JP2008275839A - Image forming apparatus, and toner, carrier and developer used for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fixing device and image forming apparatus showing improved photoreceptor filming property (contamination preventing property) in a high-speed output system, capable of performing low temperature fixing and having good toner storage property and winding prevention property at high temperature during fixing, applicable in a wide fixing temperature range and giving sufficiently high fixing strength with a fixing paper, and to provide an image forming apparatus, a process cartridge, toner, carrier and developer capable of printing high-quality images. <P>SOLUTION: The image forming apparatus includes a fixing device that fixes a visible image on a recording medium with heat and pressure, characterized in that: the system speed is 400 to 3,000 mm/sec; the surface pressure on a fixing medium is 5 N/cm<SP>2</SP>to 90 N/cm<SP>2</SP>; the toner used for forming a visible image contains at least a resin, a colorant and a release agent; the surface occupation rate Tp of the release agent in the toner is 0.1% to 4.0%; and the surface occupation rate Ta of the release agent in the toner when the toner is melted by heating at 150°C is 10.0% to 70.0%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an image forming apparatus, 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, the toner fixability, which is one of the factors that have an important influence on the image quality, deteriorates as the image forming speed, that is, the system speed of the so-called image forming apparatus, increases. It is a problem to make it. Further, the deterioration of the softening property of the resin generated for improving 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.
Thus, even with one keyword of speeding up, various side effects caused by the keyword, for example, not only the fixability 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.

An unfixed toner image on paper is fixed by heat and pressure in the fixing device, and the toner image is fixed on the paper. However, if 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 yet been possible to obtain a toner having excellent low-temperature fixability and excellent 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 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.

In addition, a toner having excellent heat-resistant storage stability and offset resistance while maintaining low-temperature fixability has been proposed (Patent Document 10: Japanese Patent Application Laid-Open No. 2007-65620). However, the toner has a toner surface occupancy Ta of less than 10.0% when the toner is heated and melted at 150 ° C. and is not compatible with a high-speed machine.

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 JP 2007-65620 A

  In view of the above-mentioned problems, the present invention has improved filming (contamination) property to a photoreceptor in a high-speed output system, low-temperature fixing is possible, toner storage stability is good, and high-temperature wrapping property is also good. A fixing device and an image forming apparatus that can be applied to a wide range of fixing temperatures and have a sufficiently high fixing strength with a fixing paper, a highly charged toner with a controlled charge characteristic, a developing system with a low carrier spent property, and a developer. High-quality toner and carrier that can be used and achieve high developer life while maintaining highly reliable images, and can reduce deterioration fog in low-temperature and low-humidity environments. It is an object of the present invention to provide an image forming apparatus, a process cartridge, toner, a carrier, and a developer capable of printing a simple image.

In order to solve the above problems, the present invention is characterized by the following.
(1) “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 is 5N. / Cm ^{2 to} 90 N / cm ² and the toner used for visible image formation contains at least a resin, a colorant, and a release agent, and the toner surface occupation ratio Tp of the release agent is An image having a toner surface occupancy Ta of from 0.1% to 4.0% and a release agent when the toner is heated and melted at 150 ° C. is 10.0% to 70.0%. Forming device ",
(2) “Image forming apparatus, wherein the surface of the fixing medium described in (1) is a component containing at least a fluororesin”;
(3) “The surface of the fixing medium described in (1) or (2) is at least a polytetrafluoroethylene resin (PTFE), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or both of them. An image forming apparatus characterized by having a composition containing at least one polymer ",
(4) “Image forming apparatus characterized in that the fixing nip width of the fixing device according to any one of (1) to (3) is 4 mm to 20 mm”,
(5) “Toner used in the image forming apparatus according to any one of (1) to (4) above, containing a wax having at least a hydrocarbon straight chain as a releasing agent, and a Tg peak of the wax , At least one image forming apparatus at 50 ° C. to 130 ° C. ”,
(6) “Toner used in the image forming apparatus according to any one of (1) to (5), wherein the wax is made of carnauba wax, polyethylene wax, polypropylene wax, synthetic ester wax, or paraffin wax. An image forming apparatus comprising at least one kind ",
(7) “Toner used in the image forming apparatus according to any one of (1) to (6), including at least a fatty acid amide compound as the releasing agent, wherein the fatty acid amide compound has a Tg peak. , At least one image forming apparatus having a temperature of 70 ° C. to 160 ° C. ”,
(8) “Toner used in the image forming apparatus according to any one of (1) to (7), wherein the resin contains at least one amorphous polyester resin. Image forming apparatus ",
(9) “An image that is used in the image forming apparatus according to any one of (1) to (8), and includes at least one crystalline polyester resin as the resin. Forming device ",
(10) “Toner used in the image forming apparatus according to any one of (1) to (9), including at least one crystalline polyester resin as the resin, and the crystalline polyester An image forming apparatus characterized in that at least one Tg peak of at least 80 ° C. to 130 ° C. is present ”,
(11) “Image forming apparatus characterized in that the toner is used in the image forming apparatus according to any one of (1) to (10), and the toner is a color toner”.
(12) “Toner used in the image forming apparatus according to any one of (1) to (11), wherein the toner has an average circularity of 0.94 or more and less than 1.00. An image forming apparatus characterized by that, "
(13) “Toner used in the image forming apparatus according to any one of (1) to (12), wherein the toner has a volume average particle diameter of 2.0 to 7.0 μm, An image forming apparatus comprising a toner having a ratio (Dv / Dn) of a diameter (Dv) to a number average particle diameter (Dn) in a range of 1.0 to 1.3 ",
(14) “The image forming apparatus according to any one of (1) to (13), wherein a latent image carrier that carries a latent image, and a charging unit that uniformly charges the surface of the latent image carrier. And exposing the charged surface of the latent image carrier on the basis of the image data, writing an electrostatic latent image, supplying toner to the electrostatic latent image formed on the surface of the latent image carrier, An image forming apparatus comprising: a developing unit that makes a visible image; a transfer unit that transfers a visible image on the surface of the latent image carrier to a transfer target; and a fixing unit that fixes the visible image on the transfer target. ,
(15) The image forming apparatus according to any one of (1) to (14), wherein the image forming apparatus integrally supports the latent image carrier and at least the developing unit, and the image forming apparatus main body. An image forming apparatus comprising a detachable process cartridge ",
(16) “Toner containing at least a resin, a colorant, and a release agent, which is used in the image forming apparatus according to any one of (1) to (15)”,
(17) “A carrier having at least magnetism, which is used in the image forming apparatus according to any one of (1) to (15)”,
(18) “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 (15)”.

According to the present invention, even in an ultra-high-speed image forming apparatus, it is excellent in low-temperature fixability and high-temperature wrapping property and can be applied to a wide range of fixing temperatures, excellent in filming properties and storage stability, and sufficiently high in fixing strength with fixing paper, Toner with highly controlled charging characteristics, development system with low carrier spent, high developer life while maintaining highly reliable images, and reduced fogging in low temperature and low humidity environments An image forming apparatus capable of performing the above can be provided.
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 those 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 according to the present invention is as follows. An image forming apparatus including a fixing device that fixes a visible image on a recording medium by heat and pressure, a system speed of 400 to 3000 mm / sec, and a pressing surface pressure of the fixing medium of 5 N / cm ² to The toner used for forming a visible image at 90 N / cm ² contains at least a resin, a colorant, and a release agent, and the toner surface occupation ratio Tp of the release agent is 0.1%. The image forming apparatus is characterized in that the toner surface occupancy Ta of the release agent when the toner is heated and melted at 150 ° C. is 10.0% to 70.0%. .

  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 fixing surface pressure. In order to form an appropriate image quality even when the system speed (moving speed of the fixing medium) is 400 to 3000 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 appropriately pressurized by its proper surface pressure is fixable. 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 photoconductor filming.

  On the other hand, the toner surface occupation ratio Tp of the toner-containing release agent is 0.1% to 4.0%, more preferably 1.0 to 4.0% as a toner suitable for the above-described image forming apparatus. Is even more important. Here, the toner surface occupation ratio Tp of the release agent indicates the occupation ratio and coverage of the release agent on the toner surface, as will be described in detail later, and indicates the ratio of the release agent covering the toner surface. When this occupation ratio Tp is less than 0.1%, it indicates that there is almost no release agent on the toner surface. In this case, the filming resistance and the carrier spent resistance are good, but the toner fixing property is good. Cannot be secured sufficiently, and hot offset is particularly likely to occur. Further, the fixing releasability is lowered, and the fixing paper is wound around the fixing medium. On the other hand, if it exceeds 4.0%, the releasing agent is present on the toner surface to some extent, so that the fixing releasability is improved, but the releasing agent adheres or causes (trigger) to cause photoconductor filming, or the carrier Spent is not preferable.

  On the other hand, the release agent in the toner has a function of effectively releasing the fixing medium and the toner surface at the time of fixing the toner. However, as described above, the release agent has the side effects of photoconductor filming and carrier spent. Therefore, it is desirable that it does not exist so much on the toner surface when it is not heated but appears to bleed out on the toner surface only when it is heated. As a function for that purpose, the occupancy rate and coverage of the release agent on the surface of the toner after melting were evaluated as the exuding property of the release agent. Specifically, it is important that the toner surface occupation ratio Ta of the release agent when the toner is heated and melted at 150 ° C. is 10.0% to 70.0%. Here, the post-melting toner surface occupancy Ta indicates the ratio of the release agent on the toner surface after heating at 150 ° C. covering the toner surface. When this Ta is less than 10.0%, the amount of bleed-out of the release agent to the toner surface during heating is small, and the original function of the release agent is not sufficiently exerted, so that the fixing paper (toner) can be applied to the fixing medium. Winding or hot offset is not preferable. On the other hand, when Ta exceeds 70.0%, the wrapping around the fixing medium and the hot offset are good, but conversely, excessive release agent remains on the fixing member, the fixed image, etc., and the fixing member is contaminated. It is not preferable because abnormal shine or the like of the image occurs.

Needless to say, controlling the state of dispersion of the release agent inside and on the toner is important as a factor for controlling the surface occupancy Tp of the release agent. Therefore, not only the content and thermal characteristics (melting point / glass transition point) of the release agent that interacts with the thermal characteristics of the resin, but in the case of a kneaded and pulverized toner, the premixed state of the release agent and the resin before kneading It is important to appropriately mix the release agent and the resin before kneading in order to control dispersibility after the subsequent kneading. The surface occupancy Tp is a characteristic that is determined by intricately intertwining the kneading method, kneading time, kneading temperature, kneading frequency, etc. during kneading.
Furthermore, control of the aforementioned release agent when containing a crystalline polyester resin or a fatty acid amide compound was extremely difficult, but control of these complex systems was the first by appropriately controlling the surface occupancy Tp of the release agent. And as a result, the object of the present application could be achieved.

As a factor for controlling the toner surface occupancy Ta of the release agent at 150 ° C. by heating and melting, not only the thermal characteristics (meltability (melting temperature), melt viscosity, melt flowability) of the release agent, but also the melting of the toner resin Properties, glass transition temperature, and release agent dispersibility also contribute greatly, and it is important how the resin melts to bleed out the release agent, which is an indicator of the bleed-out property of the release agent. In particular, since the portion of interaction with the resin is large, not only the control of Tp indicating the so-called initial dispersion state of the release agent, but also the control of how the release agent actually appears on the toner surface during heating is particularly effective. It is important to prevent wrapping around. Basically, the surface occupancy Ta becomes larger when the meltability of the resin exhibits lower viscoelasticity at a lower temperature, but since the properties of the release agent are also involved, simply discussing the viscoelasticity of the resin alone Can not.
In that sense, Tp is intended to prevent carrier spent on development, photoconductor filming, and the like by controlling the state of the initial release agent, and Ta is a fixing function that is an original function of the release agent. It can be said that the mold release property is controlled.

When pressure is applied in the evaluation of the toner alone, the release agent adheres to the pressurization medium, and the amount of the release agent on the surface of the molten toner cannot be accurately evaluated. In the system linear velocity range, since the correlation between the evaluation of the toner alone in the non-pressurized state and the releasability with the pressurized system was obtained, in the present invention, the toner was evaluated in the non-pressurized state. .
The correlation between the evaluation in the unpressurized state and the releasability with the pressurized system was obtained because the release agent bleeds out on the toner surface by sufficient heating even in the unpressurized state. Therefore, it can be said that this evaluation method is sufficiently effective.
Further, it is estimated that the pressure contact pressure range of the present invention contributes more greatly to smoothing the toner resin by pressure and fixing it to the paper medium than to bleed out the release agent.

  Further, it is more preferable that the surface of the fixing medium (fixing member) of the fixing device is a component containing at least a fluororesin, so that 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 meltability can be secured, which is more preferable.

  Further, the surface of the fixing medium has a composition containing at least one of polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a polymer of both. Therefore, 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 with respect to a high system linear speed where the moving speed of the fixing medium is 400 to 3000 mm / sec. Is not preferable because it is not transmitted to the toner and the toner meltability and the release agent cannot be sufficiently oozed out. On the other hand, if the fixing nip width exceeds 20 mm, the fixing heat and fixing pressure are sufficiently transmitted to the toner. However, in the case of the high system speed, the meltability of the toner is too high and the fixing paper is wound around the fixing medium. It is not preferable. When the fixing nip width exceeds 20 mm, even if it is a release agent in the toner that originally functions to prevent winding, if a certain amount or more of the release agent oozes out, the winding cannot be sufficiently prevented. I have also understood. Rather, it causes undesired filming of the photoreceptor as a side effect containing the release agent.

The toner used in the image forming apparatus contains at least a wax having a hydrocarbon straight chain as a releasing agent, and the Tg peak of the wax is at least 50 ° C. to 130 ° C., more preferably 70 ° C. to 120 ° C. ℃ the presence one or more, especially in the high-speed system linear velocity, low pressure pressing surface pressure of the fixing medium is ^{5N / cm 2 ~90N / cm 2} , even at low temperatures fixing environment, rapid wax It is more preferable that the toner releasability is achieved and the toner releasability functions more effectively.

  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. 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, the toner used in the image forming apparatus contains at least a fatty acid amide compound as the release agent, 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 prevent fixing hot offset and fixing wrapping due to the rapid leaching effect of the fatty acid amide compound even in the low fixing pressure and low temperature fixing environment, particularly at the high system linear speed. The adhesion of the photosensitive member filming can be reduced, which is more preferable. In addition, the fatty acid amide compound is very effective in that the heat resistant storage stability of the toner is improved. Here, when the Tg peak is less than 70 ° C., it is effective for exudation at a low temperature, but it cannot sufficiently function in terms of ensuring the heat-resistant storage stability of the toner. 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.

  Further, the toner used in the image forming apparatus contains at least one polyester resin as the resin, so that the toner can be appropriately melted and fixed even in the low fixing pressure and low temperature fixing environment. Further, it is more preferable that the heat-resistant storage stability can be achieved at the same time, and it can appropriately interact with the release agent and the fatty acid amide compound to sufficiently exhibit the bleeding effect.

  Further, the toner used in the image forming apparatus contains at least one crystalline polyester resin as the resin, so that the toner can be appropriately melted and fixed even in a low fixing pressure and low temperature fixing environment. In addition, heat-resistant storage stability can be achieved at the same time, and the unique crystal structure can interact properly during heating even when exfoliating from mold release agents and fatty acid amide compounds. preferable.

  Further, the toner used in the image forming apparatus contains at least one crystalline polyester resin as the resin, and the Tg peak of the crystalline polyester is at least 80 ° C. to 130 ° C., more preferably 90 ° C. to By existing at 130 ° C., the above-described effects can be more sufficiently 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 at the time of heating and exhibits a sufficient 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, if the Tg peak exceeds 130 ° C., it cannot be applied to the low pressure and low temperature fixing environment at the high system linear velocity, and this is not preferable because the fixing strength of the fixed image is lowered. Further, since the release agent does not dissolve appropriately, fixing winding is likely to occur, which is not preferable.

  Further, since the toner used in the image forming apparatus is a color toner, sufficient fixability is secured even at a high system linear speed, and the toner has required transparency, color clarity, gloss, etc. 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 fixing image quality is improved due to improved transferability but also on 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, it is preferable from the viewpoint of uniformity of an unfixed image, but since the toner is spherical, the toner cleaning property on the surface of the photoreceptor is lowered, and the spherical fine powder toner is not preferable because it causes filming.

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 adhesive force due to the small particle size is liable to cause photoconductor filming, which is not preferable. Further, when the volume average particle diameter exceeds 7.0 μm, it is not preferable because uniformity of toner melting property cannot be ensured. (Dv / Dn) is 1.00 when there is no particle size distribution, and the value increases when the particle size distribution is widened. However, 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.

  The image forming apparatus includes 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.

  Furthermore, in the image forming apparatus, 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. It is more preferable because the latent image carrier and developer can be efficiently exchanged in order to correspond to the lifetime system.

  FIG. 1 shows a copying machine as an image forming apparatus according to the present embodiment. The copying machine 111 includes a document reading unit 112 that reads a document to be copied, a sheet feeding unit 113 that stocks printing sheets, and an image from the document reading unit 112 on a sheet supplied from the sheet feeding unit 113. An image forming unit 114 that forms a toner image based on the signal, a fixing unit 115 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 116.

  The document reading unit 112 includes a lamp 117 and mirrors 118a and 118b that travel in the direction of arrow A to scan the document, and a CCD 119 that receives reflected light from the document. The sheet feeding unit 113 includes a plurality of trays 120a, 120b,..., And sheets of different sizes are stocked in each tray.

  The image forming unit 114 includes a photosensitive drum 121 that rotates in the direction of arrow B, a charging roller 122 that uniformly charges the surface of the photosensitive drum 121, and the surface of the uniformly charged photosensitive drum 121. A laser light source 123 that forms an electrostatic latent image based on the light reception result, a developing roller 124 that visualizes the electrostatic latent image as a toner image by supplying toner to the surface of the photosensitive drum 121, and the photosensitive drum 121. A transfer roller 125 for transferring the toner image formed on the surface of the photosensitive drum 121 to a sheet from the paper supply unit 113, and a cleaning mechanism 126 for cleaning the surface of the photosensitive drum 121 after the transfer. The paper discharge unit 116 includes a paper discharge port 127 that communicates the inside and outside of the copier 111 and a tray 128 that receives the discharged paper. The paper from the image forming unit 114 is discharged after passing through the fixing unit 115 described below. The paper passes through the paper mouth 127 and is discharged onto the tray 128.

  As shown in FIG. 2, the fixing unit 215 is provided with a heat fixing roller 229 as a fixing member that heats and fixes the unfixed toner T on the paper P, and a halogen that is provided inside the heat fixing roller 229 and heats it. A lamp 230, a pressure roller 232 that closely contacts the heat fixing roller 229 with the elastic layer 231 facing the heat fixing roller 229, and a paper jam that occurs when the paper P adheres to the heat fixing roller 229 after toner fixing. In order to achieve this, a separation claw 233 that contacts the heat fixing roller 229 and separates the paper attached thereto, a thermistor thermometer 234 that detects the surface temperature of the heat fixing roller 29, and a paper conveyance path inside the copier 211 And a detection sensor 235 that detects the paper P entering the heat fixing roller 229.

  The heat fixing roller 229 is manufactured by forming a release layer 237 on the surface of an aluminum cylindrical metal core 236. Specifically, a thin metal core having a thickness t of 0.7 mm or less is used for the metal core 236 to facilitate heating by the halogen lamp 230 and save energy, and the surface of the metal core 236 is roughened to form a primer layer. 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. A resin having the composition is applied, and the outline of the release layer 237 is formed. Thereafter, the surface of the release layer 237 is trimmed 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, which is a width where the surface release layer 237 of the heat fixing roller 229 and the elastic layer 231 of the pressure roller 232 facing each other come into contact.

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 the copying apparatus 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.
Among the three images, four images of yellow, cyan, magenta, and black are formed 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 member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.
The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. 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, for example, a charging device 60, a developing device 61, and a primary transfer device around a drum-shaped photoreceptor 40 as shown in FIG. 62, a photoconductor cleaning device 63, a charge removal device 64, and the like. Referring to the reference numerals shown in FIG. 3, 65 is a developer on the developing sleeve, 68 is a stirring paddle, 69 is a partition plate, 71 is a toner concentration sensor, 72 is a developing sleeve, 73 is a doctor, 75 is a cleaning blade, and 76 is A cleaning brush, 77 is a cleaning roller, 78 is a cleaning blade, 79 is a toner discharge auger, and 80 is a driving device.

(Process cartridge)
FIG. 4 is a schematic diagram showing a configuration of an image forming apparatus including the process cartridge of the present invention. 4, a represents the entire process cartridge, b represents a photosensitive member, c represents a charging unit, d represents a developing unit, and e represents a cleaning unit.
In the present invention, at least the photosensitive member b and the developing unit d are integrally combined as a process cartridge among the above-described components such as the photosensitive member b, the charging device unit c, the developing unit d, and the cleaning unit e. The process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

(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.

(Toner surface occupation ratio Tp of release agent)
The toner surface occupation ratio Tp of the release agent in the present invention was evaluated by the following apparatus and conditions. First, the external additive was removed from the toner surface, and then the evaluation was performed by analyzing the reflected electron image of FE-SEM.

(1) Removal of external additive (1-1) Add 4 g of toner to a mixture of 0.5 ml of dry well and 100 ml of isotone, mix well by hand shaking 50 times, and let stand for 1 hour or more.
(1-2) After stirring by hand shaking 30 times, using a homogenizer, dispersing at 20 W for 1 minute, and then repeating a 5-minute stop cycle 5 times to release the toner external additive.
(1-3) The dispersion is subjected to suction filtration, the external additive is separated from the toner, and the obtained toner base is dried.
(1-4) Ultrasonic irradiation conditions of a homogenizer (VCX-750 manufactured by Sonics & Materials) ・ Vibration time 60 seconds continuous ・ Amplitude 20 W (39%)
・ Vibration start temperature 23 ± 1.5 ℃

(2) FE-SEM reflected electron image analysis It evaluated using the Ultra55 Schottky type thermal FE-SEM (scanning electron microscope) by Zeiss. Three or more fields of view were measured at an acceleration voltage of 0.8 kV and a magnification of 1000, and 100 particles were analyzed. The toner was fixed on a carbon tape, dyed by exposure to ruthenium tetroxide vapor for 5 minutes, and then observed with FE-SEM reflected electrons. The obtained reflected electron image was binarized by image analysis software Image Plus Pro4.5.1 (Media Cybernetics, Inc.), and the release agent and other portions were identified and analyzed by contrast. The total area of the toner was similarly analyzed, and the area (occupancy) of the release agent relative to the total area of the toner was calculated by the following equation.

Occupancy rate Tp (%) = area of release agent / area of entire toner × 100 (1) Formula

Here, the mold release agent is a mold release having an average diameter converted from an area of 0.5 μm or more in consideration of the effective bleeding effect of the mold release agent and the S / N effect of analytical contrast. Only the agents were integrated and used for analysis.
The principle by which the release agent and toner can be distinguished by this method will be described. First, by analyzing reflected electrons instead of secondary electrons for general shape observation of FE-SEM, the contrast difference between the release agent 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, ruthenium tetroxide has a selective dyeing property of the material, and in the case of the component of the toner of the present invention, the release agent is not dyed and the resin and other components are dyed. As a result, the release agent portion can be observed with black contrast, and the other toner portions can be observed with white contrast. Furthermore, by setting the acceleration voltage to 0.8 kV, the charge-up phenomenon due to the electron beam of toner is prevented, and the surface analysis of several nanometers to several tens of nanometers is possible by reducing the electron beam analysis depth by the low acceleration voltage. It has become possible.

(Toner surface occupancy Ta of release agent after heating)
30 mg of toner was molded with a pressure molding machine (NAKA SEIKI TYPE NH200) at 100 N for 1 minute to prepare a toner tablet sample having a diameter of 5 mm and a thickness of 1 mm. The obtained tablet sample was placed in a heating control unit (Type 10030) manufactured by Japan High-Tech Co., Ltd., and heated from room temperature to 150 ° C. under a temperature rising rate of 10 ° C. per minute. Thereafter, rapid cooling with air was performed to prepare a heated sample.
The tablet-like sample after melting was fixed on a carbon tape, and then Ta was obtained by the same FE-SEM backscattered electron image analysis as in the Tp calculation. Measurement is 0.8kV acceleration voltage
Three fields of view were measured at a magnification of 1000 and analyzed in the same manner using the image analysis software described above.

Occupancy rate Ta (%) = area of release agent after heating / area of entire toner × 100 (2) formula

(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 indicating 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 fluororesin. 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, it is a resin having a composition containing at least one or more of polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a polymer of both. 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 well dispersed in the binder resin, and more effectively as a release agent, the fixing roller and the toner interface. As a result, it is effective against 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 petroleum waxes such as petrolatum. 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 50 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)
More preferably, the release agent contained in the toner of the present invention contains at least a fatty acid amide compound, 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. One or more fatty acid amide compounds may be mentioned. Further, it is more preferable to use both of the above-mentioned mold release agent other than the fatty acid amide compound and the fatty acid amide compound.
As the fatty acid amide compound, a compound represented by R ₁ —CO—NR ₂ R ₃ is used. In the formula, R ₁ is an aliphatic hydrocarbon group having 10 to 30 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 10 carbon atoms. Here, the alkyl group, aryl group, and aralkyl group of R ₂ and R ₃ 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 amide is 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 biphenyl 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, a polyester resin, particularly an amorphous polyester resin, which is suitable from the viewpoints of color developability and image strength, particularly as a binder resin for a full color toner, 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 glycol. Diols such as 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol; bisphenol A, hydrogenated bisphenol A, polyoxypropylenated bisphenol Bisphenol A alkylene oxide adducts such as A; other dihydric alcohols, or sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripe Taerythritol, 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.

  Examples of the acid monomer among the monomers constituting the polyester resin include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, and 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 group, alkenyl group or aryl ester include 1,2,4-benzenetricarboxylic acid, trimethyl 1,2,4-benzenetricarboxylate, triethyl 1,2,4-benzenetricarboxylate, 1,2 , 4-benzenetricarboxylic acid tri-n-butyl, 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 may be used in combination.
(AX1): Linear polyester resin using (g) and (i) (AX2): Non-linear polyester resin using (h) and / or (j) together with (g) and (i) ( 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 applies 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 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.

The trivalent or higher (3 to 8 or higher) polyol (h) is preferably a hydroxyl value of 150 to 1900. Specifically, an aliphatic polyhydric alcohol having 3 to 36 or more carbon atoms and 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 novolac, 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.

  In the present invention, the amorphous polyester resin used as the toner binder 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 color toners. The content of (a) in all the added catalysts is preferably 50 to 100%.

  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.
In addition, the amount of (c) used to obtain (AY1) is preferably 0.01 to 10%, more preferably 0.8% with respect to (AX2), from the viewpoints of low-temperature fixability and hot offset resistance. 05 to 5%.

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) acrylates, copolymers of styrene and diene monomers), epoxy resins (bisphenol A diglycidyl ether ring-opened polymers, etc.), 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 characterized by comprising a crystalline aliphatic polyester resin containing an ester bond represented by the following general formula (2) in its molecular main chain.

前記式中、Ｒは直鎖状不飽和脂肪族２価カルボン酸残基を示し、炭素数２〜２０、好ましくは２〜４の直鎖状不飽和脂肪族基である。ｎは２〜２０、好ましくは２〜６の整数である。 一般式（２）の構造の存在は固体Ｃ^１３ＮＭＲ（核磁気共鳴分析）により確認することが出来る。
さらにその分子主鎖中にエステル結合を少なくとも６０モル％以上含有する結晶性脂肪族ポリエステル樹脂であることがより好ましい。
前記直鎖状不飽和脂肪族基の具体例としては、マレイン酸、フマル酸、１，３−ｎ−プロペンジカルボン酸、１，４−ｎ−ブテンジカルボン酸等の直鎖状不飽和２価カルボン酸由来の直鎖状不飽和脂肪族基を挙げることができる。
前記一般式（２）において、（ＣＨ₂）ｎは直鎖状脂肪族２価アルコール残基を示す。
この場合の直鎖状脂肪族２価アルコール残基の具体例としては、エチレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール等の直鎖状脂肪族２価アルコールから誘導されたものを示すことができる。ポリエステル樹脂（Ａ）は、その酸成分として、直鎖状不飽和脂肪族ジカルボン酸を用いたことから、芳香族ジカルボン酸を用いた場合に比べて結晶構造を形成し易いという作用効果を示す。
ポリエステル樹脂は、（i）直鎖状不飽和脂肪族２価カルボン酸またはその反応性誘導体（酸無水物、炭素数１〜４の低級アルキルエステル、酸ハライド等）からなる多価カルボン酸成分と、（ii）直鎖状脂肪族ジオールからなる多価アルコール成分とを、常法により重縮合反応させることによって製造することができる。
この場合、多価カルボン酸成分には、必要に応じ、少量の他の多価カルボン酸を添加することができる。この場合の多価カルボン酸には、（i）分岐鎖を有する不飽和脂肪族二価カルボン酸、（ii）飽和脂肪族２価カルボン酸や、飽和脂肪族３価カルボン酸等の飽和脂肪族多価カルボン酸の他、（iii）芳香族２価カルボン酸や芳香族３価カルボン酸等の芳香族多価カルボン酸等が包含される。これらの多価カルボン酸の添加量は、全カルボン酸に対して、通常、３０モル％以下、好ましくは１０モル％以下であり、得られるポリエステルが結晶性を有する範囲内で適宜添加される。
必要に応じて添加することのできる多価カルボン酸の具体例を示すと、マロン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、セバシン酸、シトラコン酸、フタル酸、イソフタル酸、テレフタル酸等の２価カルボン酸；無水トリメット酸、１，２，４−ベンゼントリカルボン酸、１，２，５−ベンゼントリカルボン酸、１，２，４−シクロヘキサントリカルボン酸、１，２，４−ナフタレントリカルボン酸、１，２，５−ヘキサントリカルボン酸、１，３−ジカルボキシル−２−メチレンカルボキシプロパン、１，２，７，８−オクタンテトラカルボン酸等の３価以上の多価カルボン酸等を挙げることができる。
前記多価アルコール成分には、必要に応じ、少量の脂肪族系の分岐鎖２価アルコールや環状２価アルコールの他、３価以上の多価アルコールを添加することができる。その添加量は、全アルコールに対して、３０モル％以下、好ましくは１０モル％以下であり、得られるポリエステルが結晶性を有する範囲内で適宜添加される。
必要に応じて添加される多価アルコールを例示すると、１，４−ビス（ヒドロキシメチル）シクロヘキサン、ポリエチレングリコール、ビスフェノールＡエチレンオキサイド付加物、ビスフェノールＡプロピレンオキサイド付加物、グリセリン等が挙げられる。
ポリエステル樹脂において、その分子量分布は、低温定着性の点から、シャープであるのが好ましく、また、その分子量は、比較的低分子量であるのが好ましい。ポリエステル樹脂（Ａ）の分子量は、そのｏ−ジクロルベンゼン可溶分のＧＰＣによる分子量分布において、その重量平均分子量（Ｍｗ）が５５００〜６５００、その数平均分子量（Ｍｎ）が１３００〜１５００およびそのＭｗ／Ｍｎ比が２〜５であることが好ましい。
ポリエステル樹脂（Ａ）についての前記分子量分布は、横軸をｌｏｇ（Ｍ：分子量）とし、縦軸を重量％とする分子量分布図に基づくものである。本発明で用いるポリエステル樹脂（Ａ）の場合、この分子量分布図において、３．５〜４．０（重量％）の範囲に分子量ピークを有することが好ましく、また、そのピークの半値幅が１．５以下であることが好ましい。
ポリエステル樹脂において、そのガラス転移温度（Ｔｇ）および軟化温度（Ｔｍ）は、トナーの耐熱保存性が悪化しない範囲で低いことが望ましいが、一般的には、そのＴｇは８０〜１３０℃、好ましくは８０〜１２５℃であり、そのＴｍは８０〜１３０℃、好ましくは８０〜１２５℃である。ＴｇおよびＴ（Ｆ１／２）が前記範囲より高くなると、トナーの定着下限温度が高くなるため、トナーの低温定着性が悪化する
。
ポリエステル樹脂を２種以上併用する場合、および少なくとも１種のポリエステル樹脂と他の樹脂を混合する場合、予め粉体混合または溶融混合してもよいし、トナー化時に混合してもよい。溶融混合する場合の温度は、好ましくは８０〜１８０℃、さらに好ましくは１００〜１７０℃、とくに好ましくは１２０〜１６０℃である。
混合温度が低すぎると充分に混合できず、不均一となることがある。２種以上のポリエステル樹脂を混合する場合、混合温度が高すぎると、エステル交換反応による平均化などが起こるため、トナーバインダーとして必要な樹脂物性が維持できなくなる場合がある。 溶融混合する場合の混合時間は、好ましくは１０秒〜３０分、さらに好ましくは２０秒〜１０分、とくに好ましくは３０秒〜５分である。２種以上のポリエステル樹脂を混合する場合、混合時間が長すぎると、エステル交換反応による平均化などが起こるため、トナーバインダーとして必要な樹脂物性が維持できなくなる場合がある。
溶融混合する場合の混合装置としては、反応槽などのバッチ式混合装置、および連続式混合装置が挙げられる。適正な温度で短時間で均一に混合するためには、連続式混合装置が好ましい。連続式混合装置としては、エクストルーダー、コンテイニアスニーダー、３本ロールなどが挙げられる。これらのうちエクストルーダーおよびコンテイニアスニーダーが好ましい。
粉体混合する場合は、通常の混合条件および混合装置で混合することができる。
粉体混合する場合の混合条件としては、混合温度は、好ましくは０〜８０℃、さらに好ましくは１０〜６０℃である。混合時間は、好ましくは３分以上、さらに好ましくは５〜６０分である。混合装置としては、へンシェルミキサー、ナウターミキサー、およびバンパリーミキサー等が挙げられる。好ましくはへンシェルミキサーである。
また、結晶性ポリエステル樹脂の酸価は、紙と樹脂との親和性の観点から、目的とする低温定着性を達成するためにはその酸価が２０ｍｇＫＯＨ／ｇ以上であることが好ましく、一方、ホットオフセット性を向上させるには４５ｍｇＫＯＨ／ｇ以下のものであることが好ましい。
更に、結晶性ポリエステル樹脂の水酸基価については、所定の低温定着性を達成し、かつ良好な帯電特性を達成するためには５〜５０ｍｇＫＯＨ／ｇのものが好ましい。

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-state C ¹³ NMR (nuclear magnetic resonance analysis).
Further, 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 polyester resin (A) uses a linear unsaturated aliphatic dicarboxylic acid as the acid component, the polyester resin (A) exhibits an effect that a crystal structure is easily formed as compared with the case where an aromatic dicarboxylic acid is used.
The polyester resin comprises (i) a polyvalent carboxylic acid component comprising 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.) (Ii) A polyhydric alcohol component composed of a linear aliphatic diol can be produced by 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 in which 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 polyester resin, 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 polyester resin (A), the weight average molecular weight (Mw) is 5500-6500, the number average molecular weight (Mn) is 1300-1500 and The Mw / Mn ratio is preferably 2-5.
The molecular weight distribution of the polyester resin (A) is based on a molecular weight distribution diagram 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 polyester resin, 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. In general, the Tg is 80 to 130 ° C., preferably It is 80-125 degreeC, The Tm is 80-130 degreeC, Preferably it is 80-125 degreeC. When Tg and T (F1 / 2) are higher than the above ranges, the lower limit fixing temperature of the toner is increased, so that the low temperature fixing property of the toner is deteriorated.
When two or more polyester resins are used in combination, and when at least one 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 required 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 preferred.
The acid value of the crystalline polyester resin is preferably 20 mgKOH / 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.

(Toner average circularity)
The average circularity of the toner of the present invention is expressed by the circumference of a circle having the same area as the projected area of the particles / the circumference of the particles, and 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), the number average particle diameter (Dn), and the 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 is 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, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture 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.

(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.
The toner according to the present invention preferably has a volume average particle diameter of 2 to 7 μm, and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.0 to 1.3. It is more preferable that it is in the range.
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 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 resolving power decreases.

(Pulverized toner and toner production method)
The manufacturing method of the pulverized toner of 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, 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 twin screw extruder manufactured by Kobe Steel, TEM manufactured by Toshiba Machine Co., Ltd.
A die extruder, a Cay Kay twin screw extruder, a Ikegai Iron Works PCM type twin screw extruder, a Bus Conyder, etc. are 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 higher than the softening point, cutting is severe, and if the temperature is too low, 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. In this case, 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 material obtained in the pulverization step to adjust the particles to a predetermined particle size. The classification can be performed, for example, by removing the fine particle portion by 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 that are the products obtained in those steps is collected, added in a predetermined amount 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.

  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 charge control agent, additives, wax, fluidity improver, cleaning improver, magnetic material, metal soap, etc. are added to the toner material as necessary. be able to.

(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, etc. Metal complex salts of the monoazo dyes described, salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr described in Japanese Patent Publication No. 55-42752 and Japanese Patent Publication No. 59-7385 , Fe, etc. Metal complex, a copper phthalocyanine pigment obtained by sulfonation, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. For color toners other than black, naturally, the use of a charge control agent that impairs the target color should be avoided, and a white metal salt of a salicylic acid derivative is preferably used.

(External toner additive)
Examples of inorganic fine particles that are external additives added to the toner of the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, and oxide. Tin, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Can be mentioned. Among these, a metal oxide, a metal nitride, and a metal carbide are preferable, and an external additive having a number average particle size in the range of 8 to 80 nm and an external additive in the range of 120 to 300 nm are preferable. Among the inorganic fine particles, silica, alumina, and titanium oxide are preferable, and silica and titanium oxide are particularly preferable. Further, it is more preferable in terms of toner chargeability and fluidity that at least the primary particles contain titanium oxide having a primary particle number average particle size of 5 to 40 nm. The inorganic fine particles are more preferably used in an amount of 0.01 to 5% by weight based on the toner base.

  As a means of highly controlling the fluidity of the toner, not only the control of the production conditions of the external additive, but also the crushing, sieving and the like after the production of the external additive are effective. The adhesion state is also important.

As the external additive, inorganic fine particles or hydrophobized inorganic particles can be used in combination, but the average particle size of hydrophobized primary particles is 1 to 20 nm, more preferably 6 to 15 nm (specific surface area according to BET method). 100 to 400 m ² / g), and 30 to 150 nm, more preferably 90 to 130 nm (specific surface area output by BET method is 20 to 100 m ² / g) at least two kinds More preferably, the above is present on the toner surface. More preferably, the small particle size inorganic fine particles are silica or titanium oxide, and both are more preferable. Silica is more preferable for the large particle size inorganic fine particles. Further, silica produced by a wet method such as a sol-gel method is more preferable. Further, it is more preferable that inorganic fine particles having a medium particle diameter of 20 to 50 nm (specific surface area by BET method of 40 to 100 m ² / g), more preferably silica, are further present on the toner surface.
Any known inorganic 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. 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). Particularly, the hydrophobized titanium oxide fine particles include 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, and 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 obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, and thermosetting resin 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 to the toner, not only dry external addition treatment using a Henschel mixer, Q mixer, etc., but also wet external addition treatment (solvent, water (containing an activator for improving wettability as required)). Adhesion is also effective.
The external additive is mixed into the base toner. The external additive is added to the base toner 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 mixer, the number of rotations, the mixing time, the number of times of mixing, the amount of the 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 this time, if the surfactant is dispersed using a reverse polarity surfactant, the adhesion to the toner particle surface is more efficiently performed. If 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 can be neutralized, and the inorganic fine particles can be aggregated and adhered to the toner particle surfaces. 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.
Further, in order to reduce the coefficient of friction on the surface of the photoreceptor and improve the cleaning property, a metal stearate may be mixed as a lubricant with the toner of the present invention. Zinc stearate is preferred.

(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, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include 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.

(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 content ratio of the carrier and the toner in the developer is 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 resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, 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 contain electrically conductive powder etc. 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)
As the toner container of the present invention, a developer containing the image forming toner of the present invention is filled, and a conventionally known shape can be used.

(Various toner manufacturing methods)
The method for producing the toner of the present invention is not particularly limited, and includes a melt-kneading pulverization method and a polymerization method, a polyaddition reaction method using an isocyanate group-containing prepolymer, a solvent dissolution method, a solvent removal method and a pulverization method. In addition, it can 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 specific crystalline polymer and a polymerizable monomer is directly polymerized in an aqueous phase (suspension polymerization method / emulsification method). Polymerization method), a polyaddition reaction method in which a composition containing a specific crystalline polymer and an isocyanate group-containing prepolymer is directly extended / crosslinked with amines in an aqueous phase, dissolved in a solvent, desolvated and pulverized. It is preferable to employ a method, and 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 means for applying mechanical energy include means for applying strong stirring or ultrasonic vibration energy such as homomixer, ultrasonic wave, and manton gorin.

  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 in a state where the development gap was 1.26 mm, the doctor blade gap was 1.6 mm, and the reflective photosensor function was turned off so that the linear velocity was 1700 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 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 in a state where the development gap was 1.40 mm, the doctor blade gap was 1.8 mm, and the reflective photosensor function was turned off so that the linear velocity 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 applying, molding, and adjusting the surface 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 in a state where the development gap was 1.26 mm, the doctor blade gap was 1.6 mm, and the reflective photosensor function was turned off so that the linear velocity 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 in a state where the development gap was 1.31 mm, the doctor blade gap was 1.7 mm, and the reflective photosensor function was turned off so that the linear velocity 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 turned off so that the linear velocity 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 evaluation machine 6, the developing part and the fixing part of imgio NEO C600 were modified and used. The modified contents were used with the development gap 1.40 mm, the doctor blade gap 2.2 mm, and the reflective photosensor function OFF so that the linear velocity was 380 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 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 in a state where the development gap was 1.14 mm, the doctor blade gap was 1.3 mm, and the reflective photosensor function was turned off so that the linear velocity was 3200 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 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 in a state where the development gap was 1.26 mm, the doctor blade gap was 1.6 mm, and the reflective photosensor function was turned off so that the linear velocity 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 in a state where the development gap was 1.26 mm, the doctor blade gap was 1.6 mm, and the reflective photosensor function was turned off so that the linear velocity 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 with an average thickness of 0.5 μm is used. A developer was prepared by uniformly mixing and charging using a type of tumbler mixer that was rolled and stirred.

(Example of carrier production)
(Carrier 1)
-167 parts of silicone resin solution [solid content 23 wt% (SR2410: manufactured by 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 (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 measurement of the average particle size of the core material, an SRA type of 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 made 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-
1,4-butanediol 23.75 mol, ethylene glycol 1.25 mol, fumaric acid 22.75 mol, anhydrous, in a 5 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple 1.65 mol of trimellitic acid and 5.1 g of hydroquinone were added, reacted at 160 ° C. for 6 hours, then heated to 180 ° C. and reacted for 1.5 hours, and further reacted at 8.3 KPa for 2 hours to produce crystals. -Soluble polyester resin 1 was obtained. 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-
1,4-butanediol 23.75 mol, ethylene glycol 1.25 mol, fumaric acid 22.75 mol, anhydrous, in a 5 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple Crystalline polyester containing 1.65 mol of trimellitic acid and 5.1 g of hydroquinone, reacted at 160 ° C. for 5 hours, heated to 170 ° C. for 1 hour, and further reacted at 8.3 KPa for 2 hours. Resin 2 was obtained. The crystalline polyester resin 2 had a Tg peak of 78 ° 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 3-
1,4-butanediol 23.75 mol, ethylene glycol 1.25 mol, fumaric acid 22.75 mol, anhydrous, in a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple 1.65 mol of trimellitic acid and 5.1 g of hydroquinone were added, reacted at 160 ° C. for 8 hours, then heated to 180 ° C. and reacted for 1.5 hours, and further reacted at 8.3 KPa for 4 hours to produce crystals. -Soluble polyester resin 3 was obtained. The crystalline polyester resin 3 had a Tg peak of 133 ° 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

(Example of silica production)
-Synthesis of silica 1-
100 g of fine silica powder having a BET specific surface area of 300 m ² / g produced by a gas 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 condenser, a stirrer and a nitrogen inlet tube, 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 reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, 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 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.

-Synthesis of amorphous polyester resin b-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 7 hours. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to synthesize polyester resin b.
The obtained polyester resin b had a number average molecular weight (Mn) of 2,000, a weight average molecular weight (Mw) of 5,200, and a glass transition temperature (Tg) of 54 ° C.

-Synthesis of amorphous polyester resin c-
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of an ethylene oxide 2-mole adduct of bisphenol A, 326 parts of a propion oxide 3-mole adduct of bisphenol A, 278 parts of terephthalic acid, 40 of phthalic anhydride 2 parts of titanium dihydroxybis (triethanolamate) as a condensation catalyst was added, and the reaction was carried out for 10 hours while distilling off the water produced at 230 ° 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 polyester resin c.
The obtained polyester resin b had an acid value of 35, a hydroxyl value of 17, Tg of 69 ° C., Mn of 3920, and Mw of 23500.

<Example 1>
-Production of Toner A-
Amorphous polyester resin a ... 93 parts Crystalline polyester 1 ... 7 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) Name: WA-03 (manufactured by Toa Kasei Co., Ltd.) 3 parts Fatty acid amide compound (ethylenebisstearic 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, Mitsui Mining Co., Ltd.). The mixing conditions were a sufficient mixing by repeating a set of 120 seconds rotation and 60 seconds 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 part 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 circumferential 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.
100 parts by weight of carrier 1 with respect to 7 parts by weight of the obtained toner were uniformly mixed and charged using a type of tumbler mixer in which the container was rolled and stirred to prepare a developer. 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, 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 colored particles after classification were machined. Colored particles were produced without feeding to a rotary pulverizer. Subsequent treatments were manufactured 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 7>
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 8>
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 9>
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 10>
In Example 1, evaluation was made in the same manner as in Example 1 except that crystalline polyester 2 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 11>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the crystalline polyester 3 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 12>
In Example 1, the 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 stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts 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. Further, 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 [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 dodecyl diphenyl ether disulfonate ((Eleminol MON-7): manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. As a result, a milky white liquid was obtained. 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 Add 2 parts of tin oxide, react at 230 ° C for 7 hours at normal pressure, and further react for 5 hours at a reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. The mixture was reacted for 3 hours to obtain [Low molecular weight 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%), 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 in which a stir bar and a thermometer are set, 378 parts of [low molecular weight polyester 1], carnauba wax (Tg peak 81 ° C.), product name: 100 parts of WA-03 (manufactured by Toa Kasei Co., Ltd.), 947 parts of ethyl acetate The mixture was charged, heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled 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 are 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 are 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. Thereafter, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at a rotational 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.
Fluorine compound (2)

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 circumferential 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, the polyester resin b was used in place of the polyester resin a of the toner used, and colored particles were produced without supplying the classified colored particles to a mechanical rotary pulverizer. Subsequent treatments were manufactured 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.

<Comparative Example 6>
In Example 1, the polyester resin c was used instead of the polyester resin a of the toner used, and colored particles were produced without supplying the classified colored particles to a mechanical rotary pulverizer. Subsequent treatments were manufactured 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.

<Comparative Example 7>
-Preparation of toner-
・ Polyester resin a: 93 parts ・ Crystalline polyester: 1 part ・ C. 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 101 ° C.), Product name: NX-A-03 (Ceralica NODA Co., Ltd.) 1.5 parts fatty acid amide compound (ethylenebisstearic acid amide, Tg peak 140 ° C.), product name: EB-G (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 circumferential speed of 30 m / sec, and a set of 120 second rotation and 60 second rotation stop was repeated 5 times to sufficiently mix. Thereafter, 10 parts by mass of finely powdered toner collected in advance was added, and kneading was performed for 60 minutes with two rolls whose roll surface was set at 95 ° C. Thereafter, kneading was performed again for 60 minutes with two rolls having a roll surface set at 95 ° C. After rolling and cooling and coarse pulverization, a jet mill type pulverizer (I-2 type mill: manufactured by Nippon Pneumatic Kogyo Co., Ltd.) and a wind classifier (DS classifier: manufactured by Nihon Pneumatic Kogyo Co., Ltd.) are used. Colored particles were obtained.
Thereafter, 100 parts of blue colored particles, 1.5 parts of silica 1 and 0.5 parts of hydrophobized titanium oxide having a primary average particle diameter of 13 nm are mixed with a Henschel mixer (FM20C, Mitsui Mining Co., Ltd.) to obtain a toner. It was. The mixing conditions were a circumferential 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.
100 parts by weight of carrier 1 with respect to 7 parts by weight of the obtained toner were uniformly mixed and charged using a type of tumbler mixer in which the container was rolled and stirred to prepare a developer. 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 8>
-Preparation of toner-
・ Polyester resin a: 93 parts ・ Crystalline polyester: 1 part ・ C. I. Pigment Blue 15,3 ... 5 parts ・ Charge control agent (bis (3,5-di-tert-butylsalicylate-O1, O2) zinc) ・ ・ ・ 2 parts ・ Candelilla wax (Tg peak 71 ° C) , Trade name: MK-2 (Yokoseki Yushi Kogyo Co., Ltd.) 5 parts Fatty acid amide compound (ethylene bis stearic acid amide, Tg peak 140 ° C.), trade name: EB-G (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 circumferential speed of 30 m / sec, and a set of 60 second rotation and 60 second rotation stop was repeated twice for mixing. Thereafter, 10 parts by mass of finely powdered toner collected in advance was added, and kneading was performed for 60 minutes with two rolls whose roll surface was set at 95 ° C. After rolling and cooling and coarse pulverization, a jet mill type pulverizer (I-2 type mill: manufactured by Nippon Pneumatic Kogyo Co., Ltd.) and a wind classifier (DS classifier: manufactured by Nihon Pneumatic Kogyo Co., Ltd.) are used. Colored particles were obtained.
Thereafter, 100 parts of blue colored particles, 1.5 parts of silica 1 and 0.5 parts of hydrophobized titanium oxide having a primary average particle diameter of 13 nm are mixed with a Henschel mixer (FM20C, Mitsui Mining Co., Ltd.) to obtain a toner. It was. The mixing conditions were a circumferential 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.
100 parts by weight of carrier 1 with respect to 7 parts by weight of the obtained toner were uniformly mixed and charged using a type of tumbler mixer in which the container was rolled and stirred to prepare a developer. 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.

(Evaluation item)
1) Filming property Using the obtained two-component developer and each evaluation machine, a 5% image area chart is output, and a black solid (A3 ) 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

2) Low-temperature fixability After outputting 10,000 sheets of 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 at the time when one day later passed was measured. 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 10 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.
◎: Fixing starts at a very low temperature, and the fixing lower limit temperature is low, and the fixing property is very low. ○: The fixing property is very good. △: The fixing property is lower than that of the conventional system. The system linear velocity of the conventional system (imageIO NEO C600 unmodified product) which is inferior is 282 mm / sec.

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: Very high temperature winding property and excellent high temperature fixing property ○: High temperature winding property is considerably excellent Δ: High temperature winding property is superior to conventional system ×: High temperature winding property is inferior to conventional system

4) Toner environment preservability 10 g of toner is weighed and put into a 20 ml glass container, and the glass bottle is tapped 100 times with a tapping machine, and then left in a thermostatic chamber set at a temperature of 55 ° C. and a humidity of 80% for 24 hours. Then, 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 favorable ones, ◎: 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

(Fig. 1 and Fig. 2)
111 Copying machine (image forming device)
112 Document Reading Unit 113 Paper Feeding Unit 114 Image Forming Unit 115 Fixing Unit 116 Paper Discharge Unit 117 Lamp 118a Mirror 118b Mirror 119 CCD
120a tray 120b tray 120c tray 120d tray 121 photoconductor drum (photoconductor)
122 Charging roller 123 Laser light source (exposure means)
124 Developing roller (developing means)
125 Transfer roller (transfer means)
126 Cleaning mechanism 127 Paper discharge port 128 Tray 129 Heat fixing roller (fixing member)
211 Copier 215 Fixing Unit 229 Heating Fixing Roller 230 Halogen Lamp 231 Elastic Layer 232 Pressure Roller (Contact Member)
233 Separating claw 234 Thermistor thermometer 235 Detection sensor 236 Core metal 237 Release layer A Scanning direction B Rotating direction N Fixing nip width P Paper T Toner T 'Toner t Thickness

(Figure 3)
DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14, 15, 16 Support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 20 Tandem image forming part 21 Exposure apparatus 22 Secondary transfer apparatus (transfer roller)
23 roller 24 secondary transfer belt 25 fixing device 25a fixing heater 25b driven roller 25c driving roller 25d fixing temperature sensor 25e flat substrate 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 Feeding path 47 Conveying roller 49 Registration roller 50 Feeding roller 51 Manual feed tray 52 Separating roller 53 Manual feeding path 55 Switching claw 56 Ejection roller 57 Ejection tray 60 Charging device 60a Charging roller 60b Brush roller 60c Core metal 60d Conductive rubber Layer 60e Brush portion 60f Power supply 61 Developing device 62 Primary transfer device 63 Cleaning device 64 Static elimination device (static elimination lamp)
DESCRIPTION OF SYMBOLS 100 Copier body 200 Paper feed table 300 Scanner 400 Automatic document feeder

(Fig. 4)
a Whole process cartridge b Photoconductor c Charging means d Developing means e Cleaning means

Claims (18)

An image forming apparatus including a fixing device that fixes a visible image on a recording medium by heat and pressure, a system speed of 400 to 3000 mm / sec, and a pressing surface pressure of the fixing medium of 5 N / cm ² to The toner used for forming a visible image at 90 N / cm ² contains at least a resin, a colorant, and a release agent, and the toner surface occupation ratio Tp of the release agent is 0.1%. An image forming apparatus having a toner surface occupancy Ta of 10.0 to 70.0% of a release agent when the toner is heated and melted at 150 ° C.   2. The image forming apparatus according to claim 1, wherein the surface of the fixing medium is a component containing at least a fluororesin.   The fixing medium surface according to claim 1 or 2, wherein at least one of polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), or a polymer of both is provided. An image forming apparatus comprising the composition.   The image forming apparatus according to claim 1, wherein a fixing nip width of the fixing device according to claim 1 is 4 mm to 20 mm.   5. The toner used in the image forming apparatus according to claim 1, comprising a wax having at least a hydrocarbon straight chain as a release agent, wherein the wax has a Tg peak of at least 50 ° C. to 130 ° C. One or more image forming apparatuses having at least 1 ° C.   6. The toner used in the image forming apparatus according to claim 1, wherein the wax contains at least one of carnauba wax, polyethylene wax, polypropylene wax, synthetic ester wax, and paraffin wax. An image forming apparatus.   7. The toner used in the image forming apparatus according to claim 1, wherein the release agent contains at least a fatty acid amide compound, and the fatty acid amide compound has a Tg peak of at least 70 ° C. to 160 ° C. 7. One or more image forming apparatuses.   8. The image forming apparatus according to claim 1, wherein the toner includes at least one amorphous polyester resin as the resin.   The toner used in the image forming apparatus according to claim 1, wherein the resin contains at least one kind of crystalline polyester resin.   10. The toner used in the image forming apparatus according to claim 1, wherein the resin contains at least one crystalline polyester resin, and the crystalline polyester has a Tg peak of at least 80. An image forming apparatus characterized in that one or more of them exist at a temperature of from 130 ° C to 130 ° C.   11. The image forming apparatus according to claim 1, wherein the toner is a color toner. 11.   12. The toner used in the image forming apparatus according to claim 1, wherein the toner has an average circularity of 0.94 or more and less than 1.00. apparatus.   The toner used in the image forming apparatus according to claim 1, wherein the toner has a volume average particle diameter of 2.0 to 7.0 μm, a volume average particle diameter (Dv), and a number average. An image forming apparatus comprising a toner having a ratio (Dv / Dn) to a particle diameter (Dn) in a range of 1.0 to 1.3.   14. The image forming apparatus according to claim 1, wherein a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the latent image that has been charged. An exposure unit that exposes the surface of the carrier on the basis of image data and writes an electrostatic latent image, and a developing unit that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize the image. An image forming apparatus comprising: a transfer unit that transfers a visible image on the surface of the latent image carrier to a transfer target; and a fixing unit that fixes the visible image on the transfer target.   15. 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 image forming apparatus main body. An image forming apparatus.   A toner containing at least a resin, a colorant, and a release agent, which is used 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.

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