JP2009020269A - Image forming apparatus, and toner, carrier, and developer for use in the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming apparatus having improved filming property against a photoreceptor, allowing low-temperature fixing, having satisfactory toner storage properties, high-temperature fixing winding properties, and high adhesion strength with a fixing paper, in a high-speed output system, and to provide an image forming apparatus achieving a high developer life while maintaining a highly-reliable image, capable of reducing deterioration fogging in a low temperature and low humidity environment, and printing a high-quality image. <P>SOLUTION: In the image forming apparatus including a fixing device fixing a visible image on a recording medium by heat and pressure, a system speed is 400 to 3,000 mm/sec, a pressing surface pressure of the fixing medium of the fixing device is 5 to 90 N/cm<SP>2</SP>, the toner for use in the formation of the visible image includes at least an amorphous polyester resin, a crystal polyester resin, a colorant, and a releasing agent, and crystal component ratio of the crystal polyester resin in the toner is 0.10 to 20%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an image forming apparatus using electrophotographic imaging, and a toner, a carrier and a developer used therefor.

In recent years, high speed and high image quality are generally required in the electrophotographic imaging industry. In particular, toner fixability, which is one of the factors that have an important influence on image quality, deteriorates as the image forming speed, that is, the so-called system speed of the image forming apparatus, increases. It is a problem to make it. Further, the deterioration of the softening property of the resin generated to improve the fixing property and the extensive use of the release agent cause the photoconductor filming of the toner, and this phenomenon causes the deterioration of the image quality, which is a problem.
In this way, even with one keyword of speeding up, various side effects caused by it, such as not only the fixing property described above, but also developability (chargeability), heat-resistant storage stability as a toner, photoreceptor contamination (filming), etc. It has been difficult to achieve these problems simultaneously with conventional devices.

The unfixed toner image on the paper is fixed by heat and pressure in the fixing device, and the toner image is fixed to the paper. However, when the system speed increases, the unfixed toner image on the paper cannot receive a sufficient amount of heat in the fixing device. This is not preferable because the toner with poor fixing is peeled off from the paper.
It is conceivable to increase the fixing temperature in order to maintain the fixing performance as the system speed increases, but there are problems in terms of various side effects due to temperature rise in the machine, the life of fixing member consumption, energy saving, etc., and fixing improvement It was inappropriate as a response. Therefore, particularly in an ultra-high speed machine, improvement in toner fixing performance and photoconductor contamination is required, and toner, a fixing device, and an image forming apparatus having high-speed image formation with a fixing device and good fixing property even with a low heat amount are required. It is said that.

Various studies have been made to improve the fixing property of the toner.
For example, in order to improve the fixing performance of the toner itself, a method of controlling the thermal characteristics of the resin itself is known. However, lowering the Tg (glass transition temperature) of the resin will cause deterioration in heat-resistant storage stability and fixing strength. If the softening temperature is lowered due to the lower molecular weight of the resin, the occurrence of hot offset and gloss are too high (gloss control). Problems) occur. For this reason, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner that is excellent in low-temperature fixability and excellent in heat-resistant storage stability and offset resistance.

  In order to cope with such low-temperature fixing, attempts have been made to use polyester resins that are excellent in low-temperature fixing properties and relatively good in heat-resistant storage, in place of styrene-acrylic resins that have been widely used in the past (Patent Documents 1 to 3). 6: JP-A-60-90344, JP-A-64-15755, JP-A-2-82267, JP-A-3-229264, JP-A-3-41470, JP-A-11-305486 Publication). In addition, there is an attempt to add a specific non-olefinic crystalline polymer having a sharp melt property at a glass transition temperature to a binder for the purpose of improving low-temperature fixability (Patent Document 7: JP-A-62-63940). However, it cannot be said that the molecular structure and molecular weight are optimized.

  There are also attempts to use crystalline polyester having sharp melt properties (Patent Document 8: Japanese Patent No. 2931899, Patent Document 9: Japanese Patent Laid-Open No. 2001-222138), but it is not compatible with high speed machines. However, it is not an excellent toner that can achieve both low-temperature fixability and toner storability and photoconductor contamination. In addition, it has been found from various studies that even if crystalline polyester is used, almost all components are present in an amorphous state in the toner, and it has been found that the original function of crystalline polyester has not been fully exhibited. It was.

In terms of the fixing device, it is difficult to simply use the conventional device as it is, and it is necessary to have a new idea that considers the interaction with the toner characteristics as well as improving the performance of the fixing device. It has been said.
JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 JP 2001-222138 A

  In view of the above-described problems, the present invention improves the filming (contamination) property to a photoconductor in a high-speed output system, enables low-temperature fixing, has good toner storage stability, and has good fixing and high-temperature wrapping properties. It is an object of the present invention to provide an image forming apparatus having a sufficiently high fixing strength with paper. In addition, a highly charged toner, a developing system with low carrier spent, and a developer are used to achieve a high developer life while maintaining a highly reliable image, and at a low temperature and low humidity. It is an object of the present invention to provide an image forming apparatus capable of reducing deterioration fog in an environment and printing a high-quality image.

In order to solve the above problems, the present invention is characterized by the following.
(1) In an image forming apparatus including a fixing device that fixes a visible image on a recording medium by heat and pressure, the system speed is 400 to 3000 mm / sec, and the pressing surface pressure of the fixing medium of the fixing device is 5N. / Cm ^{2 to} 90 N / cm ² , and the toner used for visible image formation is a toner containing at least an amorphous polyester resin, a crystalline polyester resin, a colorant, and a release agent, and is crystalline. An image forming apparatus comprising a polyester resin having a crystal component ratio of 0.10 to 20% in the toner.

(2) The image forming apparatus according to (1), wherein the fixing medium surface has a composition containing at least a fluororesin.
(3) The fixing medium surface contains at least one polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a polymer of both. The image forming apparatus according to (1) or (2), wherein the image forming apparatus is provided.
(4) The image forming apparatus according to any one of (1) to (3), wherein a fixing nip width of the fixing device is 4 mm to 20 mm.

(5) The image forming apparatus according to any one of (1) to (4), wherein at least one Tg peak of the crystalline polyester resin is present at least at 80 ° C to 130 ° C.
(6) The toner according to (1), wherein the toner contains at least a fatty acid amide compound as a crystallinity-holding component, and at least one Tg peak of the fatty acid amide compound exists at 70 ° C. to 160 ° C. (5) The image forming apparatus according to any one of (5).
(7) The image forming apparatus according to (6), wherein the difference between the Tg peak of the crystalline polyester resin and the Tg peak of the fatty acid amide compound is within 50 ° C.
(8) The release agent contains at least a wax having a hydrocarbon straight chain, and the wax has at least one Tg peak at 40 to 130 ° C. 7) The image forming apparatus according to any one of 7).
(9) The image forming apparatus according to (8), wherein the wax contains at least one of carnauba wax, polyethylene wax, polypropylene wax, synthetic ester wax, and paraffin wax.

(10) The image forming apparatus according to any one of (1) to (9), wherein the toner is a color toner.
(11) The image forming apparatus according to any one of (1) to (10), wherein the toner is toner having an average circularity of 0.94 or more and less than 1.00.
(12) The toner has a volume average particle diameter of 2.0 to 7.0 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.0 to 1.0. The image forming apparatus according to any one of (1) to (11), wherein the toner is in a range of 1.3.

(13) A latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier is exposed based on image data, and electrostatically charged. An exposure means for writing a latent image, a developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible, and a visible image on the surface of the latent image carrier to be transferred The image forming apparatus according to any one of (1) to (12), further comprising: a transfer unit that transfers to a body; and a fixing unit that fixes a visible image on the transfer target.
(14) Any one of (1) to (13), wherein the image forming apparatus includes a process cartridge that integrally supports the latent image carrier and at least the developing unit and is detachable from the main body of the image forming apparatus. An image forming apparatus according to claim 1.
(15) A toner used in the image forming apparatus according to any one of (1) to (14).
(16) A carrier having at least magnetism, which is used in the image forming apparatus according to any one of (1) to (14).
(17) A developer containing at least a toner and a carrier, which is used in the image forming apparatus according to any one of (1) to (14).
Developer.

According to the present invention, even in an ultra-high-speed image forming apparatus, it has excellent low-temperature fixing property, filming property, high-temperature wrapping property, storage stability, sufficiently high fixing strength with fixing paper, and highly controlled charging characteristics. Providing a developing system with less toner and carrier spent, an image forming apparatus that can achieve high developer life while maintaining highly reliable images, and can reduce deterioration fog in low-temperature and low-humidity environments can do.
Further, according to the present invention, it is possible to provide the image forming apparatus and the toner, carrier, developer, and process cartridge used therefor.

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

The image forming apparatus in the present invention is as follows. In an image forming apparatus including a fixing device that fixes a visible image on a recording medium by heat and pressure, the system speed is 400 to 3000 mm / sec, and the pressing surface pressure of the fixing medium of the fixing device is 5 N / cm ^2. a ~90N / cm ^2, and toner used in the visible image formation, a toner containing at least an amorphous polyester resin and a crystalline polyester resin and a colorant and a release agent, and the crystalline polyester resin The image forming apparatus is characterized in that a crystal component ratio in the toner is 0.10 to 20%.

  According to the present invention, the image forming apparatus (fixing apparatus), the toner, and the two elements exhibit their functions effectively, and make up for the lack of functions of each other. It has been found that many conflicting problems such as filming property, low-temperature fixing property, toner storage property, carrier spent property, high durability developing property, and fogging property can be achieved at a very high level.

As an image forming apparatus, particularly as a fixing apparatus, it is first important to control the system linear velocity and the surface pressure. In order to form an appropriate image quality even when the system speed is 400 to 3000 mm / sec, preferably 500 to 2500 mm / sec, more preferably 1000 to 2500 mm / sec, the pressure surface pressure of the fixing medium is 5 N / cm ² ~90N / cm ^2, more preferably, is important to ^{10N / cm 2 ~90N / cm 2} , toner pressed properly pressurized is fixable by its proper surface pressure. When the surface pressure is less than 5 N / cm ² , it is not preferable because the toner is not sufficiently pressed against the fixing paper, the fixing image has insufficient fixing strength, and the toner is peeled off from the paper. On the other hand, if the surface pressure exceeds 90 N / cm ² , the load on the paper increases in maintaining the system speed, which is not preferable. Further, the amount of the toner release agent oozes out excessively, which is not preferable from the viewpoint of filming.

  On the other hand, as a toner suitable for the above-described image forming apparatus, a toner containing at least an amorphous polyester resin, a crystalline polyester resin, a colorant, and a release agent, and the crystalline component ratio of the crystalline polyester resin in the toner Is important to be 0.10 to 20%. Here, the amorphous polyester resin is preferable as a binder resin for the toner in controlling the chargeability, thermal characteristics, colorant, release agent and other dispersibility of various components, in order to improve the hot offset margin and heat resistant storage stability of the toner. Also effective. Crystalline polyester, on the other hand, is effective for low-temperature fixability by taking advantage of the sharp melt property at the time of fixing and melting derived from its crystal structure. On the other hand, when used in combination with amorphous polyester, some crystalline components become amorphous at the component interface, improving the binding properties as amorphous polyester, and becoming a polyester resin with more stable crystalline and amorphous parts. And the upper limit), and the balance between the heat resistant storage stability and the photoreceptor filming property is more preferable. Furthermore, it has been found that the balance between the low-temperature fixability and the heat-resistant storage stability can be achieved to a higher degree by controlling the content ratio of the crystalline component to 0.10 to 20%. Here, when the crystalline component ratio is less than 0.10%, the function of the crystalline polyester cannot be sufficiently exhibited, and the low temperature fixing property is inferior. On the other hand, if it exceeds 20%, the low-temperature fixability is sufficient, but filming of the crystalline component with respect to the photoreceptor or the like, or carrier spent tends to occur, which is not preferable because it causes image abnormality and charge reduction. Further, it is not preferable from the viewpoint of maintaining the hot offset property of the toner.

  Further, it is more preferable that the medium surface of the fixing device has a composition containing at least a fluororesin because the releasability between the fixing medium and the toner is improved and filming is less likely to occur. Further, since heat conduction at the time of fixing is sufficient, fixing melting property can be secured, and the lower limit of fixing property is more preferable.

  Furthermore, the surface of the fixing medium has at least one polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a composition containing at least one of both polymers. Further, the releasability between the fixing medium and the toner is further improved, and filming is hardly generated, which is more preferable. Further, since heat conduction during fixing becomes more sufficient, fixing meltability can be secured, which is more preferable. Furthermore, due to the physical and chemical characteristics of the surface properties in the chemical composition, the pressure transmission to the fixing paper, the non-affinity with the toner resin, and the non-adhesiveness of the release agent in the toner are further improved, resulting in better fixing characteristics It is more preferable because it can be secured.

  Further, when the fixing nip width of the fixing device is 4 mm to 20 mm, and more preferably 6 mm to 15 mm, the fixing pressure and the fixing heat are appropriately transmitted to the toner, and sufficient and not excessive melting property can be secured. When the fixing nip width is less than 4 mm, a sufficient fixing time and fixing width cannot be secured for a high system linear velocity, and the fixing pressure and fixing heat are not sufficiently transferred to the toner. It is not preferable because it cannot sufficiently exude. On the other hand, when the fixing nip width exceeds 20 mm, the fixing heat and fixing pressure are sufficiently transmitted to the toner. However, at a high system speed, the melting property of the toner is too high and the fixing paper is wound around the fixing medium. It is not preferable. At that time, it has also been found that, even in a toner release agent that originally functions for winding, exudation of a certain amount or more of the release agent cannot exert a sufficient effect. Rather, it causes filming as a side effect of the release agent, which is not preferable.

  Furthermore, the toner used in the image forming apparatus of the present invention contains at least one kind of crystalline polyester resin, and the Tg peak of the crystalline polyester is at least 80 ° C. to 130 ° C., more preferably 90 ° C. to 130 ° C. By being present at ° C., the above-described effects can be more fully exhibited. In other words, even in a low fixing pressure and low temperature fixing environment, not only the toner can be melted and fixed properly, but also heat-resistant storage can be achieved at the same time, and it is also unique to the release of release agents and fatty acid amide compounds. It is more preferable that a proper crystal structure interacts properly during heating and can sufficiently exert a bleeding effect. Here, when the Tg peak is less than 80 ° C., not only the heat-resistant storage stability of the toner cannot be secured, but also the low melting component causes hot offset, which is not preferable. On the other hand, when the Tg peak exceeds 130 ° C., it cannot be applied to a low pressure and low temperature fixing environment at a high system linear velocity, and the fixing strength of a fixed image is lowered, which is not preferable. Moreover, since it is not possible to achieve proper release of the release agent, it is not preferable because fixing wrapping easily occurs.

  The toner used in the image forming apparatus contains at least a fatty acid amide compound as a crystallinity-holding component, and the Tg peak of the fatty acid amide compound is at least 70 ° C. to 160 ° C., more preferably 90 ° C. to 150 ° C. The presence of one or more can achieve low temperature fixability due to the crystalline polyester retention effect of the fatty acid amide compound, especially in low fixing pressure and low temperature fixing environments at high system linear speeds. More preferable. Furthermore, the secondary effect of the fatty acid amide compound is preferable because not only fixing hot offset and fixing wrapping can be prevented, but also adhesion of the photoreceptor filming can be reduced. Further, it has been found that the fatty acid amide compound is very effective in terms of improving the heat resistant storage stability of the toner. Here, when the Tg peak is less than 70 ° C., the fatty acid amide compound itself is released from the toner, which is not preferable because it causes photoconductor filming and carrier spent. On the other hand, when the Tg peak exceeds 160 ° C., it cannot be sufficiently melted and oozed out with respect to the heat applied to the toner, and the effect of improving the fixing property cannot be exhibited.

  In addition, since the difference between the Tg peak of the crystalline polyester and the Tg peak of the fatty acid amide compound is within 50 ° C., the crystalline polyester and the fatty acid amide compound exert a sufficient thermal interaction, and a sufficient bond is formed at the interface. It is more preferable that the crystallinity of the crystalline polyester is easily maintained by having the adhesiveness. When the difference in Tg peak exceeds 50 ° C., the crystallinity cannot be sufficiently maintained, which is not preferable.

  The toner used in the image forming apparatus contains at least a wax having a hydrocarbon straight chain as a release agent, and the Tg peak of the wax is at least 40 ° C. to 130 ° C., more preferably 70 ° C. to 120 ° C. By having one or more at ℃, the toner releasability functions more effectively by achieving rapid wax exudation even in low pressure and low temperature fixing environments, especially at high system linear speeds. More preferred.

  Further, in the toner used in the image forming apparatus, the wax contains at least one of carnauba wax, polyethylene wax, polypropylene wax, synthetic ester wax, and paraffin wax, so that the system linear speed is particularly high. Even in a low fixing pressure and low temperature fixing environment, it is more preferable that rapid wax exudation can be achieved and at the same time the adhesion of the photosensitive member filming can be reduced.

  Further, since the toner used in the image forming apparatus is a color toner, sufficient fixability is ensured even at a high system linear speed, and the toner has required melting transparency, color clarity, gloss and the like required for the color toner. It is more preferable because it can be achieved in a higher dimension.

  Further, since the toner used in the image forming apparatus is a toner having an average circularity of 0.94 or more and less than 1.00, not only the fixing image quality is improved by improving the transferability but also on the unfixed paper. By ensuring the surface uniformity of the transfer toner, sharp melt properties function more effectively due to the effect of heat conduction uniformity when fixing the toner image, and at low system pressure and low pressure It is more preferable because sufficient fixing property can be ensured even in a temperature fixing environment. Here, when the average circularity is less than 0.94, the size of the unevenness of the unfixed image becomes too large, and heat conduction at the time of fixing is not preferable. Further, when the average circularity is 1.00 or more, it is preferable from the viewpoint of the uniformity of the unfixed image, but due to the spherical property, the toner cleaning property on the surface of the photosensitive member is deteriorated, thereby causing fine powder spherical toner filming. It is not preferable.

  The toner used in the image forming apparatus has a volume average particle diameter of 2.0 to 7.0 μm and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) is 1. Since the toner is in the range of 0.001 to 1.30, not only high resolution and fine image quality can be obtained, but also heat resistance storage stability as an effect due to the uniform particle size can be secured and fixing can be achieved. Uniformity of toner meltability at the time can be ensured, fine powder hot offset caused by submicron fine powder toner can be prevented, wax exudation property is uniform, and there are few fine powders with high relative wax content As a result, the uneven distribution of the wax is eliminated, so that the filming of the photoconductor hardly occurs, which is more preferable.

  Here, when the volume average particle size is less than 2.0 μm, the non-electrostatic adhesion due to the particle size effect increases, so that the photoconductor filming is likely to occur. Further, when the volume average particle diameter exceeds 7.0 μm, it is not preferable because uniformity of toner melting property cannot be secured. (Dv / Dn) is 1.00 when there is no particle size distribution, and the value increases when the particle size distribution is widened, but when the particle size distribution exceeds 1.30, the above-mentioned submicron fine toner This is not preferable because fine powder hot offset due to the occurrence of the toner or uneven distribution of the wax due to the wide particle size distribution occurs and the photoconductor filming is likely to occur.

  In the image forming apparatus, a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and a surface of the charged latent image carrier based on image data. An exposure unit for exposing and writing an electrostatic latent image; a developing unit for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier; A more efficient and functional image forming apparatus can be obtained by including a transfer unit that transfers the visual image to the transfer target and a fixing unit that fixes the visible image on the transfer target.

  Further, in the image forming apparatus, the image forming apparatus integrally supports the latent image carrier and at least the developing unit, and includes a process cartridge that can be attached to and detached from the image forming apparatus main body. It is more preferable because the latent image carrier and the developer can be efficiently exchanged to correspond to the system.

(Image forming device)
FIG. 1 shows a copying machine as an image forming apparatus according to the present embodiment. The copying machine 11 includes a document reading unit 12 that reads a document to be copied, a paper feeding unit 13 that stocks printing paper, and an image from the document reading unit 12 on paper supplied from the paper feeding unit 13. An image forming unit 14 that forms a toner image based on the signal, a fixing unit 15 as a fixing device that fixes the toner forming the toner image on the paper, and a paper discharge for discharging the paper after toner fixing to the outside of the apparatus. Part 16.

  The document reading unit 12 includes a lamp 17 and mirrors 18a and 18b that travel in the direction of arrow A to scan the document, and a CCD 19 that receives reflected light from the document. The paper supply unit 13 includes a plurality of trays 20a, 20b, 20c, and 20d, and sheets of different sizes are stocked in each tray.

  The image forming unit 14 includes a photosensitive drum 21 that rotates in the direction of arrow B, a charging roller 22 that uniformly charges the surface of the photosensitive drum 21, and the surface of the uniformly charged photosensitive drum 21. A laser light source 23 that forms an electrostatic latent image based on the light reception result, a developing roller 24 that visualizes the electrostatic latent image as a toner image by supplying toner to the surface of the photosensitive drum 21, and the photosensitive drum 21. A transfer roller 25 for transferring the toner image formed on the surface of the photosensitive drum 21 onto the paper from the paper supply unit 13 and a cleaning mechanism 26 for cleaning the surface of the photosensitive drum 21 after the transfer. The paper discharge unit 16 includes a paper discharge port 27 that communicates the inside and outside of the copier 11 and a tray 28 that receives the discharged paper. The paper from the image forming unit 14 is discharged after passing through the fixing unit 15 described below. The paper passes through the paper mouth 27 and is discharged onto the tray 28.

  As shown in FIG. 2, the fixing unit 15 includes a heat fixing roller 29 as a fixing medium for heating and fixing the unfixed toner T on the paper P, and a halogen that is provided inside the heat fixing roller 29 and heats it. A lamp 30, a pressure roller 32 that closely contacts the heat fixing roller 29 with the elastic layer 31 facing the heat fixing roller 29, and a paper jam caused by the paper P adhering to the heat fixing roller 29 after toner fixing are prevented. For this purpose, a separation claw 33 that contacts the heat-fixing roller 29 and separates the paper attached thereto, a thermistor thermometer 34 that detects the surface temperature of the heat-fixing roller 29, and a paper conveyance path inside the copier 11. And a detection sensor 35 that detects the paper P entering the heat fixing roller 29.

  The heat fixing roller 29 is manufactured by forming a release layer 37 on the surface of an aluminum cylindrical cored bar 36. Specifically, a thin cored bar having a thickness t of 0.7 mm or less is used for the cored bar 36 in order to facilitate heating by the halogen lamp 30 to save energy, and the primer layer is roughened by roughening the surface of the cored bar 36. After forming, preferably contains a fluororesin material, more preferably at least one polytetrafluoroethylene resin (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a polymer of both. The outline of the release layer 37 is molded. Thereafter, the surface of the release layer 37 is varnished by a smoothing device.

  As shown in FIG. 2, the fixing nip width of the present invention is indicated by a fixing nip width N as a width where the surface release layer 37 of the heat fixing roller 29 and the elastic layer 31 of the pressure roller 32 opposed to the surface release layer 37 contact each other.

FIG. 3 shows another embodiment of the present invention, and is a schematic diagram showing the configuration of a color tandem indirect transfer type image forming apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which it is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) further mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.
Then, as shown in FIG. 3, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so that it can be rotated and conveyed clockwise in the figure.

In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.
Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.
An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.

A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.
The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, under such a secondary transfer device 22 and a fixing device 25, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet in parallel with the tandem image forming device 20 described above. Is provided.

Now, when making a copy using this color image forming apparatus, the document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

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

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.

Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer body 10, the sheet is fed between the intermediate transfer body 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.
The sheet after the image transfer is conveyed by the secondary transfer device 22 and sent to the fixing device 25, and heat and pressure are applied to the fixing device 25 to fix the transferred image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.
Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  In the tandem image forming apparatus 20 described above, the individual image forming means 18 includes, in detail, a charging device, a developing device, a primary transfer device, a photoconductor cleaning device, a static eliminator, etc. around the drum-shaped photoconductor 40. I have it.

(Process cartridge)
FIG. 4 is a schematic diagram showing a configuration of an image forming apparatus including the process cartridge of the present invention.
In the present invention, among the constituent elements such as the photosensitive member, the charging device, the developing unit, and the cleaning unit, at least the photosensitive member and the developing unit are integrally coupled as a process cartridge, and the process cartridge is configured as a copying machine or a printer. It is configured to be detachable from the main body of the image forming apparatus.

(System speed (linear speed))
In the present invention, the system linear velocity was measured as follows. When A4 paper, longitudinal paper passage (length of paper passage paper: 297 mm), continuous 100 sheets, output by the corresponding image forming apparatus, the output time from the start to the end is A second, and the system speed is B, The system speed was calculated by the following formula.
B (mm / sec) = 100 sheets × 297 mm ÷ A seconds (fixing surface pressure)
The fixing pressure surface pressure in the present invention can be measured by using a general pressure sensor.

(Crystalline component ratio of crystalline polyester resin in toner)
The crystal component ratio in the toner of the present invention was evaluated using an Ultra 55 Schottky thermal FE-SEM (scanning electron microscope) manufactured by Zeiss. The toner was embedded in an epoxy resin, and a cross section was prepared by an ultramicrotome (ULTRACUT UCT manufactured by Leica, using a diamond knife). Thereafter, the crystalline polyester component in the toner was stained with OsO ₄ by exposure to osmium tetroxide (OsO ₄ ) gas for 24 hours. By detecting Os, which is a heavy element, as white contrast by the atomic number effect of the reflected electron image, the dispersion state of the crystalline polyester in the toner and the abundance ratio of the crystalline component were obtained. Here, it has been confirmed in advance that the toner-containing component is dyed OsO ₄ with raw materials, and only the crystalline polyester is dyed with a uniform white contrast. Even in the same polyester, since only a polyester having a crystal structure is dyed, it is presumed that the crystal structure is dyed selectively by physical adhesion, adsorption, bonding, or chemical reaction.

Measurement conditions of FE-SEM were as follows: a reflected electron image was measured at an accelerating voltage of 0.8 kV and a magnification of 5000 times, and three or more fields of view were measured, and 10 particles were analyzed as the number of particles. The obtained reflected electron image was binarized by image analysis software Image Plus Pro4.5.1 (Media Cybernetics, Inc), and the crystalline polyester portion was identified and analyzed by contrast. The total area of the toner was analyzed in the same manner, and the area (occupancy) of the crystalline polyester with respect to the total area of the toner was calculated by the following formula, and used as the crystal component ratio (%).
Crystal component ratio (%) = Polyester resin crystal component area / total toner area × 100
(1) Formula

  The principle of whether this method can distinguish crystalline polyester from other components of the toner will be described. First, by analyzing reflected electrons instead of secondary electrons for general shape observation of FE-SEM, the contrast difference between crystalline polyester and other resin components is detected as an image by the atomic number effect of the reflected electrons. it can. The atomic number effect is an effect that the amount of reflected electrons emitted increases as the atomic number of the sample to be detected increases, and the contrast is detected as white. On the other hand, osmium tetroxide has a selective dyeing property of the material, and in the case of the component of the toner of the present invention, it has been confirmed in advance by dyeing observation of raw materials that only the crystalline polyester is selectively dyed. As a result, the crystalline polyester portion can be observed with white contrast, and the other toner portions can be observed with gray to black contrast. Furthermore, by setting the acceleration voltage to 0.8 kV, the charge-up phenomenon due to the electron beam of the toner is prevented, and the surface analysis of several nanometers to several tens of nanometers can be performed by reducing the electron beam analysis depth by the low acceleration voltage. As a result, the state of the toner cross section can be analyzed more accurately.

(Tg peak)
The Tg peak of the release agent and resin in the present invention is a characteristic close to a so-called softening point, and is determined by the peak top showing the maximum endotherm of the DSC curve in differential scanning calorimetry (DSC). The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 200 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 200 ° C

  The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C. around the point showing the maximum peak of the DrDSC curve which is the DSC differential curve of the second temperature rise, and obtains the peak temperature using the peak analysis function of the analysis software. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg peak of the wax.

(Fixing medium surface coating resin)
The surface coating resin for the fixing medium of the present invention is preferably a fluorine resin. Specifically, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer Examples include coalescence (ETFE) and polychlorotrifluoroethylene (PCTFE).
More preferably, the resin is at least a polytetrafluoroethylene resin (PTFE), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a resin having a composition containing at least one of both polymers. preferable.

(Release agent)
As the release agent contained in the toner of the present invention, a low melting point wax having a melting point of 40 to 170 ° C. is more effectively used as a release agent in the dispersion with the binder resin. This works against the high temperature offset without applying a release agent such as oil to the fixing roller. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline and petrolatum. And petroleum wax. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
More preferably, a wax containing at least a hydrocarbon straight chain as the release agent and having one or more Tg peaks at 40 to 130 ° C. is more preferable.
More preferably, the release agent includes a wax containing at least one of carnauba wax, polyethylene wax, polypropylene wax, synthetic ester wax, and paraffin wax.

(Fatty acid amide compound)
The toner of the present invention more preferably contains at least a fatty acid amide compound as a crystalline retention component of the crystalline polyester resin, and the fatty acid amide compound has a Tg peak of at least 70 ° C. to 160 ° C., more preferably 90 ° C. One or more fatty acid amide compounds existing at ˜150 ° C. may be mentioned.
As the fatty acid amide compound, a compound represented by R1-CO-NR2R3 is used. In the formula, R1 is an aliphatic hydrocarbon group having 10 to 30 carbon atoms, and R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or carbon. It is an aralkyl group of several 7 to 10. Here, the alkyl group, aryl group, and aralkyl group of R2 and R3 may be substituted with a generally inactive substituent such as a fluorine atom, a chlorine atom, a cyano group, an alkoxy group, or an alkylthio group. However, it is more preferably unsubstituted.

Examples of preferred compounds include stearic acid amide, stearic acid methylamide, stearic acid diethylamide, stearic acid benzylamide, stearic acid phenylamide, behenic acid amide, behenic acid dimethylamide, myristic acid amide, palmitic acid amide and the like.
In the present invention, among the fatty acid amide compounds, alkylene bis fatty acid amides are particularly preferably used.
Examples of the alkylene bis saturated fatty acid amide include methylene bis stearic acid amide, ethylene bis stearic acid amide, methylene bis palmitic acid amide, ethylene bis palmitic acid amide, methylene bis behenic acid amide, ethylene bis behenic acid amide, hexamethylene bis stearic acid amide. And acid amide, hexaethylene bispalmitic acid amide, hexamethylene bisbehenic acid amide, and the like. Of these, ethylene bis stearamide is most preferred.

  Specific examples of alkylene bis fatty acid amide compounds that can be used in addition to the above include propylene bis stearic acid amide, butylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, propylene bis oleic acid amide, Butylene bis oleic acid amide, methylene bis lauric acid amide, ethylene bis lauric acid amide, propylene bis lauric acid amide, butylene bis lauric acid amide, methylene bis myristic acid amide, ethylene bis myristic acid amide, propylene bis myristic acid amide, butylene bis Myristic acid amide, Propylene bispalmitic acid amide, Butylene bispalmitic acid amide, Methylene bispalmitoleic acid amide, Ethylene bispalmitoleic acid amide, Propylene vinyl Palmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bisarachidic acid amide, ethylene bisarachidic acid amide, propylene bisarachidic acid amide, butylene bisarachidic acid amide, methylene biseicosenoic acid amide, ethylene biseicosenoic acid Amide, Propylene biseicosenoic acid amide, Butylene biseicosenoic acid amide, Methylene bis behenic acid amide, Ethylene bis behenic acid amide, Propylene bis behenic acid amide, Butylene bis behenic acid amide, Methylene bis Mention may be made of alkylene bis fatty acid amide compounds of saturated or monovalent unsaturated fatty acids such as erucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, butylene biserucic acid amide.

(Toner resin)
As the binder resin for the toner, a polyester resin, particularly an amorphous polyester resin, which is suitable as a binder resin for a full-color toner from the viewpoint of color development and image strength, is more preferably used. In a color image, several types of toner layers are stacked several times, so that the toner layer becomes thick, and cracks and defects of the image due to insufficient strength of the toner layer occur, or an appropriate gloss is lost. For this reason, a polyester resin is used to maintain an appropriate gloss and excellent strength. The polyester resin can be generally obtained by an esterification reaction of a polyhydric alcohol and a polycarboxylic acid.

  Among the monomers constituting the polyester resin, the alcohol monomer includes a trifunctional or higher polyfunctional monomer, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene. Diols such as glycol, 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol; bisphenol A, hydrogenated bisphenol A, polyoxypropylene Bisphenol A alkylene oxide adducts such as bisphenol A; other dihydric alcohols or sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tri Enterythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, tri Examples include methylolpropane, 1,3,5-trihydroxybenzene, and other trihydric or higher polyhydric alcohols.

  Among these monomers, those using a bisphenol A alkylene oxide adduct as a main component monomer are particularly preferably used. When the bisphenol A alkylene oxide adduct is used as a constituent monomer, a polyester having a relatively high glass transition point is obtained due to the nature of the bisphenol A skeleton, and the copy blocking resistance and heat resistant storage stability are good. In addition, the presence of alkyl groups on both sides of the bisphenol A skeleton acts as a soft segment in the polymer, and the color developability and image strength during toner fixing are improved. Of the bisphenol A alkylene oxide adducts, those having an ethylene group or a propylene group are preferably used.

  Among the monomers constituting the polyester resin, acid monomers include, for example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipine Alkenyl succinic acids or alkyl succinic acids such as acids, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, n-dodecyl succinic acid, anhydrides, alkyl esters of these acids, or other divalent carboxylic acids; 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxylic acid Lu-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, or anhydrides thereof, alkyl ester, alkenyl ester, aryl ester Or other trivalent or higher carboxylic acids.

  Specific examples of the alkyl ester, alkenyl ester or aryl ester include trimethyl 1,2,4-benzenetricarboxylate, triethyl 1,2,4-benzenetricarboxylate, and tri-n-butyl 1,2,4-benzenetricarboxylate. 1,2,4-benzenetricarboxylic acid isobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl 1,2,4-benzenetricarboxylic acid tris (4-isopropylbenzyl), and the like.

Furthermore, a polycondensation polyester resin can also be preferably used as the toner resin of the present invention. Examples include polyester resins (AX) and (AX), which are polycondensates of polyols and polycarboxylic acids, and modified polyester resins (AY) obtained by further reacting polyepoxides (C) and the like. (AX), (AY) and the like may be used alone or in combination of two or more.
Examples of the polyol include a diol (g) and a trivalent or higher polyol (h), and examples of the polycarboxylic acid include a dicarboxylic acid (i) and a trivalent or higher polycarboxylic acid (j). You may use together.

Examples of the polyester resins (AX) and (AY) include the following, and these can also be used in combination.
(AX1): Linear polyester resin using (g) and (i) (AX2): Non-linear using (h) and / or (j) together with (g) and (i)
Polyester resin (AY1): Modified polyester resin obtained by reacting (AX2) with (c)

As the diol (g), those having a hydroxyl value of 180 to 1900 (mg KOH / g, the same shall apply hereinafter) are preferable. Specifically, alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, etc.); 4 to 36 alkylene ether glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogen) Added bisphenol A and the like; an alkylene oxide having 2 to 4 carbon atoms of the above alicyclic diol [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) and putylene oxide (hereinafter referred to as BO) Adducts (addition mole number 1-30); adducts (additions) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) having 2 to 4 carbon atoms and alkylene oxides (EO, PO, BO, etc.) Mole number 2-30) etc. are mentioned.
Of these, preferred are alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and combinations thereof. Particularly preferred are alkylene oxide adducts of bisphenols, alkylene glycols having 2 to 4 carbon atoms. And a combination of two or more of these.
In the above and below, the hydroxyl value and the acid value are measured by the methods specified in JIS K 0070.

As the trivalent or higher (3 to 8 or higher) polyol (h), those having a hydroxyl value of 150 to 1900 are preferable. Specifically, an aliphatic polyhydric alcohol having 3 to 36 or more carbon atoms having 3 to 8 carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrate thereof such as glycerin, triethylolethane, pentaerythritol, sorbitol, Sorbitan, polyglycerin, and dipentaerythritol; saccharides and derivatives thereof such as sucrose and methyl glucoside; etc .; adducts of the above aliphatic polyhydric alcohols having 2 to 4 carbon atoms (such as EO, PO and BO) Addition mole number 1-30); Trisphenol (trisphenol PA, etc.) adduct of C2-C4 alkylene oxide (EO, PO, BO, etc.) (addition mole number 2-30); Novolac resin (phenol novolac) And cresol novolak, etc .: average degree of polymerization of 3 Alkylene oxides having 2 to 4 carbon atoms 0) (EO, PO, BO, etc.) adducts (added mole number 2 to 30), and the like.
Among these, preferred are 3 to 8 or higher aliphatic polyhydric alcohols and alkylene oxide adducts of novolac resins (addition mole number: 2 to 30), and particularly preferred are alkylene oxide adducts of novolak resins. It is.

  As the dicarboxylic acid (i), those having an acid value of 180 to 1250 (mg KOH / g, the same applies hereinafter) are preferable. Specifically, alkane dicarboxylic acids having 4 to 36 carbon atoms (such as succinic acid, adipic acid, and sebacic acid) and alkenyl succinic acids (such as dodecenyl succinic acid); alicyclic dicarboxylic acids having 4 to 36 carbon atoms [dimer acid] (Dimerized linoleic acid) etc.]; C4-C36 alkene dicarboxylic acid (maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid) , Terephthalic acid, and naphthalenedicarboxylic acid). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. As (i), acid anhydrides or lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  The trivalent or higher (3 to 6 or higher) polycarboxylic acid (j) preferably has an acid value of 150 to 1250 mg. Specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, gel permeation chromatography) (By GPC): 450-10000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.), and the like. . Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the trivalent or higher polycarboxylic acid (j), acid anhydrides or lower alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Further, together with (g), (h), (i) and (j), an aliphatic or aromatic hydroxycarboxylic acid (k) having 4 to 20 carbon atoms and a lactone (l) having 6 to 12 carbon atoms are copolymerized. You can also.
Examples of the hydroxycarboxylic acid (k) include hydroxystearic acid and hydrogenated castor oil fatty acid. Examples of the lactone (l) include caprolactone.

  Examples of the polyepoxide (c) include polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac ( Average polymerization degree 3 to 60) glycidyl etherified compound, etc.]; diene oxide (pentadiene dioxide, hexadiene dioxide, etc.) and the like. Among these, polyglycidyl ether is preferable, and ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether are more preferable.

The number of epoxy groups per molecule of (c) is preferably 2-8, more preferably 2-6, and particularly preferably 2-4.
The epoxy equivalent of (c) is preferably 50 to 500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is more preferably 300, particularly preferably 200. When the number of epoxy groups and the epoxy equivalent are within the above ranges, both developability and fixability are good. It is more preferable if the above-mentioned ranges of the number of epoxy groups per molecule and the epoxy equivalent are satisfied at the same time.

  The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ˜1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2. The types of polyol and polycarboxylic acid to be used are selected in consideration of molecular weight adjustment so that the glass transition point of the polyester toner binder to be finally adjusted is 45 to 85 ° C.

  The amorphous polyester resin used as a toner binder in the present invention can be produced in the same manner as in the usual polyester production method. For example, the reaction temperature is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 240 ° C in the presence of a titanium-containing catalyst (a) in an inert gas (nitrogen gas or the like) atmosphere. It can be performed by reacting. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure (for example, 1 to 50 mmHg) in order to improve the reaction rate at the end of the reaction.

The addition amount of the titanium-containing catalyst (a) is preferably 0.0001 to 0.8%, more preferably 0.0002 to 0.6 based on the weight of the polymer obtained from the viewpoint of polymerization activity and the like. %, Particularly preferably 0.0015 to 0.55%.
In addition, other esterification catalysts can be used in combination as long as the catalytic effect of (a) is not impaired. Examples of other esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts other than (a) (eg, titanium alkoxide, potassium titanyl oxalate, and titanium terephthalate), zirconium-containing catalysts (Eg zirconyl acetate), germanium-containing catalysts, alkali (earth) metal catalysts (eg alkali metal or alkaline earth metal carboxylates: lithium acetate, sodium acetate, potassium acetate, calcium acetate, sodium benzoate, and benzoic acid Potassium), and zinc acetate. The addition amount of these other butterflies is preferably 0 to 0.6% based on the weight of the polymer obtained. By making it within 0.6%, the coloration of the polyester resin is reduced, which is preferable for use in a color toner. The content of (a) in all the added catalysts is preferably 50 to 100% by weight.

  Examples of the method for producing the linear polyester resin (AX1) include a diol in the presence of 0.0001 to 0.8% of the catalyst (a) and, if necessary, another catalyst based on the weight of the obtained polymer. (G) and the dicarboxylic acid (i) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions to obtain (AX1).

  As a method for producing the non-linear polyester resin (AX2), for example, 0.0001 to 0.8% of the catalyst (a) with respect to the weight of the obtained polymer, and if necessary, in the presence of another catalyst, Diol (g), dicarboxylic acid (i), and trihydric or higher polyol (h) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions. The method of reacting polycarboxylic acid (j) and obtaining (AX2) is mentioned. (J) can also be reacted simultaneously with (g), (i) and (h).

Examples of the method for producing the modified polyester resin (AY1) include a method of obtaining (AY1) by adding a polyepoxide (c) to the polyester resin (AX2) and performing a molecular extension reaction of the polyester at 180 ° C. to 260 ° C. .
The acid value of (AX2) to be reacted with (c) is preferably 1 to 60, more preferably 5 to 50. When the acid value is 1 or more, (c) remains unreacted and does not adversely affect the performance of the resin, and when it is 60 or less, the thermal stability of the resin is good.
The amount of (c) used to obtain (AY1) is preferably 0.01 to 10% by weight, more preferably 0, based on (AX2) from the viewpoint of low-temperature fixability and hot offset resistance. 0.05 to 5% by weight.

Further, in the toner binder of the present invention, in addition to the above-described polyester resin, other resins and the like can be contained as necessary.
Other resins include styrene resins (such as copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers), epoxy resins (such as bisphenol A diglycidyl ether ring-opening polymer), Examples thereof include urethane resins (diols and / or polyaddition products of trivalent or higher polyols and diisocyanates, etc.).
The content of the other resin in the toner binder is preferably 0 to 40% by weight, more preferably 0 to 30% by weight, and particularly preferably 0 to 20% by weight.

(Crystalline polyester)
The crystalline polyester resin A used in the present invention is preferably composed of a crystalline aliphatic polyester resin containing an ester bond represented by the following general formula (2) in the molecular main chain.
_{-OOC-R-COO- (CH 2} ) n- (2)
In the above formula, R represents a linear unsaturated aliphatic divalent carboxylic acid residue, and is a linear unsaturated aliphatic group having 2 to 20 carbon atoms, preferably 2 to 4 carbon atoms. n is an integer of 2 to 20, preferably 2 to 6. The existence of the structure of the general formula (2) can be confirmed by solid C ¹³ NMR (nuclear magnetic resonance analysis).
Furthermore, it is more preferably a crystalline aliphatic polyester resin containing at least 60 mol% of ester bonds in the molecular main chain.

Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.
In the general formula (2), (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue.
Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic 2 such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Those derived from dihydric alcohols can be indicated. Since the crystalline polyester resin (A) uses a linear unsaturated aliphatic dicarboxylic acid as its acid component, the crystalline polyester resin (A) has an effect that it is easy to form a crystal structure compared to the case of using an aromatic dicarboxylic acid. Show.

The crystalline polyester resin is a polyvalent carboxylic acid comprising (i) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms, an acid halide, etc.). It can be produced by subjecting a component and (ii) a polyhydric alcohol component comprising a linear aliphatic diol to a polycondensation reaction by a conventional method.
In this case, a small amount of other polyvalent carboxylic acid can be added to the polyvalent carboxylic acid component as necessary. The polyvalent carboxylic acid in this case includes (i) a saturated aliphatic divalent carboxylic acid having a branched chain, (ii) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, and the like. In addition to polyvalent carboxylic acids, (iii) aromatic polyvalent carboxylic acids such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The addition amount of these polyvalent carboxylic acids is usually 30 mol% or less, preferably 10 mol% or less, based on the total carboxylic acid, and is appropriately added within the range where the resulting polyester has crystallinity.

Specific examples of polyvalent carboxylic acids that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. A divalent carboxylic acid of: trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, And trivalent or higher polyvalent carboxylic acids such as 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. it can.
A trivalent or higher polyhydric alcohol can be added to the polyhydric alcohol component, if necessary, in addition to a small amount of an aliphatic branched dihydric alcohol or cyclic dihydric alcohol. The addition amount is 30 mol% or less, preferably 10 mol% or less, based on the total alcohol, and is appropriately added within the range where the resulting polyester has crystallinity.
Examples of polyhydric alcohol added as needed include 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin and the like.

In the crystalline polyester resin (A), the molecular weight distribution is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is preferably a relatively low molecular weight. As for the molecular weight of the crystalline polyester resin (A), the weight average molecular weight (Mw) is 5500 to 6500 and the number average molecular weight (Mn) is 1300 to 1500 in the molecular weight distribution by GPC of the o-dichlorobenzene soluble component. And its Mw / Mn ratio is preferably 2-5.
The molecular weight distribution of the crystalline polyester resin (A) is based on a molecular weight distribution chart in which the horizontal axis is log (M: molecular weight) and the vertical axis is weight%. In the case of the polyester resin (A) used in the present invention, in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 3.5 to 4.0 (wt%), and the half width of the peak is 1. 5 or less is preferable.

  In the crystalline polyester resin (A), the glass transition temperature (Tg) and the softening temperature (Tm) are desirably low as long as the heat-resistant storage stability of the toner is not deteriorated. It is 130 degreeC, Preferably it is 80-125 degreeC, The Tm is 80-130 degreeC, Preferably it is 80-125 degreeC. When Tg and Tm are higher than the above ranges, the lower fixing temperature of the toner is increased, so that the low temperature fixability of the toner is deteriorated.

When two or more kinds of polyester resins are used in combination, and when at least one kind of polyester resin and another resin are mixed, powder mixing or melt mixing may be performed in advance, or they may be mixed at the time of toner formation. The temperature at the time of melt mixing is preferably 80 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 120 to 160 ° C.
If the mixing temperature is too low, sufficient mixing cannot be achieved, which may result in non-uniformity. When two or more kinds of polyester resins are mixed, if the mixing temperature is too high, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.
The mixing time in the case of melt mixing is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 10 minutes, and particularly preferably 30 seconds to 5 minutes. When two or more kinds of polyester resins are mixed, if the mixing time is too long, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.

  Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll. Of these, extruders and container kneaders are preferred.

In the case of powder mixing, it can be mixed with normal mixing conditions and mixing equipment.
As mixing conditions in the case of powder mixing, the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. The mixing time is preferably 3 minutes or more, more preferably 5 to 60 minutes. Examples of the mixing device include a Henschel mixer, a Nauter mixer, and a bumper mixer. A Henschel mixer is preferable.
The acid value of the crystalline polyester resin is preferably 20 mg KOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between the paper and the resin, In order to improve hot offset property, it is preferable that it is 45 mgKOH / g or less.
Further, the hydroxyl value of the crystalline polyester resin is preferably 5 to 50 mgKOH / g in order to achieve a predetermined low-temperature fixability and good charging characteristics.

(Coloring agent)
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together. The content of the colorant in the toner material is preferably 0.1 to 50% by mass, and more preferably 1 to 10% by mass.

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

(Toner average circularity)
The average circularity of the toner of the present invention can be measured by a flow type particle image analyzer FPIA-3000 (manufactured by SYSMEX). As a specific measuring method, 0.3 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 120 ml of water from which impure solids have been removed in advance, and about 0.2 g of a measurement sample is further added. Add. The suspension in which the sample is dispersed is obtained by carrying out a dispersion treatment with an ultrasonic disperser for about 2 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of about 5000 / μl.

(Toner particle size measurement)
The volume average particle diameter (Dv), number average particle diameter (Dn), and ratio (Dv / Dn) of the toner of the present invention can be measured by the following method. The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter, Inc.) and the like. In particular, Coulter Multisizer II was used in the present invention. The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

The toner according to the present invention preferably has a volume average particle diameter of 2.0 to 7.0 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.0. More preferably, it is in the range of -1.3.
By using a toner having a small particle diameter, the toner can be densely attached to the latent image. However, when the volume average particle diameter is smaller than the range of the present invention, in the two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, and the charging ability of the magnetic carrier is lowered. On the contrary, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed. In many cases, the variation in toner particle size becomes large.
Further, by narrowing the particle size distribution, the toner charge amount distribution becomes uniform, a high-quality image with little background fogging can be obtained, and the transfer rate can be increased. However, it is not preferable that Dv / Dn exceeds 1.30 because the charge amount distribution becomes wide and the resolution decreases.

(Toner production method)
A method for producing the toner of the present invention will be described.
As the toner of the present invention, any toners such as pulverized toner, suspension polymerization method, emulsion polymerization aggregation method, dispersion polymerization method and the like can be used.
Therefore, the method for producing the toner of the present invention is not particularly limited, and is a melt-kneading pulverization method and a polymerization method, a polyaddition reaction method using an isocyanate group-containing prepolymer, solvent dissolution, desolvation and pulverization. In addition to the method, it can also be produced by a melt spray method. Among these production methods, a melt kneading method, a polymerization method in which a monomer composition containing a crystalline polyester resin and a polymerizable monomer is directly polymerized in an aqueous phase (suspension polymerization method / emulsion polymerization method) ), A polyaddition reaction method in which a composition containing a crystalline polyester resin and an isocyanate group-containing prepolymer is directly extended / crosslinked with amines in an aqueous phase, and a method in which a solvent is dissolved and the solvent is removed and pulverized. It is preferable that a conventionally known production method can be used.

  In the polymerization method and the polyaddition reaction method using an isocyanate group-containing prepolymer, the emulsification (formation of droplets) treatment is mandatory by applying mechanical energy in the aqueous phase. Examples of the mechanical energy applying means include strong stirring such as homomixer, ultrasonic wave, and manton gorin, or ultrasonic vibration energy applying means.

(Production method of pulverized toner)
The method for producing a pulverized toner according to the present invention includes a kneading step, a pulverizing step, and a classification step, and further includes other steps as necessary.
-Kneading process-
The kneading step is a step of kneading a toner material containing at least a binder resin (amorphous polyester resin, crystalline polyester resin), a colorant, a release agent, a charge control agent, and the like. The charge control agent, the release agent, and the colorant can be melt-kneaded together with the master batch and the binder resin, or may be added when dissolved and dispersed in an organic solvent.
The above toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd. Preferably used. It is important that this melt-kneading is performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is too high, the cutting may be severe, and if the temperature is too low, the dispersion may not proceed.

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

-Classification process-
The classification step is a step of classifying the pulverized product obtained in the pulverization step to adjust the particles to a predetermined particle size. The classification can be performed by removing the fine particle portion by, for example, a cyclone, a decanter, centrifugation, or the like. After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner having a predetermined particle size, for example, an average particle size of 2 to 20 μm.

When the above pulverization and classification steps are completed, powder (fine powder toner) other than the particles obtained as products obtained in those steps is collected, and a predetermined amount is added to the toner material in the mixing step and the melt-kneading step. It is preferable to repeat the above operation.
Here, the powder (fine powder toner) other than the particles used as the product is generated in the fine particle other than the component used as the product having a desired particle size obtained in the pulverization process after the melt-kneading process and the subsequent classification process. It means fine particles other than the components that become a product having a desired particle size.
The content of the fine toner is 1 to 20% by mass with respect to the toner material, and more preferably 5 to 15 parts by mass. If the amount of the fine toner is less than 1% by mass, the consumption of the fine toner may be reduced, so that it may not be possible to contribute to cost reduction. If the amount exceeds 20% by mass, the cause is not clarified. The agglomeration property of the ink becomes high, which may cause a problem that white streaks are generated.

(Method for producing polymerized toner)
The toner of the present invention obtained by a polyaddition reaction method in which a composition containing a crystalline polyester resin and an isocyanate group-containing prepolymer is directly extended / crosslinked with amines in an aqueous phase is produced, for example, as follows. be able to.
(Modified polyester resin)
In the present invention, the following modified polyester resins can be used as the amorphous polyester resin. For example, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

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

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferable. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates such as phenol derivatives, oximes, caprolactams And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

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

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6). Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).
The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. If [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

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

  The peak molecular weight of (C) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

(Resin fine particles)
In the present invention, resin fine particles can be contained as required. The resin fine particles used have a glass transition point (Tg) of 40 to 100 ° C., a weight average molecular weight of 9000 to 200,000 is more preferable, and as described above, the glass transition point (Tg) is less than 40 ° C., and When the weight average molecular weight is less than 9,000, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the glass transition point (Tg) is 100 ° C. or higher and / or the weight average molecular weight is 200,000 or higher, the resin fine particles inhibit the adhesiveness to the fixing paper, and the minimum fixing temperature increases.

More preferably, the residual ratio with respect to the toner particles is 0.5 to 5.0 wt%. . When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.
The residual ratio of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

  The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimides Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(Production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.

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

  The toner particles are obtained by forming a dispersion composed of a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase and reacting with amines (B). As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous phase, a composition of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent in an aqueous phase is added. And a method of dispersing by shearing force. A polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), a colorant masterbatch, a release agent, a charge control agent, a crystalline polyester resin Unmodified polyester resin or the like may be mixed when forming the dispersion in the aqueous phase, but after mixing the toner raw material in advance and then dissolving or dispersing in the organic solvent, the mixture in the aqueous phase It is more preferable to add and disperse. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. It may be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

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

  The amount of the aqueous phase used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the polyester prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Amine salt types such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, and quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N - Amphoteric surfactants such as chill ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts thereof, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl ) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Etc.,

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzaza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

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

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

The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, particularly various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
Further, as a method for removing the organic solvent, air can be blown away by a rotary evaporator or the like.

  Thereafter, rough separation is performed by centrifugation, the emulsified dispersion is washed in a washing tank, and the drying process is repeated in a hot air dryer, and finally an aqueous solvent soda (containing a surfactant) in which a fluorine compound is dispersed. In the case of water, a fluorine compound is attached (chemically bonded) to the toner surface, and then the solvent is removed and dried to obtain a toner base.

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

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

As other production methods, a polymerization method, a capsule method, or the like can be used. An outline of these production methods is described below.
<Polymerization method>
(1) A polymerizable monomer, a crystalline polyester resin, and if necessary, a polymerization initiator, a colorant, a release agent and the like are granulated in an aqueous dispersion medium.
(2) The granulated monomer composition particles are classified to an appropriate particle size.
(3) The monomer composition particles having a prescribed inner particle diameter obtained by the classification are polymerized.
(4) After removing the dispersant by appropriate treatment, the polymerization product obtained above is filtered, washed with water, and dried to contain an amorphous polyester resin, a crystalline polyester resin, a colorant, and a release agent. Obtain parent particles.

<Capsule method>
(1) An amorphous polyester resin, a crystalline polyester resin, and, if necessary, a colorant, a release agent and the like are kneaded with a kneader or the like to obtain a molten toner core material.
(2) The toner core material is placed in water and stirred vigorously to form a fine particle core material.
(3) The above core material fine particles are put in a shell material solution, and a poor solvent is dropped while stirring, and encapsulated by covering the surface of the core material with a shell material.
(4) The capsule obtained as described above is filtered and dried to obtain base particles containing an amorphous polyester resin, a crystalline polyester resin, a colorant and a release agent.

  In order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner manufactured as described above. For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Also, a strong load may be given first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

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

  The toner manufactured by the toner manufacturing method of the present invention may be filled in a toner-containing container described later and mounted on the image forming apparatus as it is. Further, the carrier and the toner may be filled in the same container and mounted on the image forming apparatus.

  In addition to the binder resin, colorant, and release agent, the toner material may include additives, charge control agents, fluidity improvers, cleaning improvers, magnetic materials, metal soaps, and the like as necessary. Can be added.

(Charge control agent)
The toner for image formation according to the present invention may contain a charge control agent in the toner, if necessary.
For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Lake pigments of these basic dyes, such as Basic Green 4 (C.I. 42000), C.I. I. Solvent Black 8 (CI. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, or dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers, condensation polymers containing amino groups, Japanese Patent Publication No. 41-20153, Japanese Patent Publication No. 43-27596, Japanese Patent Publication No. 44-6397, Japanese Patent Publication No. 45-26478 Metal complex salts of monoazo dyes described, Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 59-7385, salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr , Fe, etc. Metal complex, a copper phthalocyanine pigment obtained by sulfonation, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. Naturally, color toners other than black should avoid the use of charge control agents that impair the desired color, and white metal salts of salicylic acid derivatives are preferably used.

(External toner additive)
In the present invention, as the inorganic fine particles which are external additives added to the toner, any known fine particles can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.
Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above Hoechst), and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). In particular, as hydrophobized titanium oxide fine particles, T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.

  In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred. The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

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

As a method of adding an external additive or the like to the toner, not only a dry external addition treatment using a Henschel mixer, a Q mixer, etc., but also a wet external addition treatment (solvent, water (an activator for improving wettability as necessary) Adhesion by inclusion)) is effective.
This is a mixing method of the external additive. External addition of the external additive to the base toner is performed by mixing and stirring the base toner and the external additive using a mixer, while the external additive is crushed on the toner surface. It may be a dry mix to be coated. At this time, it is important in terms of durability that external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the base toner. As these addition conditions, the blade shape of the mixers, the number of revolutions, the mixing time, the number of times of mixing, the amount of external additive, the amount of the base toner, and the surface properties (unevenness, hardness, viscoelasticity, etc.) of the base toner are important.

  Moreover, an inorganic fine particle adhesion process can be performed in a liquid as wet mixing. This step may be performed after the toner particles are formed in water and the used surfactant and the like are removed by washing. Excess surfactant present in water is removed by solid-liquid separation such as filtration and centrifugation, and the resulting cake and slurry are redispersed in an aqueous medium. Further, inorganic fine particles are added and dispersed in the slurry. Inorganic fine particles can be dispersed in an aqueous dispersion in advance. At that time, if dispersed using a surfactant having a reverse polarity, adhesion to the surface of the toner particles is more efficiently performed. In addition, when the inorganic fine particles are hydrophobized and are difficult to disperse in the aqueous dispersion, the inorganic fine particles may be dispersed after the interfacial tension is lowered by using a small amount of alcohol or the like to facilitate wetting. Thereafter, an aqueous surfactant solution having a reverse polarity is gradually added with stirring. The reverse polarity surfactant is preferably used in an amount of 0.01 to 1% by weight based on the solid content of the toner particles. By adding a surfactant having a reverse polarity, the charge of the inorganic fine particle dispersion in water is neutralized, and the inorganic fine particles can be aggregated and adhered to the surface of the toner particles. The inorganic fine particles are preferably used in an amount of 0.01 to 5% by weight based on the solid content of the toner particles.

  The inorganic fine particles adhered to the toner surface can be fixed to the toner surface by heating the slurry thereafter to prevent detachment. At that time, it is desirable to heat at a temperature higher than the Tg of the resin constituting the toner. Further, heat treatment may be performed after drying while preventing aggregation.

(Career)
When the toner of the present invention is used for a two-component developer, a magnetic carrier and a toner may be mixed and used, and the carrier to toner content ratio in the developer may be 1 10 parts by weight is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used.
These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Toner container)
The toner container is filled with a developer containing the image forming toner of the present invention, and a conventionally known shape can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. The part shown here represents part by weight. “%” Means% by weight.
(Evaluation machine)
(Evaluation machine 1)
As the evaluation machine 1, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.26 mm, the doctor blade gap of 1.6 mm, and the reflective photosensor function turned off so that the system speed was 1700 mm / sec. The fixing unit is installed the fixing unit shown in FIG. 2, the fixing surface pressure 39N / cm ^2, and a fixing nip width 10 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 2)
As the evaluation machine 2, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.40 mm, the doctor blade gap of 1.8 mm, and the reflective photosensor function turned off so that the system speed was 400 mm / sec. The fixing unit is provided with the fixing unit shown in FIG. 2 and has a fixing surface pressure of 90 N / cm ² and a fixing nip width of 4 mm. The surface of the fixing medium was used after coating, molding and surface adjustment of silicon resin. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 3)
As the evaluation machine 3, the developing part and fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.26 mm, the doctor blade gap of 1.6 mm, and the reflective photosensor function turned off so that the system speed was 1900 mm / sec. The fixing unit is provided with the fixing unit shown in FIG. 2 and has a fixing surface pressure of 5 N / cm ² and a fixing nip width of 20 mm. The fixing medium surface was coated with polychlorotrifluoroethylene (PCTFE) resin, molded and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 4)
As the evaluation machine 4, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap 1.31 mm, the doctor blade gap 1.7 mm, and the reflective photosensor function turned off so that the system speed was 1000 mm / sec. The fixing unit is provided with the fixing unit shown in FIG. 2 and has a fixing surface pressure of 39 N / cm ² and a fixing nip width of 3 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 5)
As the evaluator 5, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap 1.20 mm, the doctor blade gap 1.5 mm, and the reflective photosensor function OFF so that the system speed was 3000 mm / sec. The fixing unit is provided with the fixing unit shown in FIG. 2 and has a fixing surface pressure of 39 N / cm ² and a fixing nip width of 22 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 6)
As the evaluator 6, the developing unit and the fixing unit of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.45 mm, the doctor blade gap of 1.9 mm, and the reflective photosensor function turned off so that the system speed was 380 mm / sec. The fixing unit is installed the fixing unit shown in FIG. 2, the fixing surface pressure 39N / cm ^2, and a fixing nip width 10 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 7)
As the evaluation machine 7, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.14 mm, the doctor blade gap of 1.3 mm, and the reflective photosensor function turned off so that the system speed was 3200 mm / sec. The fixing unit is installed the fixing unit shown in FIG. 2, the fixing surface pressure 39N / cm ^2, and a fixing nip width 10 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 8)
As the evaluator 8, the developing unit and the fixing unit of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.26 mm, the doctor blade gap of 1.6 mm, and the reflective photosensor function turned off so that the system speed was 1700 mm / sec. The fixing unit is provided with the fixing unit shown in FIG. 2 and has a fixing surface pressure of 4 N / cm ² and a fixing nip width of 20 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.

(Evaluation machine 9)
As the evaluation machine 9, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap of 1.26 mm, the doctor blade gap of 1.6 mm, and the reflective photosensor function turned off so that the system speed was 1700 mm / sec. The fixing unit is provided with the fixing unit shown in FIG. 2 and has a fixing surface pressure of 93 N / cm ² and a fixing nip width of 4 mm. The fixing medium surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted. The actual temperature regions of the image carrier, the developing device, and the transfer device unit were controlled to be 30 to 45 ° C. The heating temperature of the fixing roller was set to 150 ° C.
Table 3 shows a summary of the conditions of the above evaluators.

(Evaluation of two-component developer)
When image evaluation is performed with a two-component developer, a ferrite carrier having an average particle diameter of 50 μm coated with a silicone resin obtained in the following production example with an average thickness of 0.5 μm is used. A developer was prepared by uniformly mixing and charging 5 parts by weight of each color toner using a tumbler mixer of the type in which the container rolls and stirs.

(Example of carrier production)
(Carrier 1)
167 parts of silicone resin [solid content 23% by weight (SR2410: Toray Dow Corning Silicone)]
Aminosilane 0.66 part [solid content 100% by weight (SH6020: manufactured by Toray Dow Corning Silicone)]
-300 parts of toluene was dispersed with a homomixer for 10 minutes to obtain a silicone resin coating film forming solution. Average particle size: 50 μm calcined Mn ferrite powder is used as the core material, and the temperature inside the coater is 40 ° C. by a Spira coater (manufactured by Okada Seiko Co., Ltd.) so that the coating film forming solution has a film thickness of 0.5 μm on the core material surface And dried. The obtained carrier was fired in an electric furnace at 300 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 63 μm to obtain [Carrier 1].

For the average particle size measurement of the core material, an SRA type of a Microtrac particle size analyzer (Nikkiso Co., Ltd.) was used, and the measurement was performed with a range setting of 0.7 [μm] or more and 125 [μm] or less. .
The binder resin film thickness measurement of the carrier is performed by observing the carrier cross section with a TEM (transmission electron microscope), STEM (scanning transmission electron microscope), etc. after creating the carrier cross section with FIB (focused ion beam). Since the coating film covering the carrier surface can be observed, the average value of the film thickness was used as the film thickness.

(Synthesis example of crystalline polyester resin)
-Synthesis of crystalline polyester resin 1-
The following raw materials were put into a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, reacted at 160 ° C. for 6 hours, then heated to 180 ° C. and heated for 1.5 hours. The crystal polyester resin 1 was obtained by further reacting at 8.3 KPa for 2 hours. The crystalline polyester resin 1 had a Tg peak of 110 ° C.
1,4-butanediol: 23.75 mol Ethylene glycol: 1.25 mol Fumaric acid: 22.75 mol Trimellitic anhydride: 1.65 mol Hydroquinone: 5.1 g

-Synthesis of crystalline polyester resin 2-
The following raw materials are put in a 5 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, reacted at 160 ° C for 5 hours, then heated to 170 ° C and reacted for 1 hour. Further, the reaction was carried out at 8.3 KPa for 2 hours to obtain a crystalline polyester resin 2. The crystalline polyester resin 2 had a Tg peak of 77 ° C.
1,6-hexanediol: 23.75 mol Ethylene glycol: 1.25 mol Fumaric acid: 24.40 mol Hydroquinone: 5.1 g

-Synthesis of crystalline polyester resin 3-
The following raw materials were put into a 5 liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, reacted at 160 ° C. for 8 hours, then heated to 180 ° C. and heated for 1.5 hours. The crystal polyester resin 3 was obtained by further reacting at 8.3 KPa for 4 hours. The crystalline polyester resin 3 had a Tg peak of 135 ° C.
1,4-butanediol: 21.75 mol 1,6-hexanediol: 2.00 mol Ethylene glycol: 1.25 mol Fumaric acid: 22.75 mol Trimellitic anhydride: 1.65 mol Hydroquinone: 5.1 g

(Example of silica production)
-Synthesis of silica 1-
100 g of silica fine powder having a BET specific surface area of 300 m ² / g produced by a vapor phase method was put in a reaction vessel, and 2.0 g of water was sprayed with stirring in a nitrogen atmosphere. This was sprayed with 10 g of hexamethyldisilazane, heated and stirred at 150 ° C. for 1 hour, and then cooled. Then, it was crushed by a jet mill to obtain silica particles having a primary average particle diameter of 10 nm. Then, the classification process was performed by dry classifier TC-40II (made by Nissin Engineering), the aggregate with a particle size of 50 micrometers or more was removed, and the silica 1 was obtained.

(Binder resin synthesis example)
-Synthesis of amorphous polyester resin a-
[Synthesis of linear polyester resin]
In a reactor equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts of acid and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 200 ° C. for 7 hours while distilling off water produced under a nitrogen stream. Subsequently, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value reached 5, it was taken out, cooled to room temperature and pulverized to obtain a linear polyester resin (AX1-1). (AX1-1) contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 12, Tg of 48 ° C., Mn of 5940, and Mp of 18,200. The ratio of components having a molecular weight of 1500 or less was 1.1%.

[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of EO2 molar adduct of bisphenol A, 326 parts of PO3 molar adduct of bisphenol A, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and condensation 2 parts of titanium dihydroxybis (triethanolamate) was added as a catalyst, and the reaction was carried out for 7 hours while distilling off the water produced at 210 ° C. under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 62 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-1).
(AX2-1) contained no THF-insoluble matter, and its acid value was 35, the hydroxyl value was 17, Tg was 57 ° C., Mn was 3700, and Mp was 11200. The ratio of components having a molecular weight of 1500 or less was 0.8%.
800 parts of the above-mentioned polyester (AX1-1) and 200 parts of polyester (AX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 140 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and pulverized to obtain a polyester resin a of the present invention.
The obtained polyester resin a had a number average molecular weight (Mn) of 2,800, a weight average molecular weight (Mw) of 7,200, and a glass transition temperature (Tg) of 55 ° C.

<Example 1>
-Production of Toner A-
Amorphous polyester resin a 90 parts Crystalline polyester 1 10 parts C.I. I. Pigment Blue 15: 3 ... 5 parts Charge control agent (Bis (3,5-di-tert-butylsalicylate-O1, O2) zinc)
... 2 parts, Carnauba wax (Tg peak 81 ° C), trade name: WA-03 (manufactured by Toa Kasei Co., Ltd.)
... 3 parts fatty acid amide compound (ethylene bis stearic acid amide, Tg peak 147 ° C,
Product name: EB-P (manufactured by Kao Corporation)) 2 parts

  The toner material was premixed (mixed) using a Henschel mixer (FM20C manufactured by Mitsui Mining Co., Ltd.). The mixing conditions were a sufficient mixing by repeating a set of 120 second rotation and 60 second rotation stop at a peripheral speed of 30 m / sec three times. Thereafter, 10 parts by mass of finely collected toner collected in advance was added, and kneading was performed for 45 minutes with two rolls having a roll surface set at 95 ° C. Thereafter, after rolling and cooling and coarse pulverization, a jet mill type pulverizer (I-2 type mill: manufactured by Nippon Pneumatic Industry Co., Ltd.) and a wind classifier using a swirling flow (DS classifier: manufactured by Nippon Pneumatic Industry Co., Ltd.) Blue colored particles were obtained.

A step of supplying the colored particles to a mechanical rotary pulverizer (Turbo Mill T-400RS type manufactured by Turbo Industry Co., Ltd.) at a processing speed of 10 kg / h, and pulverizing at a processing temperature of 53 ° C. and a rotor peripheral speed of 113 m / s. Was repeated three times to obtain colored particles with adjusted circularity.
Thereafter, 100 parts of colored particles, 1.5 parts of silica 1 and 0.5 parts of hydrophobized titanium oxide having a primary average particle size of 13 nm were mixed with a Henschel mixer (FM20C manufactured by Mitsui Mining Co., Ltd.) to obtain a toner. The mixing conditions were a peripheral speed of 30 m / sec, a set of 120 seconds rotation and 60 seconds rotation stop was repeated 5 times and mixed to obtain a toner.
A developer was prepared by uniformly mixing and charging 100 parts by weight of carrier 1 with respect to 7 parts by weight of the obtained toner using a type of tumbler mixer in which the container rolls and stirs. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.

<Example 2>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 used was changed to the evaluation machine 2. The evaluation results are shown in Table 2.
<Example 3>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 used was changed to the evaluation machine 3. The evaluation results are shown in Table 2.
<Example 4>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 used was changed to the evaluation machine 4. The evaluation results are shown in Table 2.
<Example 5>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 used was changed to the evaluation machine 5. The evaluation results are shown in Table 2.

<Example 6>
In Example 1, the prescription amount of the crystalline polyester 1 was 8 parts, and a fatty acid amide compound (ethylenebisstearic acid amide, Tg peak 147 ° C., trade name: EB-P (manufactured by Kao Corporation)) 1.5 Evaluation was performed in the same manner as in Example 1 except that the part was changed to the part. Table 1 shows the physical properties of the obtained toner. The evaluation results are shown in Table 2.
<Example 7>
In Example 1, the prescription amount of the crystalline polyester 1 is 25 parts, and the fatty acid amide compound (ethylenebisstearic acid amide, Tg peak 147 ° C., trade name: EB-P (manufactured by Kao Corporation)) is 4 parts. Evaluation was performed in the same manner as in Example 1 except that the change was made. Table 1 shows the physical properties of the obtained toner. The evaluation results are shown in Table 2.

<Example 8>
In Example 1, instead of carnauba wax, paraffin wax (Tg peak 48 ° C.), product name; paraffin wax 115 (manufactured by Nippon Seiwa Co., Ltd.) was used instead of carnauba wax, and the colored particles after classification were machined. Colored particles were produced without feeding to a rotary pulverizer. Subsequent treatments were made and evaluated in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.
<Example 9>
In Example 1, the same procedure as in Example 1 was used except that polypropylene wax (Tg peak 143 ° C.) and trade name; Biscol 660-P (manufactured by Sanyo Chemical Industries, Ltd.) were used instead of carnauba wax. And evaluated. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.

<Example 10>
The same procedure as in Example 1 was carried out except that the fatty acid amide compound of the toner used was oleic acid amide (Tg peak 69 ° C.), trade name; Evaluation was performed in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.
<Example 11>
In Example 1, except that the fatty acid amide compound of the toner used was ethylenebiscapric acid amide (Tg peak 161 ° C.) instead of ethylenebisstearic acid amide, trade name; Evaluation was performed in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.

<Example 12>
Evaluation was performed in the same manner as in Example 1 except that the crystalline polyester 2 was used instead of the crystalline polyester 1 of the toner used. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.
<Example 13>
In Example 1, evaluation was made in the same manner as in Example 1 except that crystalline polyester 3 was used instead of crystalline polyester 1 of the toner used. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.

<Example 14>
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner used was prepared as follows. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stirrer and a thermometer, water 683 parts, sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, butyl acrylate 110 And 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 3 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 70 ° C. for 5 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 75 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 60 ° C., and the weight average molecular weight was 110,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyldiphenyl ether disulfonate ((Eleminol MON-7): manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10-15 mmHg. Then, 44 parts of trimellitic anhydride was added to the reaction vessel, and 3 parts at 180 ° C. under normal pressure. The reaction was performed for a while to obtain [Low molecular polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 7 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
Add 600 parts of water, Pigment Blue 15: 3 water-containing cake (solid content 50%) and 1200 parts of polyester resin, mix with a Henschel mixer (Mitsui Mining Co., Ltd.), and use the two rolls at 120 ° C. for 45 minutes. After kneading, rolling and cooling and pulverization with a pulverizer gave [Masterbatch 1].

~ Creation of oil phase ~
Production Example 7
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular polyester 1], 100 parts of [Crystalline polyester 1], Carnauba / Rice wax (Tg peak 81 ° C.), trade name: WA-05 (Toa Kasei Co., Ltd.) 80 parts of fatty acid amide compound (ethylene bis stearic acid amide, Tg peak 147 ° C., trade name: EB-P (manufactured by Kao Corporation)), 947 parts of ethyl acetate, and heated to 80 ° C. with stirring. Warm and hold at 80 ° C. for 5 hours, then cool to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and [Ketimine Compound 1] 2.9 parts were put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika) at 5000 rpm for 2 minutes. Then, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at a rotation speed of 13,000 rpm for 25 minutes to obtain [Emulsified slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
1: 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
100 parts of a 10% aqueous sodium hydroxide solution was added to a 2: 1 filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 30 minutes), and then filtered under reduced pressure.
100 parts of 10% hydrochloric acid was added to the 3: 2 filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
300 parts of ion-exchanged water was added to the 4: 3 filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered twice to obtain [filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer.
Then, the following fluorine compound (2) is mixed in an aqueous solvent soda in which the following fluorine compound (2) is dispersed at a concentration of 1 wt% with respect to the toner base so that the following fluorine compound (2) is 0.1 wt. After adhering (bonding), it was dried at 45 ° C. for 48 hours with a circulating drier, and further dried on a shelf at 30 ° C. for 10 hours. Thereafter, sieved with a mesh of 75 μm, [Toner Base Particle 1] was obtained.

その後、［トナー母体粒子１］１００部、一次平均粒径１０ｎｍの疎水化処理シリカ１を１．０部と一次平均粒径１３ｎｍの疎水化処理酸化チタン０．５部をヘンシェルミキサー（三井鉱山社製 ＦＭ２０Ｃ）にて混合してトナーを得た。混合条件は、周速３０ｍ／ｓｅｃで、１２０秒回転、６０秒回転停止、のセットを５回繰り返して混合してトナーを得た。

Thereafter, 100 parts of [toner base particle 1], 1.0 part of hydrophobized silica 1 having a primary average particle diameter of 10 nm and 0.5 part of hydrophobized titanium oxide having a primary average particle diameter of 13 nm were added to a Henschel mixer (Mitsui Mining Co., Ltd.). FM20C) to obtain a toner. The mixing conditions were a peripheral speed of 30 m / sec, a set of 120 seconds rotation and 60 seconds rotation stop was repeated 5 times and mixed to obtain a toner.

<Comparative Example 1>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 was changed to the evaluation machine 6. The evaluation results are shown in Table 2.
<Comparative Example 2>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 was changed to the evaluation machine 7. The evaluation results are shown in Table 2.
<Comparative Example 3>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 was changed to the evaluation machine 8. The evaluation results are shown in Table 2.
<Comparative example 4>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation machine 1 was changed to the evaluation machine 9. The evaluation results are shown in Table 2.

<Comparative Example 5>
In Example 1, a toner was produced and evaluated in the same manner as in Example 1 except that the crystalline polyester and the fatty acid amide compound were not contained. Table 1 shows the physical properties of the obtained toner. The obtained toner was evaluated with an evaluation machine 1. The evaluation results are shown in Table 2.
<Comparative Example 6>
In Example 1, the prescription amount of the crystalline polyester 1 is 5 parts, and the fatty acid amide compound (ethylenebisstearic acid amide, Tg peak 147 ° C., trade name: EB-P (manufactured by Kao Corporation)) is 1.0. Evaluation was performed in the same manner as in Example 1 except that the part was changed to the part. Table 1 shows the physical properties of the obtained toner. The evaluation results are shown in Table 2.
<Comparative Example 7>
In Example 1, the prescription amount of the crystalline polyester 1 is 35 parts, and the fatty acid amide compound (ethylenebisstearic acid amide, Tg peak 147 ° C., trade name: EB-P (manufactured by Kao Corporation)) is 7 parts. Evaluation was performed in the same manner as in Example 1 except that the change was made. Table 1 shows the physical properties of the obtained toner. The evaluation results are shown in Table 2.

(Evaluation item)
1) Low-temperature fixability After outputting 10,000 sheets of the 5% image area chart using the obtained two-component developer and each evaluation machine, the temperature of the fixing roll is changed by 5 ° C., and the image is output and fixed. The fixability was measured after 3 days later. Ricoh full color PPC paper type 6200 was used as the transfer paper.
By changing the fixing temperature of the fixing unit alone, a copy image was obtained in which the image density by the Macbeth densitometer was 1.2. The copy image at each temperature was rubbed 50 times with a clock meter equipped with a sand eraser, the image density before and after that was measured, and the fixing rate was determined by the following formula.
Fixing rate (%) = [(image density after 10 times of sand eraser) / (previous image density)] × 100
The temperature at which a fixing rate of 70% or more was achieved was defined as the minimum fixing temperature. The criteria for determining low temperature fixability are as follows.
The evaluation results are shown as follows.
A: Fixing starts at a very low temperature, and the fixing minimum temperature is low, and the fixing property is very low. B: The fixing property is considerably excellent. B: The fixing property at a low temperature is superior to that of the conventional system. Lower fixing limit is inferior to that of unmodified products)

2) Filming property Using the obtained two-component developer and each evaluation machine, a 5% image area chart is output, and a black solid (A3) which is an evaluation image at the initial stage, 100,000 sheets, and 300,000 sheets, respectively. ) Output 3 sheets. The degree of blank image portions due to toner filming on the photoreceptor was visually evaluated. The more white-out images, the worse the image quality. The evaluation result was visually evaluated by the number of white spots on the whole solid image, and the rank evaluation was performed as follows.
◎: Remarkably excellent with few whiteout image portions ○: Remarkably excellent with few whiteout image portions △: Normal whiteout image portions △△: Slightly whiteout image portions

3) High-temperature fixing wrapping property After outputting 10,000 sheets of a 5% image area chart using the obtained two-component developer and each evaluation machine, the temperature of the fixing roll is changed by 5 ° C., and the image is output to the fixing roller. The wrapping property of the paper around was evaluated. In particular, as a compulsory test for wrapping evaluation, paper conveyance was temporarily stopped during fixing, the supply of heat was temporarily increased, and then the fixing was continued, and stricter evaluation conditions for wrapping were set.
Ricoh full color PPC paper type 6200 was used as the transfer paper.
The evaluation results are shown as follows.
A: Extremely high temperature wrapping property and excellent high temperature fixing property ○: High temperature wrapping property is considerably excellent Winding property is inferior

4) Toner Environment Preservation Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 100 times with a tapping machine, and let it stand in a thermostatic chamber set at a temperature of 55 ° C. and a humidity of 80% for 24 hours. Thereafter, the penetration was measured with a penetration tester (conditions described in the Nikka Engineering Manual). The toner stored in a low-temperature and low-humidity (10 ° C., 15%) environment was similarly evaluated for penetration, and the value with the smaller penetration was evaluated in a high-temperature and high-humidity and low-temperature and low-humidity environment. From the good one, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

1 is a schematic view showing a copying machine according to a best mode for carrying out the invention. FIG. 2 is an enlarged schematic view illustrating a fixing unit of the copier of FIG. 1. 1 is a schematic diagram illustrating a configuration of a color tandem indirect transfer type image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus including a process cartridge according to the present invention.

Explanation of symbols

Explanation 11 in FIG. 1 Copying machine (image forming apparatus)
15 Fixing unit 21 Photosensitive drum (photosensitive member)
23 Laser light source (exposure means)
24 Developing roller (developing means)
25 Transfer roller (transfer means)
29 Heat fixing roller (fixing medium)
32 Pressure roller (contact member)
Description 36 in FIG. 2 Core metal 37 Release layer P Paper (recording body)
T, T 'Toner

Explanation 10 in FIG. 3 Intermediate transfer members 14, 15, 16 Support roller 17 Intermediate transfer member cleaning device 18 Image forming means 20 Tandem image forming unit 21 Exposure device 22 Secondary transfer device (transfer roller)
23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt (fixing film)
27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photoconductor 41 Developing belt 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46, 48 paper feed path 47 transport roller 49 registration roller 50 paper feed roller 51 manual feed tray 52 separation roller 53 manual paper feed path 55 switching claw 56 discharge roller 57 paper discharge tray 100 copier main body 200 paper feed table 300 scanner 400 automatic document feeder

Claims (17)

In an image forming apparatus including a fixing device that fixes a visible image on a recording medium by heat and pressure, the system speed is 400 to 3000 mm / sec, and the pressing surface pressure of the fixing medium of the fixing device is 5 N / cm ^2. a ~90N / cm ^2, and toner used in the visible image formation, a toner containing at least an amorphous polyester resin and a crystalline polyester resin and a colorant and a release agent, and the crystalline polyester resin An image forming apparatus having a crystal component ratio in the toner of 0.10 to 20%.   The image forming apparatus according to claim 1, wherein the surface of the fixing medium has a composition containing at least a fluororesin.   The fixing medium surface has a composition containing at least one or more of polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a polymer of both. The image forming apparatus according to claim 1, wherein the image forming apparatus is an image forming apparatus.   The image forming apparatus according to claim 1, wherein a fixing nip width of the fixing device is 4 mm to 20 mm.   The image forming apparatus according to claim 1, wherein at least one Tg peak of the crystalline polyester resin is present at least at 80 ° C. to 130 ° C. 5.   6. The toner according to claim 1, wherein the toner contains at least a fatty acid amide compound as a crystallinity-holding component, and one or more Tg peaks of the fatty acid amide compound exist at least at 70 ° C. to 160 ° C. An image forming apparatus according to claim 1.   The image forming apparatus according to claim 6, wherein a difference between a Tg peak of the crystalline polyester resin and a Tg peak of the fatty acid amide compound is 50 ° C. or less.   The wax according to any one of claims 1 to 7, wherein the mold release agent contains at least a wax having a hydrocarbon straight chain, and at least one Tg peak of the wax exists at 40 ° C to 130 ° C. The image forming apparatus described.   9. The image forming apparatus according to claim 8, wherein the wax contains at least one of carnauba wax, polyethylene wax, polypropylene wax, synthetic ester wax, and paraffin wax.   The image forming apparatus according to claim 1, wherein the toner is a color toner.   The image forming apparatus according to claim 1, wherein the toner is toner having an average circularity of 0.94 or more and less than 1.00.   The toner has a volume average particle diameter of 2.0 to 7.0 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.0 to 1.3. The image forming apparatus according to claim 1, wherein the toner is in the range of 1 to 11.   A latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier is exposed based on image data, whereby an electrostatic latent image is obtained. An exposure unit for writing, a developing unit for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier and a visible image, and a visible image on the surface of the latent image carrier are transferred to a transfer target The image forming apparatus according to claim 1, further comprising: a transfer unit that performs fixing, and a fixing unit that fixes a visible image on the transfer target.   The image forming apparatus according to claim 1, wherein the image forming apparatus includes a process cartridge that integrally supports the latent image carrier and at least the developing unit and is detachable from the main body of the image forming apparatus. apparatus.   A toner for use in the image forming apparatus according to claim 1.   A carrier having at least magnetism, which is used in the image forming apparatus according to claim 1.   A developer containing at least a toner and a carrier, which is used in the image forming apparatus according to claim 1.

Images