 109 provided in the sheet feeding path 108.

  The printer unit 1 includes four process units 2Y, 2M, 2C, and 3K for forming yellow (Y), magenta (M), cyan (C), and black (K) toner images. , A receiving conveyance roller pair 31, a manual feed tray 32, a second receiving branching path 34, and the like. Also, a manual separation roller pair 35, a pre-transfer conveyance path 36, a registration roller pair 37, a conveyance belt unit 39, a fixing unit 43, a switchback device 46, a discharge roller pair 47, a discharge tray 48, an optical writing unit 50, A transfer unit 60 and the like are also provided. Note that the process units 2Y, 2M, 2C, and 2K as image carrier units have drum-shaped photoreceptors 3Y, 3M, 3C, and 3K that are image carriers arranged at a predetermined pitch.

  A pre-transfer conveyance path 36 for conveying the recording sheet P immediately before a secondary transfer nip, which will be described later, is branched into a first reception branch path 30 and a second reception branch path 34 on the upstream side in the paper conveyance direction. . After the recording sheet P sent out from the paper feed path 108 of the blank paper supply apparatus 100 is received by the first receiving branch path 30 of the printer unit 1, a pair of receiving transport rollers disposed in the first receiving branch path 30. It is sent to the pre-transfer conveyance path 36 via the conveyance nip 31.

  A manual feed tray 32 is disposed on the side surface of the housing of the printer unit 1 so as to be openable and closable with respect to the housing. The uppermost recording sheet P in the manually fed paper bundle is sent out toward the second receiving / branching path 34 by the feed roller 32a of the manual feed tray 32. Then, after being separated into one sheet by the manual feed separation roller pair 35, it is sent to the pre-transfer conveyance path 36.

  The optical writing unit 50 has a laser diode, a polygon mirror, various lenses, etc., not shown. Then, the laser diode is driven based on image information read by a scanner 160 described later and image information sent from an external personal computer. Thereby, the photoconductors 3Y, M, C, and K of the process units 2Y, M, C, and K are optically scanned. Specifically, the photoconductors 3Y, 3M, 3C, and 3K of the process units 2Y, 2M, 2C, and 2K are rotated in the counterclockwise direction in the drawing by driving means (not shown). The optical writing unit 50 irradiates the driven photoreceptors 3Y, 3M, 3C, and 3K with laser light L modulated based on the image information while deflecting them in the direction of the rotation axis of the photoreceptor. An optical scanning process is performed. Thereby, electrostatic latent images based on Y, M, C, and K image information are formed on the photoreceptors 3Y, M, C, and K, and Y, M, and C are developed by the developing devices 4Y, M, C, and K, respectively. , K toner images.

  FIG. 2 is a partially enlarged configuration diagram illustrating a part of the internal configuration of the printer unit 1 in an enlarged manner. The process units 3K, Y, M, and C for the respective colors support a photosensitive member as an image carrier and various devices disposed around it on a common support as a unit. A photosensitive member and various devices can be integrally attached to and detached from the main body. The configuration is the same except that the colors of the toners used are different. Taking the process unit 2Y for Y as an example, this has a developing device 4Y for developing an electrostatic latent image formed on the surface of the photoreceptor 3Y into a Y toner image in addition to the photoreceptor 3Y. Further, it also includes a drum cleaning device 18Y that removes transfer residual toner adhering to the surface of the photoreceptor 3Y after passing through a Y primary transfer nip described later. This copying machine has a so-called tandem configuration in which four process units 2Y, 2M, 2C, and 2K are arranged along an endless movement direction with respect to an intermediate transfer belt 61 described later.

  FIG. 3 is an enlarged configuration diagram showing the Y process unit 2Y. As shown in the figure, the process unit 2Y has a developing device 4Y, a drum cleaning device 18Y, a charging roller 16Y, and the like around the photoreceptor 3Y. It also has a static elimination lamp (not shown).

  The surface of the photoreceptor 3Y that is driven to rotate in the counterclockwise direction in the drawing has a uniform charging processing position by the charging roller 16Y before entering the optical scanning position by the optical writing unit (50) along with the rotation. pass. A charging bias in which an AC voltage is superimposed on a DC voltage is applied to the charging roller 16Y from a power source (not shown). The charging roller 16Y is disposed so as to be in contact with or close to the surface of the photoreceptor 3Y, and generates a discharge with the photoreceptor 3Y. By this discharge, the surface of the photoreceptor 3Y is uniformly charged to the same polarity as the normal charging polarity of the Y toner. As the charging member, instead of the charging roller 16Y, a charging brush roller having a metal rotating shaft member and a brush roller portion made up of a plurality of conductive raised members standing on the peripheral surface thereof may be used. Good.

  As a charging device for uniformly charging the photoreceptor 3Y, a corona discharge system such as a corotron or a scorotron may be used instead of a charging roller system or a charging brush system. However, in the charging device of the charging roller system or the charging brush system, the amount of ozone generated can be significantly reduced as compared with the corona discharge system.

  The surface of the photoreceptor 3 </ b> Y that is uniformly charged by the charging roller 16 </ b> Y attenuates the potential of the exposure portion by optical scanning with the laser beam L. As a result, an electrostatic latent image is formed on the surface of the photoreceptor 3Y. The potential of the electrostatic latent image is the same as the normal charging polarity of the Y toner as in the uniformly charged portion (background portion), but its absolute value is significantly smaller than the absolute value of the background portion potential. Yes.

  The photoreceptor 3Y is a so-called organic photoreceptor (OPC) having an organic photoconductive layer. As the photoreceptor 3Y, a drum-shaped member is used in which a photosensitive layer is formed on a surface of a conductive support made of aluminum or the like by applying a photosensitive organic photosensitive material.

  The developing device 4Y develops a latent image using a two-component developer (hereinafter simply referred to as a developer) containing a magnetic carrier (not shown) and a non-magnetic Y toner. It has an agitation unit 5Y that conveys the developer contained inside while agitating, and a developing unit 9Y that develops the electrostatic latent image on the photoreceptor 3Y. The developing device 4Y may be of a type that performs development with a one-component developer that does not include a magnetic carrier, instead of the two-component developer.

  The agitating unit 5Y is provided at a position lower than the developing unit 9Y. The first conveying screw 6Y and the second conveying screw 7Y are arranged in parallel to each other, a partition plate provided between these screws, and the bottom surface of the casing. The toner density sensor 8Y and the like provided in the printer.

  The developing unit 9Y includes a developing roll 10Y that faces the photoreceptor 3Y through the opening of the casing, a doctor blade 13Y that makes its tip close to the developing roll 10Y, and the like. Further, the developing roll 10Y has a cylindrical developing sleeve 11Y made of a nonmagnetic material, and a magnet roller 12Y provided in the inside thereof so as not to rotate. The magnet roller 12Y has a plurality of magnetic poles arranged in the circumferential direction. Each of these magnetic poles applies a magnetic force to the developer on the sleeve at a predetermined position in the rotational direction. As a result, the developer sent from the stirring unit 5Y is attracted and carried on the surface of the developing sleeve 11Y, and a magnetic brush along the magnetic field lines is formed on the sleeve surface.

  The magnetic brush is transported to a developing region facing the photoreceptor 3Y after being regulated to an appropriate layer thickness when passing through a position facing the doctor blade 13Y as the developing sleeve 11Y rotates. Then, Y toner is transferred onto the electrostatic latent image by the potential difference between the developing bias applied to the developing sleeve 11Y and the electrostatic latent image on the photoreceptor 3Y, thereby contributing to development. Further, as the developing sleeve 11Y rotates, the developing sleeve 9Y returns to the developing portion 9Y again, and after the release from the sleeve surface due to the influence of the repulsive magnetic field formed between the magnetic poles of the magnet roller 12Y, the developing sleeve 11Y returns to the stirring portion 5Y. An appropriate amount of toner is supplied to the developer in the stirring unit 5Y based on the detection result of the toner density sensor 8Y.

  The developing bias applied to the developing sleeve 11Y has the same polarity as the normal charging polarity of the Y toner, the absolute value thereof is smaller than the absolute value of the background portion potential of the photoreceptor 3Y, and the absolute value of the potential of the electrostatic latent image. Also consists of a large DC voltage. Thereby, so-called negative-positive development is performed.

  The Y toner image formed on the surface of the photoreceptor 3Y enters the primary transfer nip for Y as the surface of the photoreceptor 3Y moves. Specifically, the primary transfer roller 62Y for Y is in contact with the back surface (loop inner peripheral surface) of the endless intermediate transfer belt 61, and the intermediate transfer belt 61 is pressed toward the photoreceptor 3Y. Yes. As a result, a primary transfer nip for Y in which the front surface of the intermediate transfer belt 61 and the photoreceptor 3Y are in contact with each other is formed. A primary transfer bias having a polarity opposite to the normal charging polarity of the Y toner is applied to the primary transfer roller 62Y by a power source (not shown). With this application, a transfer electric field is formed between the electrostatic latent image on the photoreceptor 3 </ b> Y and the front surface of the intermediate transfer belt 61 in the primary transfer nip for Y. The Y toner image that has entered the primary transfer nip for Y as the photoconductor 3Y is rotated is primarily transferred from the photoconductor 3Y to the front surface of the intermediate transfer belt 61 by the action of the nip pressure or transfer electric field. The

  A small amount of untransferred toner that has not been primarily transferred to the intermediate transfer belt 61 adheres to the surface of the photoreceptor 3Y after passing through the primary transfer nip for Y. This transfer residual toner is removed from the surface of the photoreceptor 3Y by the drum cleaning device 18Y.

  As the drum cleaning device 18Y, a system that presses the cleaning blade 20Y against the photoreceptor 3Y is used. The drum cleaning device 18Y includes a cleaning blade 20Y, a lubricant application device, a leveling blade 23Y, and the like.

  The surface of the photoreceptor 3Y that has passed through the primary transfer nip for Y in accordance with the rotational drive enters a position facing the drum cleaning device 18Y. Then, a cleaning position by the cleaning blade 20Y, a lubricant application position by the lubricant application device, and a lubricant leveling position by the leveling blade 23Y are sequentially passed.

  The cleaning blade 20Y made of rubber or resin is cantilevered by a blade holder 24Y. Further, the blade holder 24Y is supported so as to be swingable with an end portion on the opposite side to the blade fixed end side as a swing shaft, and is biased toward the surface of the photoreceptor 3Y by a coil spring. As a result, the edge on the free end side of the cleaning blade 20Y that is cantilevered by the blade holder 24Y and the surface of the photoreceptor 3Y are in contact with each other. The cleaning blade 20Y scrapes off the transfer residual toner adhering to the surface of the photoreceptor 3Y at the free end side edge. The cleaning blade 20Y comes into contact with the photoconductor 3Y in a so-called counter direction in which the free end side is directed to the upstream side in the surface movement direction of the photoconductor 3Y rather than the fixed end side.

  The lubricant application device of the drum cleaning device 18Y includes an application brush roller 19Y, a solid lubricant 21Y urged toward the application brush roller 19Y, and a coil spring 22Y as an urging means for urging the solid lubricant 21Y toward the application brush roller 19Y. Etc. It also has a driving means (not shown) that rotates the application brush roller 19Y in the clockwise direction in the drawing. The application brush roller 19Y includes a rotary shaft member whose both ends in the longitudinal direction are rotatably supported by a bearing (not shown), and a brush roller portion made up of a plurality of raised brushes standing on the surface thereof. . Then, the lubricant scraped from the solid lubricant 21Y as it rotates with the linear velocity difference from the photoconductor 3Y while bringing the brush roller portion into contact with both the solid lubricant 21Y and the surface of the photoconductor 3Y. The powder is applied to the surface of the photoreceptor 3Y. By this application, a lubricant film made of lubricant powder is formed on the surface of the photoreceptor 3Y, and the adhesion between the transfer residual toner described later and the photoreceptor 3Y is weakened to improve the cleaning property of the toner. 3Y is protected from the discharge energy during the uniform charging process.

  Similarly to the cleaning blade 20Y, the leveling blade 23Y of the drum cleaning device 18Y is made of rubber, resin, or the like, and is cantilevered by the blade holder 26Y. The blade holder 26Y is supported so as to be capable of swinging with an end opposite to the blade fixed end as a swing shaft, and is biased toward the surface of the photoreceptor 3Y by a coil spring. Thereby, the edge on the free end side of the leveling blade 23Y that is cantilevered by the blade holder 26Y and the surface of the photoreceptor 3Y are in contact with each other. The leveling blade 23Y evenly distributes the lubricant powder applied to the surface of the photoreceptor 3Y at its free end side edge. As a result, a lubricant film is formed on the surface of the photoreceptor 3Y. The leveling blade 23Y comes into contact with the photoreceptor 3Y in a so-called trailing direction in which the free end side is directed to the downstream side in the surface movement direction of the photoreceptor 3Y rather than the fixed end side.

  The surface of the photoreceptor 3Y that has passed through the leveling position of the lubricant by the drum cleaning device 18Y in accordance with the rotational drive is neutralized by a neutralizing lamp (not shown). Then, after being uniformly charged again by the charging roller 16Y, optical scanning by the optical writing unit described above is performed.

  In FIG. 2, M, C, and K toner images are formed on the surfaces of the photoreceptors 3M, C, and K of the process units 2M, C, and K by the same process as the Y process unit 2Y described above. Is done.

  Below the four process units 2Y, 2M, 2C, and 2K, a transfer unit 60 as transfer means is disposed. The transfer unit 60 rotates in the clockwise direction in the figure by rotating one of the rollers while the intermediate transfer belt 61 stretched by a plurality of rollers is brought into contact with the photoreceptors 3Y, 3M, 3C, and 3K. Move endlessly. As a result, primary transfer nips for Y, M, C, and K in which the photoreceptors 3Y, 3M, 3C, and 3K come into contact with the intermediate transfer belt 61 that is an image carrier are formed.

  In the vicinity of the primary transfer nips for Y, M, C, and K, the intermediate transfer belt 61 is moved to the photosensitive members 3YY, M, C, and K by primary transfer rollers 62Y, M, C, and K disposed inside the belt loop. Pressing toward K. A primary transfer bias is applied to the primary transfer rollers 62Y, 62M, 62C, 62K by a power source (not shown). As a result, a primary transfer electric field for electrostatically moving the toner images on the photoreceptors 3Y, 3M, 3C, and 3K toward the intermediate transfer belt 61 is formed in the primary transfer nips for Y, M, C, and K. Has been.

  In the drawing, a toner image is formed on each of the primary transfer nips on the front surface of the intermediate transfer belt 61 that sequentially passes through the primary transfer nips for Y, M, C, and K with endless movement in the clockwise direction. Are sequentially superimposed and primarily transferred. By this primary transfer of superposition, a four-color superposed toner image (hereinafter referred to as a four-color toner image) is formed on the front surface of the intermediate transfer belt 61.

  A secondary transfer counter roller 72 is disposed below the intermediate transfer belt 61 in the drawing, and this is in contact with a portion of the intermediate transfer belt 61 that is wound around the secondary transfer roller 68 from the belt front surface. A secondary transfer nip is formed. As a result, a secondary transfer nip is formed in which the front surface of the intermediate transfer belt 61 and the secondary transfer counter roller 72 abut.

  In the loop of the intermediate transfer belt 61, a secondary transfer bias having the same polarity as the normal charging polarity of the toner (negative polarity in this example) is applied to the secondary transfer roller 68 by a secondary transfer power supply circuit (not shown). Yes. On the other hand, the secondary transfer counter roller 72 that forms the secondary transfer nip while being in contact with the front surface of the belt is grounded. As a result, a secondary transfer electric field is formed in the secondary transfer nip for electrostatically moving negative toner from the belt side toward the secondary transfer counter roller 72 side.

  The above-described registration roller pair (not shown) is disposed on the right side of the secondary transfer nip in the drawing, and the recording sheet sandwiched between the rollers can be synchronized with the four-color toner image on the intermediate transfer belt 61. Send to the secondary transfer nip. In the secondary transfer nip, the four-color toner images on the intermediate transfer belt 61 are secondarily transferred onto the recording sheet under the influence of the secondary transfer electric field and the nip pressure, and become a full color image combined with the white color of the recording sheet.

  The transfer residual toner that has not been transferred to the recording sheet at the secondary transfer nip is attached to the front surface of the intermediate transfer belt 61 that has passed through the secondary transfer nip. This transfer residual toner is cleaned by a belt cleaning device 75 in which a cleaning blade is in contact with the intermediate transfer belt 61. The cleaning blade sandwiches the intermediate transfer belt 61 between itself and a backup roller disposed inside the belt.

  In FIG. 1, the recording sheet P after passing through the secondary transfer nip is separated from the intermediate transfer belt 61 and transferred to the transport belt unit 39. The conveyor belt unit 39 endlessly moves the endless conveyor belt in the counterclockwise direction in the figure by the rotational driving of the driving roller while the endless conveyor belt is stretched between the driving roller and the driven roller. The recording sheet P delivered from the secondary transfer nip is conveyed along with the endless movement of the belt while being held on the belt upper tension surface, and delivered to the fixing unit 43.

  In the fixing unit 43, a fixing belt stretched by a driving roller and a heating roller containing a heat generation source is moved endlessly in the clockwise direction in the drawing as the driving roller is driven to rotate. A pressure roller disposed below the fixing belt is brought into contact with the lower tension surface of the fixing belt to form a fixing nip. The recording sheet P received by the fixing unit 43 is pressed or heated in the fixing nip, whereby the full color image on the surface is fixed. Then, the paper is sent out from the fixing unit 43 toward the paper discharge roller pair 47.

  In the single-sided print mode in which an image is formed only on the first surface of the recording sheet P, the recording sheet P sandwiched in the paper discharge nip between the rollers of the paper discharge roller pair 47 is directly discharged outside the apparatus and discharged. Stacked on the tray 48.

  A switchback device 46 is disposed below the fixing unit 43 and the conveyor belt unit 39. In the double-sided printing mode in which images are formed on both sides of the recording sheet P, the recording sheet P sandwiched in the paper discharge nip is returned in the reverse direction and enters the switchback device 46. Then, after being turned upside down in the switchback device 46, it is sent again to the secondary transfer transfer nip, and the other side of the image is subjected to image secondary transfer processing and fixing processing.

  The scanner 160 fixed on the printer unit 1 has a fixed reading unit and a moving reading unit as reading means for reading an image of a document (not shown). A fixed reading unit having a light source, a reflection mirror, an image reading sensor such as a CCD, and the like is disposed immediately below a first contact glass (not shown) fixed to the upper wall of the casing of the scanner 160 so as to contact the document. Then, when the document conveyed by the ADF 170 passes over the first contact glass, the light emitted from the light source is sequentially reflected by the document surface, and is received by the image reading sensor via the plurality of reflection mirrors. Thus, the original is scanned without moving the optical system including the light source and the reflecting mirror.

  On the other hand, the moving reading unit of the scanner 160 is disposed directly below a second contact glass (not shown) fixed to the upper wall of the casing of the scanner 160 so as to come into contact with the document, and is an optical device composed of a light source, a reflection mirror, and the like. The system can be moved in the horizontal direction in the figure. Then, in the process of moving the optical system from the left side to the right side in the figure, the light emitted from the light source is reflected by a document (not shown) placed on the second contact glass and then passed through a plurality of reflecting mirrors. The image is received by an image reading sensor fixed to the scanner body. Accordingly, the original is scanned while moving the optical system.

  In FIG. 3, the application amount (application amount per unit time) of the lubricant powder to the photoreceptor 3Y by the application brush roller 19Y is determined by the urging force of the solid lubricant 21Y by the coil spring 22Y. It is possible to adjust the coating amount to a desired value by selecting a spring constant having a desired coating amount as the coil spring 22Y. Instead of the coil spring 22Y, as shown in FIG. 4, a weight 27Y that applies a load to the solid lubricant 21Y may be provided, and the solid lubricant 21Y may be biased toward the application brush roller 19Y by the weight 27Y. . In this case, it is possible to adjust the coating amount to a desired value by selecting a weight 27Y having a weight that can provide a desired coating amount.

  A part of the lubricant powder applied to the surface of the photoreceptor 3Y is transferred from the photoreceptor 3Y to the intermediate transfer belt 61.

  FIG. 5 is an enlarged configuration diagram showing the periphery of the secondary transfer nip. As shown in the figure, an application brush roller 76 is disposed on the side of the secondary transfer counter roller 72. A solid lubricant 77 is pressed against the application brush roller 76 by a coil spring 78. The rotating application brush roller 76 applies the lubricant powder obtained by scraping from the solid lubricant 77 to the surface of the secondary transfer counter roller 72. Part of the applied lubricant powder is transferred from the secondary transfer counter roller 72 to the surface of the intermediate transfer belt 61 at the secondary transfer nip. The application brush roller 76, the solid lubricant 77, and the coil spring 78 function as a lubricant application unit that applies lubricant powder to the secondary transfer counter roller 72.

  The lubricant application device shown in FIG. 3 and the lubricant application means shown in FIG. 5 also function as means for indirectly applying the lubricant to the intermediate transfer belt 61. The amount of the lubricant application device shown in FIG. 3 that indirectly applies the lubricant powder to the intermediate transfer belt 61 is smaller than the amount applied to the photoreceptor 3Y. In the copying machine according to the embodiment, the amount of lubricant applied to the intermediate transfer belt 61 can be adjusted by adjusting the spring constant of the coil spring 78 of the lubricant applying means shown in FIG. Thereby, the surface friction coefficient of the photoreceptor 3Y and the surface friction coefficient of the intermediate transfer belt 61 can be adjusted.

  In FIG. 2, a belt cleaning device 75 having a configuration similar to that of the lubricant application device shown in FIG. 3 is provided so that the lubricant powder can be applied directly to the intermediate transfer belt 61. Good. This lubricant application device may be provided in addition to the lubricant application means shown in FIG. 5, or may be provided instead of the lubricant application means shown in FIG.

Next, toner used in the copying machine according to the embodiment will be described.
A crystalline resin is known as a resin used as a binder resin for toner. Further, as a crystalline resin, a crystalline resin having at least one of a urethane bond and a urea bond is known. The crystalline resin is a resin having a crystal structure portion, and has a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. Such a crystalline resin has a ratio (softening temperature / maximum peak temperature of heat of fusion) of a softening temperature measured by a Koka type flow tester and a maximum peak temperature of heat of fusion measured by a differential scanning calorimeter (DSC). Is in the range of 0.8 to 1.6. As a result, it exhibits the characteristic of being softened sharply by heat.

  The non-crystalline resin used as the binder resin for the toner is a resin having no crystal structure, and does not have a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The amorphous resin has a ratio between the softening temperature and the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) greater than 1.6, and exhibits a characteristic of being softened softly by heat.

  The softening temperature of the resin can be measured using a Koka flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). Specifically, a load of 2.94 MPa is applied by a plunger while heating 1 g of resin as a sample at a temperature rising rate of 3 ° C./min. Then, while extruding from a nozzle having a diameter of 0.5 mm and a length of 1 mm, the plunger drop amount of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is defined as the softening temperature.

  The maximum peak temperature of the heat of fusion of the resin can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). Specifically, as a pretreatment, a sample subjected to measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then cooled from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./min, and then 70 The temperature is lowered from 10 ° C. to 10 ° C. at a rate of 0.5 ° C./min. Then, by DSC, the temperature is increased at a rate of temperature increase of 10 ° C./min and the change in heat absorption / exotherm is measured, and a graph of “heat absorption / heat generation amount” and “temperature” is drawn. The endothermic peak temperature at 20 ° C. to 100 ° C. observed at this time is defined as “Ta *”. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is Ta *. Thereafter, the sample is stored at (Ta * -10) ° C. for 6 hours, and further stored at (Ta * −15) ° C. for 6 hours. Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 10 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of heat quantity is defined as the maximum peak temperature of heat of fusion.

  The content of the crystalline resin in the toner binder resin is preferably 50% by mass or more. This is because such a toner can maximize the compatibility between excellent low-temperature fixability and heat-resistant storage stability due to the crystalline resin. Further, the content is more preferably 65% by mass or more, still more preferably 80% by mass or more, and particularly preferably 95% by mass or more. When the content is less than 50% by mass, the heat steepness of the binder resin cannot be expressed on the viscoelastic properties of the toner, making it difficult to achieve both low-temperature fixability and heat-resistant storage stability.

  In the diffraction spectrum obtained by the X-ray diffractometer of the toner, the relationship between the integrated intensity C of the spectrum derived from the crystal structure of the binder resin and the integrated intensity A of the spectrum derived from the amorphous structure is as follows. It is preferable to satisfy such conditions. That is, the condition that the solution of “C / (C + A)” is 0.15 or more. A toner having such conditions can achieve both fixing properties and heat-resistant storage stability. Furthermore, as will be described later, it is possible to suppress the occurrence of density unevenness and color tone unevenness when using uneven paper. The solution is more preferably 0.20 or more, still more preferably 0.30 or more, and particularly preferably 0.45 or more.

  When the toner contains a wax, a diffraction peak specific to the wax often appears at a position of 2Θ = 23.5 to 24 °. However, when the wax content with respect to the total weight of the toner is 15 wt% or less, the contribution of the diffraction peak inherent to the wax is negligible. In the case of 15 wt% or more, the value obtained by subtracting the integral intensity of the spectrum derived from the crystal structure of the wax from the integral intensity of the spectrum derived from the crystal structure of the binder resin is derived from the above-mentioned “derived from the crystal structure of the binder resin”. The integrated intensity C of the spectrum to be obtained.

  The solution of “C / (C + A)” is an index indicating the amount of crystallization sites in the toner (mainly the amount of crystallization sites in the binder resin as the main component of the toner). As an X-ray diffraction measurement, for example, a two-dimensional detector-mounted X-ray diffraction apparatus (D8 DISCOVER with GADDS / Bruker) can be exemplified. In the case of a toner containing a conventionally known crystalline resin or wax to the extent of an additive, the solution is less than about 0.15. In the X-fiber diffraction measurement, a capillary having a mark tube (Lindenman glass) having a diameter of 0.70 mm is used. A toner sample is packed up to the top of the capillary tube and X-ray diffraction measurement is performed. Note that tapping is performed when filling the sample, and the number of tapping is 100 times.

Detailed conditions in the X-ray diffraction measurement are as follows.
・ Tube current: 40 mA
・ Tube voltage: 40kV
-Goniometer 2θ axis: 20.0000 °
-Goniometer Ω axis: 0.0000 °
-Goniometer φ axis: 0.0000 °
・ Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
・ Measurement time: 600 sec

  A collimator having a φ1 mm pinhole is used for the incident optical system. The obtained two-dimensional data is integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted to one-dimensional data of diffraction intensity and 2θ. Then, “C / (C + A)” is calculated based on the obtained X-ray diffraction measurement result.

Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. In the graphs of these figures, the horizontal axis indicates 2θ, and the vertical axis indicates the X-ray diffraction intensity. All of these axes are linear axes. In the X-ray diffraction spectrum of FIG. 6, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and a halo (h) is observed in a wide range including these two peaks. The main peak is derived from the crystal structure, and the halo is derived from the amorphous structure. These two major peaks and halos are expressed by the following Gaussian function.
fp1 (2θ) = ap1exp {− (2θ−bp1) 2 / (2cp12)}
fp2 (2θ) = ap2exp {− (2θ−bp2) 2 / (2cp22)}
fh (2θ) = ahexp {− (2θ−bh) 2 / (2ch2)}

In these Gaussian functions, fp1 (2θ), fp2 (2θ), and fh (2θ) indicate functions corresponding to the main peaks P1, P2, and halo, respectively. “F (2θ) = fp1 (2θ) + fp2 (2θ) + fh (2θ)”, which is the sum of three Gaussian functions, is a fitting function (FIG. 7) of the entire X-ray diffraction spectrum. Then, fitting by the least square method is performed. Nine of ap1, bp1, cp1, ap2, bp2, cp2, ah, bh, and ch are used as fitting variables. The initial values of the fitting of these fitting variables are used. For bp1, bp2, and bh, X-ray diffraction peak positions (bp1 = 21.3, bp2 = 24.2, bh = 22.5 in the illustrated example) are appropriately input to other variables, A value obtained by matching the two main peaks and the halo to the X-ray diffraction spectrum as much as possible is set. The fitting can be performed, for example, using a Microsoft 2003 Excel solver. The integrated areas (SP1, Sp2, Sp2, Sp2) of the Gaussian functions fp1 (2θ), fp2 (2θ) corresponding to the two main peaks (P1, P2) after the fitting, and the Gaussian function fh (2θ) corresponding to the halo. Sh) is obtained. Then, when (Sp1 + Sp2) is (C) and Sh is (A), a ratio “C / (C + A)) that is an index indicating the amount of crystallization sites can be calculated.

The toner has a maximum endothermic peak temperature _{T 1} of the during heating is preferably from 50 ° C. to 70 ° C., more preferably from 53 ° C. to 65 ° C., and more preferably a 58 ° C. through 62 ° C.. Maximum endothermic peak temperature T ₁ is, if it is 50 ° C. to 70 ° C., it is possible to ensure the minimum heat-resistant storage stability required of the toner, and, to exhibit unprecedented excellent low-temperature fixability Can do. Maximum endothermic peak temperatures T ₁ is lower than 50 ° C., but the better the low-temperature fixability heat resistant storage stability is deteriorated. Also, if the maximum endothermic peak temperature T ₁ is higher than 70 ° C., heat resistant storage stability conversely becomes better low-temperature fixability is degraded.

Toner is lowered maximum endothermic peak temperature _{T 2} at the time, preferably from 30 ° C. to 55 ° C., more preferably from 35 ° C. to 55 ° C., and more preferably a 40 to 55 ° C.. If the maximum endothermic peak temperature T ₂ is below 30 ° C., the rate at which the fixed image is cooled ~ solidification is slow, sometimes blocking and transporting scratches toner image (printed material) occurs. It is desirable that the maximum endothermic peak temperature T ₂ is available a high value as much as, because it is the crystallization temperature, not higher than the maximum endothermic peak temperature T ₁ of the melting point. In order to suppress toner image blocking and conveyance flaws while maintaining excellent heat-resistant storage stability and low-temperature fixability, the difference between the maximum endothermic peak temperature T ₁ and the maximum endothermic peak temperature T ₂ (T ₁ − It is desirable that T ₂ ) is in a narrow range to some extent. The difference (T ₁ -T ₂ ) is preferably 30 ° C. or less, more preferably 25 ° C. or less, and further preferably 20 ° C. or less. When the difference (T ₁ −T ₂ ) is larger than 40 ° C., the difference between the fixing temperature and the temperature at which the toner image is solidified is large, and the effect of suppressing toner image blocking and conveyance flaws cannot be obtained.

The maximum endothermic peak (T ₁ , T ₂ ) of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). Specifically, first, about 5.0 mg of toner is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature is raised from 0 ° C. to 150 ° C. at 10 ° C./min, and then lowered from 150 ° C. to 0 ° C. at 10 ° C./min. Furthermore, the temperature is raised from 0 ° C. to 100 ° C. at 10 ° C./min. Using the analysis program of the DSC system, a DSC curve at the second temperature rise is selected, and the maximum endothermic peak temperature T1 (DSC peak temperature) of the toner is measured. Similarly, the maximum heat generation peak temperature T2 of the toner when the temperature is lowered is measured.

  In the toner, the maximum peak temperature of the second heat of fusion measured by a differential scanning calorimeter (DSC) is in the range of 50 ° C. or higher and 70 ° C. or lower, and the heat of fusion of the second temperature rise is 30 J. / G or more and 75 J / g or less is preferable. This is because such a toner achieves both low-temperature fixability and heat-resistant storage stability at a higher level and is superior in hot offset resistance. When the maximum peak temperature of the heat of fusion of the toner is less than 50 ° C., toner blocking tends to occur in a high temperature environment, and when the maximum peak temperature exceeds 70 ° C., low temperature fixability is hardly exhibited. The maximum peak temperature is more preferably 55 ° C. or more and 68 ° C. or less, and further preferably 58 ° C. or more and 65 ° C. or less.

  If the heat of fusion of the toner is less than 30 J / g, the portion having a crystal structure in the toner is reduced, sharp melt properties are lowered, and it is difficult to obtain a balance between heat resistant storage stability and low temperature fixability. On the other hand, when the heat of fusion exceeds 75 J / g, the energy required to melt and fix the toner increases, and the fixability may deteriorate depending on the fixing device. The heat of fusion is more preferably 45 J / g or more and 70 J / g or less, and further preferably 50 J / g or more and 60 J / g or less.

  The maximum peak temperature of the heat of fusion of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). Specifically, the temperature of a sample used for measurement of the maximum peak temperature of heat of fusion is raised from 20 ° C. to 150 ° C. under a temperature raising rate of 10 ° C./min. Next, after cooling to 0 ° C. at a temperature decrease rate of 10 ° C./min, the temperature is increased again at a temperature increase rate of 10 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is displayed. The temperature corresponding to the maximum peak of the endothermic amount is defined as the maximum peak temperature of the heat of fusion at the second temperature increase. The endothermic amount of the endothermic peak having the maximum peak temperature at this time is defined as the second heat of fusion.

  The maximum peak temperature of the heat of fusion of the crystalline resin used as the binder resin for the toner is preferably 50 ° C. to 70 ° C., more preferably 55 ° C. to 68 ° C. from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. 60 ° C. to 65 ° C. is particularly preferable. When the maximum peak temperature is lower than 50 ° C., the low temperature fixability is improved but the heat resistant storage stability is deteriorated. When the maximum peak temperature is higher than 70 ° C., the heat resistant storage stability is improved, but the low temperature fixability is deteriorated.

  The ratio of the softening temperature of the crystalline resin to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is 0.8 to 1.6, preferably 0.8 to 1.5, 0.8 to 1.4 is more preferable, and 0.8 to 1.3 is particularly preferable. The smaller the ratio, the more rapidly the resin softens, which is superior from the viewpoint of both low-temperature fixability and heat-resistant storage stability.

  In the toner, the maximum peak temperature of the second heat of melting measured by a differential scanning calorimeter (DSC) of the toner is in the range of 50 ° C. or more and 70 ° C. or less, and the heat of fusion of the second temperature rising is 30 J / g or more and 75 J / g or less is desirable. This is because such toner achieves both low-temperature fixability and heat-resistant storage stability at a higher level and is excellent in hot offset resistance. When the maximum peak temperature of the heat of fusion at the second temperature increase is less than 50 ° C., toner blocking tends to occur in a high temperature environment. On the other hand, when the maximum peak temperature of the heat of fusion at the second temperature rise exceeds 70 ° C., the low-temperature fixability is hardly exhibited. The maximum peak temperature is more preferably 55 ° C. or more and 68 ° C. or less, and further preferably 58 ° C. or more and 65 ° C. or less.

  When the heat of fusion at the second temperature increase of the toner is less than 30 J / g, the number of sites having a crystal structure in the toner is reduced, sharp melt properties are lowered, and a balance between heat-resistant storage stability and low-temperature fixability is obtained. It becomes difficult. On the other hand, if it exceeds 75 J / g, the energy required to melt and fix the toner becomes large, and the fixability may deteriorate depending on the fixing device. The heat of fusion is more preferably 45 J / g or more and 70 J / g or less, and further preferably 50 J / g or more and 60 J / g or less.

  The maximum peak temperature of the heat of fusion of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)) in the same manner as the resin. A sample used for measurement of the maximum peak temperature of heat of fusion was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min. Next, after cooling to 0 ° C. at a temperature decrease rate of 10 ° C./min, the temperature is increased again at a temperature increase rate of 10 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is drawn. The temperature corresponding to the maximum peak of the endothermic amount was taken as the maximum peak temperature of the heat of fusion at the second temperature increase. Further, the endothermic amount of the endothermic peak having the maximum peak temperature at this time is defined as the second heat of fusion.

The toner has a storage elastic modulus G ′ (80) (Pa) at 80 ° C. of 1.0 × 10 ⁴ or more and 5.0 × 10 ⁵ or less, and a storage elastic modulus G ′ (140) (140) ( Pa) is preferably 1.0 × 10 ³ or more and 5.0 × 10 ⁴ or less. When the storage elastic modulus G ′ (80) (Pa) is less than 1.0 × 10 ⁴ Pa, a blocking phenomenon in which the fixed images stick together after continuous output of the fixed images is likely to occur. On the other hand, if it exceeds 5.0 × 10 ⁵ Pa, the melting property of the toner in a low temperature region is lowered and the gloss of the fixed image tends to be lowered. The storage elastic modulus G ′ (80) is more preferably 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁵ Pa or less, and 5.0 × 10 ⁴ Pa or more and 1.0 × 10. More preferably, it is ⁵ Pa or less.

When the storage elastic modulus G ′ (140) (Pa) of the toner is less than 1.0 × 10 ³ Pa, the hot offset resistance tends to deteriorate. On the other hand, if it exceeds 5.0 × 10 ⁴ Pa, the gloss of the fixed image tends to be low. The storage elastic modulus G ′ (140) is more preferably 1.0 × 10 ³ Pa or more and 1.0 × 10 ⁴ Pa or less, 5.0 × 10 ³ Pa or more, 1.0 × 10 ⁴ Pa. More preferably, it is as follows.

  The dynamic viscoelastic characteristic values (storage elastic modulus G ′, loss elastic modulus G ″) of the toner can be measured using a dynamic viscoelasticity measuring device (for example, ARES (manufactured by TA Instruments)). Measured under a frequency of 1 Hz, specifically, a toner sample is molded into pellets having a diameter of 8 mm and a thickness of 1 mm to 2 mm, fixed to a parallel plate having a diameter of 8 mm, and then stabilized at 40 ° C. Then, the temperature is raised to 200 ° C. at a temperature rising rate of 2.0 ° C./min at a frequency of 1 Hz (6.28 rad / s) and a strain amount of 0.1% (strain amount control mode).

  The amount of N element soluble in THF in the toner is preferably in the range of 0.3 to 2.0 wt%, more preferably in the range of 0.5 to 1.8 wt%, and 0.7 More preferably, it is -1.6 wt%. If the amount exceeds 2.0 wt%, the viscoelasticity of the toner in the melted state may become too high, resulting in a deterioration in fixing property, a decrease in gloss, and a deterioration in charging property. Further, if the amount is less than 0.3 wt%, problems such as aggregation in the image forming apparatus due to a decrease in toner toughness, contamination of members, and occurrence of high temperature offset due to a decrease in viscoelasticity in a toner melting state occur. there is a possibility.

The amount of the N element described above can be measured using a vario MICRO cube (manufactured by Elementar). Specifically, C element, H element, and N element were measured simultaneously under the conditions of 950 ° C. combustion furnace and 550 ° C. reduction furnace, helium flow rate = 200 ml / min, oxygen flow rate = 25-30 ml / min. The average value of the values measured once is calculated. In addition, when the amount of N element is less than 0.5 wt% in this measurement method, the measurement is further performed with a trace nitrogen analyzer ND-100 (manufactured by Mitsubishi Chemical Corporation). Regarding the electric furnace temperature (horizontal reactor), the pyrolysis portion = 800 ° C. and the catalyst portion = 900 ° C. The measurement conditions are the main O ₂ flow rate = 300 ml / min, the O ₂ flow rate = 300 ml / min, the Ar flow rate = 400 ml / min, and the sensitivity = Low, and the calibration curve prepared with the pyridine standard solution is quantified together. The THF-soluble matter in the toner can be obtained by placing 5 g of toner in a Soxhlet extractor in advance and extracting it with 70 mL of THF (tetrahydrofuran) for 20 hours. .

  The presence of a urea bond in the THF soluble component in the toner is important because even if the urea bond is small, an effect of improving the toughness of the toner and the offset resistance during fixing can be expected. The presence of a urea-soluble urea bond in the toner can be confirmed by 13C-NMR. Specifically, 2 g of the sample to be analyzed was immersed in 200 ml of a potassium hydroxide methanol solution having a concentration of 0.1 mol / L, placed at 50 ° C. for 24 hours, the solution was removed, and the residue was further subjected to ion-exchanged water. Until the pH is neutral and dry the remaining solids. The sample after drying was added to a mixed solvent (volume ratio 9: 1) of dimethylacetamide (DMAc) and deuterated dimethylsulfoxide (DMSO-d6) at a concentration of 100 mg / 0.5 ml, and the mixture was stirred at 70 ° C. for 12-24. After dissolving for a period of time, the temperature is set to 50 ° C. and 13C-NMR measurement is performed. The measurement frequency is 125.77 MHz, the 1H_60 ° pulse is 5.5 μs, and the reference material is 0.0 ppm tetramethylsilane (TMS). Presence of urea binding in the sample is confirmed by whether or not a signal is seen in the chemical shift of the signal derived from the carbonyl carbon of the urea binding site of the polyurea used as a standard. The chemical shift of carbonyl carbon is generally confirmed under conditions of 150 to 160 ppm. As an example of polyurea, FIG. 8 shows a 13C-NMR spectrum around the carbonyl carbon of polyurea, which is a reaction product of 4,4′-diphenylmethane diisocyanate (MDI) and water. A signal derived from carbonyl carbon is seen at 153.27 ppm.

  There is no restriction | limiting in particular as a mold release agent added to a toner, According to the objective, it can select suitably from well-known things. For example, waxes such as carbonyl group-containing waxes, polyolefin waxes, long chain hydrocarbons and the like can be 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, and dialkyl ketones.

  Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, and 1,18- Examples include octadecane 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 long chain hydrocarbons include paraffin wax and sazol wax.

  There is no restriction | limiting in particular as melting | fusing point of a mold release agent, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable and 60 to 90 degreeC is more preferable. When the melting point is less than 50 ° C., the heat resistant storage stability may be adversely affected. When the melting point exceeds 100 ° C., cold offset may easily occur during fixing at a low temperature. The melting point of the release agent can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). Specifically, first, 5.0 mg of the mold release agent is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the maximum peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point.

  The melt viscosity of the release agent is preferably 5 mPa · sec to 100 mPa · sec, more preferably 5 mPa · sec to 50 mPa · sec, and particularly preferably 5 mPa · sec to 20 mPa · sec as a measured value at 100 ° C. When the melt viscosity is less than 5 mPa · sec, the releasability may be lowered. On the other hand, when it is higher than 100 mPa · sec, the hot offset resistance and the releasability at a low temperature may be deteriorated, which is not preferable.

  There is no restriction | limiting in particular as content of the mold release agent in a toner, According to the objective, it can select suitably. It is preferably 1% by weight to 20% by weight, and more preferably 3% by weight to 10% by weight. When it is less than 1% by weight, the hot offset resistance tends to deteriorate. On the other hand, if it exceeds 20% by mass, the heat resistant storage stability, chargeability, transferability, and stress resistance tend to deteriorate, which is not preferable.

  There is no restriction | limiting in particular as a coloring agent used for a toner, According to the objective, it can select suitably from well-known coloring agents. There is no restriction | limiting in particular as a color of a coloring agent, According to the objective, it can select suitably. The toner can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, and each color toner can be obtained by appropriately selecting the type of colorant. preferable.

  Examples of the colorant for black 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, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; 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 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like. Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by weight to 15% by weight, and more preferably 3% by weight to 10% by weight. When the content is less than 1% by weight, the coloring power of the toner may be lowered. On the other hand, if it exceeds 15% by weight, poor dispersion of the pigment in the toner occurs, which may lead to a reduction in coloring power and a decrease in toner electrical characteristics. About a coloring agent, you may use as a masterbatch compounded with resin. Such a resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

  The master batch can be manufactured by applying a high shear force and mixing or kneading the resin and the colorant. 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 in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

  In order to impart appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary. Any known charge control agent can be used as the charge control agent. Since a color tone may change when a colored material is used, a material that is colorless or nearly white is preferable. 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 alone or Examples thereof include fluorine compounds, metal salts of salicylic acid, and metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited, but is 0.01% with respect to the binder resin. % By weight to 5% by weight is preferable, and 0.02% by weight to 2% by weight is more preferable. When the addition amount exceeds 5% by weight, the chargeability of the toner is too large, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image The concentration may decrease. On the other hand, if it is less than 0.01% by weight, the charge rising property and the charge amount are not sufficient, and the toner image may be easily affected.

  The toner used in the image forming apparatus according to the embodiment may contain an organically modified layered inorganic mineral. This organically modified layered inorganic mineral is an organically modified layered inorganic mineral in which at least some of the ions present between the layers of the layered inorganic mineral are modified with organic ions. The layered inorganic mineral is a layered inorganic mineral formed by overlapping layers having a thickness of several nm. The above-mentioned “modified” is synonymous with introducing organic ions into ions existing between the layers of the layered inorganic mineral, and in a broad sense is intercalation. By including an organically modified layered inorganic mineral in which at least some of the ions present between the layers of the layered inorganic mineral are modified with organic ions, the following becomes possible. That is, it can function as a crystal nucleating agent for the crystalline resin to increase the degree of crystallinity of the toner, or it can function as a filler by being dispersed in the toner oil phase to make the shape of the toner indefinite. . In addition, the layered inorganic mineral produces the greatest effect by being arranged in the vicinity of the toner surface layer. However, it is known that the organically modified layered inorganic mineral in the present invention is uniformly arranged in the vicinity of the toner surface layer without any gap. . For this reason, the structural viscosity of the binder resin in the vicinity of the toner surface layer is efficiently increased, and the image is sufficiently protected even in the state of an image having a low resin hardness just after fixing. Further, since the effect can be efficiently exhibited even with a small addition amount, it is considered that there is almost no hindrance to fixability.

  The presence state of the organically modified layered inorganic mineral in the toner can be confirmed as follows. That is, a sample in which toner particles are embedded in an epoxy resin or the like is cut with a micromicrotome or an ultramicrotome, and a cross section of the toner is observed with a scanning electron microscope (SEM) or the like. In the case of observation by SEM, it is preferable to confirm by a reflected electron image, and it is preferable because the presence of the organically modified layered inorganic mineral can be observed with a strong contrast. Further, using FIB-STEM (HD-2000, manufactured by Hitachi, Ltd.), a sample in which toner particles are embedded in an epoxy resin or the like may be cut with an ion beam, and the cross section of the toner may be observed. Also in this case, it is preferable to confirm with a reflected electron image because of easy visual recognition.

  It is also possible to confirm the vicinity of the toner surface by observing the cross section. The vicinity of the toner surface is defined as follows. That is, a cross section of a toner obtained by cutting a sample in which toner particles are embedded in an epoxy resin or the like with a micromicrotome, ultramicrotome, FIB-STEM, or the like is observed. In the observed image at that time, a region of 0 nm to 300 nm from the outermost surface of the toner to the inside of the toner is near the toner surface.

  There is no restriction | limiting in particular as said layered inorganic mineral, According to the objective, it can select suitably. Examples thereof include smectite group clay minerals (montmorillonite, saponite, hectorite, etc.), kaolin group clay minerals (kaolinite, etc.), bentonite, attapulgite, magadiite, and kanemite. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said organic modified layered inorganic mineral, According to the objective, it can select suitably. For example, an organically modified layered inorganic mineral in which at least a part of ions present between the layers of the layered inorganic mineral is modified with organic ions can be used. Among these, those in which at least part of ions between layers of the smectite group clay mineral having a smectite-based basic crystal structure are modified with an organic cation are preferable from the viewpoint of dispersion stability in the vicinity of the toner surface. Particularly preferred are those in which at least some of the ions between the layers of montmorillonite are modified with an organic cation and at least some of the ions between the layers of bentonite are modified with an organic cation.

  It can be confirmed by gas chromatography mass spectrometry (GCMS) that the organically modified layered inorganic mineral has at least part of the ions present between the layers of the layered inorganic mineral modified with organic ions. For example, a method of filtering a solution in which a binder resin in a toner as a sample is dissolved with a solvent, pyrolyzing the obtained solid with a thermal decomposition apparatus, and identifying the structure of the organic substance with GCMS is suitable. Can be mentioned. Specifically, as a thermal decomposition apparatus, Py-2020D (manufactured by Frontier Laboratories) is used, and after thermal decomposition at 550 ° C., a method of identifying with a GCMS apparatus QP5000 (manufactured by Shimadzu Corporation) is mentioned. It is done.

  Further, as the organic modified layered inorganic mineral, a metal anion is introduced by replacing a part of the divalent metal of the layered inorganic mineral with a trivalent metal, and at least a part of the metal anion is converted into an organic anion. And a layered inorganic compound modified with (1).

  A commercially available product can be used as the organically modified layered inorganic mineral. Examples of commercially available products include Bentone 3, Bentone 38, Bentone 38V (manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL (manufactured by Southern Clay). Quartium 18 bentonite; stearalkonium bentonite such as Bentone 27 (manufactured by Leox), Thixogel LG (manufactured by United catalyst), Clayton AF, Clayton APA (above, manufactured by Southern Clay), etc .; Clayton HT, Kraton PS (above, Southern) Quantum 18 / Benzalkonium bentonite such as Clay); Organic modified montmorillonite such as Clayton HY (Southern Clay); Lucentite SPN (Coop Chemical) Organic modified Sukumetaito of Ltd.) and the like. Among these, Clayton AF and Clayton APA are particularly preferable.

Moreover, as said organic modified layered inorganic mineral, what modified | denatured DHT-4A (made by Kyowa Chemical Industry Co., Ltd.) as follows is especially preferable. That is, R1 (OR2) nOSO3M (wherein R1 is an alkyl group having 13 carbon atoms, R2 is an alkylene group having 2 to 6 carbon atoms, n is an integer of 2 to 10, and M is a monovalent metal element) These are modified with a compound having an organic ion represented by the formula: Examples of the compound having an organic ion represented by R1 (OR2) _n OSO ₃ M include Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

  About the said organic modified layered inorganic mineral, you may mix with resin as needed, and you may use what was compounded as a masterbatch. In that case, there is no restriction | limiting in particular as resin, According to the objective, it can select suitably from well-known things.

  The content of the organically modified layered inorganic mineral with respect to the toner is preferably 0.1% by mass to 3.0% by mass, more preferably 0.5% by mass to 2.0% by mass, and 1.0% by mass to 1%. .5% by mass is particularly preferred. When the content is less than 0.1% by mass, the effect of the layered inorganic mineral is hardly exhibited. When the content exceeds 3.0% by mass, the low-temperature fixability tends to be inhibited.

  There is no particular limitation on the organic ion modifier, which is a compound having the organic ions and capable of modifying at least some of the ions present between the layers of the layered inorganic mineral into organic ions, and is appropriately selected according to the purpose. For example, quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts; branched, unbranched or cyclic alkyls having 1 to 44 carbon atoms, branched, unbranched or cyclic alkenyl atoms having 1 to 22 carbon atoms, Sulfates having a skeleton such as branched, unbranched or cyclic alkoxy having 8 to 32 carbon atoms, branched or unbranched or cyclic hydroxyalkyl having 2 to 22 carbon atoms, ethylene oxide, propylene oxide, sulfonates having the skeleton, Examples thereof include a carboxylate having the skeleton and a phosphate having the skeleton. Among these, quaternary alkyl ammonium salts and carboxylic acids having an ethylene oxide skeleton are preferable, and quaternary alkyl ammonium salts are particularly preferable. These may be used individually by 1 type and may use 2 or more types together. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  Various external additives can be added to the toner for purposes such as fluidity modification, charge amount adjustment, and electrical property adjustment. There is no restriction | limiting in particular as an external additive, According to the objective, it can select suitably from well-known things. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoro Examples thereof include polymers. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Japan) Aerosil Co., Ltd.). Examples of titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both 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 manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T (any Also manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

  Hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles are obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. 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 coupling agents having a fluorinated alkyl group. , Organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes, and the like.

The average particle size of the primary particles of the inorganic fine particles is preferably 1 to 100 nm, and more preferably 3 to 70 nm. If the average particle size is less than 1 nm, the inorganic fine particles are buried in the toner, and the function may not be effectively exhibited. On the other hand, when the thickness exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. As the external additive, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination. More preferably, the hydrophobized primary particles include at least two types of inorganic fine particles having an average particle size 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 BET method of an inorganic fine particle is 20-500 m < ² > / g. The amount of the external additive added is preferably 0.1 to 5% by weight and more preferably 0.3 to 3% by weight with respect to the toner. Resin fine particles can also be added as an 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 amount of resin fine particles added is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight, based on the toner.

  Any known toner production method and material can be used as long as the conditions are satisfied, and is not particularly limited. Examples thereof include a kneading and pulverizing method and a so-called chemical method of granulating toner particles in an aqueous medium. Chemical methods include, for example, suspension polymerization, emulsion polymerization, seed polymerization, dispersion polymerization, etc., in which monomers are used as starting materials; resins and resin precursors are dissolved in an organic solvent and the like in an aqueous medium. Dispersion or emulsification dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group, and an aqueous system containing resin fine particles A method of emulsifying or dispersing in a medium and reacting an active hydrogen group-containing compound with the reactive group-containing prepolymer in the aqueous medium (production method (I)); resin or resin precursor and an appropriate emulsifier A phase inversion emulsification method in which water is added to a solution consisting of the above-mentioned solutions; the resin particles obtained by these methods are aggregated in a state dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting Agglomeration , And the like. Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.) by the crystalline resin, and the production method described above. The toner obtained in (I) is more preferable.

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

  In the pulverization, the kneaded material obtained by kneading the toner material 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 classification, the pulverized product obtained by pulverization is classified and adjusted to particles having a predetermined particle size. Classification can be performed, for example, by removing fine particle portions 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 current by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used as an aqueous medium. In this method, toner base particles are produced by dispersing or emulsifying the toner. The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether. Ether solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone and other ketone solvents, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2- Examples thereof include alcohol solvents such as ethylhexyl alcohol and benzyl alcohol, and mixed solvents of two or more of these.

  In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary. As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkylbenzene sulfonic acid, phosphate ester, etc.), cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), amphoteric surfactant (carboxylic acid). Salt type, sulfate salt type, sulfonate type, phosphate ester type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.

Examples of the water-soluble polymer include cellulosic compounds (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan, Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid, Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer (parts) ) Neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like. Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  In the dissolution suspension method, it is desirable to obtain toner as follows. That is, an oil phase composition including at least a binder resin, a binder resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group, a colorant, and a release agent is prepared. This oil phase composition is dispersed or emulsified in an aqueous medium containing resin fine particles. Then, toner base particles are granulated by a method (production method (I)) of reacting an active hydrogen group-containing compound contained in the oil phase composition or an aqueous medium with a reactive group-containing prepolymer. Get toner.

  The resin fine particles can be formed using a known polymerization method, but it is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).

(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) A polyaddition or condensation resin precursor (monomer, oligomer, etc.) such as a polyester resin, polyurethane resin, or epoxy resin or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant. Thereafter, a method of preparing an aqueous dispersion of resin fine particles by heating and adding a curing agent to cure.
(C) In precursors (monomers, oligomers, etc.) of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, and may be liquefied by heating) A suitable emulsifier is dissolved. Thereafter, water is added to cause phase inversion emulsification to prepare an aqueous dispersion of resin fine particles.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. Thus, resin fine particles are obtained. Thereafter, a method of preparing an aqueous dispersion of resin fine particles by dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. To do. Thereafter, resin fine particles are dispersed in water in the presence of an appropriate dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Alternatively, resin fine particles are precipitated by cooling a resin solution previously dissolved in a solvent by heating, and the solvent is removed to form resin fine particles. Thereafter, resin fine particles are dispersed in water in the presence of an appropriate dispersant to prepare an aqueous dispersion of resin fine particles.
(G) A resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is prepared. A method of preparing an aqueous dispersion of resin fine particles by dispersing a resin solution obtained by dissolving this resin in a solvent in an aqueous medium in the presence of an appropriate dispersant and then removing the solvent by heating, decompression, etc. .
(H) A resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is prepared. A method of preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in a resin solution obtained by dissolving this resin in a solvent and then adding water to cause phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm or exceeds 300 nm, the particle size distribution of the toner may be deteriorated, which is not preferable.

  The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the concentration is too low, the productivity of the toner decreases.

  Toner compositions other than the binder resin such as a colorant and a release agent, and their master batches are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. Also good. As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The method for dispersing in an aqueous medium or emulsifying in an aqueous medium is not particularly limited. Known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  The method for removing the organic solvent from the obtained emulsified dispersion is not particularly limited, and a known method can be used. For example, it is possible to employ a method in which the temperature of the entire system is gradually increased while stirring the system under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

  As a method of washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. For example, after solid-liquid separation with a centrifuge, a filter press or the like, the obtained toner cake is re-dispersed in ion exchange water at about room temperature to about 40 ° C., and the pH is adjusted with acid or alkali as necessary. After that, the process of solid-liquid separation is repeated several times to remove impurities and surfactants, and then the toner powder is dried by an air dryer, circulation dryer, vacuum dryer, vibration fluid dryer, etc. Get. At this time, the fine particle component of the toner may be removed by centrifugation or the like. Moreover, it can be made a desired particle size distribution using a well-known classifier as needed after drying.

  In the aggregation method, for example, a toner base particle is produced by mixing and aggregating at least a resin fine particle dispersion composed of a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. . The resin fine particle dispersion is obtained by a known method, for example, emulsion polymerization, seed polymerization, phase inversion emulsification method or the like. The colorant particle dispersion and the release agent particle dispersion can be obtained by dispersing the colorant and the release agent in an aqueous medium by a known wet dispersion method or the like.

  For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used. The metal salt is not particularly limited, and monovalent metals constituting salts such as sodium and potassium; divalent metals constituting salts such as calcium and magnesium; trivalent metals constituting salts such as aluminum and the like. Can be mentioned. Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and a complex or multimer thereof are preferable. Also, heating between the agglomeration and after completion of the agglomeration can promote fusion between the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

  As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used. Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above.

  For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

  The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle size, volume average particle size and number average particle size are as follows. (Volume average particle diameter / number average particle diameter) and the like.

  The average circularity of the toner is a value obtained by dividing the perimeter of an equivalent circle having the same toner shape and projected area by the perimeter of the actual particles. This value is preferably 0.950 to 0.980, and more preferably 0.960 to 0.975. In addition, it is preferable that the particle | grains whose average circularity is less than 0.950 are 15% or less of the whole. If the average circularity is less than 0.950, satisfactory transferability and high-quality images without dust may not be obtained. On the other hand, when the average circularity exceeds 0.980, in an image forming system employing blade cleaning or the like, poor cleaning occurs on the photoreceptor or the transfer belt. Then, in the case of image formation with a high image area ratio such as a photographic image, such as a photographic image, toner that has formed an untransferred image due to poor paper feed or the like has accumulated as a transfer residual toner on the photoreceptor. The image may be soiled. Alternatively, the charging roller that contacts and charges the photosensitive member may be contaminated, and the original charging ability may not be exhibited.

  The average circularity of the toner can be analyzed as follows. That is, measurement is performed using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analysis is performed using analysis software (FPIA-2100 Data Processing Program for FPIAversion 00-10). Specifically, 0.1 to 0.5 ml of 10% by weight of a surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 ml beaker. Then, 0.1 to 0.5 g of each toner is added, and the mixture is stirred with a micropartel, and then 80 mL of ion-exchanged water is added. The obtained dispersion is subjected to dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The obtained dispersion is adjusted to a concentration of 5,000 to 15,000 / μL and then set on FPIA-2100 to measure the shape and distribution of the toner. In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity. In order to realize such a concentration, it is necessary to adjust the amount of surfactant and the amount of toner added to the dispersion. Similar to the measurement of the toner particle size described above, the required amount of the surfactant varies depending on the hydrophobicity of the toner. If a large amount is added, noise due to bubbles is generated. If the amount is small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the amount of toner added varies depending on the particle size, and it is necessary to decrease the small particle size and increase the large particle size. For example, when the toner particle diameter is 3 μm to 10 μm, the dispersion concentration is adjusted to 5,000 / μl to 15,000 / μl by adding 0.1 g to 0.5 g of toner. It becomes possible.

  The volume average particle diameter of the toner is not particularly limited and can be appropriately selected depending on the purpose. 3 μm to 10 μm is preferable, and 4 μm to 7 μm is more preferable. When the volume average particle size is less than 3 μm, in the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be lowered. On the other hand, if it exceeds 10 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase.

  The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, preferably 1.00 to 1.15. Is more preferable. About volume average particle diameter and ratio (volume average particle diameter / number average particle diameter) of volume average particle diameter and number average particle diameter, a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) is used. It is possible to measure. Specifically, measurement is performed with an aperture diameter of 100 μm, and analysis is performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). More specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker. Then, 0.5 g of toner is added, and the mixture is stirred with a micropartel, and 80 ml of ion exchange water is added. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). This dispersion is set in Multisizer III, and the particle size is measured using Isoton III (manufactured by Beckman Coulter, Inc.) as a measurement solution. In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 8 ± 2%. In this measurement method, it is important to set the concentration to 8 ± 2% from the viewpoint of measurement reproducibility of the particle diameter. Within this concentration range, no error occurs in the particle size.

  The value of the ratio Tsh2nd / Tsh1st between the shoulder temperature Tsh1st of the first heat-up melting peak and the shoulder heat Tsh2nd of the second heat-up melting peak measured by a differential scanning calorimeter (DSC) of the toner is 0.90 or more. It is preferable that it is 1.10 or less. The shoulder temperature (Tsh1st, Tsh2nd) of the melting heat peak of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). Specifically, first, 5.0 mg of toner is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. In the obtained DSC curve, the endothermic peak temperature at the first temperature rise is Tm1st, and the endothermic peak temperature at the second temperature rise is Tm2nd. At this time, when there are a plurality of endothermic peaks, the one with the largest endothermic amount is selected. For each endothermic peak, the intersections of the base line on the lower temperature side than the endothermic peak and the tangent line on the low temperature side forming the endothermic peak are denoted as Tsh1st and Tsh2nd, respectively.

  The value of the crystallinity of the toner is preferably 15% or more and 30% or less, and more preferably 20% or more and 25% or less. When the crystallinity value is less than 15%, the influence of the amorphous part contained in the toner is increased, the sharp viscoelastic response to heat unique to the crystalline resin is impaired, and the low-temperature fixability is reduced. Deterioration and heat-resistant storage stability may occur, which is not preferable. On the other hand, when the crystallinity value is larger than 30%, the decrease in hardness due to the crystalline resin cannot be suppressed, and carrier filming may occur over time due to agitation stress in the developing device, or toner and carrier Image agglomerates and image defects may occur. The crystallinity of the toner can be controlled as follows, for example. That is, change the mixing ratio of crystalline resin and amorphous resin, change the crystallinity of crystalline resin (change monomer composition, crystallinity of block resin with crystalline part and amorphous part) Changing the ratio of part to amorphous part).

  The developer contains toner and other appropriately selected components such as a carrier. The developer may be a one-component developer not containing carrier particles or a two-component developer containing carrier particles. When used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, a two-component developer is preferable from the standpoint of improving the life. In the case of a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner onto the developing roller as the developer carrying member and the blade for thinning the toner There is no fusion of the toner to the layer thickness regulating member. Therefore, good and stable developability and images can be obtained even when the developing means is used for a long time (stirring). In the case of a two-component developer, even if toner balance is performed over a long period of time, there is little fluctuation in the toner particle diameter in the developer, and good and stable developability can be obtained even with long-term stirring in the developing means. .

  There is no restriction | limiting in particular as a carrier used for a two-component developer, Although it can select suitably according to the objective, What has a core material and the resin layer (coating layer) which coat | covers a core material is preferable. The core material is not particularly limited as long as it is magnetic particles, and suitable examples include ferrite, magnetite, iron, nickel, and the like. Further, when considering adaptability to environmental aspects that have been remarkably advanced in recent years, it is preferable to use the following as the ferrite, instead of the conventional copper-zinc ferrite. That is, manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese-magnesium-strontium ferrite, lithium ferrite, and the like.

  The coating layer covering the core material of the carrier contains at least a binder resin, and may contain other components such as inorganic fine particles as necessary. The binder resin for forming the carrier coating layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, a crosslinkable copolymer containing polyolefin (eg, polyethylene, polypropylene, etc.) or a modified product thereof, styrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; consisting of an organosiloxane bond Silicone resins or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamides; polyesters; polyurethanes; polycarbonates; urea resins; melamine resins; Examples thereof include polyimide resins and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

  There is no restriction | limiting in particular as a silicone resin, According to the objective, it can select suitably from the silicone resin generally known. For example, a straight silicone resin composed only of an organosiloxane bond and a silicone resin modified with alkyd, polyester, epoxy, acrylic, urethane, etc. can be mentioned.

  Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Specific examples of the modified silicone resin include epoxy modified product: ES-1001N, acrylic modified silicone: KR-5208, polyester modified product: KR-5203, alkyd modified product: KR-206, urethane modified product: KR-305. (Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like. The silicone resin can be used alone, but it is also possible to use a crosslinking reactive component, a charge amount adjusting component, and the like at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Furthermore, examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, and aminosilane coupling agent.

  The coating layer covering the carrier core material may contain fine particles as necessary. There is no restriction | limiting in particular as microparticles | fine-particles, According to the objective, it can select suitably from conventionally well-known materials. For example, inorganic fine particles such as metal powder, tin oxide, zinc oxide, silica, titanium oxide, alumina, potassium titanate, barium titanate, aluminum borate, polyaniline, polyacetylene, polyparaphenylene, poly (para-phenylene sulfide) , Conductive polymers such as polypyrrole and parylene, and organic fine particles such as carbon black, and two or more of them may be used in combination. Those fine particles may have a surface subjected to a conductive treatment. As a method of such a conductive treatment, aluminum, zinc, copper, nickel, silver, or an alloy thereof, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin are formed on the surface of the fine particles. And indium oxide doped with antimony, tin oxide doped with antimony, zirconium oxide, and the like in the form of a solid solution or fusion. Among these, a method of conducting a conductive treatment using tin oxide, indium oxide, or indium oxide doped with tin is preferable.

  The content of the coating layer in the carrier is preferably 5% by weight or more, and more preferably 5% by weight or more and 10% by weight or less. Moreover, as thickness of a coating layer, it is preferable that they are 0.1 micrometer-5 micrometers, and it is still more preferable that they are 0.3 micrometer-2 micrometers. About the thickness of a coating layer, it can obtain | require as follows, for example. That is, after creating a carrier cross-section with FIB (focused ion beam), the cross-section of the carrier at 50 points or more was observed with a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), and the average thickness obtained Calculate as a value.

  There is no restriction | limiting in particular as a formation method of the coating layer to a carrier, It is possible to use a conventionally well-known coating layer formation method. Examples thereof include a method in which a coating layer solution in which the above-described coating layer raw materials such as a binder resin or a binder resin precursor are dissolved is applied to the surface of the core using a spraying method, a dipping method, or the like. It is preferable to promote the polymerization reaction of the binder resin or the binder resin precursor by applying the coating layer solution on the surface of the core material and heating the carrier on which the coating layer is formed. The heat treatment may be continued in the coating apparatus after the coating layer is formed. Or you may carry out by another heating means, such as a normal electric furnace and a baking kiln, after coating layer formation. The heat treatment temperature varies depending on the constituent material of the coating layer to be used, and is not generally determined, but is preferably about 120 to 350 ° C. It is particularly preferable that the temperature is equal to or lower than the decomposition temperature of the coating layer constituting material. The decomposition temperature of the coating layer constituting material is preferably an upper limit temperature of up to about 220 ° C., and the heat treatment time is preferably about 5 minutes to 120 minutes.

  The volume average particle diameter of the carrier is preferably in the range of 10 to 100 μm, and more preferably in the range of 20 to 65 μm. If the volume average particle size of the carrier is less than 10 μm, carrier adhesion due to a decrease in the uniformity of the core material particles occurs, which is not preferable. On the other hand, if it exceeds 100 μm, the reproducibility of image details is poor and a fine image cannot be obtained, which is not preferable. The method for measuring the volume average particle size is not particularly limited as long as it is a device capable of measuring the particle size distribution, and for example, it can be measured using a Microtrac particle size distribution analyzer: Model HRA9320-X100 (manufactured by Nikkiso Co., Ltd.). it can.

  The volume resistivity of the carrier is preferably 9 [log (Ω · cm)] or more and 16 [log (Ω · cm)] or less, preferably 10 [log (Ω · cm)] or more and 14 [log (Ω). -Cm)] is more preferable. When the volume resistivity is less than 9 [log (Ω · cm)], carrier adhesion occurs in the non-image area, which is not preferable. On the other hand, if it is larger than 16 [log (Ω · cm)], the so-called edge effect, in which the image density at the edge portion is emphasized during development, is not preferable. The volume resistivity can be arbitrarily adjusted within the above-described range by adjusting the thickness of the carrier coating layer and the content of the conductive fine particles as necessary.

  The volume resistivity of the carrier can be measured as follows. That is, a carrier is filled in a cell made of a fluororesin container containing electrodes 1a and 1b having a distance between electrodes of 0.2 cm and a surface area of 2.5 cm × 4 cm. Then, tapping is performed under the conditions of drop height: 1 cm, tapping speed: 30 times / min, and tapping frequency: 10 times. Next, a DC voltage of 1000 V is applied between both electrodes, and a resistance value r [Ω] after 30 seconds is measured by a high resistance meter 4329A (manufactured by Yokogawa Hewlett-Packard Co., Ltd .: High Resistance Meter). Then, the volume resistivity R [log (Ω · cm)] is calculated using a calculation formula “R = Log [r × (2.5 cm × 4 cm) /0.2 cm]”.

  When the developer is a two-component developer, the mass ratio of the toner to the carrier in the two-component developer is preferably 2.0 to 12.0% by weight, and 2.5 to 10.0% by weight. More preferably.

  The weight average molecular weight (Mw) of the crystalline resin used as the binder resin for the toner is preferably 2,000 to 100,000, more preferably 5,000 to 60,000, and more preferably 8,000 to 50,000, from the viewpoint of fixability. 30,000 is particularly preferred. When the weight average molecular weight is less than 2,000, the hot offset resistance tends to deteriorate, and when it exceeds 100,000, the low-temperature fixability tends to deteriorate.

  The weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GPC) measuring device (for example, GPC-8220 GPC (manufactured by Tosoh Corporation)). As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) is used. The resin to be measured is made into a 0.15 mass% solution with tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 100 μl of the above-mentioned THF sample solution is injected into a measuring apparatus, and measurement is performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C. In measuring the molecular weight of the sample, the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. Examples of the standard polystyrene sample described above include Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, toluene can be used. is there. An RI (refractive index) detector is used as the detector.

  The crystalline resin used as the binder resin for the toner preferably has a resin having a crystalline polyester unit. This is because it is easy to design a melting point suitable as a toner and has excellent binding properties to paper. The ratio of the crystalline resin having a crystalline polyester unit to the whole binder resin is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass or more, and further preferably 90% by mass or more. . This is because as the proportion of the crystalline resin having a crystalline polyester unit increases, the low-temperature fixability of the toner improves.

  Examples of the crystalline resin having a crystalline polyester unit include a resin composed of only a crystalline polyester unit (also simply referred to as a crystalline polyester resin). Further, a resin in which a crystalline polyester unit is connected, or a resin in which a crystalline polyester unit and another polymer are bonded (so-called block polymer or graft polymer) may be used. A crystalline resin composed only of a crystalline polyester unit has a portion having a crystal structure, but may be easily deformed by an external force. The reason is that it is difficult to crystallize all the parts of the crystalline polyester, and it is easy to deform because of the high degree of freedom of the molecular chain of the non-crystallized part (non-crystalline part). . In addition, regarding the portion having a crystal structure, generally, the higher order structure is a so-called lamellar structure in which molecular surfaces are folded while forming a plane, and a large bonding force does not work between the lamellar layers. This is because the lamellar layer is easily displaced. If the binder resin for toner is easily deformed by an external force, problems such as deformation / aggregation in the image forming apparatus, adhesion to or sticking to a member, and damage to the final output image may occur. There is sex. For this reason, the binder resin must be able to withstand a certain degree of deformation against external force and have toughness. From the viewpoint of imparting toughness of the resin, a resin in which a crystalline polyester unit having a urethane bond site, a urea bond site, and a phenylene site having large cohesive energy is connected is preferable. Also, a resin (so-called block polymer or graft polymer) in which a crystalline polyester unit and another polymer are bonded may be used. Among these, a resin having a urethane bond site or a urea bond site in the molecular chain is particularly preferable. This is because it is considered that a pseudo-crosslinking point due to a large intermolecular force can be formed between an amorphous part and a lamellar layer, and the fixing strength can be increased easily after being fixed on the paper.

  As a result of intensive studies by the present inventors, it has been found that the following phenomenon occurs in a toner mainly composed of a crystalline resin as a binder resin. In other words, the property of sharply decreasing viscoelasticity above the melting point, which has been considered effective for low-temperature fixability (sharp melt property), causes the temperature range that can be fixed to vary greatly depending on the paper type. . Therefore, the molecular weight of the binder resin used in the conventional toner having excellent low-temperature fixability is a high component, specifically, a component having a polystyrene-reduced molecular weight of 100,000 or more in gel diffusion chromatography (GPC) is constant. Add more than the amount. Further, it has been found that fixing the weight average molecular weight within a certain range enables fixing at a constant temperature and at a constant speed regardless of the type of paper.

  The component having a molecular weight of 100,000 or more is preferably contained in a proportion of 5% or more, more preferably in a proportion of 7% or more, and further preferably in a proportion of 9% or more. By containing 5% or more of a component having a molecular weight of 100,000 or more, the temperature dependency of the fluidity and viscoelasticity of the toner after melting is reduced. For this reason, even if it is a thin paper that easily transfers heat during fixing, even if it is a thick paper that does not easily transfer heat to the toner, there is no significant difference in toner fluidity and elastic modulus, and the fixing device has a constant temperature and a constant speed. It becomes possible to fix. If the proportion of the component having a molecular weight of 100,000 or more is less than 5%, the fluidity and viscoelasticity after melting the toner vary greatly depending on the temperature. For example, in fixing on thin paper, the deformability of the toner becomes too large. Then, the adhesion area to the fixing member is increased, and as a result, the paper can be wound around without being able to release from the fixing member well.

  The crystalline resin has a sharp melt property as described above, but the internal cohesive force and viscoelasticity of the toner in the molten state vary greatly depending on the molecular weight and structure of the resin. For example, when it has a urethane bond or urea bond, which is a linking group having a large cohesive energy, it behaves like an elastic body such as rubber at a relatively low temperature even when melted. On the other hand, as the temperature increases, the thermal kinetic energy of the polymer chain increases. For this reason, the agglomeration between the bonds is gradually released, and it approaches the viscous body. When such a resin is used as a binder resin for the toner, even if the fixing can be performed without any problem when the fixing temperature is low, the internal cohesive force when the toner is melted is small when the fixing temperature is high. The upper side of the image adheres to the fixing member. As a result, a so-called hot offset phenomenon may occur, and image quality is significantly impaired. In order to avoid hot offset, if the number of urethane bonds or urea bonds is increased, fixing at a high temperature can be performed without any problem. On the other hand, when fixing is performed at a low temperature, the image gloss is low, melt impregnation into the paper is insufficient, and the image is easily detached from the paper. In particular, when fixing to paper with a large thickness and unevenness on the surface, the heat transfer efficiency to the toner during fixing is low, so that the fixing state is further deteriorated, or pressure is applied to the toner with the fixing member in the recess. Since the toner is not sufficiently applied, the fixing state of the toner which is in an especially elastic state is remarkably deteriorated.

  When the molecular weight is considered as a means for controlling the viscoelasticity after melting, as a matter of course, the larger the molecular weight, the more obstacles to the movement of the molecular chain, so the viscoelasticity increases. Further, when the molecular weight is relatively large, entanglement occurs, and thus elastic behavior is exhibited. Considering the fixability to paper, a smaller molecular weight is preferable because the viscosity at the time of melting is lower. On the other hand, if there is no elasticity, hot offset occurs. However, if the molecular weight is increased as a whole, the fixability is impaired, and particularly in the case of thick paper, the heat transfer efficiency to the toner at the time of fixing is low, and the fixing state is further deteriorated. Therefore, the molecular weight of the binder resin is not excessively increased, and a high molecular weight crystalline component is included. Thereby, the viscoelasticity after melting can be suitably controlled, and a toner that can be fixed at a constant temperature and at a constant speed regardless of the type of paper such as thin paper or thick paper can be obtained.

  The range of the weight average molecular weight is preferably 20,000 or more and 70,000 or less, more preferably 30,000 or more and 60,000 or less. Further, it is particularly preferably 35,000 or more and 50,000 or less. When the weight average molecular weight exceeds 70,000, the whole binder resin is too high in molecular weight, so that the fixing property is deteriorated, the gloss is too low, and the image after fixing is easily lost due to external stress. . Also, if it is less than 20,000, even if a high molecular weight component is present, the internal cohesive force at the time of melting the toner becomes too low. Because it causes, it is not preferable.

  As a method for obtaining a toner having a binder resin having a predetermined molecular weight distribution, there is a method using two or more kinds of resins having different molecular weight distributions together and using a resin whose molecular weight distribution is controlled during polymerization. When two or more kinds of resins having different molecular weight distributions are used in combination, at least two kinds of relatively high molecular weight resins and low molecular weight resins are used. As the high molecular weight resin, a resin having a large molecular weight may be used in advance, or a modified resin having an isocyanate group at the terminal may be elongated in the production process of the toner to form a high molecular weight body. In the latter method, the high molecular weight body can be uniformly present in the toner, and in the production method in which the binder resin is dissolved in the organic solvent, the high molecular weight resin is first dissolved than the high molecular weight resin. It is preferable because it is easy.

  As a ratio in the case where the binder resin is composed of a high molecular weight resin (including a modified resin having an isocyanate group) and a low molecular weight resin, the following ratio is preferable. That is, the ratio of high molecular weight resin / low molecular weight resin is 5 / 95-60 / 40, preferably 8 / 92-50 / 50, more preferably 12 / 88-35 / 65, and even more preferably 15/85. ~ 25/75. When the number of high molecular weight substances is less than 5/95, or when the number of high molecular weight substances is larger than 60/40, it becomes difficult to obtain a toner having a binder resin having the molecular weight distribution described above.

  In the case of using a resin whose molecular weight distribution is controlled at the time of polymerization, as a method of obtaining the above-mentioned resin, in addition to a bifunctional monomer, a functional form other than a bifunctional monomer can be used as long as it is a polymerization form such as polycondensation, polyaddition or addition condensation. The molecular weight distribution can be broadened by adding a small amount of monomers having different numbers of groups. Monomers having different numbers of functional groups include tri- or higher functional monomers and monofunctional monomers. When a tri- or higher functional monomer is used, a branched structure is generated. Therefore, when a resin having crystallinity is used, it may be difficult to form a crystal structure. If a monofunctional monomer is used, the polymerization reaction is stopped by the monofunctional monomer, so that the low molecular weight resin in the case of using two or more types of resins is purified, and a part of the polymerization reaction proceeds to increase the high molecular weight component. It becomes.

  Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

  Examples of the polyol include diols, trivalent to octavalent or higher polyols. There is no restriction | limiting in particular as diol, According to the objective, it can select suitably. For example, aliphatic diols such as linear aliphatic diols and branched aliphatic diols; alkylene ether glycols having 4 to 36 carbon atoms; alicyclic diols having 4 to 36 carbon atoms; Alkylene oxide (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; diol having a carboxyl group, diol having a sulfonic acid group or sulfamic acid group, and other salts thereof A diol having a functional group of Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between low-temperature fixability and heat-resistant storage stability is good, and the resin hardness tends to be improved.

  There is no restriction | limiting in particular as linear aliphatic diol, According to the objective, it can select suitably. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -Nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20 -Eicosanediol and the like. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

  The branched aliphatic diol having 2 to 36 chain carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2-propylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol and the like can be mentioned.

  The alkylene ether glycol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.

  The alicyclic diol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

  There is no restriction | limiting in particular as alkylene oxide (henceforth AO) of alicyclic diol, According to the objective, it can select suitably. Examples thereof include adducts (number of added moles of 1 to 30) such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), and the like.

  There is no restriction | limiting in particular as bisphenol, According to the objective, it can select suitably. For example, AO (EO, PO, BO, etc.) adducts such as bisphenol A, bisphenol F, bisphenol S and the like (addition mole number: 2 to 30) and the like can be mentioned.

  There is no restriction | limiting in particular as polylactone diol, According to the objective, it can select suitably, For example, poly-epsilon-caprolactone diol etc. are mentioned.

  There is no restriction | limiting in particular as diol which has a carboxyl group, According to the objective, it can select suitably. For example, dialkyl having 6 to 24 carbon atoms such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, etc. Examples thereof include roll alkanoic acid.

  There is no restriction | limiting in particular as diol which has a sulfonic acid group or the said sulfamic acid group, According to the objective, it can select suitably. For example, sulfamic acid diols such as N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, [N, N-bis (2-hydroxyalkyl) ) Sulphamic acid (alkyl group having 1 to 6 carbon atoms) and AO adducts thereof (such as EO or PO as AO, 1 to 6 moles of AO added); bis (2-hydroxyethyl) phosphate and the like.

  There is no restriction | limiting in particular as a neutralization base of the diol which has a neutralization base, According to the objective, it can select suitably. Examples thereof include tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and alkali metals (such as sodium salts). Among these, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof are preferable.

  There is no restriction | limiting in particular as a trivalent-octavalent or more polyol used as needed, According to the objective, it can select suitably. For example, alkane polyols and intramolecular or intermolecular dehydrates (eg, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), sugars and derivatives thereof (eg, sucrose, methyl glucoside) Etc.) Trivalent to octavalent or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms; AO adducts of trisphenols (trisphenol PA, etc.) (added mole number 2 to 30); AO adducts (addition mole number: 2 to 30) of resins (phenol novolac, cresol novolac, etc.); acrylic polyols such as copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers, and the like. Among these, trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts are preferred, and novolak resin AO adducts are more preferred.

  Examples of the polycarboxylic acid include dicarboxylic acid, trivalent to hexavalent or higher polycarboxylic acid. There is no restriction | limiting in particular as dicarboxylic acid, According to the objective, it can select suitably. Suitable examples include aliphatic dicarboxylic acids such as linear aliphatic dicarboxylic acids and branched aliphatic dicarboxylic acids; and aromatic dicarboxylic acids. Among these, linear aliphatic dicarboxylic acid is more preferable.

  There is no restriction | limiting in particular as aliphatic dicarboxylic acid, According to the objective, it can select suitably. Examples thereof include alkanedicarboxylic acids having 4 to 36 carbon atoms such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid; dodecenylsuccinic acid, pentadecenylsuccinic acid, octadecenyl Alkenyl dicarboxylic acids having 4 to 36 carbon atoms such as alkenyl succinic acid such as succinic acid, maleic acid, fumaric acid and citraconic acid; alicyclic dicarboxylic acids having 6 to 40 carbon atoms such as dimer acid (dimerized linoleic acid), etc. Are preferable.

  There is no restriction | limiting in particular as aromatic dicarboxylic acid, According to the objective, it can select suitably. For example, aromatic dicarboxylic acids having 8 to 36 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc. are suitable. It is mentioned in. Examples of the trivalent to hexavalent or higher polycarboxylic acid used as needed include aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid.

  As the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, acid anhydrides as described above or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used. Good. Of the dicarboxylic acids, it is particularly preferable to use an aliphatic dicarboxylic acid (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone. A copolymer obtained by copolymerizing the above-mentioned aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) with the aliphatic dicarboxylic acid is also preferable. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

  There is no restriction | limiting in particular as a lactone ring-opening polymer, According to the objective, it can select suitably. For example, lactones such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and other monolactones having 3 to 12 carbon atoms (one ester group in the ring) as metal oxides, Lactone ring-opening polymer obtained by ring-opening polymerization using a catalyst such as an organometallic compound; monolactones having 3 to 12 carbon atoms using glycol (for example, ethylene glycol, diethylene glycol, etc.) as an initiator And a lactone ring-opening polymer having a hydroxyl group at the terminal obtained by ring-opening polymerization.

  The monolactone having 3 to 12 carbon atoms is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of crystallinity, ε-caprolactone is preferred. Moreover, as a lactone ring-opening polymerization product, you may use a commercial item, For example, highly crystalline polycaprolactone, such as H1P, H4, H5, H7 of the PLACEL series made from Daicel, etc. are mentioned.

  There is no restriction | limiting in particular as a preparation method of polyhydroxycarboxylic acid, According to the objective, it can select suitably. For example, a method of directly dehydrating and condensing hydroxycarboxylic acids such as glycolic acid and lactic acid (L-form, D-form, racemic form, etc.); 2 of hydroxycarboxylic acids such as glycolide and lactide (L-form, D-form, racemic form, etc.) Ring opening of cyclic ester (2 to 3 ester groups in the ring) corresponding to intermolecular or trimolecular dehydration condensate using a catalyst such as a metal oxide or an organometallic compound Although the method of superposing | polymerizing etc. is mentioned, the method of ring-opening polymerization is preferable from a viewpoint of adjustment of molecular weight. Among the cyclic esters, L-lactide and D-lactide are preferable from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

  Examples of a method for obtaining a resin in which a crystalline polyester unit is linked include a method in which a crystalline polyester unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and linked with polyisocyanate. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased. Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like. There is no restriction | limiting in particular as said diisocyanate, According to the objective, it can select suitably. Examples thereof include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and araliphatic diisocyanates. Among these, the carbon number except carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these Preferred is a modified product of diisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and a mixture of two or more of these. . Moreover, you may use together trivalent or more isocyanate as needed.

  There is no restriction | limiting in particular as aromatic diisocyanate, According to the objective, it can select suitably. For example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'- Diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; A mixture of the following: Can be mentioned.

  There is no restriction | limiting in particular as aliphatic diisocyanate, According to the objective, it can select suitably. For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate Examples include natomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  There is no restriction | limiting in particular as alicyclic diisocyanate, According to the objective, it can select suitably. For example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene- Examples include 1,2-dicarboxylate, 2,5- and 2,6-norbornane diisocyanate.

  There is no restriction | limiting in particular as araliphatic diisocyanate, According to the objective, it can select suitably. Examples thereof include m- and p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

  There is no restriction | limiting in particular as a modified product of diisocyanate, According to the objective, it can select suitably. For example, urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product and the like can be mentioned. Specifically, modified MDI such as urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, and modified diisocyanates such as urethane-modified TDI such as isocyanate-containing prepolymers; a mixture of two or more of these modified diisocyanates (For example, combined use of modified MDI and urethane-modified TDI). Among these diisocyanates, aromatic diisocyanates having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanates, and 4 to 15 alicyclic diisocyanates are preferable, and TDI, MDI, HDI, Hydrogenated MDI and IPDI are particularly preferred.

  Examples of a method for obtaining a resin in which a crystalline polyester unit and another polymer are bonded include a method in which a crystalline polyester unit and another polymer unit are separately prepared in advance and bonded together. Alternatively, a method may be used in which a crystalline polyester unit and any of other polymer units are produced and then bonded by polymerizing the other polymer in the presence of the produced unit. Moreover, the method obtained by polymerizing a crystalline polyester unit and another polymer unit simultaneously or sequentially in the same reaction field may be used. From the viewpoint of easily controlling the reaction as designed, the first or second method is preferable.

  As the first method, a method in which a unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and connected with polyisocyanate, as in the method for obtaining a resin in which crystalline polyester units are connected, may be mentioned. In addition to those used for polyisocyanates, it can also be obtained by introducing an isocyanate group at the end of one unit and reacting with the active hydrogen of the other unit. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.

  As the second method, when the crystalline polyester unit is prepared first, the following method can be exemplified. That is, if the polymer unit to be created later is an amorphous polyester unit, a polyurethane unit, a polyurea unit or the like, the following is performed. The terminal hydroxyl group or carboxyl group of the crystalline polyester unit is reacted with a monomer for obtaining another polymer unit. Thereby, the resin which combined the crystalline polyester unit and the other polymer can be obtained.

  As an amorphous polyester unit, the polycondensation polyester unit synthesize | combined from a polyol and polycarboxylic acid is mentioned, for example. As the polyol and polycarboxylic acid, those exemplified in the above-mentioned crystalline polyester unit can be used. In order to design so as not to have crystallinity, the polymer skeleton may be provided with many bending points and branch points. In order to give an inflection point, for example, as a polyol, bisphenol such as bisphenol A, bisphenol F, bisphenol S, etc. AO (EO, PO, BO, etc.) adduct (addition mole number 2 to 30) and its derivatives, poly As the carboxylic acid, phthalic acid, isophthalic acid, or t-butylisophthalic acid may be used. In addition, a trivalent or higher polyol or polycarboxylic acid may be used to introduce the branch point.

  Examples of the polyurethane unit include a polyurethane unit synthesized from a polyol such as a diol, a trivalent to octavalent or higher polyol, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. Among these, a polyurethane unit synthesized from diol and diisocyanate is preferable. Examples of the diol and the trivalent to octavalent or higher polyol include those similar to the diol and the trivalent to octavalent or higher polyol cited in the polyester resin. Examples of the diisocyanate and the trivalent or higher polyisocyanate include the same diisocyanates and trivalent or higher polyisocyanates.

  Examples of the polyurea unit include a polyurea unit synthesized from a polyamine such as a diamine or a trivalent or higher polyamine and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. There is no restriction | limiting in particular as diamine, According to the objective, it can select suitably, For example, aliphatic diamines and aromatic diamine are mentioned. Among these, aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms are preferable. Moreover, you may use trivalent or more amines as needed. The aliphatic diamine having 2 to 18 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine and other alkylene diamines having 2 to 6 carbon atoms; diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetra Polyalkylenediamine having 4 to 18 carbon atoms such as ethylenepentamine and pentaethylenehexamine; dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, Alkyl having 1 to 4 carbon atoms or hydroxyalkyl substitution having 2 to 4 carbon atoms of the alkylenediamine or polyalkylenediamine such as methyliminobispropylamine Alicyclic diamines having 4 to 15 carbon atoms such as 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline); piperazine, N-aminoethyl Piperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] heterocyclic diamine having 4 to 15 carbon atoms such as undecane; aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms such as xylylenediamine and tetrachloro-p-xylylenediamine Is mentioned. The aromatic diamine having 6 to 20 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2-, 1,3- and 1,4-phenylenediamine, 2,4 '-And 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m- Unsubstituted aromatic diamines such as aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine; 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine Amine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4 ' -Bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5 -Diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5 -Diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl- 2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenyl Tan, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5 Aromatic diamine having a C1-C4 nucleus-substituted alkyl group such as' -tetraisopropyl-4,4'-diaminodiphenylsulfone; unsubstituted aromatic diamine or the above-mentioned C1-C4 nucleus-substituted alkyl group Mixtures of various proportions of isomers of aromatic diamines; methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4 -Bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-di Toxi-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromodiphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino -3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) ) Sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4 '-Methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4- Aromatic diamines having a nucleus-substituted electron withdrawing group such as aminophenyl-2-chloroaniline (halogens such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups); 4,4′-di An aromatic diamine having a secondary amino group such as (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene [the unsubstituted aromatic diamine, the C1-C4 nucleus-substituted alkyl group. A part of or all of the primary amino group of the aromatic diamine having a nucleus-substituted electron-withdrawing group is a lower alkyl group such as methyl or ethyl, and a secondary amino group. And the like).

  In addition to these, low molecular weight polyamide polyamines obtained by condensation of dicarboxylic acids (dimer acids, etc.) and excess (more than 2 moles per mole of acid) polyamines (the alkylenediamine, polyalkylenepolyamine, etc.) And polyether polyamines such as hydrides of cyanoethylated polyether polyols (polyalkylene glycol and the like). Moreover, you may use what capped the amino group of the amine compound with the ketone compound etc. Among these, a polyurea unit synthesized from the diamine and the diisocyanate is preferable. Examples of the diisocyanate and the trivalent or higher polyisocyanate include those similar to the diisocyanate and the trivalent or higher polyisocyanate.

The vinyl polymer unit is a polymer unit obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of vinyl monomers include those listed below.
(1) Vinyl hydrocarbons (2) Carboxyl group-containing vinyl monomers and salts thereof (3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and their salts (4) Phosphate group-containing vinyl monomers and their salts Salt (5) Hydroxyl group-containing vinyl monomer (6) Nitrogen-containing vinyl monomer (7) Epoxy group-containing vinyl monomer (8) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfones (9) Other vinyls Monomer (10) Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc. (11) Fluorine atom element-containing vinyl monomers

  Examples of the vinyl hydrocarbon (1) include aliphatic vinyl hydrocarbons, alicyclic vinyl hydrocarbons, and aromatic vinyl hydrocarbons. Furthermore, examples of the aliphatic vinyl hydrocarbon include alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins. In addition, for example, alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene are also included. Examples of alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, and ethylidenebicycloheptene. In addition, for example, terpenes such as pinene, limonene, and indene are also included. Examples of the aromatic vinyl hydrocarbon include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, vinyl naphthalene, and the like. Examples of styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products include α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, and ethylstyrene. In addition, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like are also included.

  Examples of the carboxyl group-containing vinyl monomer (2) and salts thereof include unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids, anhydrides thereof, and monoalkyl (1 to 24 carbon atoms) esters thereof. Is mentioned. More specifically, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid and the like. Also, it is a carboxyl group-containing vinyl monomer such as itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, or cinnamic acid.

  Examples of the (3) sulfone group-containing vinyl monomer, vinyl sulfate monoester product, and salts thereof include alkene sulfonic acids having 2 to 14 carbon atoms, such as vinyl sulfonic acid, (meth) allyl sulfonic acid, and methyl vinyl. Sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms, such as α-methylstyrene sulfonic acid, etc .; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) Acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) Acryloyloxy-2-hydroxypropanesulfone 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxy Alkylene (ethylene, propylene, butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate Examples include esters.

  Examples of the phosphoric acid group-containing vinyl monomer (4) and salts thereof include (meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, ( (Meth) acryloyloxyalkyl (C1-C24) phosphonic acids, for example, 2-acryloyloxyethylphosphonic acid; and salts thereof. Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

  Examples of the hydroxyl group-containing vinyl monomer (5) include hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) Allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl Examples include ether.

  Examples of the nitrogen-containing vinyl monomer (6) include amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N -Aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothia Lumpur, and their salts. Also, amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide And cinnamic acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like. In addition, nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like are also included. Also, quaternary ammonium cation group-containing vinyl monomers: tertiary amine groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Also included are quaternized vinyl monomers (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate). Further, nitro group-containing vinyl monomers: nitrostyrene and the like can also be mentioned.

  Examples of the epoxy group-containing vinyl monomer (7) include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and p-vinylphenylphenyl oxide.

  Examples of the vinyl ester (8) include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, and benzyl methacrylate. , Phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate , Heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl Maleates (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxy Ethane, Tetraallyloxyethane, Tetraallyloxypropane, Tetraallyloxybutane, Tetrametaallyloxyethane, etc.] and other vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (Molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide 10 mol Adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].

  Examples of the vinyl (thio) ether of (8) above include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether. , Methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dibutyro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene Etc.

  Examples of the vinyl ketone (8) include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.

  Examples of the vinyl sulfones (8) include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

  Examples of other vinyl monomers in (9) include isocyanate ethyl (meth) acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate.

  The fluorine atom element-containing vinyl monomer (10) is 4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meth) acrylate, Perfluorocyclohexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H- Hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluoro Octylethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate 2- (N- Butyl perfluorooctanesulfonamido) ethyl (meth) acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate, and the corresponding compound derived from α-fluoroacrylic acid, bis-hexafluoroisopropyl itaconate Bis-hexafluoroisopropyl maleate, bis-perfluorooctyl itaconate, bis-perfluoro octyl maleate, bis-trifluoroethyl itaconate and bis -Trifluoroethyl maleate, vinyl heptafluorobutyrate, vinyl perfluoroheptanoate, vinyl perfluorononanoate and vinyl perfluorooctanoate.

  The binder resin preferably includes a crystalline resin having a urea bond in the main chain. According to Solubility Parameter Values (Polymer handbook 4th Ed), the cohesive energy of urea bonds is 50,230 [J / mol]. Since this value is about twice the cohesive energy of urethane bonds (26,370 [J / mol]), it can be expected that toner toughness and an effect of improving offset resistance during fixing can be expected even with a small amount. In order to obtain a resin having a urea bond in the main chain, a method of reacting a polyisocyanate compound and a polyamine compound can be exemplified. Alternatively, a method of reacting a polyisocyanate compound with water and reacting an amino group generated by hydrolysis of the isocyanate and the remaining isocyanate group may be used. In addition, in obtaining a resin having a urea bond in the main chain, in addition to the above-mentioned compounds, a polyol compound can be reacted at the same time to increase the degree of freedom in resin design.

  As polyisocyanate, diisocyanate, trivalent or higher polyisocyanate (hereinafter also referred to as low molecular weight polyisocyanate), and polymers having an isocyanate group at the terminal or side chain (hereinafter also referred to as prepolymer) are used. May be. Examples of the method for producing the prepolymer include a method of obtaining a polyurea prepolymer having an isocyanate group at the terminal by reacting a low molecular weight polyisocyanate with a polyamine compound described below in an excess amount of isocyanate. Alternatively, a method may be used in which a low molecular weight polyisocyanate and a polyol compound are reacted with an excess amount of isocyanate to obtain a prepolymer having an isocyanate group at the terminal. The prepolymers obtained by these methods may be used alone, or two or more types of prepolymers obtained by the same method, or two or more types of prepolymers obtained by the above two methods may be used in combination. Good. Furthermore, the prepolymer and the low molecular weight polyisocyanate may be used alone or in combination.

  The ratio of polyisocyanate used is equivalent ratio [NCO] / [NH2] of isocyanate group [NCO] and amino group [NH2} of polyamine, or equivalent ratio [NCO] / [OH] of hydroxyl group [OH] of polyol. Can be expressed as These ratios are usually preferably 5/1 to 1.01 / 1, more preferably 4/1 to 1.2 / 1, and 2.5 / 1 to 1.5 / 1. More preferably. When the molar ratio of [NCO] exceeds 5, urethane bonds and urea bonds increase too much, and when the finally obtained resin is used as a binder resin for toner, the elastic modulus in the molten state is too high and the fixability deteriorates. there's a possibility that. Further, when the [NCO] molar ratio is less than 1.01, the degree of polymerization increases and the molecular weight of the prepolymer to be produced increases, so that it is difficult to mix with other materials in the production of toner. Alternatively, the elastic modulus in the molten state is too high, and the fixability may be deteriorated.

  Examples of polyamines include diamines and trivalent or higher polyamines. Examples of the polyol include diols as described above, trivalent to octavalent or higher polyols (hereinafter also referred to as low molecular weight polyols), and polymers having hydroxyl groups at the terminals and side chains (hereinafter referred to as high molecular weights). (Described as molecular weight polyol) may be used. Moreover, as a preparation method of high molecular weight polyol, the method of making the polyurethane which has a hydroxyl group at the terminal by making low molecular weight polyisocyanate and low molecular weight polyol react with an excess amount of hydroxyl groups is mentioned. Moreover, the method of obtaining the polyester which has a hydroxyl group at the terminal by making polycarboxylic acid and a low molecular-weight polyol compound react with hydroxyl group excess amount may be sufficient.

  In order to adjust the polyurethane or polyester having a hydroxyl group at the terminal, the ratio [OH] / [NCO] of the low molecular weight polyol and the low molecular weight polyisocyanate, or the ratio [OH] / [COOH] of the low molecular weight polyol and the polycarboxylic acid. As follows. That is, it is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and still more preferably 1.3 / 1 to 1.02 / 1. When the molar ratio of the hydroxyl groups exceeds 2, the polymerization reaction does not proceed, and the desired high molecular weight polyol cannot be obtained. On the other hand, if it is less than 1.02, the degree of polymerization increases and the molecular weight of the resulting high molecular weight polyol becomes too large, making it difficult to mix with other materials in the production of toner, or having a high elastic modulus in the molten state. This is not preferable because fixing ability may be deteriorated. Examples of the polycarboxylic acid include the aforementioned dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids.

  In order for the resin to exhibit crystallinity, a polymer unit having crystallinity in the main chain may be introduced. Examples of the crystalline polymer unit having a melting point suitable as a binder resin for toner include a crystalline polyester unit and a long-chain alkyl ester unit of polyacrylic acid or polymethacrylic acid. As the crystalline polyester unit, a terminal alcohol can be easily prepared, and it is preferable because it can be easily introduced into a resin having a urea bond as a polyol compound.

  Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity. As the diol, the diols mentioned in the aforementioned polyols can be used. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

  The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between low-temperature fixability and heat-resistant storage stability is good, and the resin hardness tends to be improved.

  As dicarboxylic acid, the dicarboxylic acid mentioned in the above-mentioned polycarboxylic acid can be used. Of these, linear aliphatic dicarboxylic acids are more preferable. Of the dicarboxylic acids, it is particularly preferable to use an aliphatic dicarboxylic acid (preferably, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone. A copolymer of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) is also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

  By using a resin having a urea bond as the binder resin, and mixing with a toner constituent material other than the binder resin such as a colorant, a release agent, and a charge control agent, the toner can be obtained. Even if a urea bond is formed by mixing a polyisocyanate compound, a polyamine compound and / or water with a toner constituent material other than a binder resin such as a colorant, a release agent, and a charge control agent as necessary. Good. In particular, by using a prepolymer as the polyisocyanate compound, a crystalline resin having a high molecular weight urea bond can be uniformly introduced into the toner, so that the toner has uniform heat characteristics and chargeability and is fixable. And the toner are easy to achieve both stress resistance. Furthermore, as the prepolymer, a prepolymer obtained by reacting a low molecular weight polyisocyanate with a polyol compound in an excess amount of isocyanate is preferable because viscoelasticity is suppressed. As the polyol compound, a polyester having a hydroxyl group at the terminal by reacting a polycarboxylic acid with a low molecular weight polyol compound in an excessive amount of hydroxyl group is preferable because thermal characteristics suitable for the toner can be easily obtained. Furthermore, it is preferable that the polyester is composed of a crystalline polyester unit because the high molecular weight component in the toner becomes a sharp melt and a toner having excellent low-temperature fixability can be obtained. Further, when the toner is obtained by granulating in an aqueous medium, a urea bond can be formed under mild conditions by the water of the dispersion medium reacting with the polyisocyanate compound.

  The binder resin constituting the toner may be used alone or in combination of two or more. In addition, binder resins having different weight average molecular weights may be used in combination, and include at least a first crystalline resin and a second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin. It is preferable in that both excellent low-temperature fixability and hot offset resistance can be achieved. The second crystalline resin is obtained by extending a resin by using a binder resin precursor that is a modified crystalline resin having an isocyanate group and reacting with a compound having an active hydrogen group. It is preferable. In this case, the reaction between the binder resin precursor and the compound having an active hydrogen group is more preferably performed in the toner production process, and a crystalline resin having a large weight average molecular weight can be uniformly dispersed in the toner. Variations in characteristics between toner particles can be suppressed. The first crystalline resin is a crystalline resin having a urethane bond and / or a urea group bond in the main chain, and the second crystalline resin is a binder obtained by modifying the first crystalline resin. It is preferable that the resin precursor is reacted with a compound having an active hydrogen group and elongated. By bringing the composition structures of the first crystalline resin and the second crystalline resin close to each other, the two types of binder resins can be more easily dispersed in the toner, thereby further suppressing variation in characteristics between toner particles. Can do. Further, a crystalline resin and an amorphous resin may be used in combination, and the main component of the binder resin is preferably a crystalline resin.

  The tetrahydrofuran soluble content, molecular weight distribution, and weight average molecular weight (Mw) in the resin can be measured using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)). Is possible. As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) is used. The resin to be measured is made into a 0.15 mass% solution with tetrahydrofuran (THF) (containing stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 100 μl of the THF sample solution is injected into the measuring apparatus, and measurement is performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.

The molecular weight of the resin is calculated using a calibration curve created from a monodisperse polystyrene standard sample. As the standard polystyrene sample described above, ShowdexSTANDARD series manufactured by Showa Denko KK and toluene are used. Then, THF solutions of the following three types of monodisperse polystyrene standard samples are prepared and measured under the above conditions, and a calibration curve is created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
Solution A: S-7450: 2.5 mg, S-678: 2.5 mg, S-46.5: 2.5 mg, S-2.90: 2.5 mg, THF: 50 ml
Solution B: S-3730: 2.5 mg, S-257: 2.5 mg, S-19.8: 2.5 mg, S-0.580: 2.5 mg, THF: 50 ml
Solution C: S-1470: 2.5 mg, S-112: 2.5 mg, S-6.93: 2.5 mg, Toluene: 2.5 mg, THF: 50 ml

  An RI (refractive index) detector is used as the detector. The proportion of the component having a molecular weight of 100,000 or more and the proportion of the component having a molecular weight of 250,000 or more are the intersection of the curve with the molecular weight = 100,000 and the molecular weight = 250,000 in the integral molecular weight distribution curve. You can check from.

  The high molecular weight resin component must satisfy the condition that the resin structure is close to that of the entire binder resin, and if the binder resin has crystallinity, the high molecular weight component also needs to have crystallinity. is there. When the high molecular weight component is significantly different in structure from the other resin components, the polymer is easily phase-separated and becomes a sea-island state, so that it cannot be expected to contribute to improvement of viscoelasticity and cohesive force on the whole toner. The content ratio of the crystalline structure between the high molecular weight component and the entire binder resin is determined by the following ratio. That is, the endothermic amount (ΔH (H)) in the differential scanning calorimeter (DSC) of the insoluble matter in the mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing weight ratio = 50: 50) and the endothermic amount in the DSC of the toner. It is a ratio (ΔH (H) / ΔH (T)) of (ΔH (T)). This ratio is preferably in the range of 0.2 to 1.25, more preferably in the range of 0.3 to 1.0, and particularly preferably in the range of 0.4 to 0.8.

  The following method can be exemplified as a specific test method for obtaining an insoluble content in a mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by weight). That is, after adding 0.4 g of toner to 40 g of the above mixed solvent at normal temperature (20 ° C.) and mixing with shaking for 20 minutes, the insoluble components were settled by a centrifuge and the supernatant was removed in vacuum. It is a method obtained by making it.

  In the copying machine according to the embodiment, as the intermediate transfer belt 61 extends with time, the belt circumferential length increases with time, and the amount of misalignment of the toner images of the respective colors increases. For this reason, as the endless base material layer of the intermediate transfer belt 61, it is desirable to employ a material made of a high-strength material with little elongation over time. Further, since a high voltage such as a primary transfer bias or a secondary transfer bias is applied to the intermediate transfer belt 61, it is desirable that the intermediate transfer belt 61 is made of a material having excellent flame retardancy. In order to meet these requirements, the base layer of the intermediate transfer belt 61 is generally made of a polyimide resin or a polyamide-imide resin that is a high strength and high heat resistance resin.

  However, the base material layer made of polyimide resin or polyamideimide resin is high in strength and therefore has high surface hardness. For this reason, when a toner image is transferred to the surface, high pressure is applied to the toner layer to induce local aggregation of the toner, so that it is easy to generate a so-called hollow image in which a part of the image is not transferred. Further, since the contact followability with the photosensitive member or the recording sheet P is inferior, density unevenness due to uneven transfer pressure due to poor contact may occur. In particular, when a rough surface such as embossed paper, Japanese paper, or kraft paper is used as the recording sheet, the surface of the intermediate transfer belt 61 adheres well to the fine irregularities on the surface of the recording sheet at the secondary transfer nip. Can not do it. For this reason, it becomes easy to generate the shading unevenness and the color tone unevenness according to the sheet surface unevenness.

Next, experiments conducted by the present inventors will be described.
First, the inventors manufactured 13 types of toners from the first toner to the thirteenth toner. The manufacturing method will be described.

  First, urethane-modified crystalline polyester resin A-1 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reactor, 202 parts by weight (1.00 mol) sebacic acid, 15 parts by weight (0.10 mol) adipic acid, 177 parts by weight (1.50 mol) 1,6-hexanediol, 0.5 part by weight of tetrabutoxy titanate as a condensation catalyst was added. They were reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off generated water. Subsequently, it was made to react for 4 hours, distilling off produced | generated water and 1, 6- hexanediol in nitrogen stream, heating up gradually to 220 degreeC. Further, the reaction was performed under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 12,000 to obtain a crystalline polyester resin A′-1. The weight average molecular weight (Mw) of the obtained crystalline polyester resin A′-1 was 12,000.

  The obtained crystalline polyester resin A′-1 was transferred to a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube. Then, 350 parts by weight of ethyl acetate and 30 parts by weight (0.12 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added and reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin A-1. The resulting urethane-modified crystalline polyester resin A-1 had a weight average molecular weight (Mw) of 22,000 and a melting point of 62 ° C.

  Next, urethane-modified crystalline polyester resin A-2 was produced. A reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube was prepared. In the reactor, 202 parts by weight (1.00 mol) of sebacic acid, 189 parts by weight (1.60 mol) of 1,6-hexanediol, and 0.5 parts by weight of dibutyltin oxide as a condensation catalyst are placed. It was. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was performed under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 6,000 to obtain a crystalline polyester resin A′-2. The obtained crystalline polyester resin A′-2 had a weight average molecular weight (Mw) of 6,000. Next, the obtained crystalline polyester resin A′-2 was transferred into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. Then, 300 parts by weight of ethyl acetate and 38 parts by weight (0.15 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added and reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin A-2. The resulting urethane-modified crystalline polyester resin A-2 had a weight average molecular weight (Mw) of 10,000 and a melting point of 64 ° C.

  Next, urethane-modified crystalline polyester resin A-3 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reaction vessel, 185 parts by weight (0.91 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, and 106 parts by weight (1.18 mol) of 1,4-butanediol were added. I put it in. Further, 0.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst was added, and the reaction was performed at 180 ° C. for 8 hours while distilling off the generated water under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream. Further, the reaction was performed under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 14,000 to obtain a crystalline polyester resin A′-3. The obtained crystalline polyester resin A′-3 had a weight average molecular weight (Mw) of 14,000. The obtained crystalline polyester resin A′-3 was transferred to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube. And 250 weight part ethyl acetate and 12 weight part (0.07 mol) hexamethylene diisocyanate (HDI) were added, and it was made to react at 80 degreeC under nitrogen stream for 5 hours. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin A-3. The resulting urethane-modified crystalline polyester resin A-3 had a weight average molecular weight (Mw) of 39,000 and a melting point of 63 ° C.

  Next, crystalline polyester resin A-4 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reaction vessel, 185 parts by weight (0.91 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, and 125 parts by weight (1.39 mol) of 1,4-butanediol were added. I put it in. Further, 0.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst was added, and the reaction was performed at 180 ° C. for 8 hours while distilling off the generated water under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream. Further, the reaction was performed under reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 10,000 to obtain crystalline polyester resin A-4. The obtained crystalline polyester resin A-4 had a weight average molecular weight (Mw) of 9,500 and a melting point of 57 ° C.

  Next, crystalline polyester resin A-5 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reactor, 202 parts by weight (1.00 mol) of sebacic acid, 130 parts by weight (1.10 mol) of 1,6-hexanediol, 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst, Put. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Further, the reaction was carried out under reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 30,000 to obtain crystalline polyester resin A-5. The obtained crystalline polyester resin A-5 had a weight average molecular weight (Mw) of 27,000 and a melting point of 62 ° C.

  Next, a block resin A-6 composed of a crystalline part and an amorphous part was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reaction vessel, 25 parts by mass (0.33 mol) of 1,2-propylene glycol and 170 parts by weight of methyl ethyl ketone (MEK) were added and stirred. Thereafter, 147 parts by weight (0.59 mol) of 4,4′-diphenylmethane diisocyanate (MDI) was added and reacted at 80 ° C. for 5 hours to obtain a MEK solution of amorphous part c-1 having an isocyanate group at the terminal. It was. A reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube was used separately. In this reaction vessel, 202 parts by weight (1.00 mol) of sebacic acid, 160 parts by weight (1.35 mol) of 1,6-hexanediol, 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst, Put. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Further, the reaction was carried out under reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 9,000 to obtain crystalline polyester resin A′-6. The obtained crystalline polyester resin A′-6 had a weight average particle diameter (Mw) of 8,500 and a melting point of 63 ° C. Next, a solution prepared by dissolving 320 parts by weight of crystalline polyester resin A′-6 in 320 parts by weight of MEK as a crystalline part was added to 340 parts by weight of the MEK solution of the amorphous part c-1. The mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. And MEK was distilled off under pressure reduction and block resin A-6 was obtained. The obtained block resin A-6 had a weight average molecular weight (Mw) of 26,000 and a melting point of 62 ° C.

  Next, urethane-modified crystalline polyester resin B-1 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reactor, 113 parts by weight (0.56 mol) sebacic acid, 109 parts by weight (0.56 mol) dimethyl terephthalate, 132 parts by weight (1.12 mol) 1,6-hexanediol, Put. Further, 0.5 part by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst was added, and the reaction was carried out for 8 hours at 180 ° C. while distilling off generated water and methanol under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Further, the reaction was carried out under reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 35,000 to obtain crystalline polyester resin B′-1. The obtained crystalline polyester resin B′-1 had a weight average molecular weight (Mw) of 34,000. Next, the obtained crystalline polyester resin B′-1 was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube. And 200 weight part ethyl acetate and 10 weight part (0.06 mol) hexamethylene diisocyanate (HDI) were added, and it was made to react at 80 degreeC under nitrogen stream for 5 hours. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin B-1. The obtained urethane-modified crystalline polyester resin B-1 had a weight average molecular weight (Mw) of 63,000 and a melting point of 65 ° C.

  Next, crystalline polyester resin B-2 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reaction vessel, 230 parts by weight (1.00 mol) of dodecanedioic acid, 118 parts by weight (1.00 mol) of 1,6-hexanediol, and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst. And put. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Further, the reaction was performed under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 50,000 to obtain a crystalline polyester resin B-2. The obtained crystalline polyester resin B-2 had a weight average molecular weight (Mw) of 52,000 and a melting point of 66 ° C.

  Next, a crystalline resin precursor B′-3 was produced. Specifically, a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe was prepared. In this reaction vessel, 202 parts by weight (1.00 mol) of sebacic acid, 122 parts by weight (1.03 mol) of 1,6-hexanediol, 0.5 parts by weight of titanium dihydroxybis (condensation catalyst) Triethanolaminate was added, and the reaction was allowed to proceed for 8 hours while distilling off the generated water at 180 ° C. under a nitrogen stream, and then gradually increased to 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol, and the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight (Mw) reached about 25,000. The obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 300 parts by weight of ethyl acetate 300 and 27 parts by weight (0.16 mol) of helium. Samethylene diisocyanate (HDI) was added and allowed to react for 5 hours under a nitrogen stream at 80 ° C. Thus, a 50 wt% ethyl acetate solution of a crystalline resin precursor B′-3 having an isocyanate group at the terminal was obtained. 10 parts by weight of an ethyl acetate solution of the obtained crystalline resin precursor B′-3 was mixed with 10 parts by weight of tetrahydrofuran (THF), and 1 part by weight of dibutylamine was added thereto, As a result of GPC measurement using the obtained solution as a sample, the weight average molecular weight (Mw) of the crystalline resin precursor B′-3 was 54,000. As a result of performing DSC measurement on the sample obtained by removing, the melting point of the crystalline resin precursor B′-3 was 57 ° C.

The raw materials used for the production of the crystalline resin and the physical properties of the crystalline resin are collectively shown in Tables 1 to 3.

  Next, an amorphous resin C-1 was produced. Specifically, a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen insertion tube was prepared. In this reactor, 222 parts by weight of bisphenol A EO 2 mol adduct, 129 parts by weight of bisphenol A PO 2 mol adduct, 166 parts by weight of isophthalic acid, and 0.5 parts by weight of tetrabutoxy titanate were added. . And it was made to react for 8 hours, distilling off the water to produce | generate at 230 degreeC and a normal pressure under nitrogen stream. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value reached 2, it was cooled to 180 ° C., 35 parts by weight of trimellitic anhydride was added, and the reaction was carried out at normal pressure for 3 hours. Resin C-1 was obtained. The obtained amorphous resin C-1 had a weight average molecular weight (Mw) of 8,000 and a glass transition temperature (Tg) of 62 ° C.

  Next, an amorphous resin precursor C′-2 was produced. Specifically, a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen insertion tube was prepared. In this reaction vessel, 720 parts by weight of bisphenol A EO 2 mol adduct, 90 parts by weight of bisphenol A PO 2 mol adduct, 290 parts by weight of terephthalic acid, and 1 part by weight of tetrabutoxy titanate were placed. And it was made to react for 8 hours, distilling off the water to produce | generate at 230 degreeC and a normal pressure under nitrogen stream. Subsequently, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and amorphous resin was obtained. Then, the reaction tank provided with the cooling pipe, the stirrer, and the nitrogen insertion pipe was prepared. In this reaction vessel, 400 parts by weight of the amorphous resin, 95 parts by weight of isophorone diisocyanate, and 500 parts by weight of ethyl acetate were placed. And it was made to react at 80 degreeC under nitrogen stream for 8 hours, and the 50 weight% ethyl acetate solution of the amorphous resin precursor C'-2 which has an isocyanate group at the terminal was obtained.

  Next, a graft polymer was produced. Specifically, a reaction vessel in which a stirring bar and a thermometer were set was prepared. In this reaction vessel, 480 parts by weight of xylene and 100 parts by weight of low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128 ° C.) were sufficiently dissolved and replaced with nitrogen. It was. Thereafter, a mixed solution of 740 parts by weight of styrene, 100 parts by weight of acrylonitrile, 60 parts by weight of butyl acrylate, 36 parts by weight of di-t-butylperoxyhexahydroterephthalate, and 100 parts by weight of xylene. Prepared. This mixed solution was polymerized dropwise at 170 ° C. for 3 hours, and further maintained at this temperature for 30 minutes. Subsequently, the solvent was removed to synthesize a graft polymer. The obtained graft polymer had a weight average molecular weight (Mw) of 24,000 and a glass transition temperature (Tg) of 67 ° C.

  Next, a first release agent dispersion was prepared. Specifically, in a container set with a stirring bar and a thermometer, 50 parts by weight of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8), 30 parts by weight of graft polymer and 420 parts by weight of ethyl acetate were charged. And it heated up to 80 degreeC under stirring, and after hold | maintaining for 5 hours with 80 degreeC, it cooled to 30 degreeC by 1 hour. Then, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are filled with 80% by volume, and dispersion is performed under the condition of 3 passes. Thus, a first release agent dispersion was obtained.

Next, a master batch was manufactured. Specifically, 100 parts by weight of crystalline polyurethane resin A-1 and 100 parts by weight of carbon black (Printex 35, manufactured by Degussa) (DBP oil absorption: 42 mL / 100 g, pH: 9.5) are used as raw materials. 50 parts by weight of ion exchange water was prepared. These were mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. The kneading temperature started kneading from 90 ° C., and then gradually cooled to 50 ° C. The obtained kneaded material was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to produce a first masterbatch. According to the following Table 4, the 2nd, 3rd, 4th, 5th, 6th masterbatch was manufactured similarly to the 1st masterbatch, respectively.

Next, the 2nd oil phase, the 3rd oil phase, the 4th oil phase, and the 7th oil phase were manufactured. Specifically, in a container equipped with a thermometer and a stirrer, 54 parts by weight of urethane-modified crystalline polyester resin A-3 is added, and ethyl acetate is added in an amount such that the solid content concentration is 50% by weight. It was heated to above the melting point of and dissolved well. To this, 100 parts by weight of a 20% by weight ethyl acetate solution of the amorphous resin C-1, 60 parts by weight of the first release agent dispersion and 12 parts by weight of the second masterbatch were added. Then, the mixture was stirred at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 50 ° C., and uniformly dissolved and dispersed to obtain a second oil phase. The temperature of the second oil phase was kept at 50 ° C. in the container and was used within 5 hours from the preparation so as not to crystallize. For the third oil phase, the fourth oil phase, and the seventh oil phase, the kind and addition amount of the crystalline resin A, the kind and addition amount of the crystalline resin B, the addition amount of the amorphous resin C, and the master batch It produced similarly, only changing the kind according to following Table 5. In addition, about crystalline resin (B) in Table 5, and amorphous resin precursor C-2, when using either crystalline resin B-1 or crystalline resin B-2, oil phase preparation It was dissolved and dispersed with other toner materials in stages. Further, when using the binder resin precursor B′-3 or the non-crystalline resin precursor C-2, it is not added at the oil phase preparation stage, but is added to the oil phase and dissolved at the time of the toner base preparation described later. , Dispersed.

  Next, an aqueous dispersion of resin fine particles was produced. Specifically, a reaction vessel in which a stirring bar and a thermometer were set was prepared. In this reaction vessel, 600 parts by weight of water, 120 parts by weight of styrene, 100 parts by weight of methacrylic acid, 45 parts by weight of butyl acrylate and 10 parts by weight of alkylallylsulfosuccinate sodium salt (eleminol) JS-2, manufactured by Sanyo Chemical Industries). Furthermore, when 1 part by weight of ammonium persulfate was added and stirred at 400 rpm for 20 minutes, a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Furthermore, 30 parts by weight of a 1% aqueous solution of ammonium persulfate was added and aged at 75 ° C. for 6 hours to obtain an aqueous dispersion of resin fine particles. The volume average particle diameter of particles contained in the aqueous dispersion of the resin fine particles was 80 nm, the weight average molecular weight (Mw) of the resin was 160,000, and the glass transition temperature (Tg) was 74 ° C. .

  Next, the 1st water phase was manufactured. Specifically, 990 parts by weight of water, 83 parts by weight of an aqueous dispersion of resin fine particles, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries Ltd.) The first aqueous phase was obtained by mixing and stirring 90 parts by weight of ethyl acetate.

  Next, a second toner base, a third toner base, a sixth toner base, and a thirteenth toner base were manufactured. Specifically, a container in which a stirrer and a thermometer were set was prepared. In this container, 520 parts by weight of the first aqueous phase was placed and heated to 40 ° C. To 235 parts by weight of the second oil phase maintained at 50 ° C., 25 parts by weight of the ethyl acetate solution of the crystalline resin precursor B′-3 was added, and TK type homomixer (manufactured by Tokushu Kika Co., Ltd.) was used. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to prepare a second ′ oil phase. While stirring the first aqueous phase kept at 40 to 50 ° C. at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the second 'oil phase is added and emulsified for 1 minute. Thus, a second emulsified slurry was obtained. Next, the second emulsified slurry was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 6 hours to obtain a second slurry. The obtained second slurry was filtered under reduced pressure, and then the following washing treatment was performed. That is, 100 parts by weight of ion-exchanged water was added to the filter cake and mixed with a TK homomixer (filtered after 5 minutes at a rotation speed of 6,000 rpm (first step). The filter cake obtained in the first step was added to the filter cake. 100 parts by weight of 10% by weight aqueous sodium hydroxide solution was added, mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure (second step). 100 parts by weight of 10% by weight hydrochloric acid was added to the cake, mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered (third step). Part of ion-exchanged water was added, mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered twice to obtain a second filter cake (fourth step). The second filter cake was dried with a circulating dryer for 48 hours at 45 ° C. Thereafter, the second toner base was produced by sieving with a mesh opening of 75 μm, similarly, the third oil phase and the fourth oil phase. A third toner base, a sixth toner base, and a thirteenth toner base were manufactured using the seventh oil phase, respectively.

  Next, a fourth toner base was produced. Specifically, the fourth toner is the same as the third toner base except that the solvent removal conditions (60 ° C., 6 hours) when the third toner base is manufactured are changed to 70 ° C. and 3 hours. The mother body was manufactured.

  In addition, a fifth toner base was produced. Specifically, the fifth toner base was manufactured in the same manner as the third toner base except that the solvent removal conditions when the third toner base was manufactured were changed to 40 ° C. and 10 hours.

  A seventh toner base was also produced. Specifically, the seventh toner base is changed in the same manner as the sixth toner base except that the heating conditions (45 ° C., 48 hours) when the sixth toner base is manufactured are changed to 55 ° C., 24 hours. Manufactured.

  In addition, an eighth toner base was produced. Specifically, an eighth toner base was manufactured in the same manner as the sixth toner base except that the heating conditions when the sixth toner base was manufactured were changed to 35 ° C. and 96 hours.

  A ninth toner base was also produced. Specifically, the ninth oil base was the same as the sixth toner base except that 0.06 part by weight of a nucleating agent (ADEKA STAB NA-11, melting point 400 ° C., manufactured by ADEKA) was added to the fourth oil phase. A toner base was produced.

  A tenth toner base was also produced. Specifically, the tenth toner is the same as the sixth toner base except that 1.1 parts by weight of a nucleating agent (ADEKA STAB NA-11, ADEKA smelting point 400 ° C.) is added to the fourth oil phase. The mother body was manufactured.

Next, the 5th oil phase and the 6th oil phase were manufactured. Specifically, a container equipped with a thermometer and a stirrer was prepared. In this container, 54 parts by weight of urethane-modified crystalline polyester resin A-4 and 20 parts by weight of urethane-modified crystalline polyester resin B-2 were placed. Then, an amount of ethyl acetate in which the solid content concentration is 50% by weight was added and heated to the melting point of the resin or higher and dissolved well. To this, 40 parts by weight of an amorphous resin C-1 50% by weight ethyl acetate solution, 60 parts by weight of the first release agent dispersion, and 12 parts by weight of the third master batch were added. Then, the mixture was stirred at 50 ° C. with a TK homomixer (made by Tokushu Kika Co., Ltd.) at a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain a fifth oil phase. The temperature of the fifth oil phase was kept at 50 ° C. in the container and was used within 5 hours from the preparation so as not to crystallize. For the sixth oil phase, the types and addition amounts of the crystalline resin A, the types and addition amounts of the crystalline resin B, the addition amounts of the non-crystalline resin C, and the types of the master batch were changed according to Table 6. Manufactured in the same manner.

  Next, a second aqueous phase was produced. Specifically, 990 parts by weight of water, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), 90 parts by weight of ethyl acetate, Were mixed and stirred to obtain a second aqueous phase.

  Next, an eleventh toner base and a twelfth toner base were manufactured. Specifically, a container in which a stirrer and a thermometer were set was prepared. In this container, 520 parts by weight of the second aqueous phase was placed and heated to 40 ° C. And while maintaining at 40-50 degreeC, stirring at 13,000 rpm with TK type | system | group homomixer (made by Tokushu Kika Kogyo Co., Ltd.), a 5th oil phase is added and it emulsifies for 1 minute, and becomes 11th emulsification. A slurry was obtained. Next, the eleventh emulsified slurry was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 6 hours to obtain an eleventh slurry. The resulting eleventh slurry was filtered under reduced pressure and then subjected to the following washing treatment. That is, 100 parts by weight of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered (first step). To the filter cake obtained in the first step, 100 parts by weight of 10% by weight aqueous sodium hydroxide solution was added, mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure (second step) ). 100 parts by weight of 10 wt% hydrochloric acid was added to the filter cake obtained in the second step, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered (third step). The filter cake obtained in the third step was added with 300 parts by weight of ion exchange water, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered twice. I got a cake. The obtained eleventh filter cake was dried at 45 ° C. for 48 hours in a circulating air dryer. Thereafter, it was sieved with a mesh having an opening of 75 μm to produce an eleventh toner base. Similarly, a twelfth toner base was produced in the same manner except that the sixth oil phase was used.

  Next, a crystalline resin particle dispersion A-2 was produced. Specifically, 60 parts by weight of ethyl acetate was added to 60 parts by weight of the urethane-modified crystalline polyester resin A-2, and the mixture was stirred and dissolved at 50 ° C. to obtain a resin solution. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 2.4 parts by weight of 2% by weight An aqueous phase was obtained by mixing with an aqueous sodium hydroxide solution. To this aqueous phase, 120 parts by weight of the resin solution is added, emulsified using a homogenizer (IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to give an emulsified slurry. A-2 was obtained. Next, the emulsified slurry A-2 was charged into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 4 hours to obtain a crystalline resin particle dispersion A-2. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in obtained crystalline resin particle dispersion A-2 was measured with the particle size distribution analyzer (LA-920, product made from Horiba, Ltd.).

  Next, a crystalline resin particle dispersion B-1 was produced. Specifically, 60 parts by weight of ethyl acetate was added to 60 parts by weight of urethane-modified crystalline polyester resin B-1, mixed and stirred at 50 ° C. to obtain a resin solution. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 2.4 parts by weight of 2% by weight An aqueous phase was obtained by mixing with an aqueous sodium hydroxide solution. To this aqueous phase, 120 parts by weight of the resin solution is added, emulsified using a homogenizer (IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to give an emulsified slurry. B-1 was obtained. Subsequently, the emulsified slurry B-1 was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 4 hours to obtain a crystalline resin particle dispersion B-1. It was 0.16 micrometer when the volume average particle diameter of the particle | grains in obtained crystalline resin particle dispersion B-1 was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make).

  Next, an amorphous resin particle dispersion C-1 was produced. 60 parts by weight of ethyl acetate was added to 60 parts by weight of the amorphous resin C-1, mixed, stirred and dissolved to obtain a resin solution. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 2.4 parts by weight of 2% by weight An aqueous phase was obtained by mixing with an aqueous sodium hydroxide solution. To this aqueous phase, 120 parts by weight of the resin solution is added, emulsified using a homogenizer (IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to give an emulsified slurry. C-1 was obtained. Next, the emulsified slurry C-1 was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 4 hours to obtain an amorphous resin particle dispersion C-1. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained amorphous resin particle dispersion C-1 was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make).

  Next, the 2nd mold release agent dispersion liquid was manufactured. Specifically, 25 parts by weight of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, melting point: 75 ° C.), 5 parts by weight of an anionic surfactant (manufactured by Sanyo Chemical Industries: Eleminol MON-7), 200 Part by weight of water was mixed and melted at 95 ° C. Next, the melt was emulsified with a homogenizer (IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to obtain a second release agent dispersion.

  Next, a colorant dispersion was prepared. Specifically, 20 parts by weight of carbon black (Printex 35, manufactured by Degussa), 2 parts by weight of an anionic surfactant (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 80 parts by weight of water. Mixed. And it disperse | distributed with TK type | system | group homomixer (made by Special Machine Co., Ltd.), and obtained the coloring agent dispersion liquid.

  Next, a first toner base was manufactured. Specifically, 190 parts by weight of crystalline resin particle dispersion A-2, 63 parts by weight of crystalline resin particle dispersion B-1, and 63 parts by weight of amorphous resin particle dispersion C-1 46 parts by weight of the second release agent dispersion, 17 parts by weight of the colorant dispersion, and 600 parts by weight of water were mixed. The pH was adjusted to 10 with a 2% by weight aqueous sodium hydroxide solution. Next, 50 parts by weight of a 10% by weight magnesium chloride aqueous solution was gradually added dropwise to the solution under stirring while heating to 60 ° C. The first slurry was obtained by maintaining the temperature at 60 ° C. until the volume average particle diameter of the aggregated particles grew to 5.3 μm. The obtained first slurry was filtered under reduced pressure, and then the same washing treatment as the eleventh toner (first step to fourth step) was performed to obtain a first filter cake. The obtained 1st filter cake was dried at 45 degreeC with the circulating air dryer for 48 hours. Thereafter, the mixture was sieved with an opening of 75 μm mesh to obtain a first toner base.

  Next, first to thirteenth toners were manufactured. Specifically, 100 parts by weight of the first toner base and 2.0 parts by weight of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) as an external additive were combined with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). ), And mixed for 30 seconds at a peripheral speed of 30 m / second and rested for 1 minute. After 5 cycles of the same mixing and resting, the first toner was manufactured by sieving with a mesh having an opening of 35 μm. The second to thirteenth toners were produced in the same manner except that the toner base to be used was changed to the second to thirteenth.

Next, the inventors produced an eighth oil phase, a ninth oil phase, and a tenth oil phase. Specifically, 31.5 parts by weight of urethane-modified crystalline polyester resin A-1 was placed in a container equipped with a thermometer and a stirrer. Then, an amount of ethyl acetate in which the solid content concentration is 50% by weight was added and heated to the melting point of the resin or higher and dissolved well. To this, 100 parts by weight of a 50% by weight ethyl acetate solution of amorphous resin C-1, 60 parts by weight of the first release agent dispersion, and 12 parts by weight of the first master batch were added. Then, the mixture was stirred at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) under the condition of 50 ° C., and uniformly dissolved and dispersed to obtain an eighth oil phase. The temperature of the eighth oil phase was kept at 50 ° C. in the container and was used within 5 hours from the preparation so as not to crystallize. For the ninth oil phase and the tenth oil phase, the types and addition amounts of the crystalline resin A, the types and addition amounts of the crystalline resin B, the addition amounts of the amorphous resin C, and the types of the master batch are as follows. It produced similarly, only changing according to Table 7. The binder resin precursor B′-3 in Table 9 was not added in the oil phase preparation stage, but was added to the oil phase and dissolved and dispersed during the toner base preparation described later.

  Next, an 11th oil phase, a 12th oil phase, a 13th oil phase, a 14th oil phase, a 15th oil phase, and a 16th oil phase were produced. Specifically, first, 1 part by weight of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) was added to the eighth oil phase described above to obtain an eleventh oil phase (11). Moreover, 2 parts by weight of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) was added to the eighth oil phase to obtain a twelfth oil phase. Further, 1 part by weight of 1 part by weight of a synthetic smectite compound (Lucentite SPN, manufactured by Co-op Chemical Co.) was added to the ninth oil phase to obtain a 13th oil phase. Also, 2 parts by weight of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) was added to the ninth oil phase to obtain a fourteenth oil phase. Further, 1 part by weight of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) was added to the 10th oil phase to obtain a 15th oil phase. In addition, 2 parts by weight of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) was added to the 10th oil phase to obtain a 16th oil phase.

  Next, the 17th oil phase was manufactured. Specifically, 100 parts by weight of 50 wt% ethyl acetate solution of amorphous resin C-1 and 60 parts by weight of the first release agent dispersion were mixed. The mixed liquid was stirred at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) under the condition of 50 ° C., and uniformly dissolved and dispersed to obtain a 17th oil phase.

Next, 14th toner base to 23rd toner base were manufactured. Specifically, 520 parts by weight of the first aqueous phase was placed in a container equipped with a stirrer and a thermometer and heated to 40 ° C to 50 ° C. Further, only 25 parts by weight of the ethyl acetate solution of the crystalline resin precursor B′-3 was added to 235 parts by weight of the eighth oil phase maintained at 50 ° C. This was stirred with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain an 8 'oil phase. While stirring the first aqueous phase kept at 40 to 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 13,000 rpm, the 8 ′ oil phase was added and 1 minute was added. An eighth emulsified slurry was obtained by emulsification. Next, the eighth emulsified slurry 8 was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 60 ° C. for 6 hours to obtain an eighth slurry. The obtained eighth slurry was filtered under reduced pressure, and then the following washing treatment was performed.
(1) 100 parts by weight of ion-exchanged water (100 parts by weight) was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts by weight of 10% by weight sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3) 100 parts by weight of 10% by weight hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (5 minutes at 6,000 rpm), and then filtered.
(4) 300 parts by weight of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered twice to obtain an eighth filter cake. Got. The obtained 8th filter cake was dried at 45 degreeC with the circulating air dryer for 48 hours. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain a fourteenth toner base.
The 15th toner base to the 23rd toner base were obtained in the same manner except that the oil phase used was changed. The ninth, tenth, eleventh, twelfth, thirteenth, fourteenth, fifteenth, fifteenth, seventeenth and seventeenth oil phases are used individually for the fifteenth, sixteenth, seventeenth, eighteenth, nineteenth, twenty-first, twenty-first, twenty-second and twenty-third toner. It has been.

  Next, 14th to 23rd toners were produced. Specifically, 100 parts by weight of the 14th toner base and 1.0 part by weight of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) as an external additive were combined with a Henschel mixer (Mitsui Mining Co., Ltd.). Mixed). The mixing condition is 5 cycles of a process of stopping for 1 minute after mixing for 30 seconds at a peripheral speed of 30 m / second. After mixing, the mixture was sieved with a mesh having a mesh size of 35 μm to obtain a 14th toner. Similarly, the fifteenth, sixteenth, seventeenth, eighteenth, nineteenth, twenty-first, twenty-second, twenty-third, and twenty-third toner base material are used in the same manner, except that the fifteenth, sixteenth, seventeenth, eighteenth, nineteenth, twenty-first, twenty-first, twenty-second, and twenty-two. 23 toners were obtained.

  Next, the toner volume specific resistance value was measured for each of the first toner to the 23rd toner. Specifically, 3.0 g of toner serving as a sample was weighed into a container having a cylindrical electrode having a diameter of φ18 mm having a guard electrode, and pressure-shaped while applying a load of 6000 MPa to prepare a pellet. Further, the volume resistivity at a frequency of 1 KHz was obtained using an AC bridge type resistance measuring device (TR-10C type manufactured by Ando Electric Co., Ltd.) using the electrodes.

  Next, the degree of hydrophobicity of methanol was measured for each of the first to 23rd toners. Specifically, a powder wettability tester (WET-100P, manufactured by Reska Corporation) was prepared. A 100 ml beaker was charged with a predetermined amount of pure water (ion exchange water or commercially available purified water) and methanol, and the cap was covered and uniformly dispersed using an ultrasonic disperser. In a uniformly dispersed aqueous methanol solution, 0.5 g of toner was precisely weighed and added, and stirred while rotating the stirrer at 250 rpm. Further, methanol was added at 1.3 ml / min. As the toner begins to settle and disperse in the aqueous solution, the permeability of the solution decreases. The ratio (%) of total methanol / (total methanol + water) at the start of the decrease in the transmittance was defined as the toner hydrophobicity.

Table 8 shows properties of the first to thirteenth toners. The properties of the 14th to 23rd toners are shown in Table 9 below.

  Next, a printer tester having the same configuration as the printer unit 1 of the copying machine according to the embodiment was prepared. In this printer tester, the lubricant powder is applied to the photoreceptor 3 (Y, M, C, K) by the lubricant application device shown in FIG. 3, and the secondary transfer is opposed by the lubricant application means shown in FIG. Lubricant powder is applied to the roller 72. Further, the lubricant powder is applied to the intermediate transfer belt 61 by a lubricant application device provided in the belt cleaning device (75). The configuration of this lubricant application device is substantially the same as that shown in FIG. In addition, by applying the lubricant powder to the secondary transfer counter roller 72, it is possible to prevent the cleaning blade that cleans the surface of the secondary transfer counter roller 72 from turning up.

  The printer tester was equipped with an intermediate transfer belt 61 made of polyimide. The intermediate transfer belt 61 is manufactured as follows. That is, carbon black is dispersed in a polyamic acid solution, and the dispersion is poured into a metal drum and dried. Thereafter, the film peeled off from the metal drum was stretched at a high temperature to form a polyimide film, cut into an appropriate size, and an endless intermediate transfer belt 61 made of polyimide resin was manufactured. The film molding was performed as follows. That is, according to a general method, a polymer solution in which carbon black was dispersed was poured into a cylindrical mold, and the film was formed into a film by centrifugal molding while rotating the cylindrical mold while heating at 100 to 200 ° C. The film thus obtained was demolded in a semi-cured state and covered with an iron core, and the polyimide transfer reaction was allowed to proceed at 300 to 450 ° C. to be cured to obtain an intermediate transfer belt 61. At this time, the resistance of the belt can be adjusted by changing the carbon amount, the firing temperature, the curing speed, and the like. The intermediate transfer belt 61 thus produced had a Young's modulus of 3000 MPa. The Young's modulus (tensile elasticity) was measured according to JIS K7127. The surface friction coefficient was 0.45. For the measurement of the surface friction coefficient, HEIDON TRIBOGEAR μs 94i manufactured by Shinto Kagaku was used. The surface friction coefficient is measured after the intermediate transfer belt 61 is set in the printer tester and the steady operation is performed for one hour or more. Therefore, the surface friction coefficient is a value in a state where the lubricant powder adheres to the surface. It is.

  For the photoreceptors 3Y, 3M, 3C, and 3K, the surface friction coefficient is made as small as possible, and the surface made of a material having a small surface friction coefficient in order to satisfy the condition of surface friction coefficient A> surface friction coefficient B described later. The layer may be coated. Materials used for the surface layer of the photoreceptor include styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, olefin-vinyl monomer copolymer, chlorinated polyether, aryl , Phenol, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethyne, polyethylene terephthalate, polyimide, acrylic, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polyurethane , Resins such as polyvinyl chloride, polyvinylidene chloride, and epoxy.

  A lubricant such as fluorine resin particles, polyolefin resin particles, and silicone resin particles may be added to these resins for the purpose of reducing the friction coefficient. Specific examples of the fluororesin particles include polymers such as tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride and perfluoroalkyl vinyl ether, and copolymers thereof. Can be mentioned. Specific examples of polyolefin resin particles include homopolymers of olefins such as ethylene, propylene, and butene, copolymers with different olefins, or particles of heat-modified products thereof. Specifically, polyethylene, polypropylene , Polybutene, polyhexene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-hexene copolymer, and the like. As specific examples of the silicone resin particles, siloxane bonds are three-dimensionally bonded, have a network structure, and silicon atoms are substituted with alkyl groups, aryl groups, amino-substituted alkyl groups, dialkyl silicones, and the like in organic solvents. Insoluble.

  The surface friction coefficient of a photoreceptor provided with such a surface layer is generally about 0.1 to 0.3. The surface friction coefficient of the intermediate transfer belt 61 varies depending on the roughness of the surface, but is generally about 0.35 to 0.7 from the material.

Next, experiments conducted by the present inventors will be described.
The present inventors set a Japanese paper type recording sheet (manufactured by Ricoh Co., Ltd., continuous weight 175 kg resack paper, A4 size) in a printer testing machine. Then, the first to thirteenth toners were sequentially set on the printer testing machine, and a full-tone halftone image (first sheet) was output to the recording sheet with each toner. For the entire halftone image obtained, the presence or absence of density unevenness following unevenness on the surface of the sheet was visually confirmed. ○ = no density unevenness, Δ = density unevenness within acceptable range, x = exceeding acceptable range The evaluation was made in three stages: density unevenness. A patch image was output on a recording sheet made of plain paper. A patch image having an image area ratio of 1 [cm ² ] × 1 [cm ² ] and a toner adhesion amount of 0.85 [mg / cm ² ] is used in the sheet passing width direction. Five of them were arranged at equal intervals. The amount of toner on the intermediate transfer belt 61 immediately after primary transfer of each obtained patch image is measured, and the primary transfer rate (the amount of toner after primary transfer / the amount of toner before primary transfer) is determined based on the measurement result. Calculated.

  This experiment was performed under the condition that a coil spring having a relatively large spring constant is mounted as a coil spring in a lubricant application device that applies lubricant powder to the intermediate transfer belt 61. When the surface friction coefficient (after applying the lubricant) of the intermediate transfer belt 61 and the surface friction coefficient (after applying the lubricant) of the photoreceptor were measured, the former surface friction coefficient was 0.03 larger. Next, density unevenness was evaluated by performing a similar experiment under the condition that a coil spring having a relatively small spring constant was mounted in a lubricant application device for applying lubricant powder to the intermediate transfer belt 61. When the surface friction coefficient (after applying the lubricant) of the intermediate transfer belt 61 and the surface friction coefficient (after applying the lubricant) of the photosensitive member were measured, they were the same value. The laboratory was set in a high temperature and high humidity environment (temperature 28 ° C., relative humidity 80%).

In addition, a printer test machine in which the fixing unit of a digital full-color copying machine (Imagio MP C4500 manufactured by Ricoh Co., Ltd.) was modified was prepared and a print test was performed. In this print test, type 6200 paper manufactured by Ricoh Co., Ltd. was used as the recording sheet. As printing conditions, the linear speed of paper feed = 200 to 220 [mm / sec], the surface pressure at the fixing nip = 1.0 [kgf / cm ² ], the length of the fixing nip in the paper feeding direction (nip width) = 10 0.0 [mm] was adopted. While changing the fixing temperature, a test image was output under each fixing temperature condition, and the occurrence of cold offset and hot offset in the fixing device was confirmed. Then, a cold offset temperature (fixing lower limit temperature) that does not cause a cold offset and a hot offset temperature (fixing upper limit temperature) that does not cause a hot offset were obtained.

  More specifically, regarding the lower limit fixing temperature, the recording paper carrying the test image was passed through the fixing device under the conditions of the respective fixing temperatures while changing the fixing temperature (fixing member temperature) in increments of 2 ° C. Then, in the recording paper after passing the paper, the presence or absence of occurrence of cold offset was confirmed, and the lowest temperature at which cold offset did not occur was defined as the minimum fixing temperature. Then, the fixing lower limit temperature was ranked in three stages. The ranking is 100 ° C. (above) to 115 ° C. (less than) ○, 115 ° C. (above) to 130 ° C. (below) Δ, and 130 ° C. or more x. Such ranking of the minimum fixing temperature was performed for each of 13 types of toners.

  Regarding the upper limit fixing temperature, the recording paper carrying the test image was passed through the fixing device under the conditions of the respective fixing temperatures while changing the fixing temperature in increments of 2 ° C. Then, on the recording paper after passing the paper, the presence or absence of occurrence of hot offset was confirmed, and the maximum temperature at which hot offset did not occur was defined as the upper limit fixing temperature. Then, the fixing upper limit temperature was ranked in three stages. The ranks are 190 ° C or higher for ◯, 180 ° C (over) to 190 ° C (less than) Δ, and less than 180 ° C for x. Such a fixing upper limit temperature ranking was performed for each of the 13 types of toner.

The results of this experiment are shown in Tables 10 and 11 below.

  As shown in Tables 10 and 11, an experiment under the condition that the surface friction coefficient A of the belt is equal to the surface friction coefficient B of the photosensitive member (hereinafter referred to as “an experiment with the same friction coefficient”), or A> B. In an experiment under conditions (hereinafter referred to as “experiment with reduced photoreceptor friction”), the results were as follows. That is, only when the first toner, the second toner, the eleventh toner, the thirteenth toner, the fourteenth toner to the twenty-third toner are used, the density unevenness evaluation result (evaluation of the output image on the uneven paper) becomes x. It was. As a test, the temperature conditions in the laboratory were changed from a high temperature and high humidity environment to a normal temperature and normal humidity environment, and the same “experiment with the same friction coefficient” and “experiment with reduced photoconductor friction” were performed. As a result, the primary transfer rate was improved for all 23 types of toner. In the experiment using the first toner, the second toner, and the 14th to 22nd toners, the evaluation result of the density unevenness was improved to Δ. However, in the experiment using the eleventh toner, the thirteenth toner, and the twenty-third toner, the evaluation result of the density unevenness remained “x”. From this, among the experimental results shown in Tables 10 and 11, the following can be considered in the results of “experiment with the same friction coefficient” and “experiment with reduced photoconductor friction”. That is, in the experiment using the first toner, the second toner, and the 14th toner to the 22nd toner, the evaluation result of the density unevenness is x, respectively, because the primary transfer rate of the entire image is low. This is considered to be the cause. In addition, the evaluation results of density unevenness when the eleventh toner, the thirteenth toner, and the twenty-third toner are used are x, respectively. This is probably due to the low transfer rate.

  As shown in Tables 8 and 9, the 11th toner and the 23rd toner are those in which neither the urethane bond nor the urea bond is provided in the crystalline resin. Further, as shown in Table 8, the 13th toner has a urethane bond in the crystalline resin, but the solution of “C / (C + A)” is a very small value of 0.01. That is, the ratio of the crystalline resin in the entire binder resin is reduced. Among the other toners, the solution having the smallest solution after the 13th toner is 0.15 of the 7th toner, the 14th toner, and the 17th toner. As a result, it was found that by using the following toner, it is possible to form an image that suppresses uneven density unevenness even when a recording sheet rich in surface irregularities is used. That is, as the crystalline resin, a resin having either a urethane bond or a urea bond is used, and the crystalline resin in the entire binder resin is adjusted so that the solution of “C / (C + A)” is 0.15 or more. The toner uses a binder resin having a high ratio as a base resin. As a trial, the present inventors made various toners and conducted experiments in addition to the 23 types of toners described so far. Then, if the toner has a urethane resin or a urea bond in the crystalline resin and the binder resin that makes the solution of “C / (C + A)” 0.15 or more, the toner is a base material resin. Concentration unevenness that was similar to that was suppressed. In addition, a toner having a solution of “C / (C + A)” of 0.15 or more has an advantage that the crystalline portion is uniformly and finely dispersed within the toner without deteriorating the fixing property and the surface is not unevenly distributed. Furthermore, by containing at least one of a urethane bond and a urea bond having high hardness, it is possible to achieve both appropriate deformability and elasticity even if a crystalline part and an amorphous part are mixed. It will be possible.

  However, even such a toner causes the following phenomenon if the surface friction coefficient A of the belt is not larger than the surface friction coefficient B of the photoreceptor. That is, in a high temperature and high humidity environment, the primary transfer rate is greatly reduced, resulting in insufficient density of the entire image and uneven density on the sheet surface due to insufficient density of the entire image.

  The detailed mechanism in the case of using a toner having a binder resin that has a urethane bond or a urea bond in the crystalline resin and the solution of “C / (C + A)” is 0.15 or more is not known. is there. However, it can be speculated that the following mechanism works. In other words, the toner mainly composed of crystalline polyester has improved contact followability with a contact member at a transfer portion such as a photoconductor or paper because of the deformation characteristics inherent to the crystalline polymer material. It is presumed that a decrease in the transfer rate of the concave portion on the sheet surface due to the change in the thickness hardly appears.

  When a toner having a urethane resin or urea bond in a crystalline resin and a binder resin whose base material resin makes the solution of “C / (C + A)” 0.15 or more is used, the primary transfer rate The phenomenon of decreasing is not previously assumed. As a result of further experiments by the present inventors, a toner in which the crystalline polyester resin is contained in an amount of 50% by mass or more with respect to the total binder resin, the primary transfer rate is significantly reduced in a high temperature and high humidity environment. I found out that The reason is considered that the crystalline polyester contained in a large amount is not sufficiently crystallized for some reason, and there is a portion where the volume specific resistance is locally low in the crystalline polyester portion in the toner. In addition, there is a possibility that such a portion is exposed on the toner surface as a hydrophilic surface, and water is adsorbed and charges are discharged under high temperature and high humidity conditions. The reduction in the primary transfer rate of a toner containing a large amount of crystalline polyester cannot be sufficiently suppressed only by more reliably crystallizing the crystalline polyester. In addition, if the content of the crystalline polyester is reduced so that there is no side effect of the crystalline polyester on the toner surface after performing the crystallization more reliably, the degree of hydrophobicity and volume resistivity of the toner can be strictly controlled. If adjusted, it may be possible to suppress to a certain extent. However, such a strict adjustment is considered to have side effects such as deterioration of other toner characteristics, particularly deterioration of low-temperature fixability.

  Next, the inventors measured the average circularity of each of the 14th to 23rd toners. Specifically, a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation) was used as a measuring device. Then, analysis was performed using analysis software (FPIA-2100 Data Processing Program for FPIAversion 00-10). More specifically, 0.1 to 0.5 ml of 10% by mass surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a 100 ml glass beaker. Next, 0.1 to 0.5 g of the sample toner was added and stirred with a microspatel, and then 80 ml of ion exchange water was added to obtain a dispersion. This dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The dispersion after treatment is adjusted to a toner density of 5,000 to 15,000 / μl. This is because, from the viewpoint of measurement reproducibility of the average circularity, it is desirable to set the toner concentration of the dispersion to 5,000 to 15,000 / μl. As for the amount of the surfactant, the required amount varies depending on the hydrophobicity of the toner, as in the measurement of the toner particle diameter described above. When excessively added, noise due to bubbles is generated, and when the added amount is insufficient, the toner cannot be sufficiently wetted, resulting in insufficient dispersion. Further, the amount of toner added varies depending on the particle size, and it is necessary to reduce the amount when the particle size is small, while increasing the amount when the particle size is large. When the toner particle diameter is 3 μm to 10 μm, the toner concentration of the dispersion is adjusted to 5,000 / μl to 15,000 / μl by adding 0.1 g to 0.5 g of toner. It is possible. The dispersion liquid whose toner concentration was adjusted in this way was set in a flow type particle image analyzer, and the average circularity was analyzed using analysis software. In addition, when measuring the shape and particle size distribution of the toner particles, the concentration of the toner dispersion is appropriately adjusted. In the adjustment, it is necessary to change the conditions according to the target toner concentration, such as the amount of surfactant to be added and the amount of toner.

Next, the inventors measured the bulk volume ratio of the toner. Specifically, the bulk volume ratio of each of the 14th to 23rd toners was measured as follows. First, only 10 g of toner is put into a closed graduated cylinder (made of glass, standard product with a capacity of 50 mL), plugged, and then shaken up and down 10 times to contain air between the toner particles. Next, let it stand as soon as it finishes swinging, and measure the standing time. After standing, the volume after 5 minutes, 20 minutes, and 24 hours was read on the cylinder scale, and the respective results were shown as bulk volume V1 [ml] after 5 minutes, bulk volume V2 [ml] after 20 minutes, After 24 hours, the bulk volume was set to V3 [ml]. And the solution of V2 / V1 was made into the 1st bulk volume ratio. The solution of V3 / V1 was defined as the second bulk volume ratio. The solution of 10 [g] / V3 was determined as the bulk density of the toner for 24 hours after standing. The results are shown in Table 12 below.

  As a result of intensive studies, the present inventors have found that it is preferable that the toner of the present invention is a toner that does not cause excessive self-compression and that is compressed at an appropriate speed after replenishment. . Specifically, the conditions of “V3 / V1. ≧ 0.71, V2 / V1. ≧ 0.79” are satisfied, and the bulk density at 24 hours after the toner is left is 0.44 to 0.51 g / Preferably it is ml. These powder characteristics have the effect of making it difficult for toner aggregation to occur when the toner is agitated by the screw member in the developing device or when the toner starts to be agitated after being left for a long period of time. it is conceivable that. As means for obtaining such powder characteristics, it is considered that the shape, surface property, particle size, external additive adhesion amount and the like of the toner base particles contribute. In particular, in order to make powder characteristics favorable without hindering low-temperature fixability, it is possible to use a toner material having a urethane bond and / or a urea bond, or to blend a high molecular weight body. It is thought that it is excellent in controlling. Therefore, using a urethane bond and / or urea bond as a toner material, or blending a high molecular weight substance, suppresses burying of an external additive by improving toner hardness, suppresses an increase in toner contact area by deformation, and adherence. It is thought that it has brought about suppression.

  Next, a characteristic configuration of the copier according to the embodiment will be described. In the copying machine according to the embodiment, the toner contains a crystalline resin having at least one of a urethane bond and a urea bond in the main chain, and the solution of “C / (C + A)” is obtained. What makes it 0.15 or more is used. Then, a lubricant is applied to the photoconductor and the intermediate transfer belt 61 so that the surface friction coefficient B of the photoconductor is lower than the surface friction coefficient A of the intermediate transfer belt 61. With such a configuration, it is possible to stably suppress the occurrence of shading unevenness and color tone unevenness due to transfer pressure unevenness over a long period of time. Further, it is possible to suppress a decrease in the primary transfer rate of the toner image in a high-temperature and high-humidity environment without strictly adjusting the degree of hydrophobicity and volume resistivity of the toner.

  In addition, the surface friction coefficient A and the surface friction coefficient B in Table 8 are both numerical values under the condition where the lubricant powder is applied. In the case where the lubricant is not applied to the photoconductor and the intermediate transfer belt, the surface friction coefficient A of the intermediate transfer belt 61 may be made larger than the surface friction coefficient B of the photoconductor for those solid surfaces.

  As the intermediate transfer belt 61, a belt having a Young's modulus of 3000 [MPa] or more is used. In the copying machine according to the embodiment, the intermediate transfer belt 61 includes only a base material layer. However, in addition to the base material layer, when other layers such as a surface layer are provided, What is necessary is just to make Young's modulus 3000 or more MPa about a base material layer.

  As the base material layer of the intermediate transfer belt, one made of polyimide or polyimide amide is employed.

  The following toner is used. That is, the ratio of the resin measured to have a molecular weight of 100,000 or more by gel diffusion chromatography measurement of tetrahydrofuran-soluble content is 7% or more in the total resin, and the weight average molecular weight is 20000 or more and 70000 or less. Toner.

  In addition, the following toner is used. That is, the toner has a volume resistivity value LogR of 9.5 to 10.5 [Log (Ω · cm)] in an environment with a temperature of 28 [° C.] and a relative humidity of 80 [%].

  As the toner, toner having a hydrophobicity of 35 to 50% is used.

  In addition, the following toner is used. That is, the maximum peak temperature of the heat of fusion at the second temperature increase by a differential scanning calorimeter (DSC) is in the range of 50 [° C.] to 70 [° C.], and the heat of fusion at the second temperature increase is 30 [ J / g] and 75 [J / g] or less.

  As the toner, the endothermic measurement result ΔH (H) [J / g] of the endothermic amount with a differential scanning calorimeter (DSC) of the insoluble matter in the mixed solvent of tetrahydrofuran and ethyl acetate, and the endothermic measurement result with DSC. ΔH (T) [J / g] is used as follows. That is, the toner makes “ΔH (H) / ΔH (T)” in the range of 0.5 to 1.25.

  In addition, the following toner is used. That is, the toner includes a first crystalline resin and a second crystalline resin having a weight average molecular weight larger than that of the first crystalline resin as the crystalline resin.

  Further, as the toner, a toner in which the second crystalline resin is obtained by extending a modified crystalline resin having an isocyanate group at the terminal is used.

What has been described above is merely an example, and the present invention has a specific effect for each of the following modes.
[Aspect A]
An image carrier (e.g., photoreceptor 3) that carries a toner image, and intermediate transfer means (e.g., primary transfer roller) that intermediately transfers the toner image on the image carrier onto the surface of an intermediate transfer member (e.g., intermediate transfer belt 61). 62Y, M, C, K), wherein the toner contains a crystalline resin having at least one of a urethane bond and a urea bond in the main chain, and , C is the integrated intensity of the spectrum derived from the crystalline structure of the crystalline resin in the X-ray diffraction spectrum of the toner, and A is the integrated intensity of the spectrum derived from the amorphous structure of the amorphous resin in the X-ray diffraction spectrum. In each case, the solution of “C / (C + A)” is 0.15 or more, and the surface friction coefficient of the image carrier is lower than the surface friction coefficient of the intermediate transfer member. And it is characterized in and.

[Aspect B]
Aspect B is Aspect A, wherein the Young's modulus of the base material of the intermediate transfer member is 3000 [MPa] or more.

[Aspect C]
Aspect C is Aspect A or Aspect B, wherein the substrate of the intermediate transfer member is made of polyimide or polyimide amide.

[Aspect D]
Aspect D is any one of Aspects A to C, and the ratio of the resin measured as having a molecular weight of 100,000 or more by gel diffusion chromatography measurement of the tetrahydrofuran-soluble content of the toner is 7 [% In addition, the weight average molecular weight of the toner is 20000 or more and 70000 or less.

[Aspect E]
In the aspect E, in any one of the aspects A to D, the volume specific resistance value LogR of the toner in an environment of a temperature of 28 [° C.] and a relative humidity of 80 [%] is 9.5 to 10.5 [Log (Ω · cm)].

[Aspect F]
Aspect F is any one of Aspects A to E, characterized in that the degree of hydrophobicity of the toner is 35 to 50 [%].

[Aspect G]
In the aspect G, in any of the aspects A to F, the maximum peak temperature of the second heat of fusion by the differential scanning calorimeter (DSC) of the toner is in the range of 50 [° C.] to 70 [° C.]. And the heat of fusion at the second temperature rise is in the range of 30 [J / g] to 75 [J / g].

[Aspect H]
Aspect H is any one of Aspects A to G, and the endothermic endothermic measurement result ΔH (H) of the insoluble content of the toner in the mixed solvent of tetrahydrofuran and ethyl acetate with a differential scanning calorimeter (DSC) [ J / g] is divided by the endothermic measurement result ΔH (T) [J / g] of the toner with a differential scanning calorimeter (DSC) (ΔH (H) / ΔH (T)). It is 0.5 to 1.25.

[Aspect I]
Aspect I is any one of Aspects A to H, wherein the toner includes a first crystalline resin as the crystalline resin and a second weight average molecular weight higher than that of the first crystalline resin. A crystalline resin is included.

[Aspect J]
Aspect J is Aspect I, characterized in that the second crystalline resin is obtained by extending a modified crystalline resin having an isocyanate group at the terminal.

3Y, M, C, K: photoconductor (image carrier)
61: Intermediate transfer belt (intermediate transfer member)
62Y, M, C, K: primary transfer roller (intermediate transfer means)

JP 2009-134108 A

Claims (12)

An image forming apparatus comprising: an image carrier; and an intermediate transfer unit that intermediate-transfers a toner image on the image carrier to the surface of the intermediate transfer member,
The toner contains a crystalline resin having at least one of a urethane bond and a urea bond in the main chain;
The integrated intensity of the spectrum derived from the crystalline structure of the crystalline resin in the X-ray diffraction spectrum of the toner is C, and the integrated intensity of the spectrum derived from the amorphous structure of the amorphous resin in the X-ray diffraction spectrum is A. When expressed, the solution of “C / (C + A)” is 0.15 or more,
The image forming apparatus is characterized in that the surface friction coefficient of the image carrier is lower than the surface friction coefficient of the intermediate transfer member. The image forming apparatus according to claim 1,
An image forming apparatus, wherein the intermediate transfer member has a Young's modulus of 3000 [MPa] or more. The image forming apparatus according to claim 1, wherein:
An image forming apparatus, wherein the base material of the intermediate transfer member is made of polyimide or polyimide amide. The image forming apparatus according to any one of claims 1 to 3,
The ratio of the resin, which is determined to have a molecular weight of 100,000 or more by gel diffusion chromatography measurement of the tetrahydrofuran-soluble content of the toner, is 7% or more of the total resin, and the weight average molecular weight of the toner is 20000. The image forming apparatus is characterized by being 70000 or less. The image forming apparatus according to any one of claims 1 to 4,
The image forming apparatus, wherein the toner has a volume specific resistance LogR of 9.5 to 10.5 [Log (Ω · cm)] in an environment of a temperature of 28 [° C.] and a relative humidity of 80 [%]. . The image forming apparatus according to claim 1,
An image forming apparatus, wherein the toner has a hydrophobicity of 35 to 50%. The image forming apparatus according to claim 1,
The maximum peak temperature of the second heat of melting by the differential scanning calorimeter (DSC) of the toner is in the range of 50 [° C.] to 70 [° C.] and the heat of fusion of the second temperature increase is 30. An image forming apparatus having a range of [J / g] to 75 [J / g]. The image forming apparatus according to claim 1,
The result of endothermic measurement ΔH (H) [J / g] of the endothermic amount of the toner insoluble in the mixed solvent of tetrahydrofuran and ethyl acetate with the differential scanning calorimeter (DSC) of the toner. The endothermic measurement result ΔH (T) [J / g] (ΔH (H) / ΔH (T)) divided by 0.5) is 0.5 to 1.25. Forming equipment. The image forming apparatus according to any one of claims 1 to 8,
The image forming apparatus, wherein the toner includes, as the crystalline resin, a first crystalline resin and a second crystalline resin having a weight average molecular weight larger than that of the first crystalline resin. . The image forming apparatus according to claim 9, wherein
An image forming apparatus, wherein the second crystalline resin is obtained by extending a modified crystalline resin having an isocyanate group at a terminal. The image forming apparatus according to claim 1,
The image forming apparatus according to claim 1, wherein the toner has a condition that a first bulk volume ratio (V2 / V1) is 0.79 or more. The image forming apparatus according to claim 11, comprising:
The toner has a second bulk volume ratio (V3 / V1) of 0.71 or more, and a bulk density after standing for 24 hours of toner is 0.44 to 0.51 [g / ml]. An image forming apparatus characterized by satisfying conditions.

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