JP6075682B2 - Image forming apparatus - Google Patents

Description

  The present invention relates to an image forming apparatus including a conveying unit that conveys toner discharged from a toner storage unit toward an image forming unit.

  Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, or the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.

  In a heat fixing type image forming apparatus, since a large amount of electric power is required in the process of heat melting and fixing a toner on a recording medium such as paper, the toner has low temperature fixability from the viewpoint of energy saving. It is one of the important characteristics. In order to improve the low-temperature fixability of the toner, it is necessary to control the thermal characteristics of the binder resin that occupies most of the toner. For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-077419), low-temperature fixability and heat resistance are determined by defining the composition and thermal characteristics of a crystalline resin in a toner having a crystalline resin as a main component of a binder resin. It has been proposed that both storability can be achieved. Further, in Patent Document 2 (Japanese Patent Laid-Open No. 2009-014926), a toner containing two types of crystalline resins having different molecular weights as a binder resin (especially that a crystalline polyester resin is preferred) is used under specific fixing conditions. It has been proposed that the use can improve low-temperature fixability and suppress cracks in a fixed image. In Patent Document 3 (Japanese Patent Laid-Open No. 2010-151996), two types of crystalline polyester resins having different storage elastic moduli at 160 ° C. are contained as a binder resin, so that both low-temperature fixability and pressure storage stability are achieved. It has been proposed to be possible.

  In recent years, along with demands for miniaturization and personalization of image forming apparatuses using electrophotographic technology such as copying machines and printers, development apparatuses used for these have been miniaturized. Further, in accordance with such a request, there is known a disposable type developing device in which the developing device is replaced when the toner runs out. In addition to such a developing device, a latent image carrier (photosensitive member) on which an electrostatic latent image of a document image is formed, and a cleaning unit for removing toner remaining on the photosensitive member are integrated. In general, so-called process cartridges are also widely used.

  However, in such a miniaturized developing device, the developer containing the toner and the magnetic carrier is small and the developer agitating section is inevitably saved. Furthermore, with the recent demand for higher image quality, the toner is becoming smaller in particle size, and it is becoming more difficult to uniformly distribute and charge the supplied toner to the developer. The reason why it becomes difficult to charge the replenished toner is as follows. If the replenished toner is not well dispersed in the developer, the replenished toner slides on the surface of the developer contained in the developing device. Then, the replenishing toner that has slipped on the surface of the developer cannot be sufficiently stirred in the developer stirring section, and moves on the surface of the developer without being charged.

  When the toner in such a state is conveyed to the developing roller and conveyed to the developing area, image defects such as background contamination, density unevenness, and toner scattering occur. Such a phenomenon becomes prominent when the amount of toner replenishment increases, particularly when a document having a high image area ratio is continuously printed.

  Various proposals have been made as means for supplying toner to the developing device in order to solve the problems caused by insufficient stirring of the supply toner as described above. For example, Patent Document 4 (Japanese Patent Laid-Open No. 2005-266511) does not use a method of dropping toner from the two-component developer transport path and replenishing toner, but toner that transports only toner different from the developer transport path. A toner replenishment method is used on the conveyance path (toner storage unit), and in Patent Document 5 (Japanese Patent Application Laid-Open No. 2011-164530), a method of dividing the screw into a toner storage unit and a development storage unit is used.

  Further, as an image forming apparatus provided with another toner replenishing means, for example, the one described in Patent Document 6 is known. In this image forming apparatus, a toner containing a crystalline polyester in a binder resin is used as a toner for forming an image. Further, a transport pump is used as transport means for transporting toner for replenishment. The toner containing the crystalline polyester in the binder resin has an advantage that it can be fixed at a low temperature with a relatively low heating temperature in the fixing device, but has a disadvantage that it easily causes aggregation.

  In particular, in a configuration in which toner is transported using a transport pump composed of a Mono pump as in the image forming apparatus described in Patent Document 6, aggregation of toner containing crystalline polyester is likely to occur. The MONO pump includes a pump unit including an eccentric screw-shaped rotor and a stator that houses the rotor. A suction tube for sucking and conveying toner is connected to the suction port of the pump unit. Further, a discharge pipe for discharging and conveying toner is connected to the discharge port of the pump unit. The MONO pump generates a suction force on the suction side of the pump unit by rotating the rotor in close contact with the inner wall of the stator. With this suction force, the toner in the suction pipe is sucked into the pump section, and the toner in the pump section is discharged to the discharge pipe, thereby conveying the toner toward the image forming means at the tip of the discharge pipe. In such a configuration, toner aggregation is promoted by sandwiching the toner between the contact portions of the rotor and the stator.

  When toner containing aggregates is conveyed to the image forming means, an abnormal image may be caused. Therefore, in the image forming apparatus described in Patent Document 6, toner in which porous particles having a particle diameter of 1 mm or less are mixed with toner powder at a ratio of 10 to 15 [volume%] is used. According to Patent Document 6, by using such toner, it is possible to suppress the occurrence of toner aggregation due to the conveyance of the toner with a Mono pump.

  However, it has been found that a toner replenishing device having a toner container for storing toner and a conveying screw for conveying the toner received from the toner container to the developing device has the following new problems. . That is, when a toner containing a crystalline resin as a main component of a binder resin is accommodated in a toner container, it is excellent in low-temperature fixability, but external additives on the surface of the toner are buried during toner conveyance. As a result, it has been found that the toner is aggregated or fixed to prevent stable toner supply. The toner containing a crystalline resin as the main component of the binder resin is considered to be because the external additive is easily embedded in the toner particles because it easily aggregates and has a soft surface.

  Further, in an image forming apparatus that transports toner by a mono pump, the image forming means uses only toner powder out of toner powder and porous particles contained in the toner, so that the toner in the image forming means. The porous particle concentration gradually increases. This necessitates a particle separation means for separating the porous particles from the toner and reducing the porous particle concentration of the toner to a normal value, resulting in an increase in cost.

  According to the experiments by the present inventors, toner does not contact the contact portion between the rotor and the stator, and the toner contacts the rotor and the stator that have generated heat due to the rubbing in the conveying pump including the Mono pump. In some cases, the temperature was increased to cause aggregation. In addition, it was found that if the toner sandwiched between the contact portion between the rotor and the stator adheres to the surface of the rotor or the stator, the surface of the rotor or the stator is promoted to wear, and the suction capacity of the transport pump is reduced at an early stage. .

  The present invention has been made in view of the above background, and an object of the present invention is to provide toner by a conveying means without mixing porous particles with toner containing a crystalline resin as a main component of a binder resin. An object of the present invention is to provide an image forming apparatus capable of suppressing the occurrence of toner fixation and aggregation due to conveyance.

  As a result of intensive studies in view of the above-mentioned object, the present inventors have increased the cohesive force derived from these bonds by introducing urethane bonds and / or urea bonds into the crystalline resins, and It has been found that the hardness can be improved.

Therefore, in order to achieve the above object, the invention of claim 1 includes: an image forming unit that forms a toner image using toner; a toner storage unit that stores toner to be supplied to the image forming unit; An image forming apparatus including a transport unit configured to transport the toner discharged from the toner storage unit toward the image forming unit, wherein the toner has at least one of a urethane bond and a urea bond as a main chain. are those containing a crystalline resin comprising, the integrated intensity of a spectrum derived from the crystal structure of the binder resin in the X-ray diffraction spectrum before Symbol toner C, non-crystalline structure of the binder resin in the X-ray diffraction spectrum from to when the integrated intensity of spectrum expressed respectively by a, Ri der solutions 0.15 or more "C / (C + a)", and, among all components of the toner, Tetorahido Those carbon element, the proportion of the weight of elemental nitrogen to the sum of the weight of the hydrogen element and a nitrogen element, wherein 0.3 to 2.0 [wt%] Der Rukoto during dissolvable ingredients furan .

  In the present invention, by forming an image using such a toner, the toner having the crystalline resin as the main component of the binder resin is conveyed, as has been clarified by the experiments described later by the present inventors. It is possible to suppress the occurrence of toner sticking and aggregation.

1 is a schematic configuration diagram illustrating a printer according to an embodiment. FIG. 3 is an enlarged configuration diagram illustrating an image forming apparatus for Y of the printer together with an intermediate transfer belt. FIG. 3 is a configuration diagram illustrating a Y toner supply device of the printer together with a Y developing device and a Y toner cartridge. 1 is a schematic configuration diagram showing a fixing device used in an experiment conducted by the present inventors. The figure which shows a 13C-NMR spectrum. 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. FIG. 6 is a plan sectional view illustrating a first developer accommodating portion and a second developer accommodating portion of a developing device for Y in the printer according to the embodiment. FIG. 4 is a side view showing a toner replenishing device Y for Y for supplying toner to a developer charging chamber of the developing device together with a toner cartridge and the developing device. FIG. 3 is a cross-sectional view showing a toner supply device for Y.

Hereinafter, an embodiment of a printer that forms an image by an electrophotographic method will be described as an image forming apparatus to which the present invention is applied.
First, a basic configuration of the printer according to the embodiment will be described. FIG. 1 is a schematic configuration diagram illustrating a printer according to an embodiment. In the figure, the printer includes image forming devices 6Y, 6M, 7C, and 6K for forming yellow (Y), magenta (M), cyan (C), and black (K) toner images. In the following, the subscripts Y, M, C, and K attached to the end of the reference numerals in the drawings mean that the members or devices for Y, M, C, and K are used.

  Further, the printer according to the embodiment includes an intermediate transfer unit 15, a fixing device 20, a paper feed cassette 26 for feeding a recording sheet accommodated therein to a paper feed path in the main body housing 100, and a container mounting unit. 31 etc. are also provided.

  A container mounting portion 31 is disposed on the upper portion of the main body casing 100. To this container mounting portion 31, toner cartridges 32Y, 32M, 32C, and 32K for Y, M, C, and K that store Y, M, C, and K toners are mounted. The toner cartridges 32Y, 32M, 32C, and 32K for Y, M, C, and K can be easily attached to and detached from the container mounting portion 31.

  An intermediate transfer unit 15 is disposed below the container mounting portion 31. The intermediate transfer unit 15 stretches an endless intermediate transfer belt 8 by a plurality of rollers disposed inside the belt loop. The stretching posture is a horizontally long posture that takes a space in the horizontal direction rather than the vertical direction. Of the entire region of the intermediate transfer belt 8 in the circumferential direction, the region in which the belt front surface is directed in the vertical direction extends substantially in the horizontal direction. Below the area, image forming apparatuses 6Y, 6M, 6C, and 6K for Y, M, C, and K are arranged in the horizontal direction.

  FIG. 2 is an enlarged configuration diagram showing the Y image forming device 6 </ b> Y together with the intermediate transfer belt 8. In the figure, an image forming device 6Y for Y has a drum-shaped photoconductor 1Y as a latent image carrier. Further, it also includes a charging device 4Y, a developing device 5Y, a drum cleaning device 2Y, a static eliminator (not shown), and the like disposed around the photoreceptor 1Y. In this image forming apparatus 6Y, an image forming process including a charging process, an optical writing process, a developing process, a primary transfer process, a cleaning process, and the like is performed, and a Y toner image is formed on the surface of the photoreceptor 1. The

  In FIG. 1, the photoreceptor 1Y is rotationally driven in the clockwise direction in the drawing by a drive motor (not shown). The surface of the rotating photoreceptor 1Y is uniformly charged by a charging process at a position facing the charging device 4Y, and then moves to the optical writing position. At the optical writing position, the optical writing device 7 that scans the laser writing light by a known technique irradiates the laser writing light and attenuates the potential of the exposure portion. Thereby, an electrostatic latent image for Y is written on the surface of the photoreceptor 1Y (optical writing process).

  The optical writing device 7 deflects the traveling direction of the laser writing light composed of the laser light emitted from the light source in the sub-scanning direction by a polygon mirror that is a rotary polygon mirror that is driven to rotate, so that the surface of the photoreceptor 1Y is deflected. Optical scanning is performed in the main scanning direction. In place of the optical writing device 7 having such a laser writing system, an optical writing means having an LED array may be used.

  The surface of the photoreceptor 1Y on which the electrostatic latent image for Y is written moves to a position facing the developing device 5Y for Y. In the developing area where the Y developing device 5Y and the photoreceptor 1Y face each other, the electrostatic latent image on the photoreceptor 1Y is developed into a Y toner image by a well-known developing technique.

  In FIG. 2, the developing device 5Y for Y includes a developing roller 51Y that faces the photoreceptor 1Y, a doctor blade 52Y that faces the developing roller 51Y, a first developer container 53Y, a second developer container 54Y, and toner. It has a density sensor 56Y and the like. A transport screw 55Y for transporting the Y developer G in the rotation axis direction is disposed in each of the first developer storage portion 53Y and the second developer storage portion 54Y.

  The developing roller 51Y includes a magnet roll fixed inside, a hollow developing sleeve that encloses the magnet roller, and the like. The Y developer in the first developer accommodating portion 53Y is carried on the surface of the developing sleeve by the magnetic force generated by the magnet roll. The Y developer contains Y toner and a magnetic carrier.

  The second developer accommodating portion 54Y communicates with the toner transport pipe 43Y through an opening formed thereabove. A Y transport pump, which will be described later, is connected to the toner transport pipe 43Y. By driving the transport pump, Y toner is supplied into the second developer accommodating portion 54Y. The driving of the transport pump is controlled based on the detection result of the toner density by the toner density detection sensor 56Y. Specifically, the toner replenishment control unit 90 controls the driving of the replenishment motor 65Y of the transport pump so as to maintain the density signal sent from the toner density detection sensor 56Y within a predetermined range. As a result, a necessary amount of Y toner is replenished in the second developer accommodating portion 54Y at an appropriate timing, and the Y toner concentration of the Y developer in the developing device 5Y is maintained within a predetermined range. Similar toner density control is performed for the developing devices (M, C, and K) for M, C, and K.

  The Y toner replenished in the second developer accommodating portion 54Y is taken into the Y developer G in the second developer accommodating portion 54Y. The Y developer G is agitated in the second developer accommodating portion 54Y as the transport screw 55Y in the second developer accommodating portion 54Y is driven to rotate, and is perpendicular to the drawing sheet along the screw axis direction. It is conveyed from the near side to the far side. When the second developer accommodating portion 54Y moves to the end on the far side in the drawing, the second developer accommodating portion 54Y enters the first developer accommodating portion 53Y through a communication port (not shown).

  The Y developer G that has entered the first developer accommodating portion 53Y is agitated in the first developer accommodating portion 53Y as the transport screw 55Y in the first developer accommodating portion 53Y is rotationally driven. Along the axial direction, the sheet is conveyed from the back side to the front side in the direction orthogonal to the drawing. Then, when it moves to the end of the first developer accommodating portion 53Y on the near side in the figure, it enters the second developer accommodating portion 54Y through a communication port (not shown).

  In this way, the Y developer G is circulated and conveyed between the second developer accommodating portion 54Y and the first developer accommodating portion 53Y. At this time, the Y toner is rubbed against the magnetic carrier and frictionally charged, thereby adsorbing on the surface of the magnetic carrier. In the first developer accommodating portion 53Y, the Y developer G is carried on the surface of the developing sleeve of the developing roller 51Y by the magnetic force generated by the magnet roller of the developing roller 51Y.

  The Y developer G carried on the surface of the developing sleeve of the developing roller 51Y passes through a position facing the doctor blade 52Y as the developing sleeve rotates. At this time, the layer thickness of the Y developer layer on the surface of the developing sleeve is regulated to a predetermined thickness. The regulated Y developer G enters a developing region where the developing sleeve and the photoreceptor 1Y face each other.

  In the developing region, a developing electric field is formed between the developing sleeve to which the developing bias is applied and the electrostatic latent image on the photoreceptor 1Y. The Y developer G on the developing sleeve separates the Y toner from the magnetic carrier by the action of the developing electric field and transfers it to the electrostatic latent image on the photoreceptor 1Y. As a result, the electrostatic latent image on the photoreceptor 1Y is developed into a Y toner image.

  When the Y developer that has passed through the developing region with the rotation of the developing sleeve moves to a position facing the first developer accommodating portion 53Y, the Y developer is affected by the repulsive magnetic field generated by the repulsive magnetic pole provided in the magnet roller of the developing roller 51Y. Detach from the surface of the developing sleeve. Then, the weight returns to the conveying screw 55Y of the first developer accommodating portion 53Y by its own weight.

  The Y toner image on the photoreceptor 1Y enters the Y primary transfer nip where the photoreceptor 1Y and the intermediate transfer belt 8 are in contact with the rotation of the photoreceptor 1Y. Then, in the primary transfer nip for Y, primary transfer is performed from the surface of the photoreceptor 1Y to the surface of the intermediate transfer belt 8 (primary transfer process).

  When the surface of the photoreceptor 1Y that has passed through the primary transfer nip for Y moves to a position facing the drum cleaning device 2Y, residual toner is scraped off and cleaned by the cleaning blade 2a (cleaning process). Then, after being neutralized by a static eliminator (not shown), it is uniformly charged again by the charging device 4Y (charging process).

  Although the image forming process in the Y image forming device 6Y has been described, the same image forming process is performed in the M, C, and K image forming devices 6M, 6C, and 6K in FIG. As a result, Y, M, C, and K toner images are formed on the surfaces of the Y, M, C, and K photoconductors 1Y, 1M, 1C, and 1K.

  In FIG. 1, an intermediate transfer unit 15 includes an endless intermediate transfer belt 8 that includes four primary transfer bias rollers 9Y, 9M, 9C, and 9K disposed on the inner side of the belt loop, a secondary transfer backup roller 12, and a cleaning device. It is stretched by a backup roller 13 and a tension roller 14. Then, the intermediate transfer belt 8 is moved endlessly in the counterclockwise direction in the figure by the rotational drive of the secondary transfer backup roller 12.

  The primary transfer bias rollers 9Y, 9M, 9C, and 9K sandwich the intermediate transfer belt 8 between the photoreceptors 1Y, 1M, 1C, and 1K to form primary transfer nips for Y, M, C, and K. ing. To the primary transfer bias rollers 9Y, 9M, 9C, and 9K, a primary transfer bias having a polarity opposite to the charging polarity of the toner is applied. When the intermediate transfer belt 8 passes through the primary transfer nip for Y, M, C, and K along with endless movement, the Y, M, C, and K toner images are superimposed on the front surface of the intermediate transfer belt 8. In addition, primary transfer is performed. As a result, a four-color superimposed toner image is formed on the front surface of the intermediate transfer belt 8.

  A secondary transfer roller 19 is disposed on the right side of the intermediate transfer unit 15 in the drawing. The secondary transfer roller 19 is in contact with a portion of the intermediate transfer belt 19 that is wound around the secondary transfer backup roller 12 in the circumferential direction to form a secondary transfer nip. Around the secondary transfer nip, toner is transferred from the secondary transfer backup roller 12 side to the secondary transfer backup roller 12 to which the secondary transfer bias is applied and the secondary transfer roller 19 that is grounded. A secondary transfer electric field for electrostatic movement is formed on the side of the next transfer roller 19.

  A paper feed cassette 26 is disposed in the lower part of the housing body 100. The paper feed cassette 26 feeds the recording sheet P accommodated therein to the paper feed path by the rotational drive of the paper feed roller 27. The recording sheet P sent into the paper feed path passes through the transport nips of a plurality of transport roller pairs arranged in the paper feed path, and is then sandwiched between the resist nips of the resist roller pair 28 and temporarily stops. The registration roller pair 28 starts to rotate at a timing at which the recording sheet P can be superimposed on the four-color superimposed toner image on the intermediate transfer belt 8 at the secondary transfer nip. As a result, the recording sheet P is fed into the secondary transfer nip.

  In the secondary transfer nip, the four-color superimposed toner image on the intermediate transfer belt 8 is secondarily transferred onto the surface of the recording sheet P by the action of the nip pressure and the secondary transfer electric field. The recording sheet P that has passed through the secondary transfer nip is sent to the fixing device 20 disposed above the secondary transfer nip. The fixing device 20 forms a fixing nip by contact between a fixing roller containing a heat source such as a halogen lamp and a pressure roller pressed toward the fixing roller. In the fixing device 20, the recording sheet P sandwiched between the fixing nips is heated and pressed to fix the four-color superimposed toner image on the sheet surface.

  The recording sheet P that has passed through the fixing device 20 passes through the paper discharge nip of the paper discharge roller pair 29 and is then stacked on the stack unit 30 provided on the upper surface of the main body casing 100.

  On the surface of the intermediate transfer belt 8 immediately after passing through the secondary transfer nip, untransferred toner that has not been secondarily transferred to the recording sheet P adheres. This transfer residual toner is removed from the belt surface by the belt cleaning device 10. The belt cleaning device 10 includes a cleaning blade and a cleaning brush roller that come into contact with a portion where the intermediate transfer belt 8 is wound around the cleaning backup roller 13 in the circumferential direction. The transfer residual toner is mechanically scraped off from the belt surface by the blade and the brush roller.

  FIG. 3 is a configuration diagram showing the Y toner replenishing device together with the Y developing device 5Y and the Y toner cartridge 32Y. In the figure, in order to facilitate understanding, the arrangement postures of various devices are shown differently from the actual arrangement postures. For example, in the same figure, the toner cartridge 32Y is in a posture in which its axial direction is shifted by 90 [°] from the axial direction of the conveying screw 55Y of the developing device 5Y, but actually, it follows the axial direction of the conveying screw 55Y. The posture is The same applies to the transfer pump 38Y.

  When the toner cartridge 32Y is set in the container mounting portion (31) of the main body housing (100), one end portion (tip portion) of the toner transport tube 70Y of the container mounting portion 31 is inserted into the holding portion 34Y of the toner cartridge 32Y. . At this time, the plug member 34dY of the toner cartridge 32Y opens the toner discharge port of the holding portion 34Y. As a result, the Y toner accommodated in the container main body 33Y of the toner cartridge 32Y is discharged into the toner conveying tube 70Y through the toner discharge port.

  A flexible transport tube 71Y is connected to the rear end of the toner transport tube 70Y. The transport tube 71Y is formed of a flexible rubber material having low toner affinity. The rear end portion of the transport tube 71Y whose front end portion is connected to the toner transport tube 70Y is connected to the suction port in the pump unit 60Y of the transport pump 38Y for sucking and transporting the toner. The conveyance pump 38Y is a uniaxial eccentric screw pump called “Mono pump”, and includes an eccentric screw-like rotor 61Y, a stator 62Y for accommodating the rotor, a suction port portion 63Y, a universal joint 64Y, a replenishment motor 66Y, and the like. Yes.

  The rotor 61Y has a shape in which a shaft made of a resin or a metal material is spirally twisted. One end of the rotor 61Y is rotatably connected to the replenishment motor 66Y via the universal joint 64Y. The stator 62Y is made of a rubber material, and its hole portion is formed such that an oval cross section is twisted in a spiral shape. The rotor 61Y is inserted into the hole of the stator 62Y.

  The transport pump 38Y configured in this manner rotates the rotor 61Y in the stator 62Y in a predetermined direction by driving the replenishing motor 66Y, thereby transferring the Y toner in the toner cartridge 32Y to the transport tube 71Y and the toner transport tube. Suction through 70Y. The Y toner moved to the rear end of the transport tube 71Y by this suction enters the pump section 60Y through the suction port section 63Y of the transport pump 38Y. And it moves in the internal space in the stator 62Y of the pump part 60Y, and is discharged from the discharge hole 67Y of the pump part 60Y. Thereafter, the Y toner is replenished into the second developer accommodating portion 54Y of the developing device 5Y through the toner transport pipe 43Y.

Next, the binder resin that is the main component of the toner particles constituting the Y, M, C, and K toner powder will be described.
The types of binder resins are roughly classified into crystalline resins and amorphous resins (non-crystalline resins). Of these, it is desirable to use at least a crystalline resin. The crystalline resin is a resin having a portion having a crystal structure, and has a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The crystalline resin has a ratio (softening temperature / maximum peak temperature of the heat of fusion) of the softening temperature measured by the Koka flow tester and the maximum peak temperature of the heat of fusion measured by the differential scanning calorimeter (DSC). It becomes 0.8-1.6, and shows the property of softening with heat.

  As the binder resin, an amorphous resin may be used. In this case, the binder resin is used in combination with the crystalline resin. An amorphous resin 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 ratio of the softening temperature to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is greater than 1.6, indicating that it softens gently with heat.

  The softening temperature of the resin can be measured using a Koka flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). Specifically, while heating 1 g of resin as a sample at a heating rate of 3 ° C./min, a load of 2.94 MPa was applied by a plunger, extruded from a nozzle having a diameter of 0.5 mm and a length of 1 mm, and a flow with respect to temperature. The plunger drop amount of the tester is plotted, 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, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C. as a pretreatment, and then the temperature is lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./min. The temperature is lowered from 10 to 10 ° C. at a rate of 0.5 ° C./min. Next, by DSC, the temperature was increased at a rate of temperature increase of 10 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” was drawn. The endothermic peak temperature at is “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 endothermic peak is defined as the maximum heat of fusion peak temperature.

  As a toner binder resin, among crystalline resins, a resin having a crystalline polyester unit that is easy to control the melting point of the toner and has excellent binding properties to paper is the main component of the toner binder resin. It is preferable. The higher the content of the crystalline polyester unit in the binder resin, the better the properties of the toner can be at low temperature fixability.

  The resin having a crystalline polyester unit includes a resin composed only of a crystalline polyester unit (also simply referred to as a crystalline polyester resin), a resin in which a crystalline polyester unit is linked, and a crystalline polyester unit and another polymer bonded together. Resin (so-called block polymer, graft polymer) and the like. Although the resin composed only of the crystalline polyester unit includes many portions having a crystal structure, it has a drawback of being easily deformed by an external force. One of the reasons 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). is there. In addition, even in a portion having a crystal structure, a large bonding force does not act between the lamellar layers having the lamellar structure, so that the lamellar layer is easily displaced. It is. A lamellar structure is a structure in which planes formed by folding molecular chains of higher-order crystal structures are stacked.

  If the binder resin for toner is easily deformed by an external force, it may cause problems such as deformation and aggregation in the image forming apparatus, adhesion or sticking to a member, and scratches on the final output image. Comes out. For this reason, the binder resin must have toughness that is not easily deformed by an external force. From the viewpoint of such toughness, the binder resin may be a resin in which a crystalline polyester unit having a urethane binding site, a urea binding site, a phenylene site or the like having a large cohesive energy, or a crystalline polyester unit and another polymer. A resin in which is bonded (so-called block polymer, graft polymer) or the like is preferable. Among them, a resin having a urethane bond site or a urea bond site in the molecular chain is particularly preferable. Such a resin is considered to be able to form a pseudo-crosslinking point due to a large intermolecular force between an amorphous part and a lamellar layer, and can be easily wetted even after fixing on paper and can increase the fixing strength. Because.

  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 for synthesizing the polycondensed polyester unit include diols, trivalent to octavalent or higher polyols, and the like. The type of diol is not particularly limited and can be appropriately selected according to the purpose. For example, an aliphatic diol such as a linear aliphatic diol or a branched aliphatic diol; an alkylene ether glycol having 4 to 36 carbon atoms; an alicyclic diol having 4 to 36 carbon atoms; Alkylene oxide of formula diol (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; diol having carboxyl group, diol having sulfonic acid group or sulfamic acid group, and salts thereof Examples thereof include diols having other functional groups. 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 above-mentioned 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 the low-temperature fixability and the heat-resistant storage stability is good, and the resin hardness tends to be improved.

  There is no restriction | limiting in particular in the kind of linear aliphatic diol mentioned above, 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 etc. can be illustrated. Among these, from the viewpoint of availability, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are included. preferable.

  Moreover, the kind of the branched aliphatic diol having 2 to 36 chain carbon atoms described above is not particularly limited and can be appropriately selected depending on the 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 exemplified. .

  Moreover, the kind of C4-C36 alkylene ether glycol mentioned above does not have a restriction | limiting in particular, According to the objective, it can select suitably. For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like can be exemplified.

  Moreover, the kind of alicyclic diol having 4 to 36 carbon atoms described above is not particularly limited and can be appropriately selected depending on the purpose. For example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and the like can be exemplified.

  Moreover, the kind of the above-described alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO) is not particularly limited and can be appropriately selected depending on the purpose. Examples include adducts (additional mole number 1-30) such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), and the like. Can do.

  Moreover, the kind of bisphenol mentioned above does not have a restriction | limiting in particular, According to the objective, it can select suitably. For example, AO (EO, PO, BO, etc.) adducts such as bisphenol A, bisphenol F, bisphenol S, etc. (addition mole number: 2 to 30), etc.

  Moreover, the kind of polylactone diol mentioned above does not have a restriction | limiting in particular, According to the objective, it can select suitably. For example, poly-ε-caprolactone diol and the like can be mentioned.

  Moreover, the kind of diol having a carboxyl group described above is not particularly limited and can be appropriately selected according to the purpose. 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.

  Moreover, the kind of diol which has the sulfonic acid group mentioned above or the said sulfamic acid group does not have a restriction | limiting in particular, 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 in the kind of neutralization base of diol which has these neutralization bases, According to the objective, it can select suitably. For example, the said C3-C30 tertiary amine (triethylamine etc.), an alkali metal (sodium salt etc.), etc. are mentioned. Among these, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof are preferable.

  Moreover, the kind of the trivalent to octavalent or higher polyol already listed as used as necessary is not particularly limited, and can be appropriately selected according to the purpose. 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) Trivalent to octavalent or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms such as AO adducts (added moles 2 to 30) of trisphenols (trisphenol PA and the like); novolac resins ( Phenol novolak, cresol novolak, etc.) AO adducts (addition mole number: 2 to 30); 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 for synthesizing the polycondensed polyester unit include dicarboxylic acid, trivalent to hexavalent or higher polycarboxylic acid, and the like. Among these, the kind of dicarboxylic acid is not particularly limited and can be appropriately selected according to the purpose. 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.

  Moreover, there is no restriction | limiting in particular in the kind of aliphatic dicarboxylic acid mentioned above, 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.

  Moreover, the kind of aromatic dicarboxylic acid mentioned above does not have a restriction | limiting in particular, 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, and 4,4′-biphenyldicarboxylic acid are preferable. It is done.

  In addition, examples of the trivalent to hexavalent or higher polycarboxylic acid already listed as being used as necessary include, for example, aromatic polycarbons having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid. Examples thereof include carboxylic acid.

  In addition, as the above-mentioned dicarboxylic acid and trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) May be used.

  Among the dicarboxylic acids, the above-mentioned aliphatic dicarboxylic acids (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) are particularly preferably used alone, but the aromatic dicarboxylic acid and the aromatic Those obtained by copolymerizing dicarboxylic acids (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 [mol%] or less.

  The kind of the lactone ring-opening polymer that is one kind of the crystalline polyester unit is not particularly limited and can be appropriately selected depending on the purpose. 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) are used as metal oxides and organic metals. A lactone ring-opening polymer obtained by ring-opening polymerization using a catalyst such as a compound; using a glycol (for example, ethylene glycol, diethylene glycol, etc.) as an initiator, ring-opening the monolactone having 3 to 12 carbon atoms Examples thereof include a lactone ring-opening polymer having a hydroxyl group at the terminal, obtained by polymerization.

  Moreover, the kind of C3-C12 monolactone mentioned above does not have a restriction | limiting in particular, Although it can select suitably according to the objective, (epsilon) -caprolactone is preferable from a crystalline viewpoint. Moreover, you may use a commercial item as a lactone ring-opening polymer mentioned above. Examples of commercially available products include highly crystalline polycaprolactones such as H1P, H4, H5, and H7 of the PLACEL series manufactured by Daicel Corporation.

  The method for preparing polyhydroxycarboxylic acid, which is a kind of crystalline polyester unit, is not particularly limited and can be appropriately selected depending on the purpose. 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 polymerization of a cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to an intermolecular or intermolecular dehydration condensate using a catalyst such as a metal oxide or an organometallic compound A method is mentioned. From the viewpoint of adjusting the molecular weight, a method of ring-opening polymerization is preferred. 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 method is used, since a urethane bond site can be introduced into the resin skeleton, the toughness of the resin can be increased. Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like. The type of diisocyanate is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and araliphatic diisocyanates. Among these, the carbon number excluding 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. . If necessary, trivalent or higher isocyanates may be used in combination.

  There is no restriction | limiting in particular in the kind of aromatic diisocyanate mentioned above, 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; diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] ), Phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, etc. Can be mentioned.

  Moreover, there is no restriction | limiting in particular in the kind of aliphatic diisocyanate mentioned above, 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.

  Moreover, there is no restriction | limiting in particular in the kind of alicyclic diisocyanate mentioned above, 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.

  Further, the type of the araliphatic diisocyanates described above is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include m- and p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

  In addition, the type of the above-mentioned modified diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, and oxazolidone groups. 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 the following methods. That is, it is 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 either a crystalline polyester unit or another polymer unit is prepared in advance, and then the other polymer is polymerized in the presence of the prepared 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 method exemplified first or the method exemplified second is preferable.

  As a specific example of the method exemplified at the beginning, a unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and connected with polyisocyanate in the same manner as in the above-described method for obtaining a resin in which a crystalline polyester unit is connected. The method of doing is mentioned. As the polyisocyanate, those already described can be used, and an isocyanate group can be introduced at the terminal of one unit and reacted with active hydrogen of the other unit. When such a method is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.

  As a specific example of the second exemplified method, the following method can be exemplified. That is, first, a crystalline polyester unit is prepared. Next, a polymer unit such as an amorphous polyester unit, a polyurethane unit, or a polyurea unit is created. Thereby, the hydroxyl group or the carboxyl group at the terminal of the crystalline polyester unit can be reacted with the monomer for obtaining another polymer unit to obtain a resin in which the crystalline polyester unit and another polymer are bonded.

  Examples of the non-crystalline polyester unit used for the binder resin include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid. About a polyol and polycarboxylic acid, what was illustrated with 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 addition, in order to give an inflection point, for example, bisphenol such as AO (EO, PO, BO, etc.) addition product (addition mole number 2 to 30) such as bisphenol A, bisphenol F, bisphenol S, etc. as a polyol and its derivatives As the polycarboxylic 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 described above 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 the diol and the diisocyanate is preferable.

  Examples of the diol and the trivalent to octavalent or higher polyol described above include the same as the diol and the trivalent to octavalent or higher polyol cited in the polyester resin. In addition, examples of the diisocyanate and the trivalent or higher polyisocyanate described above include the same diisocyanates and trivalent or higher polyisocyanates as described above.

  Examples of the polyurea units described above include polyurea units synthesized from polyamines such as diamines and trivalent or higher polyamines, and polyisocyanates such as diisocyanates and trivalent or higher polyisocyanates. There is no restriction | limiting in particular in the kind of diamine, According to the objective, it can select suitably. Examples include aliphatic diamines and aromatic diamines. Among these, C2-C18 aliphatic diamines and C6-C20 aromatic diamines are preferable. Further, if necessary, the above trivalent amines may be used.

  The kind of aliphatic diamine having 2 to 18 carbon atoms described above is not particularly limited and can be appropriately selected depending on the purpose. For example, alkylenediamine having 2 to 6 carbon atoms such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine; diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepenta C4-18 polyalkylenediamines such as amine and pentaethylenehexamine; dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropyl C1-C4 alkyl or C2-C4 hydroxyalkyl substituted product of the alkylenediamine such as amine or the polyalkylenediamine; Cycloaliphatic diamines having 4 to 15 carbon atoms such as cyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline); piperazine, N-aminoethylpiperazine, 1,4- Diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane C4-C15 heterocyclic diamine such as xylylenediamine, tetrachloro-p-xylylenediamine and the like, and aromatic ring-containing aliphatic amines such as tetrachloro-p-xylylenediamine.

  The kind of C6-C20 aromatic diamine mentioned above does not have a restriction | limiting in particular, According to the objective, it can select suitably. For example, 1,2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, Unsubstituted aromatic diamines such as thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 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'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5 An aromatic diamine having a C1-C4 nucleus-substituted alkyl group such as tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone; Mixtures of various proportions of the isomers of the unsubstituted aromatic diamine to the aromatic diamine having a nuclear substituted alkyl group having 1 to 4 carbon atoms; methylene bis-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-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo Phenylmethane, 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-amino Nuclear substituted electron withdrawing groups such as phenyl-2-chloroaniline (halogens such as Cl, Br, I, F; An aromatic diamine having an alkoxy group such as methoxy and ethoxy; a nitro group; a secondary amino group such as 4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc. Aromatic diamines [the unsubstituted aromatic diamine, the aromatic diamine having a C1-C4 nucleus-substituted alkyl group, and a mixture of these isomers in various proportions, the aroma having the nucleus-substituted electron-withdrawing group In which part or all of the primary amino group of the group diamine is replaced by a secondary amino group with a lower alkyl group such as methyl or ethyl]. In addition to these, low molecular weight polyamides obtained by condensation of dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines (such as alkylene diamines and polyalkylene polyamines). Polyamide polyamines such as polyamines; 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 tri- or higher polyisocyanate described above include the same diisocyanates and tri- or higher polyisocyanates as described above.

The binder resin may contain a vinyl polymer unit. The vinyl polymer unit is a polymer unit obtained by homopolymerizing or copolymerizing vinyl monomers. The following can be illustrated as a vinyl-type monomer.
・ Vinyl hydrocarbons.
-Carboxyl group-containing vinyl monomers and salts thereof.
-Sulfone group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof.
-Phosphoric acid group-containing vinyl monomers and salts thereof.
-Hydroxyl group-containing vinyl monomers.
・ Nitrogen-containing vinyl monomers.
-Epoxy group-containing vinyl monomers.
-Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones.
・ Other vinyl monomers.
・ Fluorine atom element-containing vinyl monomers.

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

  Examples of the carboxyl group-containing vinyl monomer and salt thereof described above can be exemplified as follows. Namely, unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and anhydrides and monoalkyl (1 to 24 carbon atoms) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, maleic acid Carboxyl group-containing vinyl monomers such as monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, cinnamic acid Etc.

  Examples of the sulfone group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof include the following. That is, alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, 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) acryloyl Amino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid , 3- (Meth) acrylamide- -Hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene, butylene: single, random, block) sulfuric acid of mono (meth) acrylate And esters [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and the like.

  Examples of the phosphoric acid group-containing vinyl monomer and the salt thereof include the following. That is, (meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids, For example, 2-acryloyloxyethylphosphonic acid; and salts thereof.

  In addition, what was demonstrated as a salt of a vinyl-type monomer until now, for example, alkali metal salt (sodium salt, potassium salt, etc.), alkaline earth metal salt (calcium salt, magnesium salt, etc.), ammonium salt, amine salt, or quaternary Ammonium salts and the like.

  The following can be illustrated as a hydroxyl group containing vinyl monomer mentioned above. That is, 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 ether, and the like.

  The following can be illustrated as a nitrogen-containing vinyl-type monomer mentioned above. 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-vinylthio Pyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof. 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 Cinnamate amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like. Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like. 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 And quaternized vinyl monomers (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate). Also, nitro group-containing vinyl monomers: nitrostyrene and the like.

  The following can be illustrated as an epoxy group containing vinyl-type monomer mentioned above. That is, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, and the like.

  Examples of the vinyl ester, vinyl (thio) ether, vinyl ketone, and vinyl sulfones described above include the following. That is, vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate 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, heptadec (Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (Two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, Tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] 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 (meta ) 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.]. Also, vinyl (thio) ethers such as 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, and the like. Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone and the like. Also, vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, and the like.

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

  The following can be illustrated as a fluorine atom element containing vinyl-type monomer mentioned above. That 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-octa Fluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorode (Meth) acrylate, trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) Acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate, and the corresponding compounds derived from α-fluoroacrylic acid, bis-hexafluoroisopropyl itaconate, bis-hexafluoroisopropyl maleate, bis -Perfluorooctyl itaconate, bis-perfluorooctyl maleate, bis-trifluoroethyl itaconate and bis-trifluoroethyl maleate, vinyl heptafluorobutyrate Such as vinyl perfluoroheptanoate, vinyl perfluorononanoate and vinyl perfluorooctanoate.

  As the binder resin, a crystalline resin having a urea bond in the main chain is preferably contained. According to Solubility Parameter Values (Polymer handbook 4th Ed), the cohesive energy of urea bonds is 50230 [J / mol], which is about twice the cohesive energy of urethane bonds (26370 [J / mol]). Even if it exists, the toughness of a toner and the offset tolerance improvement effect at the time of fixing can be expected. As a method for obtaining a resin having a urea bond in the main chain, the following can be exemplified. That is, a polyisocyanate compound and a polyamine compound are reacted, or a polyisocyanate compound and water are reacted. And it is the method of reacting the amino group generated by the hydrolysis of isocyanate and the remaining isocyanate group. In obtaining a resin having a urea bond in the main chain, in addition to the above-described compounds, a polyol compound can be reacted at the same time, thereby increasing the degree of freedom in resin design.

  Examples of the polyisocyanate described above include diisocyanates, trivalent or higher polyisocyanates (hereinafter also referred to as low molecular weight polyisocyanates), and polymers having isocyanate groups at the terminals and side chains (hereinafter also referred to as prepolymers). May be used.

  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 kinds of prepolymers obtained by the same method may be used. Two or more types of prepolymers obtained by the two methods described above may be used in combination, or one type or a plurality of types of prepolymers and low molecular weight polyisocyanates may be used in combination.

The use ratio of polyisocyanate is equivalent ratio [NCO] / [NH ₂ ] of isocyanate group [NCO] and amino group [NH ₂ } of polyamine, or equivalent ratio of polyol hydroxyl group [OH] [NCO] / [ OH] is 5/1 to 1.01 / 1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. If the molar ratio of [NCO] exceeds 5, urethane bonds and urea bonds increase too much, and if 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. If the molar ratio of [NCO] is less than 1.01, the degree of polymerization increases and the molecular weight of the prepolymer produced increases, making it difficult to mix with other materials in the production of toner. Or, the elastic modulus in the molten state is too high, and the fixability may be deteriorated.

  Examples of the polyamine described above include diamines, trivalent or higher polyamines, and the like.

  In addition to diols, trivalent to octavalent or higher polyols (hereinafter also referred to as low molecular weight polyols), polyols having a hydroxyl group at the terminal or side chain (hereinafter referred to as high molecular weight polyols). May be used.

  Examples of the method for producing the high molecular weight polyol include a method of obtaining a polyurethane having a hydroxyl group at the terminal by reacting a low molecular weight polyisocyanate and a low molecular weight polyol with an excessive amount of hydroxyl group. 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. Is adjusted to 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and 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, so that a desired high molecular weight polyol cannot be obtained. On the other hand, if it is less than 1.02, the degree of polymerization becomes high and the molecular weight of the high molecular weight polyol that can be obtained becomes too large, so that it becomes difficult to mix with other materials in producing the toner. Further, the elasticity in the molten state is too high, and the fixability may be deteriorated.

  Examples of the polycarboxylic acid described above include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids, and the like.

  In order to give the resin 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. Among them, the crystalline polyester unit is preferable because it can be easily prepared from a terminal alcohol and is easily introduced into a resin having a urea bond as the 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 above-mentioned 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 the low-temperature fixability and the 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, Among these, linear aliphatic dicarboxylic acid is more preferable. Among the dicarboxylic acids, it is particularly preferable to use the above-mentioned aliphatic dicarboxylic acids (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone. A copolymer obtained by copolymerizing the above-mentioned aliphatic dicarboxylic acid with the above-mentioned aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) is also the same. Is preferable. The copolymerization amount of the aromatic dicarboxylic acid described above is preferably 20 [mol%] or less.

  In order to incorporate a crystalline resin having a urea bond in the main chain into the binder resin of the toner, a resin having a urea bond formed in advance is used, and other than the binder resin such as a colorant, a release agent, and a charge control agent. What is necessary is just to mix with a toner constituent material and to make particles. Furthermore, 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. May be. In particular, by using a prepolymer as the polyisocyanate compound, a crystalline resin having a uniform high molecular weight urea bond can be included in the toner, so that the thermal characteristics and chargeability of the toner are uniform. This is preferable because both the fixing property and the stress resistance of the toner can be easily achieved. 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 preferred in terms of suppressing viscoelasticity. 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. Further, 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, the urea bond can be formed under mild conditions by the water of the dispersion medium reacting with the polyisocyanate compound.

  As the toner binder resin, one kind may be used alone, or two or more kinds may be used in combination. In addition, binder resins having different weight average molecular weights may be used in combination, and include at least a second crystalline resin and a second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin. However, it is preferable in that both excellent low-temperature fixability and hot offset resistance can be achieved.

  The second crystalline resin described above is obtained by extending the resin by using the binder resin precursor, which 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. In addition, variation in characteristics among toner particles can be suppressed.

  Furthermore, the first crystalline resin described above is a crystalline resin having a urethane bond and / or a urea group bond in the main chain, and the second crystalline resin is the first crystalline resin. It is preferable that the modified binder 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 are more easily dispersed in the toner, and the variation in characteristics between toner particles is further increased. Can be suppressed. The crystalline resin may be a combination of the crystalline resin and the amorphous resin, and the main component of the binder resin is preferably the crystalline resin.

Next, experiments conducted by the present inventors will be described.
The inventors produced 19 types of toner. First, a method for producing these toners will be described.
[Production of Urethane Modified Crystalline Polyester Resin A-1]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 15 parts by weight (0.10 mol) of adipic acid, 177 parts by weight of 1,6-hexanediol (1 .50 mol) and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off generated water. 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, and the weight average molecular weight was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until Mw reached approximately 12000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 12,000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, and 350 parts by weight of ethyl acetate and 30 parts by weight (0.12 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin A-1. This urethane-modified crystalline polyester resin A-1 had a weight average molecular weight of Mw 22000 and a melting point of 62 ° C.

[Production of Urethane Modified Crystalline Polyester Resin A-2]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 189 parts by weight of 1,6-hexanediol (1.60 mol), and dibutyltin oxide as a condensation catalyst 0.5 part by weight was added, and the reaction was performed at 180 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. 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, and the weight average molecular weight was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until Mw reached approximately 6000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 6000.

  This crystalline polyester 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 and 38 parts by weight (0.15 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was 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. This urethane-modified crystalline polyester resin A-2 had a weight average molecular weight Mw of 10,000 and a melting point of 64 ° C.

[Production of Urethane Modified Crystalline Polyester Resin A-3]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 185 parts by weight (0.91 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, 106 parts by weight of 1,4-butanediol (1 .18 mol) and 0.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 14000, to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 14,000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts by weight of ethyl acetate and 12 parts by weight (0.07 mol) of hexamethylene diisocyanate (HDI) were added, and nitrogen was added. The reaction was carried out at 80 ° C. for 5 hours under an air stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin A-3. This urethane-modified crystalline polyester resin A-3 had a weight average molecular weight Mw of 39000 and a melting point of 63 ° C.

[Production of Urethane Modified Crystalline Polyester Resin A-4]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 166 parts by weight (0.82 mol) of sebacic acid, 26 parts by weight (0.18 mol) of adipic acid, 131 parts by weight of 1,4-butanediol (1 .45 mol) and 0.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 8000 to obtain a crystalline polyester resin. This crystalline polyester tree had a weight average molecular weight Mw of 8,000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 250 parts by weight of ethyl acetate and 33 parts by weight (0.13 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was 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-4. This urethane-modified crystalline polyester resin A-4 had a weight average molecular weight Mw of 17000 and a melting point of 54 ° C.

[Production of Urethane Modified Crystalline Polyester Resin A-5]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 202 parts by weight (1.00 mol) of sebacic acid, 18 parts by weight (0.12 mol) of adipic acid, 139 parts by weight of 1,6-hexanediol (1 .18 mol), and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst. 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. Furthermore, under a reduced pressure of 5 to 20 mmHg, the reaction was continued until the weight average molecular weight Mw reached about 18000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 18000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 250 parts by weight of ethyl acetate and 15 parts by weight (0.06 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was 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-5. This urethane-modified crystalline polyester resin A-5 had a weight average molecular weight Mw of 42000 and a melting point of 62 ° C.

[Production of urethane-modified crystalline polyester resin A-6]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 149 parts by weight (1.26 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst 0.5 part by weight was added. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 9000 to obtain a crystalline polyester tree. This crystalline polyester resin had a weight average molecular weight Mw of 9000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts by weight of ethyl acetate and 28 parts by weight (0.11 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was 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-6. This urethane-modified crystalline polyester resin A-6 had a weight average molecular weight Mw of 30000 and a melting point of 67 ° C.

[Production of Urethane Modified Crystalline Polyester Resin A-7]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 191 parts by weight of 1,6-hexanediol (1.62 mol), and tetrabutoxy titanate as a condensation catalyst 0.5 part by weight was added. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and 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 continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 4000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 4000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 300 parts by weight of ethyl acetate and 35 parts by weight (0.14 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was 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-7. This urethane-modified crystalline polyester resin A-7 had a weight average molecular weight Mw of 8500 and a melting point of 64 ° C.

[Production of Crystalline Polyester Resin A-8]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 185 parts by weight (0.91 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, 125 parts by weight of 1,4-butanediol (1 .39 mol) and 0.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 10,000 to obtain crystalline polyester resin A-8. This crystalline polyester resin A-8 had a weight average molecular weight Mw of 9,500 and a melting point of 57 ° C.

[Production of Crystalline Polyester Resin A-9]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 130 parts by weight (1.10 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst 0.5 part by weight was added. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 30,000 to obtain a crystalline polyester resin A-9. This crystalline polyester resin A-9 had a weight average molecular weight Mw of 27000 and a melting point of 62 ° C.

Tables 1 and 2 below show the composition and properties of the crystalline resins described so far (crystalline resins with the symbol A as the resin name).

[Production of Block Resin A-10 Composed of Crystalline Part and Amorphous Part]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 25 parts by weight (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 the mixture was reacted at 80 ° C. for 5 hours to contain an amorphous part c-1 having an isocyanate group at the terminal. Got.

  Further, in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 202 parts by weight (1.00 mol) of sebacic acid, 160 parts by weight (1.35 mol) of 1,6-hexanediol, and tetracondensation as a condensation catalyst. 0.5 part by weight of butoxy titanate was added. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and 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 continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 9000 to obtain a crystalline polyester resin. This crystalline polyester had a weight average molecular weight Mw of 8500 and a melting point of 63 ° C.

  As a crystalline part, 320 parts by weight of this crystalline polyester was dissolved in 340 parts by weight of the previously produced MEK solution and reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, MEK was distilled off under reduced pressure to obtain a block resin A-10. The obtained block resin A-10 had a weight average molecular weight Mw of 26000 and a melting point of 62 ° C.

[Production of Block Resin A-11 Composed of Crystalline Part and Amorphous Part]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 39 parts by weight (0.51 mol) of 1,2-propylene glycol and 270 parts by weight of methyl ethyl ketone (MEK) were added and stirred, and then 4,4 ′ -228 parts by weight (0.91 mol) of diphenylmethane diisocyanate (MDI) was added. And it was made to react at 80 degreeC for 5 hours, and the MEK solution containing the amorphous part c-2 which has an isocyanate group at the terminal was obtained.

  In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 160 parts by weight (1.35 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst 0.5 part by weight was added, and the reaction was performed at 180 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 8000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 7500 and a melting point of 62 ° C.

  As a crystalline part, 320 parts by weight of this crystalline polyester resin was dissolved in 540 parts by weight of the previously produced MEK solution and reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, MEK was distilled off under reduced pressure to obtain a block resin A-11. This block resin A-11 had a weight average molecular weight Mw of 23000 and a melting point of 61 ° C.

The compositions and properties of the block resins A-10 and A-11 are shown in Table 3 below.

[Production of urethane-modified crystalline polyester resin B-1]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 113 parts by weight (0.56 mol) of sebacic acid, 109 parts by weight (0.56 mol) of dimethyl terephthalate, 132 parts by weight of 1,6-hexanediol ( 1.12 mol) and 0.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst were added. And it was made to react for 8 hours, distilling off produced | generated water and methanol at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 35000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 34,000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 200 parts by weight of ethyl acetate and 10 parts by weight (0.06 mol) of hexamethylene diisocyanate (HDI) were added, and a nitrogen stream was added. The reaction was allowed to proceed at 80 ° C. for 5 hours. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain urethane-modified crystalline polyester resin B-1. This urethane-modified crystalline polyester resin B-1 had a weight average molecular weight Mw of 63,000 and a melting point of 65 ° C.

[Production of urethane-modified crystalline polyester resin B-2]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 204 parts by weight (1.01 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, 136 parts by weight of 1,6-hexanediol (1 .15 mol), and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst. The reaction was carried out for 8 hours at 180 ° C. while distilling off the water produced 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. Furthermore, the reaction was continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 20000 to obtain a crystalline polyester resin. This crystalline polyester resin had a weight average molecular weight Mw of 20000.

  This crystalline polyester resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 200 parts by weight of ethyl acetate and 15 parts by weight (0.06 mol) of 4,4′-diphenylmethane diisocyanate (MDI) were added. In addition, the mixture was 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 B-2. This urethane-modified crystalline polyester resin B-2 had a weight average molecular weight Mw of 39000 and a melting point of 63 ° C.

[Production of crystalline polyester resin B-3]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 230 parts by weight (1.00 mol) of dodecanedioic acid, 118 parts by weight (1.00 mol) of 1,6-hexanediol, and tetrabutoxy as a condensation catalyst. 0.5 part by weight of titanate was added. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and the reaction was carried out for 4 hours while distilling off water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, under a reduced pressure of 5 to 20 mmHg, the reaction was continued until the weight average molecular weight Mw reached about 50000 to obtain a crystalline polyester resin B-3. This crystalline polyester resin B-3 had a weight average molecular weight Mw of 52,000 and a melting point of 66 ° C.

[Production of Crystalline Resin Precursor B′-4]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 122 parts by weight (1.03 mol) of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst. 0.5 parts by weight of (triethanolaminate) was added. And it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, the temperature was gradually raised to 220 ° C., and 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 continued under a reduced pressure of 5 to 20 mmHg until the weight average molecular weight Mw reached about 25000. 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 and 27 parts by weight (0.16 mol) of hexamethylene diisocyanate (HDI) were added. And it was made to react at 80 degreeC under nitrogen stream for 5 hours, and the 50 weight% ethyl acetate solution of crystalline resin precursor B'-4 which has an isocyanate group at the terminal was obtained.

  10 parts by weight of this ethyl acetate solution was mixed with 10 parts by weight of tetrahydrofuran (THF), and 1 part by weight of dibutylamine was added thereto, followed by stirring for 2 hours. 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′-4 was 54,000. Moreover, as a result of performing DSC measurement about the sample obtained by removing a solvent from the said solution, melting | fusing point of crystalline resin precursor B'-4 was 57 degreeC.

Table 4 below shows the composition and properties of the crystalline resin described so far with the symbol B attached to the resin name.

[Production of Amorphous Resin C-1]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube, 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 Put. 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 5-20 mmHg, and when the acid value became 2, it cooled to 180 degreeC. And 35 weight part of trimellitic anhydride was added and it was made to react at a normal pressure for 3 hours, and amorphous resin C-1 was obtained. This amorphous resin C-1 had a weight average molecular weight Mw of 8000 and a melting point of 62 ° C.

[Production of Amorphous Resin Precursor C′-2]
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 are placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube. It was. 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.

  Next, 400 parts by weight of the aforementioned amorphous resin, 95 parts by weight of isophorone diisocyanate, and 500 parts by weight of ethyl acetate were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen insertion tube. 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.

Using the above resins, 19 types of toners were produced as follows.
[Production of graft polymer]
In a reaction vessel equipped with a stirrer and a thermometer, 480 parts by mass of xylene and 100 parts by mass of low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128 ° C.) are sufficiently dissolved and dissolved. Replaced. Thereafter, a mixed solution of 740 parts by mass of styrene, 100 parts by mass of acrylonitrile, 60 parts by mass of butyl acrylate, 36 parts by mass of di-t-butylperoxyhexahydroterephthalate, and 100 parts by mass of xylene was dropped at 170 ° C. for 3 hours. After polymerization, the temperature was maintained for 30 minutes. Subsequently, the solvent was removed to synthesize a graft polymer. This graft polymer had a weight average molecular weight Mw of 24,000 and a melting point Tg of 67 ° C.

[Preparation of release agent dispersion]
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, 420 parts of ethyl acetate was added. And they were heated up to 80 degreeC, stirring them in a container, and were hold | maintained at 80 degreeC for 5 hours. Thereafter, it is cooled to 30 ° C. at 1 hour and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (Ultra Visco Mill, manufactured by Imex) with a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec. A release agent dispersion was obtained by dispersing under conditions of 3 passes.

[Manufacture of master batch]
100 parts by weight of crystalline polyurethane resin A-1, 100 parts by weight of carbon black (Printex 35, manufactured by Degussa) (DBP oil absorption: 42 mL / 100 g, pH: 9.5), and 50 parts by weight of ion-exchanged water And Henschel mixer (Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. Kneading was started at a kneading temperature of 90 ° C., and then the kneading temperature was gradually cooled to 50 ° C. The obtained kneaded material was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to produce a first masterbatch.

The crystalline polyurethane resin A-1 used as a raw material is changed to crystalline polyurethane resin A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A -10, other points in place of the a-11 in the same manner to produce a second master batch to 11 master batch. Further, the crystalline polyurethane resin A-1 used as a raw material, other points in place of the non-crystalline resin C-1 in the same manner to produce a twelfth master batch.

For reference, showing the relationship between the various master batches and resin in the following Table 5.

[Manufacture of oil phase]
Put 31.5 parts by weight of urethane-modified crystalline polyester resin A-1 in a container equipped with a thermometer and a stirrer, add ethyl acetate in an amount to make the solid content concentration 50% by weight, and exceed the melting point of the resin Until well dissolved. 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 above-mentioned release agent dispersion, and 12 parts by weight of the second master batch were added. Then, the mixture was stirred at a rotation speed of 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a temperature of 50 ° C., and uniformly dissolved and dispersed to obtain a first oil phase. The temperature of the first oil phase was kept at 50 ° C. in the container and used within 5 hours in a state where crystallization was prevented.

The same except that 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 master batch types are changed as shown in Table 6 below. The second oil phase, the third oil phase, the fifth oil phase, the seventh oil phase, the eighth oil phase, the ninth oil phase, the tenth oil phase, the thirteenth oil phase, the fourteenth oil phase, the fifteenth oil phase, An oil phase, a nineteenth oil phase, was produced.

  In addition, about crystalline resin B in Table 6, and amorphous resin precursor C-2, when using any of crystalline resin B-1, B-2, B-3, an oil phase It was used by dissolving and dispersing together with other toner materials in the production stage. On the other hand, when the binder resin precursor B′-4 or the amorphous resin precursor C-2 is used, it is not added at the oil phase preparation stage, but is added to the oil phase at the toner base preparation described later. Used by dissolving and dispersing.

[Production of aqueous dispersion of resin fine particles]
In a reaction vessel equipped with a stirring bar and a thermometer, 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, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) 10 parts by weight) and 1 part by weight of ammonium persulfate were added. And when it stirred for 20 minutes at 400 rotation / min, the white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by weight of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 6 hours to obtain an aqueous dispersion of resin fine particles. The particles contained in the aqueous dispersion of the resin fine particles had a volume average particle size of 80 [nm], the resin component had a weight average molecular weight Mw of 160000, and a melting point of 74 ° C.

[Preparation of first aqueous phase]
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.), and 90 parts of ethyl acetate The first aqueous phase was obtained by mixing and stirring parts by weight.

[Manufacture of toner base]
In a separate container equipped with a stirrer and a thermometer, 520 parts by weight of the first aqueous phase was placed and heated to 40 ° C. 25 parts by weight of an ethyl acetate solution of the crystalline resin precursor B′-5 is added to 235 parts by weight of the first oil phase maintained at 50 ° C., and the number of revolutions is increased by a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). The first oil phase was prepared by stirring at 5000 rpm and uniformly dissolving and dispersing. Then, the first oil phase after adjustment was added while stirring at 13000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) with the adjusted first aqueous phase maintained at 40 to 50 ° C. Emulsification was promoted for 1 minute to obtain a first emulsified slurry. Next, the first 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 first slurry. The first slurry was filtered under reduced pressure, and then washed as described later.

  The cleaning process was performed as follows. That is, first, 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 6000 rpm), and then filtered to obtain a filter cake. Next, 100 parts by weight of a 10 wt% aqueous sodium hydroxide solution was added to the filter cake, mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure to obtain a filter cake. And after adding 100 weight part of 10 weight% hydrochloric acid to this filter cake, it mixed with TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered to obtain a filter cake. Next, 300 parts by weight of ion-exchanged water was added to this filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered twice to obtain a filter cake. Furthermore, this filter cake was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the first toner base was manufactured by sieving with a mesh of 75 μm.

  The oil phases used as raw materials are from the first oil phase to the second oil phase, the third oil phase, the fifth oil phase, the seventh oil phase, the eighth oil phase, the ninth oil phase, the tenth oil phase, the thirteenth oil phase. The same operation was performed except that the oil phase, the 15th oil phase, and the 19th oil phase were replaced. Thus, the second toner base, the third toner base, the fifth toner base, the seventh toner base, the eighth toner base, the ninth toner base, the tenth toner base, the fourteenth toner base, the fifteenth toner base, and the nineteenth base. A toner base was produced.

[Manufacture of oil phase]
In a container equipped with a thermometer and a stirrer, 62 parts by weight of urethane-modified crystalline polyester resin A- 1 and 12 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 a 50% by weight ethyl acetate solution of amorphous resin C-1, 60 parts by weight of the above-described release agent dispersion, and 12 parts by weight of the second master batch were added. Then, the mixture was stirred at a rotational speed of 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a temperature of 50 ° C., and uniformly dissolved and dispersed to obtain a fourth oil phase. In addition, the temperature of the 4th oil phase was used within the time after manufacture in the state which prevented crystallization by keeping at 50 degreeC in a container.

Other than the point that the kind and the addition amount of the crystalline resin A, the kind and the addition amount of the crystalline resin B, the addition amount of the amorphous resin C, and the kind of the masterbatch are changed as shown in the following Table 7. Similarly, a 16th oil phase, a 17th oil phase, and an 18th oil phase were produced.

[Adjustment of aqueous phase]
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.) and 90 parts by weight of ethyl acetate were mixed and stirred, and the second aqueous phase was mixed. Obtained.

[Manufacture of toner base]
In a separate container in which a stirrer and a thermometer are set, 520 parts by weight of the second aqueous phase is placed, heated to 40 ° C., and kept at 40-50 ° C. The fourth oil phase was added while stirring at 13,000 rpm, and emulsification was promoted for 1 minute to obtain a fourth emulsified slurry. Next, the fourth 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 fourth slurry. The obtained fourth slurry was filtered under reduced pressure, and then washed as described later.

  The cleaning process was performed as follows. 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 6000 rpm), and then filtered to obtain a filter cake. 100 parts by weight of a 10% by weight aqueous sodium hydroxide solution was added to the filter cake, mixed with a TK homomixer (rotation speed: 6000 rpm for 10 minutes), and then filtered under reduced pressure to obtain a filter cake. 100 parts by weight of 10 wt% hydrochloric acid was added to this filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6000 rpm), and then filtered to obtain a filter cake. To this filter cake, 300 parts by weight of ion-exchanged water was added and mixed with a TK homomixer (rotation speed: 6000 rpm for 5 minutes), and then filtered twice to obtain a filter cake. The filter cake was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with an opening of 75 μm mesh to produce a fourth toner base.

  The 16th toner base, the 17th toner base, and the 18th toner are the same except that the oil phase used as the raw material is changed from the second oil phase to the 16th oil phase, the 17th oil phase, and the 18th oil phase. The mother body was manufactured.

[Production of crystalline resin particle dispersion (A-2)]
60 parts by weight of ethyl acetate was added to 60 parts by weight of 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 dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution After adding 120 parts by weight of the resin solution described above to the aqueous phase mixed, and emulsifying with a homogenizer (IKA, Ultra Tarrax T50), emulsifying with a Menton Gorin high-pressure homogenizer (Gorin), An emulsified slurry was obtained. Subsequently, the above-mentioned 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 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 this crystalline resin particle dispersion (A-2) was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make).

[Production of crystalline resin particle dispersion (A-5)]
60 parts by weight of ethyl acetate was added to 60 parts by weight of urethane-modified crystalline polyester resin A-5, 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 dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution 120 parts by weight of the resin solution described above was added to the aqueous phase mixed with the above. Then, emulsification was promoted using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an emulsified slurry. Subsequently, the above-mentioned 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 4 hours to obtain a crystalline resin particle dispersion (A-5). It was 0.18 micrometer when the volume average particle diameter of the particle | grains in this crystalline resin particle dispersion (A-5) was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

[Production of Crystalline Resin Particle Dispersion (B-1)]
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 dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution 120 parts by weight of the above-mentioned resin solution was added to the aqueous phase mixed with and emulsification was promoted using a homogenizer (manufactured by IKA, Ultra Turrax T50). Then, it emulsified with a Menton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an emulsified slurry. Next, the aforementioned 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 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 this crystalline resin particle dispersion (B-1) was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

[Production of Amorphous Resin Particle Dispersion (C-1)]
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 dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution 120 parts by weight of the resin solution described above was added to the aqueous phase mixed with the above. And emulsification was promoted using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an emulsified slurry. Subsequently, the above-mentioned 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 4 hours to obtain a crystalline resin particle dispersion (C-1). It was 0.15 micrometer when the volume average particle diameter of the particle | grains in this crystalline resin particle dispersion liquid (C-1) was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

[Preparation of release agent dispersion]
Paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, melting point 75 ° C.) 25 parts by weight, anionic surfactant (manufactured by Sanyo Kasei Kogyo Co., Ltd .: Eleminol MON-7), 200 parts by weight of water are mixed, and 95 ° C. And melted. Next, this melt was emulsified with a homogenizer (IKA, Ultra Tarrax T50) and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to obtain a release agent dispersion.

[Preparation of colorant dispersion]
Carbon black (Printtex35, manufactured by Degussa) 20 parts by weight, anionic surfactant (Eleminol MON-7, manufactured by Sanyo Chemical Industries Co., Ltd.) 2 parts by weight, and water 80 parts by weight are mixed, and a TK homomixer (special machine) To obtain a colorant dispersion.

[Manufacture of sixth toner base]
190 parts by weight of crystalline resin particle dispersion (A-2), 63 parts by weight of crystalline resin particle dispersion (B-1), 63 parts by weight of amorphous resin particle dispersion (C-1) 46 parts by weight of the agent dispersion, 17 parts by weight of the aforementioned colorant dispersion, and 600 parts by weight of water were mixed and adjusted to pH 10 with a 2% by weight aqueous sodium hydroxide solution. Next, with stirring, 50 parts by weight of a 10% by weight magnesium chloride aqueous solution was gradually added dropwise to this solution and heated to 60 ° C. A 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 slurry was filtered under reduced pressure, and then washed as described later.

  The cleaning process was performed as follows. 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 6000 rpm), and then filtered to obtain a filter cake. 100 parts by weight of a 10% by weight aqueous sodium hydroxide solution was added to the filter cake, mixed with a TK homomixer (rotation speed: 6000 rpm for 10 minutes), and then filtered under reduced pressure to obtain a filter cake. 100 parts by weight of 10 wt% hydrochloric acid was added to this filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6000 rpm), and then filtered to obtain a filter cake. To this filter cake, 300 parts by weight of ion-exchanged water was added and mixed with a TK homomixer (rotation speed: 6000 rpm for 5 minutes), and then filtered twice to obtain a filter cake. The filter cake was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with an opening of 75 μm mesh to produce a sixth toner base.

[Production of Eleventh Toner Base]
190 parts by weight of a crystalline resin particle dispersion (A-5), 63 parts by weight of a crystalline resin particle dispersion (B-1), 63 parts by weight of an amorphous resin particle dispersion (C-1), the above-mentioned mold release 46 parts by weight of the agent dispersion, 17 parts by weight of the aforementioned colorant dispersion, and 600 parts by weight of water were mixed and adjusted to pH 10 with a 2% by weight aqueous sodium hydroxide solution. Next, with stirring, 50 parts by weight of a 10% by weight magnesium chloride aqueous solution was gradually added dropwise to this solution and heated to 60 ° C. A slurry was obtained by maintaining the temperature at 60 ° C. until the volume average particle diameter of the aggregated particles grew to 5.9 μm. The slurry was filtered under reduced pressure, and then washed as described later.

  The cleaning process was performed as follows. 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 6000 rpm), and then filtered to obtain a filter cake. 100 parts by weight of a 10% by weight aqueous sodium hydroxide solution was added to the filter cake, mixed with a TK homomixer (rotation speed: 6000 rpm for 10 minutes), and then filtered under reduced pressure to obtain a filter cake. 100 parts by weight of 10 wt% hydrochloric acid was added to this filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6000 rpm), and then filtered to obtain a filter cake. To this filter cake, 300 parts by weight of ion-exchanged water was added and mixed with a TK homomixer (rotation speed: 6000 rpm for 5 minutes), and then filtered twice to obtain a filter cake. The filter cake was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain an eleventh toner base.

[Manufacture of twelfth toner base]
60 parts by weight of urethane-modified crystalline polyester resin A-1, 20 parts by weight of urethane-modified crystalline polyester resin B-1, 20 parts by weight of non-crystalline resin C-1, paraffin wax (NNP, HNP) −9, melting point 75 ° C.) 5 parts by weight and 12 parts by weight of the second master batch were premixed using a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.). Thereafter, the mixture was melted and kneaded at a temperature of 80 ° C. to 120 ° C. with a biaxial kneader (Ikegai, PCM-30). The obtained kneaded material was cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill. Next, the mixture was finely pulverized using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.) while adjusting the pulverization air pressure as appropriate so that the weight average particle diameter was 6.2 ± 0.3 μm. Thereafter, with a gas classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I), the louver opening so that the weight average particle size is 7.0 ± 0.2 μm, and the amount of fine powder of 4 μm or less is 10% by number or less. Was appropriately adjusted to obtain a twelfth toner base.

[Production of toner]
A peripheral speed of 100 parts by weight of the first toner base and 1.0 part by weight of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) as an external additive using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) Five cycles of mixing at 30 m / sec for 30 seconds and resting for 1 minute were performed. Thereafter, the mixture was sieved with a mesh having an opening of 35 μm to obtain a first toner.

  Similarly, the second to 19th toners were obtained except that the toner base used as the raw material was changed from the first toner base to the 2nd to 19th toner bases.

  For these 19 types of toner, the particle size distribution (volume average particle diameter Dv, number average particle diameter Dn, Dv / Dn), nitrogen element amount, presence or absence of urea bond, Tsh2nd / Th1st, storage elastic modulus G ′ (80), storage The elastic modulus G ′ (140) was measured. The particle size distribution was measured using a particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

  Specifically, the nitrogen element amount is the ratio of the weight of the nitrogen element to the sum of the weights of the carbon element, the hydrogen element, and the nitrogen element in the components that can be dissolved in tetrahydrofuran among all the components of the toner. About this nitrogen element amount, it measured as follows using vario MICRO cube (made by Elemental). That is, first, components soluble in tetrahydrofuran were extracted from the toner. Specifically, 5 g of toner was put in a Soxhlet extractor and extracted with 70 ml of THF (tetrahydrofuran) for 20 hours, and then the above components were obtained by removing THF under reduced pressure by heating. It was.

The obtained sample was set in a vario MICRO cube, and a combustion furnace temperature = 950 ° C., a reduction furnace temperature = 550 ° C., a helium flow rate = 200 ml / min, an oxygen flow rate = 25-30 ml / min, a carbon element, a hydrogen element, Elemental nitrogen was measured simultaneously. The average of two measurements for each of these three elements was determined. And the ratio of the weight of the nitrogen element with respect to the sum of the weight of three elements was calculated | required as the amount of nitrogen elements. In addition, when the amount of nitrogen elements was less than 0.5 wt%, the measurement was further performed with a trace nitrogen analyzer ND-100 (manufactured by Mitsubishi Chemical Corporation). At this time, the temperature of the electric furnace (horizontal reactor) was set to pyrolysis portion = 800 ° C. and catalyst portion = 900 ° C. The calibration curve prepared with the pyridine standard solution was quantified under the conditions of main O ₂ flow rate = 300 ml / min, O ₂ flow rate = 300 ml / min, Ar flow rate = 400 ml / min, sensitivity = Low.

  Specifically, the presence or absence of a urea bond is the presence or absence of a urea bond in a component that can be dissolved in tetrahydrofuran among all the components of the toner. The presence or absence of a urea bond was measured by carbon nuclear magnetic resonance spectroscopy (hereinafter referred to as 13C-NMR). Specifically, 2 g of the sample was immersed in 200 ml of a potassium hydroxide methanol solution having a concentration of 0.1 mol / l and placed at 50 ° C. for 24 hours. Thereafter, the solution was removed, the residue was further washed with ion exchange water until the pH became neutral, and the remaining solid was dried. 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 time, the temperature was set to 50 ° C., and 13C-NMR measurement was performed.

  Various conditions were set such that the measurement frequency was 125.77 MHz, the 1H — 60 ° pulse was 5.5 μs, and the reference material was tetramethylsilane (TMS): 0.0 ppm. Presence of urea binding in the sample is confirmed by checking whether 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 sample. The chemical shift of carbonyl carbon is generally seen at 150-160 ppm. As an example of polyurea, FIG. 5 shows a 13C-NMR spectrum near the carbonyl carbon of polyurea, which is a reaction product of 4,4′-diphenylmethane diisocyanate (MDI) and water. As shown in the figure, a signal derived from carbonyl carbon is observed at 153.27 ppm.

The value of the ratio Tsh2nd / Tsh1st of the shoulder temperature Tsh1st of the first heat-up melting heat peak and the shoulder temperature Tsh2nd of the second heat-up melting heat peak measured by a differential scanning calorimeter (DSC) of the toner is 0.90 or more and 1 10 or less is preferable. 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)). That is, first, toner 5.0 [mg] 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 increased from 0 [° C.] to 150 [° C.] at a temperature rising rate of 10 [° C./min], and then from 150 [° C.] to 0 [° C.] at a temperature decreasing rate of 10 [° C./min]. Then, the temperature is further increased to 150 [° C.] at a temperature increase rate of 10 [° C./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.

  Moreover, about storage elastic modulus G '(80) and storage elastic modulus G' (140), as a dynamic viscoelastic characteristic value (storage elastic modulus G ', loss elastic modulus G "), a dynamic viscoelasticity measuring apparatus ( ARES (manufactured by TA Instruments) was measured as follows: a sample was molded into a pellet having a diameter of 8 mm and a thickness of 1 mm to 2 mm, and fixed to a parallel plate having a diameter of 8 mm. With a stable temperature of 40 ° C. as an initial value, the temperature is raised to 200 ° C. at a frequency of 1 Hz (6.28 rad / s) and a strain amount of 0.1% (strain amount control mode) at a rate of temperature rise of 2.0 ° C./min. And measured.

  The toner ratio (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). . In this ratio (C) / ((C) + (A)), (C) is the integrated intensity of the spectrum derived from the crystal structure of the binder resin in the diffraction spectrum obtained by the X-ray diffractometer of the toner. . (A) is the integrated intensity of the spectrum derived from the amorphous structure. X-ray diffraction measurement is performed using a two-dimensional detector-mounted X-ray diffractometer (D8 DISCOVER with GADDS / Bruker). As the capillary used for the measurement, a capillary having a diameter of 0.70 [mm] made of a mark tube (Lindenman glass) is used. The sample is packed up to the top of the capillary tube and measured. In addition, 100 times of tapping is performed when packing a sample.

The detailed measurement conditions are as follows.
Tube current: 40 mA.
Tube voltage: 40 kV.
Goniometer 2θ axis: 20.0000 [°].
Goniometer Ω axis: 0.0000 [°].
Goniometer φ axis: 0.0000 [°].
Detector distance: 15 [cm] (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2.
Measurement time: 600 sec.

  A collimator having a pin hole of φ1 [mm] 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. A method for calculating the above-described ratio (C) / ((C) + (A)) will be described based on the obtained X-ray diffraction measurement result. Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. In these figures, the horizontal axis represents 2θ, the vertical axis represents X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum in 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. It is done. Their main peaks are derived from the crystal structure, and halos are derived from the amorphous structure.

The two major peaks and halos described above are represented by three Gaussian functions.
fp1 (2θ) = ap1exp {− (2θ−bp1) 2 / (2cp12)}
fp2 (2θ) = ap2exp {− (2θ−bp2) 2 / (2cp22)}
fh (2θ) = ahexp {− (2θ−bh) 2 / (2ch2)}

  In these equations, fp1 (2θ), fp2 (2θ), and fh (2θ) indicate functions corresponding to the main peaks P1, P2, and halo. Fitting by the least square method was performed using f (2θ) = fp1 (2θ) + fp2 (2θ) + fh (2θ), which is the sum of the three functions, as a fitting function (FIG. 7) of the entire X-ray diffraction spectrum.

  There are nine fitting variables, ap1, bp1, cp1, ap2, bp2, cp2, ah, bh, and ch. As initial values of the fitting of each variable, the peak positions of X-ray diffraction (bp1 = 21.3, bp2 = 24.2, bh = 22.5 in the example in the figure) are set in bp1, bp2, and bh, The values obtained by matching the two main peaks and the halo with the X-ray diffraction spectrum as much as possible were set by appropriately inputting the variables. The fitting was performed using an Excel 2003 solver manufactured by Microsoft.

  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. From (Sh), when (Sp1 + Sp2) is (C) and Sh is (A), a ratio (C) / ((C) + (A)), which is an index indicating the amount of crystallization sites, is calculated.

The relationship between various toners and their properties is shown in Table 8 below.

  Next, the inventors manufactured a magnetic carrier to be mixed in the developer. Specifically, 100 parts by weight of a silicone resin (organostraight silicone), 5 parts by weight of γ- (2-aminoethyl) aminopropyltrimethoxysilane, 10 parts by weight of carbon black, and 100 parts by weight of toluene are homogenized. A resin layer coating solution was prepared by dispersing with a mixer for 20 minutes. Then, the above-mentioned resin layer coating solution was applied to the surface of spherical ferrite (1000 parts by weight) having a volume average particle size of 35 μm using a fluidized bed coating apparatus to obtain a magnetic carrier.

  Next, the present inventors manufactured 19 types of developers, namely the first developer to the 19th developer, using the first toner to the 19th toner individually. The ratio of the toner and the magnetic carrier was 95 parts by weight of the magnetic carrier with respect to 5 parts by weight of the toner (any one of the first toner to the 19th toner).

  Note that the ratio (C) / ((C) + (A)) of the toner used in the printer according to an embodiment described later is 0.15 or more from the viewpoint of achieving both fixability and heat-resistant storage stability. To preferred. It is more preferably 0.20 or more, further preferably 0.30 or more, and particularly preferably 0.45 or more. When the toner contains 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, so that it may not be considered. When the wax content exceeds 15 [wt%], the value obtained by subtracting the integrated intensity of the spectrum derived from the crystal structure of the wax from the integrated intensity of the spectrum derived from the crystal structure of the binder resin is described above. It will be replaced with “integral intensity (C) of spectrum derived from the crystal structure of the binder resin”. Conventionally known toners containing a crystalline resin or wax to the extent of additives have a ratio of less than about 0.15.

The inventors prepared a printer tester. Using this printer testing machine, the fixability ((hot offset resistance / fixing width) of each of the first developer to the 21st developer was tested. A solid image of 3 cm × 8 cm was developed above and transferred onto the entire surface of a transfer paper (Ricoh Co., Ltd., type 6200) from the photoconductor. The value was set to 85 ± 0.10 [mg / cm ² ].

  Next, a fixing device 950 shown in FIG. 4 was prepared. The fixing device 950 includes a fixing roller 951 that includes a heater 952, and a roller 953 that forms a fixing nip in contact with the fixing roller 951. For each of the 21 types of developers, a plurality of print papers on which test images were printed were prepared. Then, for each test image with the developer, a process for fixing the test image on the print paper was performed at each temperature while changing the temperature of the fixing roller 951 of the fixing device 950. Then, the fixing lower limit temperature was evaluated by checking the fixing degree of the test image after fixing. Similarly, the fixing upper limit temperature at which hot offset does not occur was evaluated based on visual evaluation of the presence or absence of hot offset. Further, the difference between the lower limit fixing temperature and the upper limit fixing temperature was defined as the fixing width.

Note that the sheet feeding speed with respect to the fixing nip was set to 280 mm / sec. The roller contact pressure was set to 2.0 kgf / cm ² . The fixing nip width (length in the roller surface movement direction) was set to 11.2 mm.

  In general, the wider the fixing width, the better the hot offset resistance, and about 50 ° C. is the average temperature range of the conventional full-color toner.

Next, the inventors conducted an experiment for evaluating the heat-resistant storage stability (penetration) for each toner. Specifically, a 50 ml glass container was filled with toner and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JISK 2235-1991), and then evaluated based on the criteria listed below. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.
〔Evaluation criteria〕
A: Needle penetration is 25 mm or more.
○: Penetration 15 mm or more and less than 25 mm.
Δ: Needle penetration is 5 mm or more and less than 15 mm.
X: The penetration is less than 5 mm.

[Toner adhesion]
Next, the inventors conducted an experiment to examine the adhesion of 19 types of toner to the inner wall of a transport pump (for example, the transport pump 38Y) in the toner replenishing device. Specifically, a printer testing machine having the same configuration as the printer according to the embodiment was prepared. Then, a continuous print test was performed in which a toner cartridge (32K) for K of the printer tester was filled with the toner to be tested and a test image was continuously printed. The mixing ratio of the toner of the K developer and the magnetic carrier in the developing device for K of the printer tester was approximately 93 parts by weight of the magnetic carrier with respect to 7 parts by weight of the toner.

  In the continuous print test, the fixing temperature in the fixing device 20 is kept at the toner lower limit fixing temperature +10 [° C.] based on the detection result of the surface temperature of the fixing roller.

First, the first print test was performed.
Specifically, an operation of continuously printing a chart image having an image area ratio of 0.5% on an A4 size recording paper at a temperature of 32 ° C. was continuously performed for 8 hours. In this first print test, the room temperature is set to a relatively high temperature of 32 ° C., so that the toner sandwiched between the rotor and the stator of the transport pump composed of the mono pump is easily fixed by heat and pressure.

  In the first print test, the presence or absence of pump malfunction (lock) due to the toner sticking to the rotor and stator due to low heat resistance and pressure resistance was examined. Naturally, it is desirable that the toner has high heat resistance and pressure resistance and does not cause malfunction (lock) of the transport pump.

  In addition, a toner having low heat resistance and pressure resistance may form a large agglomerate even if the transport pump is not locked. When this agglomerate is supplied into the developing device, white streaks may be generated on the image by being sandwiched between the doctor blade (52) and the developing roller (51). In the first print test, the occurrence of white streaks was also examined. Since this test is an accelerated test, if the number of streaks is 3 or less, it can be considered that there is almost no problem in practical use. Even if there are four or more bands, especially stripes, even characters can be removed, the quality cannot be maintained depending on the installation environment.

  In the first print test, when the 18th toner having an extremely small fixing width is used, continuous printing can be performed because the 18th toner frequently causes jamming of the recording paper due to hot offset to the fixing roller. could not. For this reason, the evaluation was impossible.

  In the first print test, when the 19th toner was used as the toner, the transport pump was locked. The 19th toner is considered to be because the lower limit fixing temperature + 10 ° C. was a relatively high temperature of 150 ° C. and the temperature inside the machine was severely increased. (It can also be said that the margin for establishment as a system has narrowed due to the high fixing minimum temperature).

Next, a pseudo print test was performed.
In this pseudo print test, a single toner replenishing device was used instead of the printer tester. Toner consumption (hereinafter referred to as 500K) when a test chart image having an image area ratio of 5% is output to 500 [thousand] recording sheets in a configuration in which toner discharged from a conveyance pump of a toner replenishing device is placed in a container. The toner supply operation corresponding to the equivalent supply amount) was performed. The amount of toner discharged from the transport pump is different by 20 g immediately before the toner supply amount corresponding to the toner consumption amount when outputting to a recording sheet of 250 [thousand sheets] and immediately before the supply amount equivalent to 500K. The container was received and passed through a sieve having an opening of 106 μm to collect agglomerates. Then, the weight of the aggregate was measured as the aggregate amount.

  The aggregate amount correlates with the image quality, and if the aggregate amount in 20 g is 5 mg or less, the image has almost no problem, and if it is 5 to 10 mg, the effect on the image is slight (small black spots in the solid black). Is a level that is not conspicuous at several levels. The amount of aggregate that can withstand practical use is considered to be 10 mg / 20 g or less.

Next, a second print test was performed.
Specifically, the conveyance pump subjected to the pseudo print test and the toner were set in a printer testing machine, and all solid images were continuously output on 20 recording sheets. The solid image of the printed paper was checked for black spots and white spots. Further, for K, a pseudo print test with toner replenishment corresponding to continuous printing of 500 [thousand sheets] was performed, and then the K transport pump was disassembled and the weight of the rotor was measured. Then, a difference from the initial weight of the measurement result was obtained as a toner fixing weight ΔW.

  This combination of the pseudo print test and the second print test is for examining the state of deterioration of the transport pump over time. The toner adhesion to the rotor is investigated by weight, and the degree of influence on the image at that time is evaluated. Yes. The toner adhesion weight ΔW to the rotor, which is confirmed after the second print test is performed, is preferably small, and it is naturally desirable that there is no image abnormality.

  When the 16th toner was used, the stator was scraped by the toner lump fixed to the rotor, and this caused air leakage between the rotor and the stator in the pump unit, which caused toner conveyance failure. For this reason, it was impossible to evaluate because 500 [thousand sheets] continuous printing could not be performed.

The results of the above experiment are shown in Table 9 below.

[Additional experiment]
Next, the inventors performed additional experiments.
This additional experiment was conducted for the purpose of investigating the effectiveness of adding metal soap to the toner powder.

  The metal soap contained in the toner powder has stearic acid groups such as zinc stearate, barium stearate, iron stearate, nickel stearate, cobalt stearate, copper stearate, strontium stearate, calcium stearate, etc. The thing etc. can be illustrated. Also, the same fatty acid groups zinc oleate, barium oleate, lead oleate, zinc oleate, barium oleate, iron oleate, nickel oleate, cobalt oleate, copper oleate, strontium oleate, olein Those having an oleic acid group such as calcium acid may be used. Further, those having a palmitic acid group such as zinc palmitate, barium palmitate, lead palmitate, iron palmitate, nickel palmitate, cobalt palmitate, copper palmitate, strontium palmitate, calcium palmitate, etc. . As described above, those listed are likely to be organic solid metal soaps and have good compatibility with toners. In additional experiments, zinc stearate was used as the metal soap, but is not limited thereto.

  A toner containing metal soap was produced. Specifically, 100 parts by weight of the first toner base described above and 1.0 part by weight of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) as an external additive are combined with a Henschel mixer (Mitsui Mining Co., Ltd.). 4 cycles of mixing at a peripheral speed of 30 m / second for 30 seconds and resting for 1 minute. Thereafter, 0.15 parts of zinc stearate was added, mixed for 30 seconds at a peripheral speed of 30 m / sec, and subjected to 2 cycles of resting for 1 minute. Then, it was sieved with a mesh having an opening of 45 μm to obtain a twentieth toner.

  The 21st to 34th toners were obtained in the same manner except that the 2nd to 15th toner bases were used in place of the first toner base as the toner base used as the raw material. The 20th, 21st, 22nd, 23rd, 24th, 25th, 26th, 27th, 28th, 29th, 30th, 31st, 32th, 33th and 34th toners are mixed with zinc stearate as a metal soap, The composition is almost the same as that of the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelve, thirteenth, fourteenth and fifteenth toners. The reason why the mesh with a larger mesh size was used when producing the 20th to 34th toners than when producing the 1st to 15th toners is that the metal soap is easily clogged. .

  Using the 21st to 34th toners, the 21st to 34th developers were produced. The mixing ratio of the toner and the magnetic carrier was the same as that of the first developer. That is, 7 parts by weight of toner and 93 parts by weight of magnetic carrier were mixed.

  Next, a first print test, a pseudo print test, and a second print test were performed as in the previous experiment. The twentieth toner had the same toner base as the first toner, so the fixability and storage stability were exactly the same as the first toner. Similarly, the 21st to 34th toners had exactly the same fixability and storage stability as the 2nd to 15th toners. However, a difference was observed in the result of the toner fixing weight ΔW.

The results of the additional experiment are shown in Table 10 below.

  Referring to Table 9, the results of the first print test, the pseudo print test, and the second print test are excellent in the first to fifteenth toners, whereas those of the sixteenth to nineteenth toners are those You can see that the test results are getting worse.

  When the properties common to the 16th to 19th toner groups having poor results are examined, it is found that none of them has a urea bond. However, the four toners, the fourth toner, the sixth toner, the eleventh toner, and the twelfth toner, which performed well, do not have urea bonds.

  Therefore, when the other properties of the group of the 16th to 19th toners and the group of the 4th, 6th, 11th and 12th toners are compared, the binder resin ratio (crystalline property) There is a significant difference in the mass% of the entire polyester unit binding). Specifically, in the group of the 16th toner to the 19th toner having poor results, the 16th toner and the 17th toner do not contain any urethane-modified crystalline polyester unit. Further, the 21st toner having poor results contains only 15% by mass of the crystalline polyester unit. For this reason, the amount of N element is extremely small. In addition, the 19th toner with poor performance has a very low value (0.01) of the ratio of the crystalline polyester unit ((C) + ((C) + (A)). The groups of 4 toner, 6th toner, 11th toner and 12th toner are based on urethane-modified crystalline polyester, and all of them have a large amount of N element and a ratio ((C) + ((C) + ( A)) is 0.15 or more.

  For the nineteenth toner, only a pseudo print test was performed because there was a problem with paper passing. Further, only one sheet was passed after a toner replenishment operation corresponding to 500 [thousand] prints was performed. This paper jammed after passing through the fixing device, but as long as the image was seen, there was no abnormal image due to white streaks or aggregates. Furthermore, the fixing weight ΔW to the rotor was also measured. The results are as described in Table 9 above.

  The twentieth toner has a narrow fixing width, so that there are many problems such as refinement of fixing control when used in an image forming apparatus, and it can be said that it is a toner that is difficult to use practically. There seems to be no problem with the defect.

  The poor fixability of the eighteenth toner is that G ′ (140) showing viscoelasticity after melting is very low due to the fact that it contains only one type of crystalline polyurethane resin. This is considered to be the cause. In order to avoid this, as the crystalline resin, the first crystalline resin and the second crystalline resin, preferably the second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin are used. It is desirable to use it.

Next, a characteristic configuration of the printer according to the embodiment will be described.
In view of the results of the experiments described so far, the printer according to the embodiment uses toner having the following properties (contained in a toner cartridge). That is, it contains a crystalline resin having at least one of a urethane bond and a urea bond in the main chain, and a spectrum derived from the crystal structure of the binder resin in the X-ray diffraction spectrum of the toner. When the integrated intensity is represented by C and the integral intensity of the spectrum derived from the amorphous structure of the binder resin in the X-ray diffraction spectrum is represented by A, the property that the solution of “C / (C + A)” is 0.15 or more. Toner. The ratio of the crystalline polyester unit in the binder resin in the toner is desirably 50% by mass or more.

  Conventional low-temperature fixing toners contain at least crystalline polyester as a binder resin to improve low-temperature fixability. However, since crystalline polyester alone tends to cause image chipping, an amorphous resin is also used. A large amount was contained. In addition, the amorphous resin has been a cause of easily causing toner aggregation and fixation accompanying toner conveyance by the conveyance pump. Even in a conventional image forming apparatus using a low-temperature fixing toner, in order to cope with the toner aggregation and fixation, the surface of the rotor of the mono pump is plated or a metal soap such as zinc stearate is externally added to the toner. It was necessary to customize for low-temperature fixing toner such as, and this was a factor of cost increase.

  On the other hand, the toner used in the printer according to the embodiment includes a crystalline resin having a urethane bond or a urea bond in the main chain, thereby strengthening the bonding force between the crystalline resins and fixing the toner at the fixing nip. Be resistant to pressure. This makes it possible to suppress the occurrence of image defects without relying on an amorphous resin. For this reason, the amorphous resin is not included at all, or even if it is included, the ratio can be significantly reduced as compared with the conventional case. This makes it possible to form a sharp image with no missing image despite containing a crystalline polyester unit as a main component.

  As the crystalline resin used as the binder resin for the toner, it is more preferable to use a resin having a urea bond in the main chain. This is because by having a urea bond in the main chain, the structure of the resin is strengthened and can be made very strong against pressure. By making the pressure resistance higher, it is possible to create a low-temperature fixing system with a high degree of design freedom (= easy to design at low cost). In addition, since the degree of freedom in design is high, it is possible to reduce the cost by commonly using it in many machines.

  As the toner, the ratio of the weight of nitrogen element to the sum of the weights of carbon element, hydrogen element and nitrogen element in the components soluble in tetrahydrofuran is 0.3 to 2.0 [wt%] among all the components. It is desirable to use one. This is for the reason explained below. In other words, the presence of the urethane bond “—O—CO—NH—” in the toner makes it possible to maintain pressure resistance. However, when the number of urethane bonds increases beyond a certain ratio, the low temperature fixability is hindered because the urethane bonds themselves are non-crystalline sites. Therefore, the amount of urethane bonds needs to be large enough to be strong against pressure and small enough not to inhibit low-temperature fixing. The ratio can be confirmed by performing CHN analysis, and it has been found that an appropriate urethane bond amount is obtained when the ratio is 0.3 to 2.0 [wt%].

  As the toner, it is desirable to use a toner containing a first crystalline resin and a second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin. 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 the binder obtained by modifying the first crystalline resin. It is preferred 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 are more easily dispersed in the toner, and the variation in characteristics between toner particles is further increased. Can be suppressed. The crystalline resin may be a combination of the crystalline resin and the amorphous resin, and the main component of the binder resin is preferably the crystalline resin. The second crystalline resin may be obtained 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 to extend the resin. 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.

  When designing a low-temperature fixing toner using a crystalline resin, if it is designed with only a toner having a low average molecular weight, it will surely melt easily, but it will also easily adhere to the fixing agent, and will easily become hot when the temperature rises. Offset is likely to occur. In order to actually establish an image forming apparatus system, it is easier to use a toner that melts at a low temperature and at the same time generates a hot offset at a higher temperature. In particular, in recent years, plain paper has become slightly thinner and thicker, and if you want to use them at the same process speed, the fixing temperature setting margin must be wide (= wide temperature range). If the toner is not melted without problems such as hot offset, it is difficult to establish, and the number of sheets that cannot be used with high productivity as an image forming apparatus increases. For this reason, it is desirable to use toner having a wide fixing temperature setting range.

  By using two types of crystalline resins, a low average molecular weight resin and a high resin, low temperature fixability can be achieved for low molecular components with uneven surfaces such as paper. However, it is difficult to bond hot-offsets due to the presence of the polymer component for those having low wettability. By using such a toner, it is possible to provide a user-friendly image forming apparatus having a high margin for setting the paper type.

  Further, it is desirable to use a toner obtained by extending a modified crystalline resin having an isocyanate group at the terminal. This is because by extending a resin having an isocyanate group (—NCO) at the terminal, urethane groups can be introduced into the resin at a certain ratio. By limiting the proportion of urethane bonds in the toner to a certain extent, it is possible to obtain a toner that establishes heat, pressure, and low-temperature fixing.

  Further, it is desirable to use a toner containing a metal soap externally added to the toner particles. Sliding properties are improved by inserting metal soap into the place where metal and rubber rub against each other. Further, the surface of the rotor is constantly refreshed by repeating the phenomenon that the surface of the rotor is covered with metal soap and peeled off, and toner sticking is prevented. As a result, toner aggregation is suppressed. A system margin can be ensured by further externally adding toner that is strong against pressure.

  As shown in Table 10, it can be seen that the toner containing the metal soap reduces ΔW compared to the toner not containing the toner. This means that the durability margin over time has been improved by the addition of metal soap (in this example, zinc stearate). In addition, the amount of aggregates may vary depending on how the sieve is struck, but since the weight is less susceptible to measurement variations, ΔW is considered to be a more reliable result.

  In order to achieve both low-temperature fixability and heat-resistant storage stability at a higher level and to have excellent hot offset resistance, the toner has a heat of fusion at the second temperature increase measured by a differential scanning calorimeter (DSC). It is preferable to use one having a maximum peak temperature in the range of 50 ° C. or more and 70 ° C. or less and a heat of fusion at the second temperature increase of 30 J / g or more and 75 J / g or less. When the maximum peak temperature of the heat of fusion of the toner is less than 50 ° C., toner blocking is likely to occur in a high temperature environment, and when it 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 particularly preferably 58 ° C. or more and 65 ° C. or less.

  When the heat of fusion 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 it is difficult to obtain a balance between heat resistant storage stability and low temperature fixability. 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 particularly preferably 50 J / g or more and 60 J / g or less.

  The maximum peak temperature of the heat of fusion of the crystalline resin is preferably 50 ° C. to 70 ° C., more preferably 55 ° C. to 68 ° C., and particularly preferably 60 ° C. to 65 ° C. from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. 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.

  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 to be 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./minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./minute, and then again the heating rate Measure the endothermic change by increasing the temperature at 10 ° C / min, draw a graph of "endothermic amount" and "temperature", and set the temperature corresponding to the maximum peak of the endothermic amount to the second heat of fusion The maximum peak temperature of Further, the endothermic amount of the endothermic peak having the maximum peak temperature at this time is defined as the second heat of fusion.

Further, as the toner, the storage elastic modulus G ′ (80) (Pa) at 80 ° C. is 1.0 × 10 ⁴ or more and 5.0 × 10 ⁵ or less, and the storage elastic modulus G ′ (140) at 140 ° C. ) (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. Storage modulus G '(80) is 1.0 × ¹⁰ 4 Pa or more, more preferably 1.0 × ¹⁰ 5 Pa or less, 5.0 × ¹⁰ 4 Pa or more, particularly preferably 1.0 × ¹⁰ 5 Pa or less .

When the storage elastic modulus G ′ (140) (Pa) 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. Storage modulus G '(140) is, 1.0 × ¹⁰ 3 Pa or more, more preferably 1.0 × ¹⁰ 4 Pa or less, 5.0 × ¹⁰ 3 Pa or more, particularly 1.0 × ¹⁰ 4 Pa or less preferable.

  As the toner, it is preferable to use a toner in which the amount of N element soluble in THF is in the range of 0.3 to 2.0 wt%. More preferably, it is in the range of 0.5 to 1.8 wt%, and more preferably 0.7 to 1.6 wt%. If it exceeds 2.0 wt%, the viscoelasticity in the molten state of the toner may become too high, resulting in deterioration of fixability, reduction of gloss, deterioration of chargeability, and the like. Further, if it is less than 0.3 wt%, there is a possibility of causing 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 molten toner state. .

  Further, the weight average molecular weight Mw of the crystalline resin of the toner is preferably 2000 to 100,000, more preferably 5000 to 60000, and particularly preferably 8000 to 30000 from the viewpoint of fixability. When the weight average molecular weight Mw is less than 2000, the hot offset resistance tends to deteriorate, and when it exceeds 100000, the low temperature fixability tends to deteriorate.

Next, a modified example of the printer according to the embodiment will be described. Unless otherwise specified below, the configuration of the printer according to the modification is the same as that of the embodiment.
FIG. 8 is a plan sectional view showing the first developer accommodating portion 53Y and the second developer accommodating portion 54Y of the developing device for Y in the printer according to the embodiment. A second transport screw 56Y is disposed in the second developer accommodating portion 54Y. The second developer accommodating portion 54Y is connected to a developer charging chamber arranged in the screw axis direction with respect to the second developer accommodating portion 54Y, and both communicate with each other.

  An input toner transport screw portion 57Y is formed at the upstream end of the second transport screw 56Y in the developer transport direction. The charged toner conveying screw portion 57Y is located in the developer charging chamber. In the printer according to the embodiment, the toner is charged from above into the second developer accommodating portion 54Y. However, in the printer according to the embodiment, the developer is accommodated in the developer loading chamber that accommodates the charged toner conveying screw portion 57Y. On the other hand, toner is supplied from above. There is almost no magnetic carrier in the developer charging chamber, and only newly charged toner is accommodated.

  When the second transport screw 56Y rotates, the input toner transport screw portion 57Y that rotates integrally with the second transport screw 56Y feeds the toner in the developer input chamber into the second developer storage portion 54Y. The sent toner spreads uniformly around the rotating shaft member of the second conveying screw 56Y. Therefore, unlike the case where the toner is put into the second conveying screw 56Y holding the developer around the rotating shaft member from above, the toner above the developer, the developer below the toner, It is possible to avoid the occurrence of a situation where the toners are slid to each other to cause poor mixing of the toner with the developer.

  FIG. 9 is a side view showing the Y toner replenishing device 80Y for supplying toner to the developer charging chamber, together with the toner cartridge 32Y and the developing device 5Y. The toner replenishing device 80Y includes a sub hopper portion 81 that receives toner discharged from the opening of the toner cartridge 32, and a transport pipe 82Y that sends toner from the sub hopper portion 82 to the developing device 5Y. A screw member that conveys the toner with rotation is disposed in the conveyance tube 82Y. The toner transported in the transport pipe 82Y is put into the developer charging chamber of the developing device 5Y via the tip of the transport pipe 82Y.

  FIG. 10 is a cross-sectional view showing the Y toner replenishing device 80Y. In the drawing, only the cross section of the transport pipe 82Y is shown, but actually, the pipe section located on the upstream side in the toner transport direction from the cross section is directed downward in the vertical direction from the position of the cross section. It extends. A toner end detection sensor 83Y and a stirring device 85Y are disposed in the sub hopper 81Y of the toner replenishing device 80Y. The stirrer 85Y stirs the toner in the sub hopper 81Y by rotating the plate stirrer while sliding the tip of the flexible plate stirrer against the inner wall of the sub hopper 81Y. To do. During the stirring, a part of the toner passes over the partition wall 84Y of the sub hopper 81Y and enters the transport pipe 82Y. Then, the inside of the transport pipe 82Y is transported by the screw member along the longitudinal direction of the pipe, and is put into the developer charging chamber of the developing device (5Y).

  When the toner is likely to be fixed and aggregated, the toner is fixed to the plate-like stirring member 85Y of the stirring device 85Y, or the toner is hardened in a spiral space in the screw member in the conveying tube 82Y. Then, the solid matter is transported into the developing device to cause an abnormal image, or the toner solidified in the spiral space of the screw member disturbs the toner transport to make the toner replenishment amount unstable, or the screw member rotates. May be locked. Among these problems, the first image that occurs is an abnormal image due to a large fixed matter of toner. Specifically, there are white-out images in which the fixing member adheres to the photosensitive member and the periphery of the image is not transferred, and white streaked images in which the fixed matter inhibits the pumping of the developer by the developing roller of the developing device. .

  Although the Y developing device and toner replenishing device have been described, the M, C, and K developing devices and toner replenishing device have the same configuration as that for Y.

The inventors prepared a printer testing machine having the same configuration as the printer according to the example. Then, the image quality was evaluated based on the result of test printing by this printer testing machine. As the image quality, the above-described white spots and white stripes were evaluated.
[Outline of image]
After outputting 50,000 chart images with an image area ratio of 0.5%, visual evaluation was performed for the presence or absence of white spots in the image area when the full paper image was output. The following four levels were adopted as evaluation criteria.
A: The image area is in a good state with no white spots in the form of white spots.
◯: A good state in which only a small amount of white spot-like portions are seen in the image area.
Δ: Slightly white spots are observed in the image area, but there is no problem in actual use.
X: A level that causes a problem in practical use since a large number of white spots are observed in the image area.

[White streaks and spots of images due to toner aggregates]
A chart image with a 20% image area ratio was output to 1000 recording sheets by a printer testing machine. Then, after leaving for 2 months in a high temperature and high humidity environment where temperature = 40 ° C. and humidity = 70%, a test print was performed. Then, white streaks and spot images due to clogging of a doctor blade (for example, 52Y) caused by toner aggregates were evaluated. The following four levels were adopted as evaluation criteria.
A: An excellent state in which there are no white stripes in the image area and there is no aggregated spot image.
◯: A good state where there is no white streak in the image area and a spot image due to aggregates is very slightly observed.
Δ: There are no white streaks in the image area, and a slight spot image due to aggregates is seen, but there is no problem in practical use.
X: Level in which white streaks are seen in the image area and the doctor blade is clogged, causing a problem in actual use.

Table 11 below shows the results of experiments performed on toners of toner numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, 13, 15, and 16.

  As shown in Table 11, it can be seen that almost the same result as that of the printer of the embodiment using the MONO pump is obtained in terms of ease of toner fixing.

6Y, M, C, K: Image forming device (image forming means)
32Y, M, C, K: Toner cartridge (toner accommodating means)
38Y: Conveyance pump

JP 2010-0777419 A JP 2009-014926 A JP 2010-151996 A JP 2005-266511 A JP 2011-164530 A JP 2010-85478 A

Claims (7)

An image forming unit that forms a toner image using toner, a toner storage unit that stores toner to be supplied to the image forming unit, and a toner discharged from the toner storage unit toward the image forming unit An image forming apparatus including a conveying unit that conveys the image;
The toner contains a crystalline resin having at least one of a urethane bond and a urea bond in the main chain ;
Each table of the integrated intensity of spectrum in A derived integrated intensity of spectrum C, and non-crystalline structure of the binder resin in the X-ray diffraction spectrum derived from the crystal structure of the binder resin in the X-ray diffraction spectrum before Symbol toner when state, and are solutions of 0.15 or more "C / (C + a)",
The ratio of the weight of nitrogen element to the sum of the weights of carbon element, hydrogen element and nitrogen element in the components soluble in tetrahydrofuran among the total components of the toner is 0.3 to 2.0 [wt%]. Oh image forming apparatus according to claim Rukoto. The image forming apparatus according to claim 1,
An image forming apparatus, wherein the toner contains a crystalline resin having a crystalline polyester unit. The image forming apparatus according to claim 1, wherein:
An image forming apparatus, wherein the toner contains a crystalline resin having a urea bond in the main chain. The image forming apparatus according to any one of claims 1 to 3 ,
The toner includes, as a crystalline resin, a first crystalline resin and a second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin. Image forming apparatus. The image forming apparatus according to claim 4 .
The 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 to 5,
The ratio Tsh2nd / Tsh1st between the shoulder temperature Tsh1st of the first heat-up melting peak and the shoulder temperature Tsh2nd of the second heat-up peak measured with a differential scanning calorimeter (DSC) of the toner is 0.90 or more. 1. An image forming apparatus having a value of 10 or less. The image forming apparatus according to claim 1 to 6,
An image forming apparatus, wherein the toner comprises a metal soap externally added to toner particles.

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