JP2006085036A - Toner, fixer, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fixer which prevents an image from staining by preventing toner from fusing and flowing from the fixer, and gives a high density and high definition image, and provide an image forming apparatus using the fixer, and a toner used in the fixer. <P>SOLUTION: In the toner used in the fixer 25 including: a fixing member 25' fixing the toner; a cleaning member 257 cleaning the fixing member 25'; and a supply member 259 supplying an active substance 260 which increases an elastic modulus G' of the toner collected on the cleaning member 257, difference between an elastic modulus G'1 of the toner before supplied with the active substance and an elastic modulus G'2 of the toner after supplies with the active substance satisfies the relation of 0<G'2-G'1≤10,000 Pa. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a fixing device and an image forming apparatus using toner used as a developer for fixing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like.

In image formation in the electrophotographic system, the pressure heating system using a heating roller or a heating belt passes through the recording medium while the surface of the heating roller having releasability with respect to the toner and the toner image surface of the recording medium are in contact under pressure. By fixing the toner image, the toner image is fixed. In this method, since the surface of the heat roller and the toner image on the recording medium come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the recording medium is extremely good, and the fixing can be performed quickly. it can.
However, since the surface of the heating roller and the toner image are in contact with each other under a molten state and pressure, a part of the toner image is adhered and transferred to the surface of the fixing roller, and the adhered toner moves between the rotating rollers. There is a case where a phenomenon occurs in which the recording medium is re-transferred to the next recording medium and the recording medium is soiled. This phenomenon is affected by the fixing conditions of the fixing device and the thermal characteristics of the toner.
In this electrophotographic image formation, particularly color image formation, the toner on the recording medium forms a toner layer in which a plurality of toners overlap each other, so that the fixing speed is high and the surface temperature of the heating roller is high. Increases the temperature difference between the toner layer in contact with the heating roller and the lowermost toner layer in contact with the recording medium. In this case, since the heating roller having a high temperature contacts the uppermost toner, hot offset is likely to occur. Conversely, if the temperature of the heating roller is set low in order to prevent this hot offset, the toner in the lowermost layer will not be sufficiently melted, so that the cold offset that adheres to the heating roller without fixing the toner on the recording medium will be generated. Arise. However, in recent years, there has been a demand for a toner having a wide fixing temperature range that is applicable from a case where the fixing speed is high to a case where the fixing speed is low and that is excellent in offset resistance.

  On the other hand, in recent years, a high-quality image with excellent reproducibility of fine lines has been demanded. In response to this demand, the particle size of the toner has been reduced and the resolution and sharpness of the image have been increased. On the other hand, the fixability of a halftone portion formed with a small particle size toner is lowered, particularly when the fixing speed is high. This is because the amount of toner adhering to the halftone part is small, and the toner transferred to the concave part of the recording medium has a small amount of heat applied from the heating roller, and the fixing pressure is also suppressed by the convex part of the recording medium. To be lower. In addition, since the toner transferred to the convex portion of the recording medium at the halftone portion has a thin toner layer, the force applied to each toner is larger than that of the solid black portion where the toner layer thickness is high. Are likely to occur, resulting in a low-quality fixed image.

Therefore, in order to achieve both toner fixing properties and offset resistance, the toner has been studied mainly as a binder resin to date. In Patent Document 1, it is a chromatograph measured by gel permeation chromatography (GPC) of a resin for toner, and at least in a region having a molecular weight of 10 ^{3 to} 7 × 10 ^{4 and} a region having a molecular weight of 10 ⁵ to 2 × 10 ^6. A molecular weight distribution of a resin having one or more maximum values is disclosed. Patent Documents 2 and 3 disclose that a fixing agent and offset resistance are both achieved by introducing a release agent such as polyethylene while regulating the molecular weight of the vinyl copolymer. Patent Document 4 discloses a technique in which low-temperature fixing and hot offset are improved by a combination of a low-viscosity resin and a high-viscosity resin.
In addition, Patent Documents 5 to 8 disclose a technique for widening the molecular weight distribution of the binder resin and balancing the storage stability, the fixing property, and the hot offset.

  On the other hand, in an electrophotographic image forming apparatus, a pressure roller or the like is pressed against a heating roller or the like having a heat source therein, and the recording medium is conveyed through the recording medium after image transfer between them. Most of them include a fixing device for fixing the toner image on the upper side. In this type of fixing device, it is known that when an offset occurs, the offset toner adheres to the pressure roller, and reversely transfers from the heating roller and the pressure roller to the recording medium to contaminate the recording medium. In order to prevent such an offset, in the conventional fixing device, for example, the surface of the heating roller is coated with fluorine. However, it is difficult to completely prevent the offset depending on the environmental conditions and the type of the recording medium, and there is a problem that the reverse transfer is caused and the recording medium is soiled.

This problem is particularly noticeable when a small-sized recording medium is passed compared to the maximum size that can be passed. This is because, in the case of a small size, since the sheet passing area is small and the area in contact with the heating roller is small, the temperature falls only in the narrow area, and the temperature detection means corresponding to that part supports the lighting of the heat source. This is because the temperature rises unnecessarily to the temperature of the paper passing area, and the toner on the cleaning member corresponding to the non-paper passing area melts and reversely transfers. Therefore, some conventional fixing devices are provided with a cleaning member such as a cleaning roller in contact with the heating roller or pressure roller to remove the toner adhering to the heating roller or pressure roller. That is, there is a technique that removes toner from the difference in surface releasability by pressing a cleaning member made of a solid metal material against a heating roller or pressure roller having improved surface releasability.
Therefore, for example, in Patent Document 12, in order to solve such a problem of reverse transfer, in a conventional fixing device, in order to make the temperature distribution of the heating roller uniform in the width direction, the heating roller is exposed to wind. What prevents the temperature of the non-sheet-passing region from excessively rising is disclosed. Further, for example, as described in Patent Document 13, there is an air vent that is provided along the cleaning roller to circulate the air in the fixing device as the cleaning roller rotates, thereby preventing the temperature of the cleaning roller from rising.

Japanese Patent Laid-Open No. 5-107803 Japanese Patent Laid-Open No. 5-289399 JP-A-5-313413 JP-A-5-297630 Japanese Patent Laid-Open No. 5-053722 JP-A-6-027733 JP-A-6-074426 JP-A-6-118702 JP-A-11-33665 JP-A-11-149180 JP 2000-292981 A Japanese Patent Laid-Open No. 9-325550 JP 2002-123119 A

  However, it is difficult to prevent this offset and to prevent the recording medium from being stained only by improving the fixing conditions of the fixing device and the thermal characteristics of the toner. Further, even if a cleaning member is simply provided, there is a problem that the toner melts again from the cleaning member and stains the recording medium.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and a problem thereof is a fixing device that prevents the toner from melting out from the fixing device and prevents image smearing, and an image forming apparatus using the same. And a toner used for the same.
Furthermore, an object of the present invention is to provide a fixing device, an image forming apparatus, and a toner used therefor, which can obtain a high-density and high-definition image.

The features of the present invention, which is a means for solving the above problems, are listed below.
1. The toner of the present invention includes a fixing member that fixes the toner, a cleaning member that cleans the fixing member, and a supply member that supplies a reactive substance that increases the elastic modulus G ′ of the cleaned toner to the cleaning member. In the toner used in the apparatus, the toner includes an elastic modulus G′1 at 120 ° C. of the toner before the reactive substance is supplied and an elastic modulus G′2 at 120 ° C. of the toner after the reactive substance is supplied. The difference between and satisfies the relationship 0 <G′2-G′1 ≦ 10000 Pa.
2. In the toner of the present invention, the fixing member further includes a fixing roller and a pressure roller.
3. In the toner of the present invention, the fixing member further includes a fixing belt.
4). The toner of the present invention is further characterized in that the supply member is disposed in the vicinity of the cleaning member in the fixing device and has a roller shape.
5. In the toner of the present invention, the fixing device further includes a pressing member that presses the cleaning member against the fixing member.
6). In the toner of the present invention, the fixing device further includes an adjustment mechanism for adjusting a nip width between the fixing member and the cleaning member.
7). The toner of the present invention is further characterized in that the reactive substance is a metal compound.

8). The toner of the present invention is further characterized in that the metal compound is a salicylic acid metal compound.
9. The toner of the present invention is further characterized in that the toner contains a release agent.
10. In addition, the toner of the present invention further includes a charge control agent.
11. The toner of the present invention is further characterized by having an average circularity of 0.94 or more.
12 The toner of the present invention further has a volume average particle size of 3.0 to 8.0 μm,
The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40.
13. The toner of the present invention is further characterized in that the shape factor SF-1 is in the range of 100 to 180 and the shape factor SF-2 is in the range of 100 to 180.
14 The toner of the present invention further has a spindle shape, and the spindle shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (provided that r1 ≧ r2 ≧ r3), and the major axis r1. And the ratio (r2 / r1) of the minor axis r2 is in the range of 0.5 to 1.0, and the ratio of the thickness r3 to the minor axis r2 (r3 / r2) is in the range of 0.7 to 1.0. It is characterized by that.
15. In the toner of the present invention, the fixing device further dissolves or disperses at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, and a colorant in an organic solvent. The toner composition is dispersed in an aqueous medium and stretched and / or crosslinked.

16. The fixing device of the present invention is provided in an image forming apparatus, and uses the toner according to claim 1 in a fixing device that fixes a visible image on a recording member with heat and / or pressure. .
17. An image forming apparatus of the present invention includes an image carrier that carries a latent image, a charging device that uniformly charges the surface of the image carrier, an exposure device that writes an electrostatic latent image on the surface of the charged image carrier, A developing device that visualizes an electrostatic latent image formed on the surface of the image carrier, a transfer device that transfers a visible image on the surface of the image carrier to a recording member, and untransferred residual toner on the image carrier The fixing device according to claim 16 is used in an image forming apparatus comprising a cleaning device that cleans the image and a fixing device that fixes the visible image on the recording member with heat and / or pressure.
18. The image forming apparatus of the present invention further includes a process cartridge that integrally supports the image carrier and at least one device selected from at least a charging device, a developing device, and a cleaning device, and is detachable. It is characterized by that.

According to the present invention, there is provided a toner that prevents the toner from melting out from the fixing device by the means for solving the problem and prevents the toner from being smeared on the recording medium due to the melting from the cleaning member, a fixing device using the toner, and an image. A forming device could be provided.
Further, it is possible to provide a toner that does not generate an offset and can obtain a high-quality image with high accuracy and reproducibility, and a fixing device and an image forming apparatus using the toner.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

FIG. 1 is a schematic diagram showing the configuration of a fixing device in which the toner of the present invention is used. The fixing device 25 supplies a fixing member 25 ′ for fixing toner, a cleaning member 257 for cleaning the fixing member 25 ′, and a reactive substance 260 for increasing the elastic modulus G ′ of the cleaned toner. A supply member 259. As shown in FIG. 1, the fixing member 25 ′ includes a fixing roller 251 and a heating roller 252.
FIG. 2 is a schematic view showing another configuration of the fixing device in which the toner of the present invention is used. Here, the fixing member 26 ′ includes a fixing belt 264. The fixing belt 264 is stretched around a plurality of rollers 261 and 263. One of the plurality of rollers drives the fixing belt 264 with power from the image forming apparatus main body.

In the fixing device 25, as shown in FIG. 1, the fixing roller 251 as the fixing means 25 ′ forms a nip with the pressure roller 252 as the pressure means on the outer periphery of a metal core such as stainless steel or aluminum. For this purpose, for example, an elastic layer formed into a ring shape with a heat-resistant elastic material such as foamed silicone rubber or liquid silicone rubber is provided. A release layer is provided on the surface layer of the elastic layer in order to improve the release properties of the transfer paper and toner. For the release layer, a material having heat resistance and low surface energy is used. For example, silicone resin, fluororesin, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), It is used as a heat-resistant tube made of a polymer resin such as tetrafluoroethylene-hexafluoropropylene copolymer (FEP). A heat source such as a halogen heater for accelerating the temperature rise of the fixing roller 251 is disposed in the core of the fixing roller 251.
The pressure roller 252 as a fixing member includes an elastic layer made of a heat-resistant elastic material such as fluorine-based rubber or silicone rubber on the outer periphery of a metal core made of stainless steel, aluminum, or the like, and has the same thickness as the fixing roller 251. In addition, a release layer made of fluorine resin or the like is provided on the surface layer. The pressure roller 252 is pressed toward the fixing roller 251 by a pressure member such as a spring (not shown), and pressurizes toner with the fixing roller 251 for a certain period of time by elastically deforming the elastic layer. -Form a nip that can be heated.

  In order to improve the releasability from the toner on the fixing roller 251 and prevent the occurrence of offset, an application roller 255 for applying an oil such as silicone oil for improving the releasability, toner adhered to the fixing roller 251, paper A cleaning roller 256 is provided as a cleaning member for cleaning the powder. Further, since the toner adheres to the pressure roller 252 from the fixing roller 251 that is in contact with paper dust when not recording, a cleaning roller 257 may be provided on the pressure roller 252. Further, in order to control the heaters of the members in the fixing device 25 such as the fixing roller 251 and the pressure roller 252, a temperature sensor 258 such as a thermistor is provided to detect the temperature of each member.

  Here, the diameter of the cleaning roller 257 is set within a range in which the cleaning roller 257 can be disposed in the fixing device 25. If the cleaning roller 257 is too large, the start-up of the fixing device 25 is delayed, which is not preferable. However, when the cleaning roller 257 is large, the surface area is increased correspondingly, and the amount of toner that can be collected by the cleaning roller 257 increases. Further, the thickness of the toner wound around the cleaning roller 257 per unit recovery amount of the cleaning roller 257 is reduced, the change in the toner thickness amount due to the number of prints is small, and the mechanical pressure and thermal force on the pressure roller 252 are reduced. The amount of change is small and the stability of the fixing device is excellent. On the other hand, when the cleaning roller 257 has a small diameter, the thickness of the wound toner varies depending on the number of prints, so that the mechanical pressure and the thermal change with respect to the pressure roller 252 are large, and the melting is reversed. May be put out. Further, by setting the surface of the cleaning roller 257 to a predetermined roughness Rz, it is possible to make the application property of the reactive substance uniform. When the roughness Rz is small, dripping occurs after coating, and when the roughness Rz is large, the presence of the reactive substance can be coarse and dense. Here, although a single cleaning roller 257 has been described, a plurality of pressure rollers 252 may be provided. Further, the cleaning roller 257 may be provided together with the fixing roller 251 or alone.

The cleaning roller 256 is made of a metal core such as aluminum or stainless steel. A rod-shaped roller having a diameter of 10 to 30 mm is used. Further, the surface of the cleaning roller 257 is in the range of 3 to 50 μm in terms of ten-point average roughness Rz (hereinafter simply referred to as “roughness Rz”). The surface roughness Rz can be formed by blasting such as shot blasting, sand blasting, or liquid honing, and sand blasting that is easy to process is particularly preferable. On the surface, for example, an elastic layer formed into a ring shape with a heat-resistant elastic material such as foamed silicone rubber or liquid silicone rubber may be provided.
In addition, a pressing member that presses the cleaning roller against a pressure roller or the like is provided. As the pressing member, an elastic body such as a spring material or a rubber material is used. In particular, a spring material is preferable from the viewpoint of durability because of its simple structure. With this pressing member, it is possible to easily collect the toner by pressing the cleaning roller against the pressure roller. Further, an adjusting mechanism can be provided to press the cleaning roller and the pressure roller. This prevents the cleaning roller from being driven by the pressure roller or the like because the toner layer on the surface of the cleaning roller becomes thick due to the toner collected by the cleaning roller. The adjustment mechanism may be adjusted by a pressing member, or a mechanism such as a gear or a solenoid for moving the cleaning roller may be provided in order to keep a separate distance between the cleaning roller and the roller.

  Further, a reactive substance that increases the viscoelasticity of the toner may be coated on the outer periphery thereof. The cleaning roller 257 is coated with a reactive substance that increases the viscoelasticity of the binder resin. As a reactive substance that increases viscoelasticity, there is a substance that increases the molecular weight by a crosslinking or elongation reaction with a binder resin. A substance that increases viscoelasticity by reacting with a functional group having polarity in the binder resin and crosslinking is preferable. Here, the substance to be cross-linked is different from amines and ketones used for cross-linking or elongation of monomers in a solvent. Examples of the material that increases the viscoelasticity include metal compounds, specifically, metal salts of naphthenic acid or higher fatty acids, azo metal complexes, salicylic acid metal salts, or metal complexes of zinc, chromium, iron, zirconium, and the like. In addition, a chelate compound selected from silicon, zirconium, and aluminum, or a metal alcoholate thereof may be used. By coating these onto the cleaning roller 257, the toner transferred to the cleaning roller 257 is cross-linked and viscoelasticity is increased, thereby preventing re-melting from the cleaning roller 257 and recording paper or the like. It can prevent contamination.

  Further, the fixing device 25 includes a supply member 259 for supplying the reactive substance 260. The supply member 259 is disposed in the vicinity of the cleaning roller 257 in the fixing device 25 and has a roller shape. This supply member (hereinafter referred to as “supply roller”) 259 has a brush made of resin fiber, and rotates and rubs the molded body 260 of the reactive substance to scrape the brush 259 and pressurize it. A reactive substance is adhered to the roller 252. At this time, the toner transferred from the heating roller 251 to the pressure roller 252 causes the reactive substance 260 to adhere to the surface, and is collected by the cleaning roller 257 when the toner reaches the cleaning roller 257. The toner collected on the cleaning roller 257 reacts with the reactive substance 260 and crosslinks to increase the viscoelasticity and firmly adhere to the cleaning roller 257. After that, even if the temperature rises, the viscoelasticity increases, and it does not melt and reattach to the pressure roller 252 to stain the recording paper or the like.

In addition, the toner of the present invention is used in the fixing device 25 described above, and the elasticity G′1 at 120 ° C. of the toner before the reactive substance 260 is supplied and the toner 120 after the reactive substance is supplied. The difference from the elastic modulus G′2 at ° C. satisfies the relationship 0 <G′2−G′1 ≦ 10000 Pa.
In addition to the fixing conditions of the fixing device 25, the thermal characteristics of the toner affect the toner dissolution. In particular, the storage elastic modulus of the toner (hereinafter simply referred to as “elastic modulus”) is a large factor of fixing and melting and has a great influence. The larger the elastic modulus, the faster the return due to the deformation of the toner, and the deformation progresses to a place where the tensile strength is large. Therefore, increasing the elastic modulus can prevent toner offset, and when the toner is collected on the cleaning roller 257, the larger the elastic modulus of the toner, the more the toner can be prevented from melting. . However, if the elastic modulus of the toner is too large, it causes an increase in the minimum fixing temperature. For this reason, the elastic modulus of the toner needs to be in an appropriate range, and is preferably in the range of 7000 to 20000 Pa.
Further, on the cleaning roller 257 of the fixing device 25, the elastic modulus G′1 at 120 ° C. of the toner before the reactive substance 260 is supplied and the elastic modulus at 120 ° C. of the toner after the reactive substance 260 is supplied. The difference from G′2 satisfies the relationship 0 <G′2−G′1 ≦ 10000 Pa. The elastic modulus G′2 of the toner after the reactive substance 260 is supplied and the elastic modulus G′1 of the toner before the reactive substance 260 is supplied satisfy G′2−G′1> 0. At least the elastic modulus of the toner before the reactive substance is supplied is set to an elastic modulus in the range of 5000 to 20000. Further, G′2-G′1 ≦ 10000 Pa is set. Since the elastic modulus G′2 of the toner after the reactive substance 260 is supplied becomes harder as it increases, the surface of the pressure roller 252 and the fixing roller 251 is prevented from being damaged by the recovered toner.
This storage elastic modulus is measured as follows. 0.8 g of toner is molded into 20 mm diameter pellets and fixed on a 20 mmφ parallel plate using a RheoStress RS50 manufactured by HAAKE. The measurement conditions are a frequency of 1 Hz, a temperature of 80 to 210 ° C., a strain of 0.1, and a temperature increase rate of 3 ° C./min.

Further, as shown in FIG. 2, the fixing device 26 includes a heating roller 263, a fixing roller 261, a pressure roller 262 that is a pressure unit that comes into pressure contact with the fixing roller 261, and a heating roller 263 and a fixing roller 261. And a fixing belt 264 which is a fixing means 26 'which is stretched between the two.
The fixing roller 261 and the pressure roller 262 are provided with an elastic layer made of a heat-resistant elastic material on the outer periphery of a metal cored bar in substantially the same manner as the fixing roller 261 and the pressure roller 262 of the fixing device 26 shown in FIG. . The thickness of the elastic layer is adjusted as appropriate. Further, a release layer made of a fluorine-based resin or the like is provided on the surface layer of the elastic layer in order to improve the release property of the transfer paper and toner. A halogen heater is disposed inside each of the core bars. The pressure roller 263 is pressed against the fixing roller 261 with a fixing belt 264 interposed therebetween by a pressure member such as a spring (not shown), and is fixed between the fixing roller 261 by deforming the elastic layer. Form a nip where the toner can be pressed and heated for a long time.

The fixing belt 264 is made of an endless belt-like substrate made of heat-resistant resin or metal. Examples of the material of the heat resistant resin include polyimide, polyamideimide, polyether ether ketone, and examples of the material of the metal belt include nickel, aluminum, and stainless steel. A resin and a multilayer may be formed. In particular, a belt obtained by electroforming nickel on a polyimide resin is preferable because it has strength and elasticity and is durable. The thickness is preferably 100 μm or less. Since the fixing belt 264 is in pressure contact with the transfer paper and toner, the fixing belt 264 has an elastic layer made of highly releasable silicone rubber or the like and a heat-resistant release layer made of a fluorine resin having a small friction coefficient.
The heating roller 263 is a member for stretching and heating the fixing belt 264 that is being stretched. For this reason, a heat source such as a halogen lamp or nichrome wire is provided inside the heating roller 263. The heating roller 263 is a thin-walled roller of a hollow metal cylinder such as aluminum, carbon steel, stainless steel, etc., but by using an aluminum cylinder having a thickness of 1 to 4 mm with good thermal conductivity, The temperature distribution can be reduced. Further, the surface of the heating roller 263 is subjected to alumite treatment in order to prevent abrasion with the fixing belt 264.
A temperature sensor 265 for detecting the temperature of the outer peripheral surface of the fixing belt 264 is disposed on the outer peripheral surface of the heating roller 263 with the fixing belt 264 interposed therebetween. The operation of the heater inside the heating roller 263 and the like is controlled by a temperature control device (not shown) according to a detection signal from the temperature sensor.

Similarly to the fixing device including the fixing roller and the pressure roller, the fixing device including the fixing belt includes a pressing member and an adjusting mechanism, and the elastic modulus G ′ of the toner before the reactive substance is supplied. A toner satisfying the relationship of 0 ≦ G′2−G′1 ≦ 10000 Pa in the difference between 1 and the elastic modulus G′2 of the toner after the reactive substance is supplied can be used.
The toner used in the fixing devices 25 and 26 of the present invention contains wax as a release agent. It became clear that the state of the wax in the toner greatly affects the releasability of the toner at the time of fixing, and the wax is finely dispersed in the toner and is in the vicinity of the surface inside the toner. By the presence of a large amount, good fixing releasability can be obtained. In particular, it is preferable that the wax has a long diameter and is dispersed to 1 μm or less. In this way, the release agent is contained in the toner, and the release agent is contained in the toner, so that the toner offset to the fixing roller 251 can be reduced, and the toner collected by the cleaning roller 257 of the pressure roller can be reduced. Can be reduced.

  Known waxes can be used, and include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes, and the like. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerine tribehenene. Polyalkanol ester (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amide (ethylenediamine dibehenyl amide, etc.); polyalkylamide (Trimellitic acid tristearyl amide, etc.); and dialkyl ketones (distearyl ketone, etc.). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat-resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause cold offset during fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

The toner used in the fixing device of the present invention contains a charge control agent. In particular, a high charge amount can be imparted by fixing the charge control substance to the surface of the toner. That is, by fixing to the surface of the toner, the amount and state of presence on the toner surface are stabilized, and the charge amount can be stabilized. In particular, in the toner having the configuration of the present invention, the charge amount stability is increased.
Examples of charge control agents include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), Examples thereof include alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts and metal salts of salicylic acid derivatives.
The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents and release agents can be melt-kneaded together with the masterbatch and resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

  The toner used in the fixing devices 25 and 26 of the present invention has an average circularity of 0.94 or more. An average circularity of the toner of 0.94 or more is excellent in dot reproducibility and good transferability, so that high image quality can be obtained. When the average circularity is less than 0.94 and the toner is separated from the sphere, it is difficult to obtain a high-quality image with sufficient transferability or no dust. The circularity of the toner is a value obtained by optically detecting particles and dividing by the perimeter of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids are removed in advance is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner are measured at a dispersion concentration of 3,000 to 10,000 pieces / μL.

The toner has a volume average particle size of 3.0 to 8.0 μm and a ratio (Dv / Dn) of the volume average particle size (Dv) to the number average particle size (Dn) of 1.00 to 1.n. It is in the range of 40. By using a toner having such a particle size and particle size distribution, it is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance, particularly when used in a full color image forming apparatus. High glossiness is obtained. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but conversely with respect to transferability and cleaning properties. Is disadvantageous. In addition, when the volume average particle size is smaller than the above range, in the two-component developer, the toner is fused to the surface of the magnetic carrier during long-term agitation in the developing device, and the charging ability of the magnetic carrier is reduced. When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. On the contrary, when the volume average particle size of the toner is larger than the above range, 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 the particle size of the toner becomes large.
On the other hand, if Dv / Dn exceeds 1.40, the charge amount distribution becomes wide and the resolving power decreases, which is not preferable. The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II and a Coulter Multisizer II (both manufactured by Coulter). In the present invention, a counter-counter TA-II type is used, connected to an interface (manufactured by Nikka Giken) that outputs number distribution and volume distribution, and a PC 9801 personal computer (manufactured by NEC). did.

Further, the toner has a shape factor SF-1 in the range of 100 to 180, and a shape factor SF-2 in the range of 100 to 180.
FIG. 3 is a diagram schematically showing the shape of the toner for explaining the shape factor SF-1 and the shape factor SF-2.
The shape factor SF-1 indicates the ratio of the roundness of the toner shape, and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
If the shape factor SF-1 of the toner is close to 100, the shape of the toner is close to a sphere, and the contact between the toner and the toner or between the toner and the photosensitive member becomes a point contact. -Adhesion force between the toners becomes weak and fluidity increases. Also, the adhesion force between the toner and the photosensitive member decreases, and the transfer rate increases. On the other hand, if the value of the shape factor SF-1 is greater than 180, the shape factor SF-1 becomes indefinite, which is not preferable because developability and transferability deteriorate.

The shape factor SF-2 indicates the ratio of the uneven shape of the toner, and is represented by the following formula (2). This is a value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane by the figure area AREA and multiplying by 100 / 4π.
SF-2 = {(PERI) ² / AREA} × (100 / 4π) (2)
The closer the value of SF-2 is to 100, the smoother the unevenness of the toner surface. In order to improve the cleaning property, it is preferable that the surface has moderate unevenness. However, when the shape factor SF-2 is larger than 180, the unevenness becomes conspicuous so that the toner is scattered on the image. This is not preferable because the image quality is lowered.
Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.) and introducing it into an image analyzer (LUSEX 3: manufactured by Nireco). Analyzed and calculated.

  Further, the shape of the toner used in the fixing device of the present invention is a substantially spherical shape, and can be represented by the following shape rule. FIG. 4 is a diagram schematically showing the shape of the toner according to the present invention. In (a), when a substantially spherical toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the present invention has a major axis and The ratio to the minor axis (r2 / r1) (see (b)) is 0.5 to 1.0, and the ratio of the thickness to the minor axis (r3 / r2) (see (c)) is 0.7 to 1. Preferably it is in the range of 0.0. When the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of being away from the true spherical shape, and high-quality image quality cannot be obtained. On the other hand, when the ratio of thickness to minor axis (r3 / r2) is less than 0.7, it becomes close to a flat shape and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, it becomes a rotating body having the major axis as the rotation axis, the toner fluidity can be improved, and the image can be printed at a high transfer rate. Since it is a faithful transfer, a high-quality image can be obtained. In addition, since the mixing with the magnetic carrier is good, the charge amount distribution can be narrowed, and high-accuracy image reproduction is possible. Note that r1, r2, and r3 were measured with a scanning electron microscope (SEM) while changing the angle of field of view and taking pictures.

  The toner used in the fixing devices 25 and 26 of the present invention includes production methods such as a pulverization method and a polymerization method, but is not limited to these production methods. As an example of the pulverization method, first, the above-mentioned resin, pigment or dye as a colorant, charge control agent, release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, and then batch type. The constituent materials are well kneaded using a two-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader, or the like, and cut after rolling and cooling. The toner kneaded product after cutting is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier or Coanda effect using a swirling airflow Is classified to a predetermined particle size by a classifier using Thereafter, inorganic fine particles are externally added by a mixer and mixed to obtain a toner.

Further, the toner of the present invention is preferably a toner having a small particle size and a nearly spherical shape so as to output a high-quality and high-definition image. As a method for producing such a toner, there are a suspension polymerization method, an emulsion polymerization method, a polymer suspension method and the like in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. Hereinafter, these toner production methods and materials, additives, and the like used in the production methods will be described. (Suspension polymerization method) An oil-soluble polymerization initiator, an emulsification method to be described later in an aqueous medium in which a colorant, a release agent and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersants are contained. To emulsify and disperse. Thereafter, after the polymerization reaction to form particles, a wet treatment for attaching the inorganic fine particles A to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing. Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. . Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

(Emulsion polymerization aggregation method) A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, a wet treatment of inorganic fine particles A described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

(Polymer Suspension Method) The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. In the oil phase of the toner composition, a colorant such as resin, prepolymer and pigment, a release agent, a charge control agent and the like are dissolved or dispersed in a volatile solvent. An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles. Thereafter, wet processing of inorganic fine particles, which will be described later, may be performed. In order to introduce a functional group into the toner particles, a copolymer with a monomer having a functional group used in the suspension polymerization method, or a functional group of an acid group as an acid monomer in the case of a polyester resin is used. It can be obtained by using one having three or more or esterifying the terminal hydroxyl group of the obtained polyester resin with a compound having a plurality of acid groups. Further, as a dispersion stabilizer in an aqueous medium, which will be described later, an acid group-containing surfactant, polar polymer, organic or inorganic resin fine particles can be used, and an acid group can be introduced by remaining on the toner particle surface. Examples of the acid group include a carboxyl group, a sulfone group, a sulfonic acid group, and a phosphoric acid group.
The toner used in the fixing devices 25 and 26 of the present invention has a toner composition in which at least a polymer having a site capable of reacting with a compound having an active hydrogen group, polyester, and a colorant are dispersed in an organic solvent. What disperse | distributes a thing in an aqueous medium, and is extended and / or bridge | crosslinked is preferable. Below, the constituent material and manufacturing method of the toner will be described. Here, the constituent material and production example of the toner by the wet polymerization method will be described, but the toner of the present invention may be a dry melt kneading method.

(Modified polyester)
There are bonding groups other than ester groups and functional groups contained in acid and alcohol monomer units in the polyester resin, and resin components with different configurations are bonded in the polyester resin through covalent bonds, ionic bonds, etc. Indicates a state.
For example, the polyester terminal is reacted with something other than an ester bond. Specifically, a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced into the terminal and further reacted with an active hydrogen compound to modify or extend the terminal. Further, compounds having a plurality of active hydrogen groups include those in which polyester ends are bonded to each other (urea-modified polyester, urethane-modified polyester, etc.). In addition, a reactive group such as a double bond is introduced into the polyester main chain, radical polymerization is caused therefrom, and a carbon-carbon bond graft component is introduced into the side chain or the double bonds are bridged. Included (styrene modified, acrylic modified polyester, etc.).
In addition, a resin component having a different structure is copolymerized in the polyester main chain or reacted with a terminal carboxyl group or hydroxyl group. For example, those having a terminal copolymerized with a silicone resin modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group are included (silicone-modified polyester and the like).

(Synthesis example of modified polyester)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid and 70 parts of fumaric acid, and 2 parts of dibutyltin oxide were added. The mixture was reacted at 230 ° C. for 8 hours and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours, then cooled to 160 ° C., 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Next, the mixture was cooled to 80 ° C., 200 parts of styrene, 1 part of benzoyl peroxide and 0.5 part of dimethylaniline were added in ethyl acetate and reacted for 2 hours. The ethyl acetate was distilled off, and the weight average molecular weight was 92,000. Polystyrene graft-modified polyester (1) was obtained.
Examples of the urea-modified polyester (i) include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B). As the polyester prepolymer (A) having an isocyanate group, a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group are further added to the polyisocyanate (3). Examples include reacted products. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (an alcoholic hydroxyl group and a phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. Among these, an alcoholic hydroxyl group is preferable. is there.
Examples of the polyol (1) include diol (1-1) and trivalent or higher polyol (1-2). (1-1) alone or (1-1) and a small amount The mixture of (1-2) is preferable. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6. -Hexanediol etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol etc.) Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of alicyclic diol; Examples include adducts of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.). Of these, preferred are alkylene oxide adducts of alkylene glycols and bisphenols having 2 to 12 carbon atoms, and particularly preferred are alkylene oxide adducts of bisphenols and those having 2 carbon atoms. It is combined use with ˜12 alkylene glycol. The trivalent or higher polyol (1-2) includes 3 to 8 or higher polyvalent aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol. Trihydric or higher phenols (trisphenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acids (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, Terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). The polycarboxylic acid (2) may be reacted with the polyol (1) using an acid anhydride or a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) described above.
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, etc.); alicyclic polyisocyanates -Toro (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanate (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); Aro-aliphatic diisocyanate (α , Α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; those polyisocyanates blocked with phenol derivatives, oximes, caprolactams, etc .; and two or more of these Combined use is mentioned.

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

The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to average. 2.5 pieces. If it is less than 1 per molecule, the molecular weight of the modified polyester will be low, and the hot offset resistance will deteriorate.
As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of B1 to B5 are blocked. (B6) and the like. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Furthermore, if necessary, the molecular weight of the modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The ratio of amines (B) is equivalent ratio [NCO] / equivalent ratio of isocyanate group [NCO] in prepolymer (A) having isocyanate group to amino group [NHx] in amines (B). [NHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the modified polyester (i) may contain a urethane bond as well as a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The main peak molecular weight of the modified polyester of the present invention is usually 1000 to 10000, preferably 2000 to 8000. When the amount of the component having a molecular weight of less than 1000 is increased, the heat resistant storage stability tends to be deteriorated. When the component having a molecular weight of 10,000 or more is increased, the low-temperature fixability is simply decreased, but it is possible to suppress the decrease as much as possible by a balance control. . Further, the content of a polymer component having a molecular weight of 30000 or more is 1% to 10%, and preferably 3 to 6% although it varies depending on the toner material. If it is less than 1%, sufficient hot offset resistance cannot be obtained, and if it is 10% or more, the gloss and transparency are deteriorated.
Moreover, it leads to hot offset improvement by using the polyester resin which contains 1-25% of THF insolubles. In addition, the toner is further pulverized by contact stress caused by a developing roller, a toner supply roller, a layer thickness regulating blade, a frictional charging blade, and the like due to long-term stirring inside the one-component developing device. This is effective for problems such as generation of ultrafine particles and deterioration of image quality due to the fluidizing agent embedded in the toner surface. Although THF-insoluble matter is effective for hot offset in color toner, it is negative for gloss and transparency of OHP, but it is effective within 1 to 10% for widening the mold release width. There is also a case that demonstrates.

(Unmodified polyester)
In the present invention, not only the modified polyester (i) can be used alone, but also the unmodified polyester (ii) can be contained as a toner-binder component together with the (i). By using (ii) in combination, the low-temperature fixability and glossiness when used in a full color apparatus are improved, which is preferable to single use. Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i), and the preferred one is the same as (i). Further, (ii) is not limited to unmodified polyester, but may be modified with, for example, a urea bond or a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The peak molecular weight of (ii) is usually 1000-20000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is preferably 10-30. By giving an acid value, it tends to be negatively charged, and the fixability tends to be further improved. However, when the acid value exceeds 30, particularly when used in a high temperature and high humidity environment, the toner charge amount may decrease, and problems such as background smearing on the image may occur.

  In the present invention, the glass transition point (Tg) of (ii) is 35 to 55 ° C, preferably 40 to 55 ° C. If it is less than 35, the heat resistant storage stability of the toner deteriorates, and if it exceeds 55 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester toners. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm 2 is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or more. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

  Here, a release agent and a charge control agent are used, but these have been described above, and known ones can be appropriately selected and used.

(External additive)
As the external additive, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.
Such external additives 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 a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Further, as a cleaning property improver for removing the developer after transfer remaining on the photosensitive member or the primary transfer medium, for example, fatty acid metal salts such as zinc stearate and calcium stearate, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. Examples thereof include fine polymer 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.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphtho-louero-S, Hansaero (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), permanentoiero -(NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Kad Miu Mured, Cadmium mar-Curi red, Antimony vermilion, Permanent red 4R, Para red, Faucet red, Parachlorol Nitroaniline Red, Resource 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, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bold-5B, Toluidine Marun, Permanent Bold-F2K, Heliobold-BL, Bold- 10B, Bonmarine Light, Bonmarum Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone , Polyazo red, chrome bar million, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline bull lake, peak cock bull lake, victoria bull lake , Metal-free phthalocyanine bull, phthalocyanine bull, fast sky bull, indense rumble (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone bull, fast violet B, methyl violet lake, cobalt purple, Manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphtho green B, green gold, acid green -Key, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin. The binder resin to be kneaded with the master batch production or the master batch includes styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substitutes in addition to the above-mentioned modified and unmodified polyester resins. Polymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrenic copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, Examples include polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. Can be used alone or in combination The
In this master batch, a master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, the so-called flushing method is a method in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. -Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Manufacturing method of toner in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (e.g., methyl cellosolve), and lower ketones (e.g., acetone, methyl ethyl ketone). Is mentioned.
As a method for stably forming a dispersion comprising the prepolymer (A) and the unmodified polyester (ii) in the aqueous medium, the prepolymer (A) and the unmodified polyester (ii) are formed in the aqueous medium. Examples thereof include a method of adding a toner raw material composition and dispersing it by shearing force. Prepolymer (A), unmodified polyester (ii) and other toner compositions (hereinafter referred to as toner raw materials) colorants, colorant master batches, mold release agents, charge control agents, etc. Although mixing may be performed when forming the dispersion in the medium, it is more preferable to mix the toner raw material in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium. It may be added later. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the modified polyester (i) or the prepolymer (A) has a low viscosity and is easily dispersed.
The amount of the aqueous medium used relative to 100 parts of the toner composition containing the prepolymer (A) and the unmodified polyester (ii) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the toner composition is not well dispersed, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used with resin fine particles as needed. The use of a dispersant is preferred in that the particle size distribution becomes sharp and the dispersion is stable.
The step of synthesizing the urea-modified polyester from the prepolymer (A) may be carried out by adding amines (B) before dispersing the toner composition in the aqueous medium, or after dispersing in the aqueous medium. A reaction may be caused from the particle interface by adding the compound (B). In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

  As an dispersant for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water, anionic surface active soot such as alkylbenzene sulfonate, α-olefin sulfonate, and phosphate ester, alkyl Amine salt types such as amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, chlorides Quaternary ammonium salt type cationic surfactants such as benzethonium, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine And N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms and a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 31- [omega-fluoroalkyl (C6 -C11) oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) mono-N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethylanolamide N-propyl-N- (2hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, mono-fluoroalkyl (C6-C16) ethyl phosphoric acid Examples include esters.
As product names, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florad FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS 1-101, DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-l10, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink and Company) Xtop EF-1 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), Phgent F-100, F150 (manufactured by Neos), etc. Can be mentioned.

  Further, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6C10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include SURFLON S-121 (Asahi Glass Co., Ltd.), Florad FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Manufactured by Daikin Industries Co., Ltd.), MegaFuck F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), Phgentent F1300 (manufactured by Neos), etc. Is mentioned.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant that is hardly soluble in water.
Further, it is particularly preferable to stabilize the dispersed droplets with a polymeric protective colloid. For example, (meth) acrylic acid containing acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or a hydroxyl group Monomers such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3-chloro-2-hydroxypropyl, 3-chloro-2-monohydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Ethers of vinyl alcohol or vinyl alcohol, such as methylol acrylamide, N-methylol methacrylamide, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or vinyl alcohol Esters of compounds containing a carboxyl group, such as pinyl acetate, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, etc. , Homopolymers or copolymers such as those having a nitrogen atom such as pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, polyethylene Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, poly Polyoxyethylenes such as oxyethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like can be used.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed away after the elongation and / or crosslinking reaction.

Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the prepolymer (A) and the unmodified polyester (ii) are soluble can be used. The use of a solvent is preferable in that the particle size distribution is sharpened. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of the solvent with respect to 100 parts of prepolymer (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.
The elongation and / or crosslinking reaction time is selected depending on the reactivity depending on the combination of the isocyanate group structure of the prepolymer (A) and the amines (B), but usually 10 minutes to 40 hours, preferably 2 to 24. It's time. The reaction temperature is usually 0 to 150 ° C, preferably 5 to 50 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation. is there. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient target quality can be obtained by short-time treatment such as spray dryer, belt dryer, rotary kiln and the like.
When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferably performed in a liquid in terms of efficiency.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

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

The toner can be mixed with a magnetic carrier and used as a two-component developer. In this case, the carrier to toner content ratio in the developer is preferably 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. 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 non- Monomers including a fluoro terpolymers such, 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.

  In addition, when preparing the developer, in order to improve the fluidity, storage stability, developability, and transferability of the developer, the hydrophobic silica fine particles listed above are further listed in the developer produced as described above. Inorganic fine particles such as powder may be added and mixed. For mixing external 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 external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and 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, a Henschel mixer, and the like.

An image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 5 is a schematic diagram showing a configuration of an embodiment of an image forming apparatus according to the present invention. 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) mounted thereon.
The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having various units for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided. Above the tandem type image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoreceptor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.
A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 252 against a fixing belt 254 which is an endless belt.
The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer 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 conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .

  The developing device 4 of the image forming unit 18 uses a developer containing the above toner. In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.

  Further, the photosensitive member 40 and the developing device are integrally supported, and the process cartridge can be formed to be detachable from the image forming apparatus main body. In addition, the process cartridge may include a charging unit and a cleaning unit.

The operation of the image forming apparatus is as follows.
First, a document is set on the document table 30 of the automatic document feeder 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Hold it down.
When a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32. When the document is set on the other contact glass 32, the scanner 300 is immediately driven. The first traveling body 33 and the second traveling body 34 are traveled. 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 reflects 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.

  Further, 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 belt 10 is rotated and conveyed. At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan monochrome images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer belt 10, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.

On the other hand, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated to feed out the sheets from one of the paper feed cassettes 44 provided in the paper bank 43 in multiple stages, and the paper is separated one by one by the separation roller 45 and fed. The paper is put into a path 46, transported by a transport roller 47, led to a paper feed path 48 in the copying machine main body 100, and abutted against a 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 belt 10, the sheet is fed between the intermediate transfer belt 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 image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and the 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 belt 10 after image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after image transfer, and is prepared for re-image formation by the tandem image forming apparatus 20.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In addition, a part shows a weight part.
Example 1
(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), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) A dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [Fine Particle Dispersion 1] measured with LA-920 was 0.10 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content Tg was 57 ° C.

(Preparation of aqueous phase)
<Production Example 2>
990 parts of water, 80 parts of [fine particle dispersion 1], 40 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give a milky white liquid. Got. 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, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 45 parts of trimellitic anhydride to the reaction vessel, and add 2 parts at 180 ° C. under normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25 mgKOH / g.

(Prepolymer synthesis)
<Production Example 4>
In a reaction vessel equipped with a condenser, 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, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 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 stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

(Synthesis of master batch)
<Production Example 6>
Carbon black (Cabot Corp. Legal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

(Create oil phase)
<Production Example 7>
In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 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. Carbon black and WAX were dispersed under 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 one pass 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)
<Production Example 8>
[Pigment / WAX Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 6.6 parts in a container, and TK homomixer (made by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1].

(Variation)
<Production Example 9>
1365 parts of ion-exchanged water, 35 parts of carboxymethylcellulose (CMC Daicel-1280: manufactured by Daicel Chemical Industries, Ltd.) in an aqueous solution stirred and mixed with 1000 parts of [Emulsified slurry 1], and a TK homomixer (special machine) The mixture was mixed at 2,000 rpm for 1 hour to obtain [Deformed slurry 1].

(Solvent removal)
<Production Example 10>
[Deformed 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 performed at 45 ° C for 4 hours to obtain [Dispersed slurry 1].

(Washing ⇒ drying)
[Dispersion Slurry 1] After 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of 10% sodium hydroxide aqueous solution was added to the filter cake of (1), ultrasonic vibration was applied and mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. . This ultrasonic alkali cleaning was performed again (two ultrasonic alkali cleanings).
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was. [Filtration cake 1] was dried at 45 ° C. for 48 hours with a circulating drier, and sieved with a mesh having an opening of 75 μm, whereby toner base 1 was obtained.

Next, 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was adjusted to 50 m / The mixing process was set to sec. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes.
Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec.

[Evaluation item]
(Low temperature fixability)
The evaluation of the minimum fixing temperature is carried out by using a device in which the fixing unit of the Ricoh Co., Ltd. immagio NEO450, which is composed of an image forming apparatus having a cleaning roller for cleaning the pressure roller, is modified, and a type 6200 made by Ricoh. Paper was set and a copy test was conducted. The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was defined as the minimum fixing temperature. In order to shorten the warm-up time (ensure low temperature fixability), the required temperature is 170 ° C. or lower. A sample having a temperature of 170 ° C. or lower was given as “◯”, and a sample having a temperature exceeding 170 ° C. was taken as “X”.
(Hot offset property)
Fixing was evaluated in the same manner as the above-described minimum fixing temperature, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature. Since there is a temperature fluctuation range of the fixing roller, 220 ° C. or higher is necessary to prevent image smearing due to hot offset. A sample having a temperature of 220 ° C. or higher was rated as “◯”, and a value exceeding 220 ° C. was defined as “X”.
(Cleaning roller melts out)
The cleaning roller melts out by performing a copying test using an image forming apparatus having an image forming apparatus having a cleaning roller 7 for cleaning the pressure roller. Evaluation was performed as follows according to the number of generated sheets. O was not generated at 100K, and X was generated at 100K.
(Image quality)
The image quality was comprehensively judged on transfer failure and image quality deterioration (specifically, a background image was generated). For the transfer failure, 50000 sheets were passed through an imagio NEO 450 manufactured by Ricoh Co., Ltd., and then a solid black image was passed, and the transfer failure level of the image was visually judged. As for the background stain image, 50,000 sheets are passed through the Ricoh Co., Ltd. imagio NEO 450, and then the blank image is stopped during development, and the developer on the photoconductor after development is taped. The difference between the image density of the transferred and untransferred tape was measured with a spectrodensitometer (manufactured by X-Rite) and quantitatively evaluated. Evaluation was made with a circle having good image quality and a circle having poor image quality.

表１から明らかなように、上記トナー製造において、油相作成、乳化工程における諸条件を振り、評価を行った。これら物性とその評価結果をまとめて表１に示す。表１より、反応性物質が供給される前のトナーの１２０℃における弾性率Ｇ’１と反応性物質が供給された後のトナーの１２０℃における弾性率Ｇ’２との差が、以下の関係 ０＜Ｇ’２−Ｇ’１≦１００００Ｐａ を満足する実施例１、２のトナーについては低温定着性○、ホットオフセット性○、画像品質○、溶け出し○、定着部材損傷無し○であった。
一方で比較例１、２では、上記の範囲から外れており、この時、低温定着性○、ホットオフセット性○、画像品質○であったが、溶け出しまたは定着部材のいずれかに不具合が生じる結果だった。 The evaluation results are shown in Table 1.

As is apparent from Table 1, in the toner production, various conditions in the oil phase preparation and emulsification processes were varied and evaluated. These physical properties and the evaluation results are summarized in Table 1. From Table 1, the difference between the elastic modulus G′1 at 120 ° C. of the toner before the reactive substance is supplied and the elastic modulus G′2 at 120 ° C. of the toner after the reactive substance is supplied is as follows. Regarding the toners of Examples 1 and 2 satisfying the relationship 0 <G′2-G′1 ≦ 10000 Pa, the low-temperature fixability ○, the hot offset property ○, the image quality ○, the melt-out ○, and the fixing member were not damaged ○. .
On the other hand, Comparative Examples 1 and 2 were out of the above ranges, and at this time, they were low-temperature fixability ○, hot offset property ○, and image quality ○, but a problem occurred in either the melting or fixing member. It was a result.

FIG. 2 is a schematic diagram illustrating a configuration of a fixing device in which the toner of the present invention is used. FIG. 6 is a schematic diagram illustrating another configuration of a fixing device in which the toner of the present invention is used. It is the figure which represented typically the shape of the toner in order to demonstrate shape factor SF-1 and shape factor SF-2. It is a figure which shows typically the shape of the toner which concerns on this invention. 1 is a schematic diagram illustrating a configuration of an embodiment of an image forming apparatus according to the present invention.

Explanation of symbols

4 Developing device 10 Intermediate transfer belt (intermediate transfer member)
18 Image forming means 21 Exposure device 25 Fixing device 250 Fixing member 251 Fixing roller 252 Pressure roller 255 Coating roller 256 Fixing roller cleaning roller 257 Pressure roller cleaning roller 258 Temperature sensor 259 Supply roller 260 Molded body 26 (having fixing belt) Fixing device 260 Fixing member 261 Fixing roller 262 Pressure roller 263 Heating roller 264 Fixing belt 265 Coating roller 266 Fixing roller cleaning roller 267 Pressure roller cleaning roller 268 Temperature sensor 269 Supply roller 270 Molded body 40 Photoconductor (latent image carrier)
22 Secondary transfer device 62 Primary transfer means 100 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (18)

In a toner used in a fixing device, comprising: a fixing member that fixes toner; a cleaning member that cleans the fixing member; and a supply member that supplies a reactive substance that increases the elastic modulus G ′ of the toner cleaned to the cleaning member. ,
In the toner, the difference between the elastic modulus G′1 at 120 ° C. of the toner before the reactive substance is supplied and the elastic modulus G′2 at 120 ° C. of the toner after the reactive substance is supplied is as follows. Satisfying the relationship 0 <G′2-G′1 ≦ 10000 Pa
Toner characterized by the above. The toner according to claim 1.
The fixing member includes a fixing roller and a pressure roller. The toner according to claim 1.
The toner, wherein the fixing member includes a fixing belt. The toner according to any one of claims 1 to 3,
The supply member is disposed in the vicinity of the cleaning member in the fixing device,
A toner characterized by having a roller shape. In the toner according to any one of claims 1 to 4,
The fixing device is provided with a pressing member that presses a cleaning member against the fixing member. The toner according to any one of claims 1 to 5,
The toner is characterized in that the fixing device includes an adjustment mechanism for adjusting a nip width between the fixing member and the cleaning member. The toner according to any one of claims 1 to 6,
The toner according to claim 1, wherein the reactive substance is a metal compound. The toner according to claim 7,
The toner, wherein the metal compound is a salicylic acid metal compound. The toner according to any one of claims 1 to 8,
The toner includes a release agent. The toner according to claim 1,
The toner includes a charge control agent. The toner according to any one of claims 1 to 10,
The toner has an average circularity of 0.94 or more. The toner according to any one of claims 1 to 11,
The toner has a volume average particle size of 3.0 to 8.0 μm,
A toner having a ratio (Dv / Dn) of a volume average particle diameter (Dv) to a number average particle diameter (Dn) in a range of 1.00 to 1.40. The toner according to any one of claims 1 to 12,
The toner has a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180. The toner according to any one of claims 1 to 13,
The toner has a spindle shape, and the spindle shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (provided that r1 ≧ r2 ≧ r3), and the major axis r1 and the minor axis r2. The ratio (r2 / r1) is in the range of 0.5 to 1.0, and the ratio (r3 / r2) of the thickness r3 to the minor axis r2 is in the range of 0.7 to 1.0. Toner. The toner according to any one of claims 1 to 14,
The fixing device disperses, in an aqueous medium, a toner composition in which at least a polymer having a site capable of reacting with a compound having an active hydrogen group, polyester, and a colorant are dissolved or dispersed in an organic solvent. The toner is characterized by being extended and / or crosslinked. In a fixing device provided in an image forming apparatus and fixing a visible image on a recording member with heat and / or pressure,
The fixing device using the toner according to claim 1. An image carrier that carries a latent image, a charging device that uniformly charges the surface of the image carrier, an exposure device that writes an electrostatic latent image on the surface of the charged image carrier, and a surface formed on the surface of the image carrier. A developing device that visualizes an electrostatic latent image, a transfer device that transfers a visible image on the surface of the image carrier to a recording member, a cleaning device that cleans untransferred residual toner on the image carrier, and recording An image forming apparatus comprising: a fixing device that fixes a visible image on a member with heat and / or pressure;
The image forming apparatus uses the fixing device according to claim 16. The image forming apparatus according to claim 17.
The image forming apparatus integrally includes an image carrier and at least one device selected from a charging device, a developing device, and a cleaning device, and includes an attachable / detachable process cartridge. Forming equipment.

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