JP2017021256A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method with which low-temperature fixability of a toner is improved; durability of the toner is improved by suppressing cracks and chipping of the toner; and image stability is improved for a long period.SOLUTION: There is provided an image forming method including specific steps, wherein in a three-point bending test in which the distance between fulcrums (L) of a toner sample is 15.0 mm, the toner sample obtained by fusing a toner and molding a resulting toner to have a length (l) of 30.0 mm, a width (w) of 13.0 mm, and a thickness (t) of 4.0 mm, the distortion energy u per unit volume to be calculated is 0.20 MPa or more.SELECTED DRAWING: None

Description

  The present invention relates to an image forming method using electrophotographic toner.

  In recent years, energy saving has been considered as a technical problem in image forming apparatuses. Among them, the fixing temperature is particularly required to be lowered, and the toner is required to improve the so-called “low temperature fixing property” that can be fixed with lower energy.

  As a technique for improving the low-temperature fixability, it is known that a crystalline polyester resin is used for the toner to achieve both low-temperature fixability and heat-resistant storage stability. The crystalline polyester resin has the characteristics that it does not show a clear glass transition due to the regular arrangement of molecular chains, is hard to soften at a temperature lower than the crystalline melting point, and rapidly softens when the crystalline melting point is exceeded. .

  Patent Document 1 describes a toner that achieves both heat-resistant storage stability and low-temperature fixability by using a resin in which a crystalline part having an aliphatic polyester as an essential constituent and a non-crystalline part are combined.

  Further, the toner is subjected to various impacts in the image forming apparatus. For example, an impact by a conveying screw in the developing device, a pressure by a regulating blade, and a pressure by a blade in the cleaning device are received. When the toner is cracked or chipped by such an impact, image defects such as streaks or white spots are likely to occur on the image due to contamination of the regulating blade by finely divided toner or filming on the photoreceptor.

  However, in general, a crystalline resin has a lower strength than the amorphous resin, and there is a problem in the reliability of the powder. Even in the block polymer in which the crystalline resin and the amorphous resin described in Patent Document 1 are combined, there is room for improving the problem of toner cracking and chipping.

  Patent Document 2 describes a toner in which a core using a block polymer composed of crystalline polyester and amorphous polyester is coated with a shell of amorphous polyester. According to this method, it is described that the durability of the toner is improved and the filming on the photosensitive member is suppressed.

  In recent years, several image forming apparatuses are known from the viewpoint of further miniaturization, higher image quality, and higher speed.

  The first is an image forming apparatus using an intermediate transfer member. Patent Document 3 discusses reduction of parts in a toner recovery process and reduction of waste toner boxes from the viewpoint of miniaturization. In Patent Document 3, after the transfer residual toner on the intermediate transfer member is reversely charged using a charging roller, the reversely charged residual toner is returned to the image carrier, and the toner is collected by the image carrier cleaning device. Describes a technique for reducing the cleaning mechanism and waste toner box of the intermediate transfer member. Further, in Patent Document 4, in the step of reversely charging the transfer residual toner on the intermediate transfer member, the charging unevenness of the transfer residual toner is reduced by using a fixed charging brush provided on the intermediate transfer member, and the intermediate transfer A technique for improving the cleanability on the body is described.

  Second, in response to a request for a large number of copies or prints at a high speed, Patent Document 5 discloses a toner replenishment configuration in which a replaceable refill toner container in the image forming apparatus is replaced with a new refill toner container. An image forming apparatus that uses and replenishes toner is described. Patent Document 6 describes an image forming apparatus that uses a large-capacity cartridge including a plurality of toner storage units. Patent Document 7 describes that the MD-1 hardness of the elastic layer and the surface layer of the toner carrier is controlled to suppress the damage of the toner particles and improve the durability of the toner.

Third, there is known an apparatus that pays attention not only to the function of supplying toner by the toner supply member and the function of triboelectric charging but also to the function of scraping off the toner remaining on the surface of the toner carrier. When the toner that has not been developed in the developing region remains without being scraped off from the surface of the toner carrier, the charge amount differs between the toner remaining on the toner carrier and the toner newly supplied by the toner supply member. For this reason, it is difficult to form an image with uniform density. Further, since the toner remaining on the surface of the toner carrying member continues to generate heat due to rubbing, the toner easily deteriorates, the toner adheres to the surface of the toner carrying member, and filming due to the toner tends to occur. Therefore, Patent Document 8 describes that the function of scraping off the toner is improved by setting the linear speed ratio of the linear speed V _SP of the toner supply member and the linear speed V _DR of the toner carrier within a certain range. Yes. Thus, filming is suppressed by suppressing heat generation at the contact portion between the toner supply member and the toner carrier. In Patent Document 9, the hardness of the toner supply roller (toner supply member) is reduced, and the toner supply roller is flexibly brought into contact with the toner carrier at the contact portion with the toner carrier, thereby supplying the toner. Stabilizing the amount is described.

JP 2010-168529 A JP 2007-057816 A Japanese Patent Application Laid-Open No. 09-050167 JP 2009-223260 A JP 2010-060731 A JP 2002-323813 A JP 2009-0775379 A JP 2006-208619 A JP 2006-126453 A

  However, as a result of the study by the present inventors, it has been found that there is the following problem when the image forming apparatus and the toner described in Patent Document 2 are combined to further increase the process speed.

  In the first image forming apparatus described in Patent Document 4, due to the increase in speed, the load in the developing device is increased, and fine powder due to cracking and chipping is likely to occur. As a result, the fine powder generated in the developing device easily adheres to the fixed charging brush and easily accumulates in the fixed charging brush, thereby hindering the charge imparting function of the fixed charging brush. For this reason, it becomes difficult to uniformly charge the residual toner on the intermediate transfer member, and cleaning defects occur, and it has been found that there is room for improvement in long-term image stability.

  In the image forming apparatuses such as Patent Documents 5 and 6, due to the increase in speed, for example, the pressure in the rubbing between the toner carrier and the toner layer regulating member in the developing device is received, and the toner is cracked and chipped, and fine powder is generated. Likely to happen. Image defects such as streaks and white spots are likely to occur due to contamination of the toner layer regulating member by the generated fine powder and filming on the toner carrier. In the case of the image forming apparatus having the toner replenishment configuration described in Patent Document 5, the toner properties such as the charge amount and the charge distribution are changed in the developing device by mixing the deteriorated toner and the newly replenished toner. It tends to be more uneven. In addition, since an image forming apparatus having a toner replenishment configuration generally has a developing device that is used for a long period of time, toner once deteriorated contributes to development as compared to newly replenished toner. Since it becomes difficult, the fine powder by a crack and a chip | tip becomes easy to accumulate | store. In the case of an image forming apparatus using a large-capacity cartridge having a plurality of toner storage portions described in Patent Document 6, since the cartridge is used for a long period of time, it is difficult for toner once deteriorated to contribute to development. It becomes easy to accumulate fine powders due to cracks and chips. Accumulation of fine powder in this way causes fogging on the image and filming due to adhesion to the toner carrier or toner layer regulating member, so there is room for improvement in long-term image stability. I understood it. Furthermore, the technology described in Patent Document 7 has room for improvement in terms of suppressing toner cracking and chipping and achieving long-term image stability in order to meet the demand for higher speed. It turns out that. Furthermore, it has been found that it is still insufficient in terms of member contamination such as filming in high-speed printing.

  In the third image forming apparatus described in Patent Document 8, when the linear velocity between the toner carrier and the toner supply member increases as the speed increases, the ability to scrape residual toner only by controlling the linear velocity ratio. It was found that the toner was difficult to maintain, the toner was cracked and chipped, and fine powder was generated. Further, in the method for softening the toner supply roller described in Patent Document 9, since the area of the contact portion is enlarged, if the linear velocity of the toner carrier increases, the chance of rubbing with the toner increases. It was found that the connected toner was cracked and chipped, resulting in fine powder. In the methods of Patent Documents 8 and 9, it is found that there is room for improvement in terms of long-term image stability because filming tends to occur on the surface of the toner carrying member due to accumulation of fine powder.

  The object of the present invention is to improve the low-temperature fixability and the durability and durability of the toner by suppressing cracking and chipping of the toner even if the image forming apparatus mentioned in the above-mentioned literature is further increased in speed, and image stability over a long period of time. It is an object of the present invention to provide an image forming method with improved image quality.

A first aspect of the present invention is a charging step of charging the image carrier by a charging means;
Exposing the charged image carrier to form an electrostatic latent image;
A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier;
A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier;
A primary transfer step for primary transfer of the toner image onto an intermediate transfer member;
A composite toner image forming step in which the steps from the charging step to the primary transfer step are performed for each color, and a composite toner image is formed by superimposing a plurality of toner images formed for each color on the intermediate transfer member;
A secondary transfer step for secondary transfer of the composite toner image to a transfer material;
A fixing process for fixing the composite toner image that has been secondarily transferred onto a transfer material to obtain a fixed toner image, and a fixed charging brush for the transfer residual toner remaining on the intermediate transfer body after the second transfer process. The transfer residual toner to which the charge is applied is reversely transferred from the intermediate transfer member onto the image carrier, and the reverse transfer residual toner is provided opposite to the image carrier. A process of collecting with a cleaning device,
An image forming method comprising:
The loss elastic modulus at 80 ° C. of the toner is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁶ Pa or less,
The distance between the fulcrums (L) of the toner sample formed by melting the toner and forming the length (l) 30.0 mm, the width (w) 13.0 mm, and the thickness (t) 4.0 mm is 15.0 mm. In the three-point bending test,
The maximum bending stress of the toner sample obtained by the following formula (1) from the maximum load F _MAX (N) measured at a temperature of 25 ° C. is σ _MAX (MPa),
When the maximum value of the bending elastic modulus E of the toner sample obtained from the slope (ΔF / Δs) of the load-deflection curve by the following equation (2) is E _MAX (MPa),
The present invention relates to an image forming method, wherein the strain energy u per unit volume calculated from the values of σ _MAX and E _MAX by the following formula (3) is 0.20 MPa or more.
σMAX = (3 × F _MAX × L) / (2 × w × t ² ) (1)
E = L ³ / (4 × w × t ³ ) × (ΔF / Δs) (2)
u = σ _MAX ² / (2 × E _MAX ) (3)
(ΔF (N) represents the amount of change in load between any two points selected so that the amount of change in deflection Δs is 0.2 mm.)

A second aspect of the present invention is a charging step in which the image carrier is charged by a charging means;
Exposing the charged image carrier to form an electrostatic latent image;
A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier;
A development step of forming a toner image on the electrostatic latent image with toner on the toner carrier, and a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member;
An image forming method comprising:
MD-1 hardness of the toner carrier is 35 or more and 65 or less,
The loss elastic modulus at 80 ° C. of the toner is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁶ Pa or less,
The distance between the fulcrums (L) of the toner sample formed by melting the toner and forming the length (l) 30.0 mm, the width (w) 13.0 mm, and the thickness (t) 4.0 mm is 15.0 mm. In the three-point bending test,
The maximum bending stress of the toner sample determined by the above formula (1) from the maximum load F _MAX (N) measured at a temperature of 25 ° C. is σ _MAX (MPa),
When the maximum value of the flexural modulus E of the toner sample obtained from the slope (ΔF / Δs) of the load-deflection curve by the above formula (2) is E _MAX (MPa),
Strain energy u per unit volume calculated from the value of the sigma _MAX and the _{E MAX} by the above formula (3) is an image forming method, characterized in that at least 0.20 MPa.

A third aspect of the present invention is a charging step in which the image carrier is charged by a charging means.
Exposing the charged image carrier to form an electrostatic latent image;
A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier;
A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier; and
A transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member;
An image forming method comprising:
A toner supply member for supplying the toner contacts the toner carrier,
The toner carrier and the toner supply member are arranged such that the surfaces of the toner carrier and the toner supply member rotate in opposite directions at the abutting portions.
The distance between the fulcrums (L) of the toner sample formed by melting the toner and forming the length (l) 30.0 mm, the width (w) 13.0 mm, and the thickness (t) 4.0 mm is 15.0 mm. In the three-point bending test,
The maximum bending stress of the toner sample determined by the above formula (1) from the maximum load F _MAX (N) measured at a temperature of 25 ° C. is σ _MAX (MPa),
When the maximum value of the flexural modulus E of the toner sample obtained from the slope (ΔF / Δs) of the load-deflection curve by the above formula (2) is E _MAX (MPa),
The present invention relates to an image forming method, wherein the strain energy u per unit volume calculated from the values of σ _MAX and E _{MAX by} the above formula (3) is 0.20 MPa or more.

  According to the present invention, even if the speed of various types of image forming apparatuses is further increased, the low temperature fixability and the cracking and chipping of the toner are suppressed, thereby improving the durability of the toner and improving the image stability in the long term. An image forming method can be provided.

The schematic diagram (A) which shows the method of the 3 point | piece bending test used for evaluation of a toner, and the load-deflection curve figure (B) obtained by a 3 point | piece bending test are shown. FIG. 3 is a diagram illustrating an example of a toner manufacturing apparatus. It is the schematic of the measurement sample and jig | tool which measure the viscoelasticity of this invention. 1 is a schematic sectional view of an image forming apparatus used in an image forming method according to a first aspect of the present invention. FIG. 4 is a schematic cross-sectional view of an image forming apparatus used in an image forming method according to a second aspect of the present invention. FIG. 6 is a cross-sectional view (A) of the developing device in the image forming apparatus of FIG. 5 and a cross-sectional view (B) showing the longitudinal direction of the developing device. Sectional drawing (A) which shows the image development apparatus of the 2nd aspect of this invention in several places along a conveyance direction, A perspective view (B) which shows a developing chamber cross-sectional area variable member (volume variable block). FIG. 3 is a cross-sectional view of a developing device for a large capacity cartridge having a plurality of toner storage portions. Sectional drawing (A) of the axial direction which shows an example of a toner carrier (B). FIG. 5 is a schematic cross-sectional view of an image forming apparatus used for an image forming method according to a third aspect of the present invention. (A), (b) Measuring method of hardness of toner supply member at 1 mm compression.

  The image forming method of the present invention will be described below with reference to embodiments.

  The image forming method according to the first aspect of the present invention includes the following steps. A charging step of charging the image bearing member with a charging means; An exposure process in which an electrostatic latent image is formed by exposing a charged image carrier. A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier; A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier. A primary transfer process in which a toner image is primarily transferred onto an intermediate transfer member. A composite toner image forming process in which a process from a charging process to a primary transfer process is performed for each color and a composite toner image is formed by superimposing a plurality of toner images formed for each color on an intermediate transfer member. A secondary transfer process in which the composite toner image is secondarily transferred to a transfer material. A fixing step of fixing a secondary transferred composite toner image on a transfer material to obtain a fixed toner image.

  In the first image forming method, the transfer residual toner remaining on the intermediate transfer body after the secondary transfer step is charged with a fixed charging brush, and the transfer residual toner to which the charge is applied is transferred onto the intermediate transfer body. To the image carrier. The reversely transferred residual toner is collected by a cleaning device provided opposite to the image carrier. By using such a configuration, the waste toner box of the intermediate transfer member can be reduced, and the image forming apparatus can be downsized.

  FIG. 4 is a schematic configuration diagram of the image forming apparatus according to the first aspect of the present invention. The image forming apparatus in FIG. 4 is an electrophotographic color (multicolor image) printer having a tandem configuration in which photosensitive drums as a plurality of image carriers are arranged in a vertical direction in an up and down direction, and an intermediate transfer belt is used as an intermediate transfer body. is there.

  PY, PM, PC, and PBk are first to fourth image forming units (image forming units) for forming toner images of yellow (Y), magenta (M), cyan (C), and black (Bk), respectively. Unit), which are arranged in the image forming apparatus main body in parallel from the bottom to the top. These first to fourth image forming units PY, PM, PC, and PBk have the same configuration and electrophotographic image forming function except that the colors of the toner images formed are different as described above. Yes. That is, each of the first to fourth image forming units has the following members. Image carrier 1, charging roller 2 as charging means in charging process, irradiation device 3 as exposure means, developing device 4 as developing means including step of regulating toner on toner carrier with toner layer regulating member, primary A primary transfer roller 5 as a transfer unit and a blade cleaning device 6 as a cleaning unit. In each of the first to fourth image forming units, the four process devices of the image carrier 1, the charging roller 2, the developing device 4, and the blade cleaning device 6 can be attached to and detached from the image forming apparatus main body in a lump. As a process unit (process cartridge).

  The intermediate transfer member 30 is an endless belt-like intermediate transfer belt. The intermediate transfer member extends over the whole of the four image forming units on the image carrier side (the front side of the printer) of the first to fourth image forming units and between a plurality of support rollers (not shown). It is stretched and arranged in the vertical direction. In each of the first to fourth image forming units, the primary transfer roller 5 is brought into pressure contact with the image carrier 1 through the intermediate transfer member 30. A contact portion between each image carrier 1 and the intermediate transfer member 30 is a primary transfer portion.

  In each of the first to fourth image forming units, each rotationally driven image carrier 1 is uniformly charged to a predetermined polarity and potential by a charging roller 2 to which a charging bias is applied from a power supply circuit (not shown). Is done. The charged image carrier 1 is subjected to light image exposure according to an image pattern of each color of yellow, magenta, cyan, and black, which is a color separation component image of a full-color image, by the irradiation device 3, and each image carrier. An electrostatic latent image of image information is formed on 1. Each of the electrostatic latent images is developed as a toner image by the developing device 4. As a result, each color toner image is formed on the surface of each image carrier 1 of the first to fourth image forming units at a predetermined sequence control timing.

  Then, the toner images of the respective colors formed on the surfaces of the image carriers 1 are transferred to the primary transfer portions of the first to fourth image forming portions with respect to the surfaces of the image carriers 1 and the intermediate transfer member 30. The images are sequentially superimposed and transferred to the primary transfer roller 5 by a primary transfer bias applied from a power supply circuit (not shown). As a result, an unfixed full-color toner image (mirror image) is synthesized and formed on the surface of the intermediate transfer member 30 that is rotationally driven. After the toner image is primarily transferred, the transfer residual toner remaining on each image carrier 1 is removed by the cleaning blade of the blade cleaning device 6. Then, it is stored in the cleaning device 6.

  The opposing roller 32a of the secondary transfer roller 32 is disposed inside the intermediate transfer member 30 on the lower end side of the intermediate transfer member 30, and the secondary transfer roller 32 sandwiches the intermediate transfer member 30 between the opposing transfer roller 32a. Further, it is disposed in contact with the outer surface of the intermediate transfer member 30. A contact portion between the secondary transfer roller 32 and the intermediate transfer member 30 is a secondary transfer portion.

  The CPU drives the conveying means (pickup roller) 31 at a predetermined sequence control timing to separate and feed one sheet of the transfer material P in the paper feed cassette 40, and feeds it to the secondary transfer section at a predetermined timing. . The unfixed full-color toner image synthesized and formed on the intermediate transfer member 30 is transferred onto the surface of the transfer material P by a secondary transfer bias applied from a power supply circuit (not shown) to the secondary transfer roller 32 in the secondary transfer portion. It will be batch-transcribed. The transfer material P that has passed through the secondary transfer portion is separated from the surface of the intermediate transfer body 30 and sent to the fixing device 7 by the transport belt 35.

  The transfer residual toner remaining on the intermediate transfer member 30 is charged by the fixed charging brush 33 and the charging roller 34, and the transfer residual toner to which the charge is applied is reversely transferred from the intermediate transfer member onto the image carrier. The transfer residual toner reversely transferred to the image carrier 1 is removed by the cleaning blade of the blade cleaning device 6. And it is stored by the storage part in the cleaning blade apparatus 6. FIG.

  The fixed charging brush is a non-rotating type. In FIG. 4, the fixed charging brush 33 and the charging roller 34 are fixed to and contacted with the intermediate transfer belt at a position where a cleaning blade is normally disposed. It is in a state. In the present embodiment, the fixed charging brush uses a brush member made of conductive fibers.

The fixed charging brush has a resistance value controlled by adding carbon or metal powder to a fiber such as rayon, acrylic, or polyester. The average bristle diameter is preferably 5 μm or more and 200 μm or less, and the brush hair density is preferably 1 × 10 ⁶ or more and 1 × 10 ⁹ or less (lines / m ² ) so that the transfer residual toner can be uniformly contacted. The toner remaining on the intermediate transfer member is collected with the brush, charged, and collected onto the first image carrier. When the average bristle diameter of the fixed charging brush is within the above range, the toner holding ability is high and streak-like image defects are further suppressed. Furthermore, the durability of the brush itself is improved.

  In the non-magnetic one-component developing method, a toner layer regulating member is brought into contact with the surface of the toner carrying member and regulated to form a uniform toner layer and conveyed to the image carrying member. In the image forming method according to the first aspect, the contact pressure between the toner regulating member and the toner carrier is preferably 10.0 N / m or more and 50.0 N / m or less. When the contact pressure is 10.0 N / m or more, the toner regulation is uniform and the coating state of the toner carrier tends to be uniform. When the contact pressure is 50.0 N / m or less, the regulation force is appropriately controlled, so that contamination of the regulation member and the toner carrier due to toner deterioration, toner adhesion due to lack of toner, and fogging are further suppressed. Is done. The contact pressure on the surface of the toner carrier is more preferably 20.0 N / m or more and 45.0 N / m or less.

  In the image forming method according to the first aspect, the peripheral speed of the toner carrier is preferably 200 mm / s or more and 450 mm / s or less. When the peripheral speed of the toner carrier is 200 mm / s or more, the toner supply amount becomes sufficient, and the density thinning when the print productivity is increased is further suppressed. When the peripheral speed of the toner carrier is 450 mm / s or less, toner deterioration due to the regulating member is further suppressed. The peripheral speed of the toner carrier is more preferably 300 mm / s or more and 400 mm / s or less.

  The image forming method according to the second aspect of the present invention includes the following steps. A charging step of charging the image bearing member with a charging means; An exposure process in which an electrostatic latent image is formed by exposing a charged image carrier. A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier; A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier. A transfer process in which the toner image is transferred to a transfer material with or without an intermediate transfer member.

  FIG. 5 shows a preferred schematic configuration of an image forming apparatus having a mechanism for replenishing toner according to the second embodiment of the present invention. In the present invention, the present invention is embodied in an image forming apparatus that performs monochromatic image formation, but the present invention is not limited to this.

  A drum-shaped photoconductor 29 as an image carrier is supported on the image forming apparatus main body shown in FIG. 5 so as to be rotatable in the clockwise direction indicated by an arrow in the drawing. When image formation is started, the surface of the photoreceptor 29 is uniformly charged by a charging roller 31 that is a charging unit. An exposure device 32, which is an exposure means, performs exposure corresponding to image information on the charged photoreceptor surface, and an electrostatic latent image is formed on the photoreceptor surface. The electrostatic latent image is visualized by the toner supplied to the photoconductor 29 by the developing device 11 to form a toner image. It is preferable to use a non-magnetic one-component toner as the toner. A transfer electric field is formed between the photoconductor 29 and the transfer roller 33 as a transfer means, and the toner image is electrostatically transferred onto the recording medium P. The unfixed toner image on the recording medium P is heated and pressurized by the fixing device 34 and fixed on the recording medium P. At this time, transfer residual toner or the like remaining on the surface of the photoconductor 29 after the transfer of the toner image is removed by a cleaning device 30 including a blade-shaped cleaning member, and the photoconductor 29 is in a state where image formation can be continued. .

  Next, FIG. 6A shows a cross-sectional view of the developing device 11 provided in the image forming apparatus main body of FIG. The toner container 12 provided in the developing device 11 is partially opened on the side facing the photoconductor, and the toner carrier 1 is rotatably supported by the toner container 12 so as to be partially exposed from the opening. The toner carrier 1 is in contact with the photosensitive member with a predetermined contact pressure. The supply roller 2 as the toner supply / recovery means is an elastic roller formed of an elastic body or the like, and is disposed at a position where the insulating sponge roller contacts the toner carrier 1. The toner container 12 is provided with a toner layer regulating member 3 that slidably contacts the toner carrier 1 and regulates the thickness of the toner layer. This toner layer regulating member 3 is processed into a leaf spring shape with SUS (stainless steel) and is in contact with the toner carrier 1 with a predetermined contact pressure. The toner supplied onto the toner carrying member 1 is regulated in thickness by the toner layer regulating member 3 and is given an electric charge to form a thin toner layer on the toner carrying member 1 and develop it on the photoreceptor. Is done. Further, the toner that is not developed and is carried on the toner carrier 1 is peeled off from the toner carrier 1 by the rubbing by the supply roller 2. Part of the peeled toner is supplied again onto the toner carrier 1 by the supply roller 2 together with the toner newly supplied onto the supply roller 2, and the rest is collected in the toner container 12. .

  Next, inside the replenishing toner cartridge 8 which is a toner replenishing mechanism, the agitating member 7 for agitating the toner in the replenishing toner cartridge 8 and the agitating chamber 9 from the replenishing toner cartridge 8 are replenished. The replenishing roller is disposed on the opening 6. Accordingly, when a replenishment command signal is output from the developing device, a constant amount of toner per driving time is replenished to the agitating chamber 9 and the toner amount in the toner container 12 is always kept constant. As a replenishment command system, there are a system in which a piezo sensor is provided in the toner container 12 to detect the presence or absence of toner, a light detection system, an inductance detection system, and a system in which the amount of toner consumed is calculated from the image printing ratio.

  FIG. 6B is a cross-sectional view showing the longitudinal direction of the developing device 11. In FIG. 6B, the partition wall divides the lower side including the toner carrier 1 into the upper and lower chambers where the developing chamber 10 is provided and the upper side including the stirring member 5 is the stirring chamber 9. The developing chamber 10 and the stirring chamber 9 are connected only by openings provided only at both ends. A toner conveying means 4 in the longitudinal direction is disposed in the developing chamber 10. The toner conveying means 4 conveys the toner in the developing chamber in the longitudinal direction, and sends the toner falling from the opening of the inlet 19 toward the central longitudinal direction of the developing chamber 10, and the toner in the developing chamber 10 is opened in the opening of the outlet 20. To the stirring chamber 9 again. A stirring member 5 having a plurality of blades is disposed in the stirring chamber 9, and the blades alternately stir up the toner by rotation to stir the developer. The toner conveying means 4 and the agitating member 5 are connected to the toner carrier 1 and the supply roller 2, and both rotate while the toner carrier 1 is rotating, and almost synchronize with the end of image formation. Thus, the rotation is stopped.

  A particularly preferable configuration of the image forming apparatus having a mechanism for supplying the toner will be described with reference to FIG. As shown in FIG. 7A, the developing chamber has a different cross-sectional shape on the upstream side in the transport direction and a cross-sectional shape on the downstream side, and changes the volume of the developing chamber filled with the toner. As shown by the hatched portion in FIG. 7, S is defined as a cross-sectional area surrounded by the toner container 12 excluding the transport region of the toner transport unit 4 in the upper region in the gravity direction than the rotation axis of the supply roller 2.

  Accordingly, a developing chamber cross-sectional area variable member (hereinafter simply referred to as “volume variable block”) by a wedge-shaped block indicated by B in FIG. 7B is simply embedded in the developing chamber 10 (corresponding to 10 in FIG. 6). It can be retrofitted. That is, in the transport space formed in the longitudinal direction between the toner transport means 4 and the supply roller 2, the variable volume block B can be retrofitted from one upstream side to the other downstream side. The cross-sectional area S1 on the upstream side in the conveying direction indicated by the oblique lines in FIG. 7A is smaller than the cross-sectional area S2 on the downstream side in the conveying direction indicated by the oblique lines in FIG. 7A. , S1 <S2 is satisfied. Furthermore, the cross-sectional area S2 becomes smaller than the cross-sectional area S3 on the downstream side in the conveying direction indicated by the oblique lines in FIG. 7A, and the cross-sectional area S1 continuously changes from the cross-sectional area S3 to develop Change the volume of the chamber. The developing device according to the second aspect of the present invention provides the following effects. If the cross-sectional area S is increased along the transport direction (shaded area in FIG. 7A), the toner supplied from the stirring chamber is not partially coated in the vicinity of the developing chamber entrance. Further, the toner supply can be relaxed along the transport direction, and the toner supplied from the inlet can be uniformly coated in the longitudinal direction over the entire area of the developing roller 1, and density unevenness can be improved.

The image forming method according to the second aspect of the present invention may be an image forming apparatus using a large capacity cartridge having a plurality of toner storage portions as shown in FIG. In the cartridge shown in FIG. 8, the toner storage frame 1 has a plurality of toner storage units 2, and each toner storage unit 2 is connected through an opening, and the toner storage frame 1 holds the developing member 3. Connected to the developing unit 4. The number of toner storage portions 2 included in the toner storage frame 1 is not particularly limited, but is preferably 2 or more, and more preferably 3 or more. Since the toner storage frame 1 has a plurality of toner storage portions 2, it is possible to improve the charge rising of the toner near the developing portion 3. Each toner storage unit 2 has at least one agitating member 5 in the storage unit, and moves the toner in the toner storage unit by the stirring member 5 to supply the toner to the developing unit 4. Further, the toner storage unit 2 has a space for storing a large amount of toner having a total capacity of 1000 cm ³ or more, and the process cartridge can satisfy the following formula (4) with respect to the space for storing the toner. It becomes possible to cope with the higher speed.
0.2 ≦ Ct / (X × Dt) ≦ 0.8 (4)
(X: total capacity of toner storage unit (cm ³ ), Ct: stored toner mass (g), Dt: toner tap density (g / cm ³ ))

  The above formula (4) indicates that the filling rate is 0.2 or more and 0.8 or less in terms of toner tap density with respect to the total capacity of the toner storage unit. When the toner tap density is 0.2 or more, an effect of increasing the total capacity of the toner storage unit can be obtained. On the other hand, when it is 0.8 or less, clogging of toner in the toner storage portion is reduced and stirring becomes easy. When the ratio is preferably 0.3 or more, and more preferably 0.4 or more, the total capacity of the toner storage unit can be fully utilized. The tap density of the toner is a value measured using a powder tester manufactured by Hosokawa Micron Corporation.

  In the image forming method according to the second aspect of the present invention, the developing property and durability are improved by controlling the MD-1 hardness of the toner carrier. The MD-1 hardness of the toner carrier can be determined using a micro rubber hardness meter MD-1 type, Type A (manufactured by Polymer Design Co., Ltd.). As shown in FIG. 9A, the toner carrier used in the image forming method according to the second aspect of the present invention has a conductive elastic layer D2 on the outer periphery of a good conductive shaft D1. Have. The MD-1 hardness of the conductive elastic layer D2 needs to be 35 or more and 65 or less. The toner carrier used in the image forming method according to the second aspect of the present invention has a conductive resin further on the outer periphery of the conductive elastic layer D2, as shown in FIG. A structure having the layer D3 may be employed. The conductive elastic layer D2 and the conductive resin layer D3 may be either a single layer or multiple layers, but at least the MD-1 hardness of the surface layer (conductive resin layer D3) needs to be 35 or more and 65 or less.

  When the MD-1 hardness of the toner carrier is smaller than 35, the hardness of the surface layer is too low, so that the toner thin layer on the toner carrier tends to be non-uniform. As a result, the developability of the toner deteriorates, and the toner stack on the image becomes uneven, resulting in a decrease in image density. On the other hand, when the MD-1 hardness of the toner carrier is greater than 65, the toner carrier hardness is too high, and it is difficult to obtain an effect of suppressing mechanical stress between the toner carrier and the toner layer regulating member. As a result, the toner carrier is likely to be broken and chipped, and the toner carrier that tends to cause filming in the toner carrier preferably has an MD-1 hardness of 40 to 60. More preferably, the MD-1 hardness is 45 or more and 60 or less.

As the highly conductive shaft D1, a metal cylinder having an outer diameter of 4 to 10 mm made of aluminum, iron, SUS, or the like is used. The conductive elastic layer D2 uses an elastomer such as EPDM or urethane, or other resin molding as a base material. In addition to these base materials, an electronic conductive material such as carbon black, metal, metal oxide, or an ionic conductive material such as sodium perchlorate is blended to adjust the volume resistivity. The volume resistivity is preferably 10 ³ to 10 ¹⁰ Ωcm. The thickness of the conductive elastic layer D2 is preferably 0.3 to 10.0 mm, more preferably 1.0 to 5.0 mm. Specific examples of the base material include polyurethane, natural rubber, butyl rubber, nitrile rubber, polyisoprene rubber, polybutadiene rubber, silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, Acrylic rubber and mixtures thereof are mentioned. Preferably, silicone rubber or ethylene-propylene-diene rubber is used. Examples of the electronic conductive material used for imparting conductivity to the conductive elastic layer D2 include conductive carbon such as ketjen black EC and acetylene black, SAF, ISAF, HAF, FEF, GPF, SRF, FT, Examples thereof include carbon for rubber such as MT, carbon for color (ink) subjected to oxidation treatment, and metals and metal oxides such as copper, silver, and germanium. Among these, carbon black (conductive carbon, carbon for rubber, carbon for color (ink), etc.) is preferable because the conductivity can be easily controlled with a small amount. These conductive powders are usually suitably used in the range of 0.5 to 50 parts by mass, particularly 1 to 30 parts by mass with respect to 100 parts by mass of the base material. Examples of the ion conductive material used for imparting conductivity to the conductive elastic layer D2 include inorganic ion conductive materials such as sodium perchlorate, lithium perchlorate, calcium perchlorate, and lithium chloride. Examples thereof include organic ionic conductive substances such as modified aliphatic dimethyl ammonium etosulphate and stearyl ammonium acetate. These conductivity-imparting agents such as an electron conductive substance and an ion conductive substance are usually suitably used in a range of 0.5 to 50 parts by mass, particularly 1 to 30 parts by mass with respect to 100 parts by mass of the base material. .

  As the base material of the conductive resin layer D3 covering the conductive elastic layer D2 of the conductive roller having the configuration shown in FIG. 9B, polyamide resin, urethane resin, urea resin, imide resin, melanin resin, fluorine Examples thereof include resins, phenol resins, alkyd resins, silicone resins, polyester resins, polyether resins and the like, and mixtures thereof. Urethane resin is preferably used as a base material for conductive resin layer D3 because it has a large ability to charge toner by friction and has wear resistance.

At this time, the urethane resin is composed of an isocyanate component and a polyol component. As the polyol component, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polyolefin polyol, polymer polyol and the like are used.
Specifically, a unit (BO) represented by the following formula (3),

(In the formula, l represents a positive integer.

  A unit (PO) represented by the following formula (4), and

(In the formula, m represents a positive integer.)
A unit represented by the following formula (5),

It is preferable that it is contained in the polyether polyol which has. At this time, a polyether polyol in which all the units represented by the formulas (3) to (5) are contained in one molecule, or at least one type of units represented by the formulas (3) to (5) are contained in one molecule. Any polyether polyol can be used. Preferably, the polyether polyol used as a raw material for urethane always includes all units represented by formula (3), formula (4), and formula (5).

  At this time, the polyether polyol (BO) having a unit represented by the formula (3) is preferably of a type having two or more hydroxyl groups. The polyether polyol (PO) having a unit represented by the formula (4) is preferably of a type having one hydroxyl group. The polyether polyol (EO) having a unit represented by the formula (5) is preferably a type having one hydroxyl group. In each unit, it is preferable to use the above-mentioned type because the effect of the present invention is promoted. Furthermore, it is more preferable that the polyether polyol (PO-EO) having the unit represented by the formula (4) and the unit represented by the formula (5) simultaneously has one hydroxyl group.

  Furthermore, adjusting the mass ratio of BO, PO, and EO of the polyether polyol used to be BO: PO: EO = 100: 3: 2 to 100: 25: 20 promotes the effect of the present invention. preferable. It is also preferable to adjust the polyether polyol used so that the mass ratio of BO: (PO-EO) is BO: (PO-EO) = 100: 5 to 100: 40.

  Specific examples of the isocyanate component of the urethane resin include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), Examples thereof include phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), and cyclohexane diisocyanate. Among these, aromatic isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI) preferable. In particular, diphenylmethane diisocyanate (MDI) is preferred because it can improve the restorability of the toner carrier after local loading.

This isocyanate component is adjusted so that the mass ratio with respect to the total polyol used is isocyanate: polyol = 20: 80 to 60:40. The conductive resin layer D3 is formed by blending the base material with a conductivity-imparting agent such as an electronic conductive material or an ionic conductive material, and adjusting the volume resistivity. The volume resistivity is preferably 10 ³ to 10 ¹¹ Ωcm. Moreover, it is preferable to use the thickness of the conductive resin layer D3 in the range of 0.5 to 200 μm.

  The thicknesses of the conductive elastic layer D2 and the conductive resin layer D3 were determined by cutting a roller on which the conductive elastic layer D2 and the conductive resin layer D3 were formed, measuring the cross section at nine points, and calculating the average value. When the thickness was thin as in the case of the conductive resin layer, the cross section was measured at 9 points using a video microscope (magnification 3000 times) and the average value was obtained.

  The kneading of the resin serving as the base material with a conductivity-imparting agent such as an electronic conductive material or an ionic conductive material is used to form the surface roughness of the toner carrier as needed using a ball mill or the like. The coarse particles are added and dispersed. Then, it can carry out by adding a hardening agent or a curing catalyst etc. timely, and stirring. The obtained composition is applied by a method such as spraying or dipping.

  Or the following method is mentioned. A method in which a conductive elastic layer or a conductive resin layer is integrally formed by injecting the composition obtained into a cavity of a molding die in which a core metal is preliminarily disposed and heating to cause reaction hardening or solidification. . From a slab or block separately formed using the above composition in advance, by cutting or the like, it is cut into a predetermined shape and dimensions such as a tube shape, and a cored bar is press-fitted into this to form a conductive elastic layer or A method of manufacturing by coating a conductive resin layer. Or the method which combined these methods suitably. If desired, the outer diameter may be further adjusted to a predetermined outer diameter by cutting or polishing treatment.

  Examples of the roughening particles include rubber particles such as EPDM, NBR, SBR, CR, and silicone rubber, or elastomer particles such as polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, and polyamide-based thermoplastic elastomer (TPE). Or resin particles such as PMMA particles, urethane resin particles, fluorine resin, silicone resin, phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, polyacrylonitrile resin alone or They can be used in combination. At this time, the surface roughness Rz of the toner carrying member is adjusted to 1 to 15 μm. At this time, the surface roughness of the roller is Rz according to JIS B0601: 2001.

  In the second aspect of the present invention, it is preferable to employ a developing system using a non-magnetic one-component toner. In the non-magnetic one-component development method, a toner layer regulating member is brought into contact with the surface of the toner carrying member to regulate it, thereby forming a uniform toner layer and developing it on the photoreceptor. In this case, the contact pressure between the toner layer regulating member and the toner carrier is preferably 10.0 N / m or more and 50.0 N / m or less. When the contact pressure is 10.0 N / m or more, toner regulation is sufficient, and the coating state of the toner carrier tends to become more uniform. When the contact pressure is 50.0 N / m or less, the regulating force is appropriately controlled, so that contamination of the regulating member and the toner carrier due to toner deterioration, toner adhesion due to lack of toner, fogging, and the like. Is further suppressed. The contact pressure on the surface of the toner carrier is more preferably 20.0 N / m or more and 45.0 N / m or less.

  In the image forming method according to the second aspect, the peripheral speed of the toner carrier is preferably from 300 mm / s to 600 mm / s. When the peripheral speed of the toner carrier is 600 mm / s or less, the toner deterioration due to the friction between the toner layer regulating member and the toner carrier is further suppressed, and the fusion of the toner to the toner layer regulating member is further suppressed. . The peripheral speed of the toner carrier is more preferably 450 mm / s or more and 600 mm / s or less. Furthermore, it is preferably 500 mm / s or more and 600 mm / s or less.

  The image forming method according to the third aspect of the present invention includes the following steps. A charging step of charging the carrier with charging means. An exposure process in which an electrostatic latent image is formed by exposing a charged image carrier. A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier; A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier. A transfer process in which the toner image is transferred to a transfer material with or without an intermediate transfer member. Furthermore, in the third aspect of the present invention, a toner supply member for supplying toner contacts the toner carrier, and each surface of the toner carrier and the toner supply member is in contact with each other. It arrange | positions so that it may rotate in a reverse direction.

  FIG. 10 is a configuration diagram showing a schematic configuration of the image forming apparatus according to the third aspect of the present invention. In this image forming apparatus, a charging roller 2, an exposure device 3, a developing device 4, a transfer belt 5, and a cleaning device 6 are sequentially arranged around a drum-shaped photosensitive drum 1 that is an image carrier. The charging roller 2 is a charging unit that uniformly charges the surface of the photosensitive drum 1. The exposure device 3 is exposure means for irradiating the photosensitive drum 1 with a laser beam or the like modulated based on image information. The developing device 4 is a developing unit that develops the electrostatic latent image formed on the photosensitive drum 1 to form a toner image. The transfer belt 5 is an intermediate transfer member that transfers a toner image formed on the photosensitive drum 1. The cleaning device 6 is a cleaning unit that removes toner remaining on the photosensitive drum 1 after transfer. In the image forming apparatus having the above configuration, the surface of the photosensitive drum 1 rotating in the direction of the arrow a is uniformly charged by the charging roller 2 to a predetermined positive or negative charging potential. Thereafter, a laser beam modulated based on the image information is scanned and irradiated in the photosensitive drum axial direction. As a result, an electrostatic latent image is formed on the surface of the photosensitive drum 1. The electrostatic latent image formed on the surface of the photosensitive drum 1 is developed by attaching toner charged by the developing device 4 in the developing region to become a toner image. Thereafter, the toner image formed on the surface of the photosensitive drum 1 is temporarily transferred onto the transfer belt 5 by supplying the transfer belt 5 with a charge having a polarity opposite to that of the toner image. The transfer paper P is transported by a transport device (not shown), and is transported by a registration roller pair 7 to a secondary transfer portion where the transfer belt 5 and the secondary transfer roller 8 face each other at a predetermined timing. Then, the toner image on the transfer belt 5 is transferred to the transfer paper P by applying a charge having a polarity opposite to that of the toner image to the secondary transfer roller 8. Next, the transfer paper P is separated from the transfer belt 5 and sent to a fixing device (not shown). After the toner image is fixed on the transfer paper P by the fixing device, the transfer paper P is discharged out of the device. The surface of the photosensitive drum 1 after the toner image is transferred to the transfer belt 5 is cleaned by the cleaning device 6, and the toner remaining on the photosensitive drum 1 is removed.

  Next, the developing device 4 used in the image forming method according to the third aspect of the present invention will be described. The developing device 4 includes a toner carrier 11, a toner supply member 12, and a toner layer regulating member 13 that are exposed to a part of the peripheral surface from the opening and face the photosensitive drum 1. The toner storage chamber 9 includes a toner transport member 14. The toner carrier 11 carries and conveys toner. The toner supply member 12 contacts the toner carrier 11 and supplies toner to the toner carrier. The toner layer regulating member 13 has the free end thereof facing the upstream side in the rotation direction of the toner carrying body and abuts against the toner carrying body to regulate the thickness of the toner layer carried on the toner carrying body. In the developing device 4, the toner accommodated in the toner storage chamber 9 is sent by the toner conveying member 14 to the developing chamber 10 where the toner carrier 11 is disposed. The transferred toner is stored in the contact portion between the toner carrier 11 and the toner supply member 12, and mechanically rubs at the contact portion between the toner supply member 12 and the toner carrier 11 as the toner supply member 12 rotates. Is done. The toner is triboelectrically charged by this rubbing, and is carried and supplied on the toner carrier 11. The toner supplied to the toner carrier 11 is thinned to an appropriate layer thickness by the toner layer regulating member 13 that is in contact with the toner carrier 11 via the toner. At the same time, the toner supplied to the toner carrier 11 is sandwiched between the toner carrier 11 and the toner layer regulating member 13, so that each of the surface of the toner carrier 11 and the surface of the toner layer regulating member 13 is applied. And is triboelectrically charged to the desired polarity. Then, the toner carrying member 11 is conveyed to a developing region which is a portion facing the photosensitive drum 1 by rotation in the arrow direction. In the developing device 4, the toner carrier 11 and the toner supply member 12 are configured to rotate so that their surfaces move in opposite directions at the contact portion. In the development area, the toner layer on the surface of the toner carrier 11 develops the electrostatic latent image on the photosensitive drum 1 by a developing electric field generated by a voltage application unit (not shown), and is visualized as a toner image. The toner layer that is not used for development in the development region and remains on the toner carrier 11 is scraped off at a contact portion with the toner supply member 12 and mixed with newly supplied toner by the rotation of the toner supply member 12. The When the toner carrier and the toner supply member are arranged so that the surfaces of the toner carrier and the toner supply member move in the reverse direction from the forward direction at the contact portion, the circumferential speed of the toner supply member surface becomes equal when the peripheral speed of the toner carrier is made equal. The relative peripheral speed difference between the toner carrier and the toner supply member can be obtained at a lower speed. Therefore, the toner can be sufficiently scraped off in a state where the pressure of the toner received from the toner supply member and the toner carrier at the contact portion is reduced. Further, since the mixing with the toner newly supplied by the toner supply member proceeds smoothly, the charge amount of the toner on the toner carrying member becomes uniform, and the uniformity of the image density also increases.

  In the image forming method according to the third aspect of the present invention, the peripheral speeds of the toner carrier and the toner supply member can be arbitrarily changed. The peripheral speed on the surface of the toner supply member is Vs, the peripheral speed on the surface of the toner carrier is Vd, and the ratio of the peripheral speed on the surface of the toner supply member and the toner carrier is Vs / Vd. When the peripheral speed ratio Vs / Vd is a positive value, it indicates that the surface of the toner supply member and the surface of the toner carrier are rotated in the opposite directions at the contact portion, and when Vs / Vd is a negative value, In the contact portion, the surface of the toner supply member and the surface of the toner carrying member are rotated in the forward direction. When the value of Vs / Vd is 1.00, the peripheral speed of the surface of the toner supply member and the peripheral speed of the surface of the toner carrier are constant, and when Vs / Vd is 0, the toner supply member is stopped. Means that When the absolute value of Vs / Vd is smaller than 1.00, the peripheral speed of the toner supply member surface is smaller than the peripheral speed of the toner carrier surface. When the absolute value of Vs / Vd exceeds 1.00, the peripheral speed on the surface of the toner supply member is larger than the peripheral speed on the surface of the toner carrier. In the image forming method according to the third aspect, Vs / Vd is preferably 0.50 or more and 3.00 or less. More preferably, it is 0.60-2.00. More preferably, it is 0.70-1.00. Vs / Vd is in the above-mentioned range, and by using together the toner that holds the strain energy described later, it is possible to further suppress the cracking and chipping of the toner while maintaining the toner scraping ability of the toner supply member. become. When Vs / Vd is 0.50 or more, the ability of the toner supply member to scrape the toner on the toner carrying member is improved, and toner deterioration is further suppressed. When Vs / Vd is 3.00 or less, the rubbing of the toner at the contact portion between the toner carrying member and the toner supply member is appropriately controlled, the chargeability of the toner surface is maintained, and the toner is fused to the member. We suppress wearing more. Thereby, toner filming and streak-like image defects can be further suppressed.

  In the image forming method according to the third aspect, the peripheral speed of the toner carrier is likely to be effective at a high speed of 300 mm / s or higher. The peripheral speed of the toner carrier is more preferably 450 mm / s or more, and particularly preferably 500 mm / s or more. Further, when the peripheral speed of the toner carrier is 600 mm / s or less, toner deterioration due to sliding between the toner supply member and the toner carrier is further suppressed, and the toner chargeability is reduced and the toner is more fused. It is suppressed.

  By forming an electric field between the toner supply member and the toner carrier, it is possible to assist the toner supply member in scraping off the toner by applying a reverse polarity bias to the toner charged from the toner carrier. become. For this reason, the toner can be smoothly replaced on the surface of the toner carrying member, charging failure due to toner deterioration can be reduced, and fog on the image and uneven image density can be easily reduced. In addition, by forming an electric field between the toner layer regulating member and the toner carrier, it is possible to suppress adhesion of fine toner powder to the toner layer regulating member and to suppress generation of streaks on the image.

(Toner supply member)
The inventors of the present invention use a toner supply member that retains moderate flexibility and a toner having the strain energy to maintain the supply of toner to the toner carrier, while preventing filming due to toner cracks and chipping. It was found that it can be suppressed.

  As shown in FIG. 11A, the toner supply member 12 includes a cylindrical cored bar 15 and a polyurethane foam which is a foamed elastic body formed on the outer periphery of the cored bar 15 except for both ends of the cored bar 15. A roller-shaped surface layer 16 is provided. The metal core 15 can be made of a metal such as iron. The outer diameter of the cored bar is preferably 2 to 10 mm. The surface layer 16 made of polyurethane foam has a plurality of cell openings communicating with the inside thereof on the surface. The thickness of the surface layer is preferably 1 to 20 mm. When the thickness is within this range, the toner supply member has better toner transportability. The toner supply member may have an adhesive layer, an elastic layer, or the like as necessary between the core metal and the surface layer.

The load when the toner supply member is compressed by 1 mm is preferably 200 g or more and 400 g or less, more preferably 250 or more and 350 g or less. By using a toner that retains strain energy, which will be described later, when the load at 1 mm compression is in this range, even if the peripheral speed on the surface of the toner supply member increases, excessive pressure is applied at the contact portion with the toner carrier. It becomes easy to disappear. Therefore, the toner can be scraped off from the toner carrying member without causing cracking or chipping of the toner. Further, due to insufficient scraping ability of the toner supply member, the toner staying on the surface of the toner carrying member is not overcharged and the uneven charging of the toner on the surface of the toner carrying member is eliminated. It becomes easy to improve. When the load at the time of 1 mm compression is 200 g or more, the area of the contact portion with the toner carrier becomes appropriate, and the increase in the frictional strength of the toner is reduced even if the speed is increased. When the load at the time of 1 mm compression is 400 g or less, the hardness of the toner supply member is moderately controlled, and the toner carrier and the toner supply member are prevented from cracking and chipping by rubbing between the toner carrier and the toner carrier surface. The occurrence of ming is further suppressed. The density of the polyurethane foam is preferably 0.05 to 0.20 g / cm ³ . Hereinafter, materials used as raw materials for polyurethane foam in the present invention will be described. The polyurethane foam as the surface layer of the toner supply member of the present invention comprises a polyol component (component (A)), an isocyanate component (component (D)), and optionally used catalyst, foaming agent, foam stabilizer, and other auxiliary agents. Is obtained by mixing and foaming.

<Component (A): Polyol component>
In this invention, the polyol component containing the component (B) mentioned later and a component (C) is used as a component (A). You may further contain the well-known compound which can be used as a polyol component for forming a polyurethane foam. It is preferable that 85-100 mass% is contained in the said component (A) in the sum total of the said component (B) and the said component (C).

  In the present invention, the component (B) is a copolymer having an ethylene oxide unit at the terminal. The content of the ethylene oxide unit in the component (B) is 5 mol% or more, preferably 5 to 50 mol%, the total unsaturation is 0.05 meq / g or less, and the weight average molecular weight exceeds 4800. A polyether polyol of 10,000 or less is used. The polyether polyol as the component (B) may be one kind or a combination of two or more kinds.

  By having the ethylene oxide unit in a component (B) at the terminal, the reactivity which forms a urethane foam can be ensured and molding can be performed.

  The polyether polyol as component (B) is obtained by addition polymerization of propylene oxide and ethylene oxide to an initiator such as glycerin, trimethylolpropane, ethylene glycol, propylene glycol, pentaerythritol, sorbitol, and block addition of ethylene oxide at the chain end. Is obtained. The amount of ethylene oxide to be added can be appropriately set in consideration of the ethylene oxide content, weight average molecular weight and the like of the target copolymer.

  Here, the total unsaturation degree of the polyether polyol used as the component (B) needs to be 0.050 meq / g or less. Preferably, it is 0.035 meq / g or less. The total degree of unsaturation is measured by the method described in JIS K-1557.

  In general, the polyether polyol used as the component (B) contains a monool component of several percent to several tens of percent. The content of the monool component indicates that the content of the monool component is lower as the total unsaturation value is smaller. A polyether polyol having a small total unsaturation is considered to have a uniform network structure when it reacts with a polyisocyanate to form a polyurethane foam.

  Moreover, when such a polyether polyol with a small monool component is used, the addition ratio of isocyanate (isocyanate index = number of NCO groups / number of active hydrogen groups × 100) can be reduced. The reason for this is that in polyether polyols with a small monool component, there is little reaction between the monool component and the isocyanate that becomes non-uniform in the network structure, so that the isocyanate index can be reduced. By reducing the isocyanate index, the hardness can be further reduced. When the isocyanate index is 60 or more and 120 or less, the moldability of the toner supply member is good and the hardness is also good.

  Furthermore, the weight average molecular weight of the polyether polyol used as the component (B) is preferably more than 4800 and 10000 or less. When the weight average molecular weight is 10,000 or less, the viscosity becomes good, and handling, casting, and uniform mixing with isocyanate are easy. When the weight average molecular weight is 4800 or more, the hardness of the toner supply member becomes good. More preferably, it is 5000-85000.

  The polyether polyol used as the component (B) preferably has a hydroxyl value of 20 to 50 mgKOH / g and an average functional group number of 2.0 to 4.0. When the hydroxyl value is 50 mg KOH / g or less and the average number of functional groups is 4.0 or less, the hardness of the toner supply member becomes good. The hydroxyl value is more preferably 20 to 40 mgKOH / g. The hydroxyl value is measured by the method described in JIS K-1557.

  In the present invention, a polyether polyol having a weight average molecular weight of 2000 or more and 7000 or less, which is a random copolymer having an ethylene oxide unit of 60 to 95 mol%, preferably 60 to 80 mol%, is used as the component (C). . The polyether polyol as the component (C) may be one kind or a combination of two or more kinds.

  By using a polyether polyol, which is a random copolymer having an ethylene oxide unit content in the above range, as the component (C), a toner supply member having more excellent cell opening stability can be obtained.

  The polyether polyol used as component (C) can be obtained by random copolymerization using a combination of ethylene oxide and propylene oxide monomers. The polymerization method can be appropriately set in consideration of the polymerizability of ethylene oxide and propylene oxide, the target weight average molecular weight, and the like.

  Here, it is preferable that the weight average molecular weight of the polyether polyol used as a component (C) is 2000-7000. When the weight average molecular weight is within this range, the hardness suitable for use as a toner supply member can be obtained.

  Since component (C) contains a large number of ethylene oxide units, it is excellent in compatibility (dispersibility) with water. In addition, since the component (C) has a cell bubble-breaking effect, not only the cells inside the toner supply member can be made into continuous cells but also the cells on the skin surface can be opened. In other words, in order to open cells on the skin surface, it is not necessary to increase the foaming pressure in the mold by increasing the content of water as a foaming agent, so it is possible to reduce the by-produced aromatic polyurea Become. Furthermore, the composition as a raw material can be easily mixed, and a small mold like the toner supply member of the present invention can be formed.

  The component (C) is preferably contained in the component (A) in an amount of 5 to 50% by mass. It is preferably more than 10% by mass and 50% by mass or less. By being in this range, it is possible to obtain a toner supply member having more excellent cell opening stability.

  In the present invention, an isocyanate component containing diphenylmethane diisocyanate (MDI) or a derivative thereof is used as component (D). By using the component (D) as an isocyanate component, a toner supply member having low hardness and good compression set in a high temperature and high humidity environment can be obtained.

  As a derivative of diphenylmethane diisocyanate, for example, modified MDI, polymeric MDI, or the like can be used. One kind of diphenylmethane diisocyanate or a derivative thereof may be used, or two or more kinds thereof may be used in combination. You may use the thing prepolymerized with the polyol.

  Moreover, you may contain the well-known compound which can be used as an isocyanate component for forming a polyurethane foam. For example, aliphatic polyisocyanates such as toluylene diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate and derivatives thereof, alicyclic polyisocyanates such as isophorone diisocyanate, and derivatives thereof may be contained. You may use the thing prepolymerized with the polyol. These may be used alone or in combination of two or more. It is preferable to contain toluylene diisocyanate or a derivative thereof.

  The total amount of diphenylmethane diisocyanate or a derivative thereof contained in 100 parts by mass of component (D) is preferably 3 to 80 parts by mass.

In the present invention, a catalyst can be used as necessary. There is no restriction | limiting in particular in the kind of catalyst, You may use a conventionally well-known thing. For example, amine-based catalysts (triethylenediamine, bis (dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexanediamine, 1,8-diazabicyclo (5,4,0) undecene-7, 1, 5-diazabicyclo (4,3,0) nonene-5, 1,2-dimethylimidazole, N-ethylmorpholine, N-methylmorpholine, etc.), organometallic catalysts (tin octylate, tin oleate, dibutyltin dilaurate, Dibutyltin diacetate, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, etc.), acid salt catalysts with reduced initial activity of the amine-based catalyst and organometallic catalyst ( Carboxylate, formate, octylic acid, borate, etc.) are used. One kind of this catalyst may be used, or two or more kinds may be used in combination.
In the present invention, a foaming agent can be used as necessary. In particular, water is suitably used as a blowing agent because it reacts with polyisocyanate to generate carbon dioxide. In addition, chlorofluorocarbons (HFC-134A, etc.), hydrocarbons (cyclopentane, etc.) developed for the purpose of protecting the global environment, other blowing agents, and these in combination with water The gist of the invention is not impaired.

  In the present invention, a foam stabilizer can be used as necessary. Examples of the foam stabilizer include water-soluble polyether siloxane from polydimethylsiloxane and ethylene oxide (EO) / propylene oxide (PO) copolymer, sodium salt of sulfonated ricinoleic acid, and polysiloxane / polyoxyalkylene copolymer. And the like. Among these foam stabilizers, water-soluble polyether siloxane from polydimethylsiloxane and EO / PO copolymer is preferred.

  In the present invention, as the auxiliary agent, an appropriate amount of a crosslinking agent, a flame retardant, a colorant, an ultraviolet absorber, an anti-aging agent, an antioxidant, a conductivity imparting agent and the like can be used as necessary. Addition of these other auxiliaries as necessary does not impair the gist of the present invention.

  In the present invention, the method for producing the polyurethane foam is not particularly limited and may be a conventional method. An example is as follows. First, the polyol component as the component (A), the polyisocyanate component as the component (D), and the catalyst, foaming agent, foam stabilizer, and other auxiliaries used as desired are mixed homogeneously, and then reaction-cured. Thus, a polyurethane foam is obtained.

  Although there is no restriction | limiting in particular about the temperature and time at the time of mixing each raw material, Mixing temperature is 10-90 degreeC normally, Preferably it is the range of 20-60 degreeC, and mixing time is 1 second-10 minutes normally. Preferably, it is about 3 seconds to 5 minutes.

  Further, when the reaction is cured, a polyurethane foam can be produced by foaming by a conventionally known method. There is no restriction | limiting in particular about the foaming method here, Any methods, such as the method of using a foaming agent and the method of mixing bubbles by mechanical stirring, can be used. The expansion ratio may be determined as appropriate and is not particularly limited.

  There is no restriction | limiting in particular about the joining method of the polyurethane foam used as a metal core and a surface layer. For example, a core metal is previously disposed inside a mold (molding die) and the above raw material mixture is cast-cured, or the raw metal mixture is molded into a predetermined shape to be a surface layer in advance and A method of bonding can be used. In either method, an adhesive layer can be provided between the cored bar and the polyurethane foam as necessary, and a known material such as an adhesive or a hot melt sheet can be used as the adhesive layer. There is no restriction | limiting in particular as a formation method of the surface layer part which consists of polyurethane foams. For example, in addition to the above-described method of casting into a mold having a predetermined shape, a method of cutting a polyurethane foam in a block state into a predetermined size by cutting, a method of obtaining a predetermined size by polishing, or these methods Or the like can be used as appropriate.

  In particular, a method in which a metal core is previously disposed in a mold (molding die) and the raw material mixture is cast-cured is preferable. More specifically, first, a rod-shaped cored bar is placed in a predetermined mold for toner supply member. As the mold, a pipe-shaped mold or a split mold can be used, but a pipe-shaped mold is more preferable. Then, the raw material mixture is poured into the molding die, subjected to a foaming reaction, and the resulting molded product is taken out from the molding die, whereby a toner supply member can be obtained.

(toner)
The toner used in the image forming method according to the first to third aspects of the present invention will be described. The inventors of the present invention have studied by paying attention to the strain energy per unit volume of the toner.

  Strain energy represents energy absorption until the material breaks when an external force is applied to the material, and is an index representing the toughness of the material. If the load on the toner due to pressure or impact exceeds the energy allowed by the toner, it is considered that cracking and chipping are caused.

  One of the tests for evaluating the strain energy per unit volume of toner is a three-point bending test. Strain energy is measured by supporting the specimen on both sides and applying a load in the middle. A schematic diagram showing a method of a three-point bending test is shown in FIG.

  The toner used in the image forming method according to the first to third aspects is a test piece obtained by molding a toner sample molded into a length (l) of 30.0 mm, a width (w) of 13.0 mm, and a thickness (t) of 4.0 mm Used as The distance between supporting points (L) is 15.0 mm, and the measurement is performed at a temperature of 25 ° C.

The maximum bending stress σ _MAX (MPa) of the toner sample is obtained by the following formula (1) from the maximum load F _MAX (N) at break.
σ _MAX = (3 × F _MAX × L) / (2 × w × t ² ) (1)

The flexural modulus E (MPa) of the toner sample is obtained from the slope (ΔF / Δs) of the load-deflection curve obtained by the measurement according to the following formula (2). Here, ΔF (N) represents the amount of change in load between any two points selected so that the amount of change in deflection Δs is 0.2 mm.
E = L ³ / (4 × w × t ³ ) × (ΔF / Δs) (2)

  Here, the bending stress is a physical property value indicating the magnitude of the force generated inside the toner when an external force is applied to the toner, and the maximum bending stress represents the magnitude of the force that the toner can withstand against the external force. Yes. The flexural modulus is a physical property value that indicates the difficulty of deformation when an external force is applied to the toner. The higher the flexural modulus, the harder the toner is to be deformed.

The strain energy u per unit volume of the toner sample is calculated by the following equation (3) from the maximum bending stress σ _MAX and the maximum value E _MAX of the bending elastic modulus E.
u = σ _MAX ² / (2 × E _MAX ) (3)

  By controlling the strain energy u per unit volume of the toner to be 0.20 MPa or more, the toner can be prevented from cracking and chipping in the developing device, and the durability of the toner is improved. Preferably it is 0.30 MPa or more. More preferably, it is 0.50 MPa or more. On the other hand, the upper limit of the strain energy u per unit volume of the toner is not particularly limited, but is usually 3.0 MPa or less.

  By controlling the strain energy u per unit volume of the toner to be 0.20 MPa or more, cracking and chipping of the toner is suppressed, and the durability of the toner is improved, whereby the image forming method according to the first aspect Then, it turned out that there were the following effects. By suppressing the cracking and chipping of the toner, the generation of fine powder can be suppressed, and the reduction in the proportion of the fine powder amount in the toner staying in the fixed charging brush can be suppressed. As a result, the fine powder is less likely to adhere to and accumulate on the fixed charging brush, and filming on the intermediate transfer member and occurrence of fog on the image can be suppressed. Thus, it has been found that long-term image stability is improved.

  By controlling the strain energy u per unit volume of the toner to be 0.20 MPa or more, in the image forming method according to the second aspect, accumulation of fine powder generated due to toner cracking and chipping can be suppressed. As a result, it has been found that contamination of the toner layer regulating member and filming on the toner carrying member are suppressed, and images such as streaks and white spots are less likely to occur.

  By controlling the strain energy u per unit volume of the toner to be 0.20 MPa or more, in the image forming method according to the third aspect, fine powder generated due to cracking or chipping of the toner layer regulating member or the toner carrier. Can be suppressed. Thereby, it was found that fogging on the image is suppressed and long-term image stability is improved.

Furthermore, according to the image forming method according to the first to third aspects of the present invention, the maximum value E _MAX of the bending elastic modulus E of the toner is controlled in the range of 100 MPa to 650 MPa, whereby the durability of the toner is increased. This can be further improved. A preferable range of the maximum value E _MAX of the flexural modulus E of the toner is 200 MPa or more and 450 MPa or less, and a more preferable range is 250 MPa or more and 400 MPa or less, and further preferably 300 MPa or more and 380 MPa or less.

In the image forming method according to the first aspect, when the maximum value E _MAX is 650 MPa or less, the bending elastic modulus is not too large, and the toner in the toner layer regulating step is easily deformed appropriately. Is sufficiently charged. As a result, the toner on the toner carrier after the toner layer regulation is more easily charged, and fogging of the toner adhering to the non-image portion on the image carrier is sufficiently suppressed. Further, the toner on the fixed charging brush is easily deformed moderately, the frictional force of the toner on the intermediate transfer member is reduced, and the intermediate transfer member is easily prevented from being scraped or scratched during long-term use. On the other hand, if the maximum value E _MAX is 100 MPa or more, the flexural modulus is not too small, excessive deformation of the toner is suppressed, and toner packing in the fixed charging brush is suppressed. This further suppresses the occurrence of streaks on the image due to the clogged toner fused to the intermediate transfer member.

In the image forming methods according to the second and third aspects, by setting the maximum value E _MAX within the above range, the toner on the toner carrier is more uniformly charged, and long-term image stability is improved. The reason is as follows. The toner is charged by rubbing between the toner carrier and the toner layer regulating member. However, as the speed of the image forming apparatus increases, the time for which the toner is rubbing is shortened. When the maximum value E _MAX is 650 MPa or less, the flexural modulus is not too large, and the toner is rubbed and deformed moderately in a short time to secure a contact area with the member, and sufficient charging is performed. It becomes easy. As a result, the occurrence of fog on the image is further suppressed. On the other hand, if the maximum value E _MAX is 100 MPa or more, the flexural modulus is not too small and the toner is prevented from being excessively deformed, and the toner is melted into the member by the friction between the toner carrier and the toner layer regulating member. Wearing is further suppressed. Thereby, filming is suppressed and streaks on the image are further suppressed.

  In order to increase the maximum bending stress of the resin, there are a method of increasing the molecular weight and a method of introducing a crosslinked structure. However, the flexural modulus also increases at the same time, and as a result, it is difficult to increase the strain energy.

  Therefore, a toner having toner particles containing a binder resin containing a crystalline polyester resin is preferable, and such a toner is effective in controlling strain energy. More preferably, a block polymer obtained by chemically bonding a crystalline polyester resin portion and an amorphous polyurethane resin portion is used for the binder resin. Such an amorphous polyurethane resin forms a physical cross-linked structure between molecules by a hydrogen bond generated between an NH group of a urethane bond and a carbonyl group. Therefore, it is considered that when the urethane bond concentration is increased, the number of cross-linking points between the molecules of the amorphous polyurethane resin increases, and the strain energy can be increased.

  The content of the block polymer is preferably 50.0% by mass or more of the binder resin, more preferably 60.0% by mass or more, and particularly preferably 70.0% by mass or more.

  The content of the component derived from the crystalline polyester resin is preferably 50.0% by mass or more and 85.0% by mass or less in the binder resin. The component derived from the crystalline polyester resin includes a crystalline polyester resin portion in the block polymer and a crystalline polyester resin added as necessary in addition to the block polymer. When it is 50.0% by mass or more, the low-temperature fixability of the toner is further improved, and when it is 85.0% by mass or less, hot offset is further suppressed. The lower limit of the content of the component derived from the crystalline polyester resin is preferably 60.0% by mass or more, and more preferably 70.0% by mass or more. Moreover, it is preferable that the upper limit of content of the component originating in crystalline polyester resin is 82.5 mass% or less, and it is more preferable that it is 80.0 mass% or less. In addition, it can confirm that resin has crystallinity by showing a clear endothermic peak in the endothermic measurement using a differential scanning calorimeter (DSC).

  A block polymer is a polymer in which polymers are linked by a covalent bond within one molecule. The block polymer is an AB type diblock polymer, an ABA type triblock polymer, a BAB type triblock polymer, an ABAB... Type multiblock polymer of a crystalline polyester resin (A) and an amorphous polyurethane resin (B). Either form may be sufficient. The crystalline polyester resin preferably uses an aliphatic diol having 4 to 20 carbon atoms and an aliphatic dicarboxylic acid as raw materials.

  The aliphatic diol is preferably linear. It is preferable that it is a straight-chain type because the crystallinity of the polyester is easily increased. Examples of the aliphatic diol include the following. In some cases, it is also possible to use a mixture. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among these, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferable from the viewpoint of melting point.

  An aliphatic diol having a double bond can also be used. Examples of the aliphatic diol having a double bond include the following. 2-butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol.

  As the aliphatic dicarboxylic acid, a linear dicarboxylic acid is particularly preferable from the viewpoint of crystallinity. For example, the following can be mentioned. In some cases, it is also possible to use a mixture. Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid. Or the lower (for example, C1-C8) alkylester and acid anhydride of these aromatic dicarboxylic acid. Of these, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, or lower alkyl esters or acid anhydrides thereof are preferred.

  In addition to the aliphatic dicarboxylic acid, an aromatic carboxylic acid may be contained. Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid. Of these, terephthalic acid is preferable because it is easily available and a polymer having a low melting point is easily formed.

  A dicarboxylic acid having a double bond can also be used. A dicarboxylic acid having a double bond can be suitably used to reduce hot offset at the time of fixing, because the entire resin can be crosslinked using the double bond. Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, the lower alkyl ester or acid anhydride of dicarboxylic acid which has these double bonds is also mentioned. Among these, fumaric acid or maleic acid is preferable in terms of cost.

The method for producing the crystalline polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation or transesterification can be performed depending on the type of monomer. Produced separately. The production of the crystalline polyester resin is preferably carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. The reaction system is preferably subjected to a reaction while reducing the pressure in the reaction system and removing water and alcohol generated during condensation. When the monomer is not dissolved or compatible with the reaction temperature, it is preferable to dissolve the monomer by adding a high boiling point solvent as a solubilizing agent. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. When there is a monomer having poor compatibility in the copolymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance, and then polycondense together with the main component. Examples of the catalyst that can be used in the production of the conductive polyester resin include the following. Titanium catalysts such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide; tin catalysts such as dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide.

  The crystalline polyester resin is preferably alcohol-terminated in preparing the block polymer. Therefore, in the preparation of the crystalline polyester resin, the molar ratio of the acid component to the alcohol component (alcohol component / carboxylic acid component) is preferably 1.02 or more and 1.20 or less.

  The amorphous polyurethane resin is a reaction product of a diol and a diisocyanate, and those having various functionalities can be obtained by appropriately adjusting the kind of the diol and the diisocyanate. Examples of the diisocyanate include the following. Aromatic diisocyanates having 6 to 20 carbon atoms, aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and diisocyanates thereof (excluding carbon in the NCO group, the same shall apply hereinafter) Modified product (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, hereinafter also referred to as modified diisocyanate), and two or more of these Mixture of.

  Examples of the aromatic diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), α, α, α ', α'-tetramethylxylylene diisocyanate. Examples of the aliphatic diisocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate. Examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate. Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are MDI and IPDI. And XDI. Moreover, in addition to the above-mentioned diisocyanate, a trifunctional or higher functional isocyanate compound can also be used for the amorphous polyurethane resin.

  Examples of the diol that can be used for the amorphous polyurethane resin include the following. Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol, polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); alkylene oxide (ethylene oxide, propylene oxide) adduct of bisphenols; alkylene oxide (ethylene oxide, propylene oxide) adduct of the alicyclic diol; polyester diol. The alkyl part of the alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

  As a method for preparing the block polymer, there is a method in which a crystalline polyester resin and an amorphous polyurethane resin are prepared separately, and then the alcohol terminal of the crystalline polyester and the isocyanate terminal of the amorphous polyurethane are urethanized. is there. The synthesis can also be performed by mixing and heating a crystalline polyester having an alcohol terminal and a diol and a diisocyanate constituting an amorphous polyurethane. In this case, at the initial stage of the reaction when the concentrations of the diol and the diisocyanate are high, these selectively react to form a polyurethane, and after the molecular weight increases to some extent, the urethane between the isocyanate terminal of the polyurethane and the alcohol terminal of the crystalline polyester. Happens.

  When making the whole quantity of binder resin into a block polymer, it is preferable that a block polymer contains 50.0 mass% or more and 85.0 mass% or less of crystalline polyester resin site | parts (component derived from crystalline polyester resin). When the content of the crystalline polyester resin portion in the block polymer is 50.0% by mass or more, the sharp melt property of the crystalline polyester is easily expressed effectively. More preferably, it is 60.0 mass% or more and 82.5 mass% or less. More preferably, it is 70.0 mass% or more and 80.0 mass% or less.

  The block polymer preferably has a number average molecular weight (Mn) of 8,000 to 30,000 in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) solubles. The block polymer preferably has a weight average molecular weight (Mw) of 15,000 or more and 60,000 or less in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) soluble matter. A more preferable range of Mn is 10,000 or more and 25,000 or less, and a more preferable range of Mw is 20,000 or more and 50,000 or less. Moreover, it is preferable that Mw / Mn is 6 or less. A more preferable range of Mw / Mn is 3 or less. Furthermore, the peak temperature Tm of the maximum endothermic peak measured with a differential scanning calorimeter (DSC) is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 55 ° C. or higher and 75 ° C. or lower.

There is also a method in which a block polymer and another resin are used in combination as a binder resin. Therefore, in addition to the block polymer, the flexural modulus can be arbitrarily controlled by using a polyester resin in combination. The content of the polyester resin is preferably 5.0% by mass or more and 40.0% by mass or less in the binder resin. By setting it in the above range, it becomes easy to satisfy the range of the maximum value E _MAX of the bending elastic modulus E of the toner. A more preferable range is 10.0% by mass or more and 30.0% by mass or less in the binder resin.

As the polyester resin used in combination with the block polymer, either a crystalline polyester resin or an amorphous polyester resin can be used, but it is more preferable to use a crystalline polyester resin. By using the crystalline polyester resin together with the block polymer, it becomes easy to satisfy the range of the maximum value E _MAX of the flexural modulus E of the toner without impairing the low-temperature fixability. As the crystalline polyester resin used in combination with the block polymer, a resin similar to the crystalline polyester resin used for the block polymer can be used.

  The crystalline polyester resin preferably has a number average molecular weight (Mn) of 5,000 or more and 25,000 or less in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) soluble matter. The crystalline polyester resin preferably has a weight average molecular weight (Mw) of 10,000 or more and 50,000 or less in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) soluble matter. A more preferable range of Mn is 8,000 or more and 20,000 or less, and a more preferable range of Mw is 15,000 or more and 40,000 or less. Moreover, it is preferable that Mw / Mn is 6 or less. A more preferable range of Mw / Mn is 3 or less. Furthermore, the peak temperature Tm of the maximum endothermic peak measured with a differential scanning calorimeter (DSC) is preferably 50 ° C. or higher and 85 ° C. or lower, and more preferably 55 ° C. or higher and 80 ° C. or lower.

  As an amorphous polyester resin used in combination with a block polymer, it is preferable to use an aliphatic diol and / or an aromatic diol as an alcohol component. Examples of the aliphatic diol include the following. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Examples of aromatic diols include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Can be mentioned. The following are mentioned as a carboxylic acid component which comprises the amorphous polyester resin used together with a block polymer. An alkyl group having 1 to 20 carbon atoms of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid aromatic dicarboxylic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid or Aliphatic dicarboxylic acids of succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids, and alkyl (1 to 8 carbon atoms) esters of these acids. From the viewpoint of fixability, a trihydric or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound may be contained.

  The method for producing the amorphous polyester is not particularly limited, and may be a known method. For example, a production method in which an alcohol component and a carboxylic acid component are subjected to polycondensation in an inert gas atmosphere at a temperature of 180 ° C. or higher and 250 ° C. or lower using an esterification catalyst as necessary. The amorphous polyester resin preferably has a glass transition temperature (Tg) of 50 ° C. or higher from the viewpoint of heat resistant storage stability. More preferably, the glass transition temperature is 55 ° C. or higher.

  In one preferred embodiment, the toner particles in the toner of the present invention contain a wax. The wax is not particularly limited, and examples thereof include the following.

  Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax Waxes based on fatty acid esters such as aliphatic hydrocarbon ester waxes; and partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax; fatty acids such as behenic monoglyceride A partially esterified product of a monohydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats. Particularly preferably used waxes are aliphatic hydrocarbon waxes and ester waxes. The ester wax used in the present invention is preferably a tri- or higher functional ester wax, more preferably a hexa-functional or higher ester wax. The tri- or higher functional ester wax is an ester of a trivalent or higher alcohol and an aliphatic monocarboxylic acid, or a trivalent or higher ester of a carboxylic acid and an aliphatic monoalcohol. The hexafunctional or higher ester wax is an ester of an alcohol having a valence of 6 or more and an aliphatic monocarboxylic acid, or an ester of a carboxylic acid having a valence of 6 or more and an aliphatic monoalcohol.

  The wax content in the toner is preferably 1.0% by mass or more and 20.0% by mass or less, more preferably 2.0% by mass or more and 15.0% by mass or less.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or higher and 120 ° C. or lower as measured by a differential scanning calorimeter (DSC). More preferably, it is 60 degreeC or more and 90 degrees C or less.

  The toner particles in the toner of the present invention may contain a colorant. Examples of the colorant preferably used in the present invention include organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic powder. In addition, it is possible to use colorants conventionally used in toners. it can.

  Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.

  Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

  Examples of the colorant for cyan include the following. Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are preferably used.

  The colorant used for the toner used in the image forming method of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The colorant is preferably added in an amount of 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin. When magnetic powder is used as the colorant, the amount added is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner in the toner of the present invention may contain a charge control agent in the toner particles as necessary. Further, the toner particles may be externally added. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  Examples of the charge control agent include those that control the toner to be negatively charged. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Examples of controlling the toner to be positively charged include the following. Examples include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds and imidazole compounds.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

  In the toner of the present invention, the toner particles may have a core-shell structure in which a shell phase is formed on the surface of a core containing a binder resin and a colorant, and the shell phase may contain a resin having an organic polysiloxane structure. One of the preferred forms. Thereby, the releasability with respect to a member can be raised and member contamination can be suppressed. The shell phase is desirably formed uniformly and densely on the surface of the core.

  The resin forming the shell phase preferably has an organic polysiloxane structure in the molecule. Among them, a vinyl unit (hereinafter also referred to as a silicone unit) to which an organic polysiloxane structure represented by the following formula (I) is bonded is preferable.

In the above formula ^{(I), R 1, R} 2, and R ³ represents an alkyl group having a straight-chain or branched than 5 or 1 carbon atoms, preferably a methyl group. n is an integer of 3 or more and 200 or less. R ⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group.

  As other vinyl monomers copolymerized with the vinyl monomer having the organic polysiloxane structure, monomers of ordinary resin materials can be used. Examples are given below.

  Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins; alkadienes such as butadiene, isoprene, 1,4- Pentadiene, 1,6-hexadiene and 1,7-octadiene.

  Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene; terpenes such as pinene, limonene, indene.

  Aromatic vinyl hydrocarbons: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl Styrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene; and vinylnaphthalene.

  Carboxyl group-containing vinyl monomers and metal salts thereof: unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (1 to 27 carbon atoms) esters such as acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl Ester, cinnamic acid carboxyl group-containing vinyl monomer.

  Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, vinyl Methoxy acetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl acrylate and alkyl methacrylate having 1 to 11 carbon atoms (linear or branched) (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, 2- Tilhexyl acrylate, 2-ethylhexyl methacrylate, dialkyl fumarate (dialkyl fumarate) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl Maleate (maleic acid dialkyl ester) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), polyallyloxyalkanes (diallyloxyethane) , Triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane), vinyl monomers having a polyalkylene glycol chain (polyethylene glycol (molecular weight 300) monoacrylate, polyethylene glycol ( Molecular weight 300) Monomethacrylate , Polypropylene glycol (molecular weight 500) monoacrylate, polypropylene glycol (molecular weight 500) monomethacrylate, methyl alcohol ethylene oxide (ethylene oxide is hereinafter abbreviated as EO) 10 mol adduct acrylate, methyl alcohol ethylene oxide (ethylene oxide is hereinafter referred to as EO) (Abbreviated) 10 mol adduct methacrylate, lauryl alcohol EO 30 mol adduct acrylate lauryl alcohol EO 30 mol adduct methacrylate), polyacrylates and polymethacrylates (polyacrylates and polymethacrylates of polyhydric alcohols: ethylene glycol diacrylate, ethylene Glycol dimethacrylate, propylene glycol diacrylate, propylene glycol di Methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate. Polyethylene glycol dimethacrylate.

  Furthermore, a vinyl monomer having a crystalline polyester moiety is also preferably used. As a method for producing a vinyl monomer having a crystalline polyester moiety, the crystalline polyester resin and a hydroxyl group-containing vinyl monomer are urethanated with a diisocyanate as a binder. By doing so, the method of introduce | transducing the unsaturated group which can be radically polymerized into a polyester chain, and manufacturing the monomer which has a urethane bond is mentioned. For this reason, the crystalline polyester resin is preferably alcohol-terminated. Therefore, in the preparation of the crystalline polyester resin, the molar ratio of the acid component to the alcohol component (alcohol component / carboxylic acid component) is preferably 1.02 or more and 1.20 or less.

  Hydroxy styrene, N-methylol acrylamide, N-methylol methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, allyl alcohol , Methallyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, An example is sucrose allyl ether. Of these, preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate.

  The method for producing the toner of the present invention is not particularly limited, but toner formation by a dissolution suspension method is preferable. In the dissolution suspension method, a resin solution is prepared by dissolving or dispersing a binder resin and, if necessary, other additives in an organic solvent, and the resin solution is dispersed in a dispersion medium to form liquid particles of the resin solution. In this method, after forming the dispersion, particles are obtained by removing the organic solvent from the dispersion of liquid particles.

  Hereinafter, a dissolution suspension method using carbon dioxide as a dispersion medium will be described. First, a) a binder resin and optionally other additives are mixed with an organic solvent capable of dissolving the binder resin to prepare a resin solution. Next, b) the resin solution is mixed with a dispersion medium containing carbon dioxide in which a dispersant is dispersed to form (granulate) droplets of the resin solution. And c) toner particles are obtained by removing the organic solvent contained in the droplets. The organic solvent can be removed by extracting the organic solvent contained in the granulated droplets into a carbon dioxide phase. Thereafter, the carbon dioxide is separated by releasing the pressure, and the produced toner particles are taken out. The carbon dioxide preferably used in the present invention is liquid or supercritical carbon dioxide.

  Liquid carbon dioxide is a gas-liquid boundary line passing through a triple point (temperature = −57 ° C., pressure = 0.5 MPa) and a critical point (temperature = 31 ° C., pressure = 7.4 MPa) on the phase diagram of carbon dioxide. , The temperature of the part surrounded by the isotherm of the critical temperature, and the solid-liquid boundary line, and carbon dioxide under pressure. Moreover, the carbon dioxide in a supercritical state represents carbon dioxide under temperature and pressure conditions above the critical point of the carbon dioxide.

  Further, the organic solvent capable of dissolving the binder resin is not particularly limited as long as it can dissolve the binder resin. However, when a solution having a binder resin content of 30% by mass is prepared, the organic solvent is visually insoluble. Solvents with no are preferred. Specific examples include the following. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and di-n-butyl ketone; ester solvents such as ethyl acetate, butyl acetate and methoxybutyl acetate; ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve and butyl cellosolve An amide solvent such as dimethylformamide or dimethylacetamide; an aromatic hydrocarbon solvent such as toluene, xylene or ethylbenzene;

  The dispersion medium containing carbon dioxide may contain an organic solvent as another component. In this case, it is preferable that carbon dioxide and the organic solvent form a homogeneous phase.

  Hereinafter, a method for producing toner particles using carbon dioxide as a dispersion medium will be described as an example.

  First, in the organic solvent that can dissolve the binder resin, add the binder resin and other additives such as a colorant and wax as necessary, such as a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser. It is dissolved or dispersed uniformly by an appropriate disperser. Next, the resin solution thus obtained is dispersed in a dispersion medium containing carbon dioxide to form droplets. At this time, a dispersing agent is dispersed in carbon dioxide as a dispersion medium. As the dispersant, any of a resin fine particle dispersant, an inorganic fine particle dispersant, and a mixture thereof may be used, and two or more kinds may be used in combination according to the purpose. When the resin fine particles are used as a dispersant, the resin fine particles adsorbed on the surface of the droplets remain as they are after the toner particles are formed, so that a shell phase of the toner particles can be formed.

  Therefore, it is preferable to use the resin that forms the shell layer described above as the resin fine particle dispersant. In addition, vinyl resin, urethane resin, epoxy resin, ester resin, polyamide, polyimide, silicone resin, fluorine resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, aniline resin, ionomer resin, polycarbonate, cellulose and these Mixtures can be used.

  The particle diameter of the resin fine particle dispersant is preferably 30 nm or more and 300 nm or less in terms of number average particle diameter. More preferably, it is 50 nm or more and 200 nm or less.

  Further, the blending amount of the resin fine particle dispersant is preferably 1.0 part by mass or more and 35.0 parts by mass or less based on the solid content in the resin solution used for forming the droplet, and the stability of the droplet Or can be adjusted appropriately according to the desired particle size.

  Examples of the inorganic fine particle dispersant include fine particles such as silica fine particles, alumina fine particles, titania fine particles, and composite oxide fine particles thereof. Silica fine particles are preferable. A sol-gel method is preferable as a method for producing silica fine particles.

  The inorganic fine particle dispersant is preferably used by hydrophobizing and controlling the degree of hydrophobicity. By controlling the degree of hydrophobicity, the inorganic fine particles are likely to be positioned at the interface between the droplet and the hydrophobic dispersion medium, and the dispersion stability of the droplet is easily improved. Examples of the hydrophobizing agent include chlorosilane compounds, alkoxysilane compounds, silazane compounds, silicone oils, siloxanes, fatty acids, and metal salts thereof. Among these, alkoxysilanes, silazanes, and straight silicone oils are preferably used because they can be easily subjected to a hydrophobic treatment. Such hydrophobizing agents can be used alone or in admixture of two or more.

  In the toner production method, any method may be used as a method of dispersing the dispersant in a dispersion medium containing carbon dioxide. As a specific example, there is a method in which the dispersant and carbon dioxide are charged in a container and directly dispersed by stirring or ultrasonic irradiation. Moreover, the method which introduce | transduces the dispersion liquid which disperse | distributed the said dispersing agent in the organic solvent to the container charged with carbon dioxide using a high pressure pump is mentioned.

  In the present invention, any method may be used as a method of dispersing the resin solution in a dispersion medium containing carbon dioxide. As a specific example, there is a method of introducing the resin solution into a container containing carbon dioxide in which the dispersant is dispersed, using a high-pressure pump. Further, carbon dioxide in which the dispersant is dispersed may be introduced into a container charged with the resin solution.

  In the method for producing a toner of the present invention, the dispersion medium containing carbon dioxide is preferably a single phase. When granulating by dispersing the resin solution in carbon dioxide, part of the organic solvent in the droplets moves into the dispersion medium. At this time, if the carbon dioxide phase and the organic solvent phase exist in a separated state, the stability of the droplets is likely to be impaired. Therefore, the temperature and pressure of the dispersion medium and the amount of the resin solution with respect to carbon dioxide are preferably adjusted within a range in which carbon dioxide and the organic solvent can form a homogeneous phase.

  Further, regarding the temperature and pressure of the dispersion medium, it is preferable to consider the granulation properties (ease of forming droplets) and the solubility of the constituent components in the resin solution in the dispersion medium. The temperature of the dispersion medium is preferably in the temperature range of 10 ° C. or higher and 40 ° C. or lower. Moreover, the pressure in the container forming the dispersion medium is preferably 2.0 MPa or more and 20.0 MPa or less, and more preferably 2.0 MPa or more and 15.0 MPa or less. The pressure can be controlled by the amount of carbon dioxide introduced.

  After the granulation step is completed in this way, in the solvent removal step, the organic solvent remaining in the droplets is removed through a dispersion medium containing carbon dioxide. Specifically, a dispersion medium containing carbon dioxide is further mixed with a dispersion medium in which droplets are dispersed, and the remaining organic solvent is extracted into a carbon dioxide phase, and carbon dioxide containing the organic solvent is further extracted. It is preferable to carry out by substituting with carbon dioxide. In the mixing of the dispersion medium and carbon dioxide, carbon dioxide having a higher pressure may be added to the dispersion medium, and the dispersion medium may be added to carbon dioxide having a lower pressure.

  And as a method of further substituting carbon dioxide containing an organic solvent with carbon dioxide, there is a method of circulating carbon dioxide while keeping the pressure in the container constant. At this time, it is preferable to perform the above substitution while capturing the formed toner particles with a filter.

  If the carbon dioxide is not sufficiently substituted and the organic solvent remains in the dispersion medium, the organic solvent dissolved in the dispersion medium is condensed when the container is decompressed in order to recover the obtained toner particles. As a result, the toner particles may be redissolved or the toner particles may coalesce. Therefore, the replacement with carbon dioxide is preferably performed until the organic solvent is completely removed. The amount of carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, and still more preferably 1 to 30 times the volume of the dispersion medium.

  When depressurizing the container and taking out the toner particles from the dispersion medium containing carbon dioxide in which the toner particles are dispersed, the container may be depressurized to normal temperature and normal pressure at once, but by providing multiple pressure-controlled containers in multiple stages. The pressure may be reduced stepwise. The decompression speed is preferably set within a range where the toner particles do not foam. Note that the organic solvent and carbon dioxide used in the present invention can be recycled.

  In the toner used in the image forming method of the present invention, an inorganic fine powder may be further externally added to the obtained toner particles to form a toner. In the inorganic fine powder, the number average particle diameter of primary particles is preferably 1 nm or more and 200 nm or less, and more preferably 5 nm or more and 150 nm or less. Examples of the inorganic fine powder include fine powder such as silica fine powder, titania fine powder, alumina fine powder, and double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder or titania fine powder is preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside of the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride, titanium chloride or the like together with a silicon halogen compound in the production process.

  Moreover, it is more preferable to use the inorganic fine powder hydrophobized from the viewpoint of improving developability and transferability. As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium Compounds. Silicone oil is preferred. More preferably, the inorganic fine powder is treated with silicone oil at the same time or after the hydrophobic treatment of the inorganic fine powder with a coupling agent. These treatment agents may be used alone or in combination.

  The addition amount of the inorganic fine powder is preferably 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner particles. More preferably, it is 0.2 to 3.5 parts by mass.

From the viewpoint of fixability, the toner of the present invention has a loss elastic modulus G ″ (80) at 80 ° C. of 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁶ Pa or less in measuring the viscoelasticity of the toner. When the loss elastic modulus G ″ (80) is 1.0 × 10 ⁴ Pa or more, the viscosity of the toner does not become too low, and the hot offset resistance is good. On the other hand, when the loss elastic modulus G ″ (80) is 1.0 × 10 ⁶ Pa or less, the low-temperature fixability is improved. Preferably, the loss elastic modulus G ″ (80) at 80 ° C. is 2.0 × 10 ^4. It is Pa or more and 8.0 * 10 < ⁵ > Pa or less, More preferably, it is 3.0 * 10 < ⁴ > Pa or more and 7.0 * 10 < ⁵ > Pa or less.

  The toner particles of the present invention preferably have a weight average particle diameter (D4) of 3.0 μm or more and 8.0 μm or less. More preferably, it is 5.0 μm or more and 7.0 μm or less.

  The toner of the present invention preferably has a number average molecular weight (Mn) of 8,000 or more and 30,000 or less in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) soluble matter. Further, the toner of the present invention preferably has a weight average molecular weight (Mw) of 15,000 or more and 60,000 or less in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) soluble matter. By setting it within this range, it is possible to impart an appropriate viscoelasticity to the toner. A more preferable range of Mn is 10,000 to 25,000, and a more preferable range of Mw is 20,000 to 50,000. Further, Mw / Mn is preferably 6 or less. A more preferable range of Mw / Mn is 3 or less.

  Measurement methods for various physical properties of the toner and toner material of the present invention will be described below.

<Method of measuring loss elastic modulus of toner>
Measurement is performed using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific). The outline of the measurement is described in ARES operation manuals 902-30004 (August 1997 version) and 902-00153 (July 1993 version) published by Rheometrics Scientific, Inc., and is as follows.
・ Measurement jig: torsion rectangular
Measurement sample: A rectangular parallelepiped sample having a width of about 12 mm, a height of about 20 mm, and a thickness of about 2.5 mm is prepared from toner particles using a pressure molding machine (maintain 15 kN for 1 minute at room temperature). The pressure molding machine uses a 100 kN press NT-100H manufactured by NPa Systems.

As shown in FIG. 3, the jig and the sample are left at room temperature (23 ° C.) for 1 hour, and then the sample is attached to the jig. As shown in FIG. 3, the measurement unit is fixed so that the width is about 12 mm, the thickness is about 2.5 mm, and the height is 5 mm. The temperature is adjusted over 10 minutes to the measurement start temperature of 30.00 ° C., and then measured with the following settings.
・ Measurement frequency: 6.28 radians / second ・ Measurement distortion setting: initial value is set to 0.1% and measurement is performed in automatic measurement mode ・ Sample extension correction: adjustment in automatic measurement mode ・ Measurement temperature : Temperature rise from 30 ° C to 150 ° C at a rate of 2 ° C / min. Measurement interval: Viscoelasticity data is measured every 30 seconds, ie every 1 ° C. RSI Orchestrator (control, data) operating on Microsoft Windows 2000 Data collection and analysis software) (Rheometrics Scientific) through the interface.

  Of the measured data, the value of the loss elastic modulus of the toner at 80 ° C. is read.

<Measurement method of maximum bending stress, flexural modulus, strain energy u>
-Preparation of Toner Sample The toner is weighed in a mold having a length (l) of 30.0 mm and a width (w) of 13.0 mm so that the thickness after molding is 4.0 mm or more. The toner put in the mold is put into an oven and left at a temperature of 150 ° C. for 2 hours to melt the toner. Turn off the power, let it cool naturally for 12 hours, and remove it after confirming that the temperature in the oven is at room temperature. The molded toner is cut out so that the thickness (t) is 4.0 mm and used as a toner sample.
-Measurement of three-point bending test The three-point bending test of the toner sample prepared above is performed as follows. For the three-point bending test, an electric measuring stand (MX2-500N) manufactured by Imada Co., Ltd. and DIGITAL FORCE GAUGE (ZP-500N) are used. The measurement is performed at a temperature of 25 ° C.

  FIG. 1A shows a schematic diagram of a three-point bending test. The radius of the indenter in FIG. 1A is 5.0 mm, the radius of the support base is 5.0 mm, and the distance between supporting points (L) is 15.0 mm.

  The surface of the toner sample cut out on the left and right support bases is the indenter side, and the original uncut surface is the support base side, so that the center of the toner sample in the longitudinal direction and the center of the fulcrum are aligned. Put it on. A force is applied to the central portion of the toner sample in the longitudinal direction with an indenter.

The moving speed of the indenter is set to 2.0 mm / min, and a load F (N) applied to the indenter and a displacement amount (hereinafter also referred to as deflection) s (mm) are measured. The measurement was performed from a displacement amount s of 0 mm to a maximum of 20.0 mm, and the load F _MAX (N) until breaking was recorded in increments of 0.1 seconds. If the fulcrum breaks into three parts other than the central part, the result is not adopted and a new test is performed.

The load-deflection curve obtained by the measurement is as shown in FIG. 1B, and the maximum bending stress, bending elastic modulus, and strain energy are obtained by calculation from the following equations.
Maximum bending stress σ _MAX (MPa);
σ _MAX = (3 × F _MAX × L) / (2 × w × t ² ) (1)
Flexural modulus E (MPa);
E = L ³ / (4 × w × t ³ ) × (ΔF / Δs) (2)
Strain energy per unit volume u (MPa);
u = σ _MAX ² / (2 × E _MAX ) (3)
(ΔF / Δs) is the slope of the load-deflection curve obtained by measurement, and ΔF (N) is the amount of change in load between any two points selected so that the amount of change in deflection Δs is 0.2 mm. Represents. In the measurement of the present invention, the value of the bending elastic modulus E is measured by obtaining all the values of the load change ΔF in the range where Δs is 0.2 mm starting from each recorded point, and the maximum value E _MAX ( MPa).

  In the measurement of the present invention, 10 tests are performed, and a 95% confidence interval is calculated from the standard deviation of the average value by the method prescribed in ISO2062. We extracted the data within the confidence interval and adopted the average value.

<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)>
The molecular weight (Mn, Mw) of the crystalline polyester resin, block polymer, and toner in tetrahydrofuran (THF) is measured by GPC as follows.

First, a sample is dissolved in THF at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) are used.

<Method for measuring number average particle diameter of primary particles of resin fine particles>
The number average particle size of the primary particles of the resin fine particles is observed using a scanning electron microscope S4700 (manufactured by Hitachi, Ltd.), the particle size of 100 particles is measured, and the average value is the number average particle size of the primary particles. The diameter.

<Measurement method of particle diameter of colorant particles and wax particles>
The particle diameters of the colorant particles and the wax particles are measured using a Microtrac particle size distribution measuring apparatus HRA (X-100) (manufactured by Nikkiso Co., Ltd.), with a range setting of 0.001 μm to 10 μm, and a volume average particle diameter (μm Or nm). In addition, water was selected as a dilution solvent.

<Measuring method of melting point of crystalline polyester, block polymer, and wax>
Melting | fusing point of crystalline polyester, block polymer, and wax was measured on condition of the following using DSC Q1000 (made by TA Instruments).
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 200 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in a silver pan, and measured using an empty silver pan as a reference. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 20 ° C., and then heated again. In the case of crystalline polyester and block polymer, the peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 20 ° C. to 200 ° C. is defined as the melting point of the crystalline polyester and block polymer in the first temperature raising process. In the case of wax, the peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 20 ° C. to 200 ° C. is set as the melting point of the wax in the second temperature raising process.

<Measurement method of weight average particle diameter (D4) and number average particle diameter (D1) of toner particles>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner particles are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman・ Set the value obtained using Coulter). By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker (1) installed in the sample stand, the electrolyte solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. The measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4), and the graph / volume in the dedicated software is graph / When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement method of brush hair average diameter>
The measurement of the average diameter of the bristle was performed using a photograph of the fixed charged brush bristle magnified 500 to 1000 times with an electron microscope FE-SEM (S-4700, manufactured by Hitachi, Ltd.). The diameter of 12 fixed charging brush hairs was arbitrarily measured on the enlarged photograph, and the average value of 10 hairs excluding the maximum value and the minimum value was determined as the average long diameter of the hair of the fixed charging brush.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Synthesis of Crystalline Polyester Resin 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Sebacic acid 124.1 parts by mass-1,6-hexanediol 75.9 parts by mass-Dibutyltin oxide 0.1 parts by mass

  After replacing the interior of the system with nitrogen by depressurization, the mixture was stirred at 180 ° C. for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing the stirring, and was further maintained for 2 hours. Crystalline polyester resin 1 was synthesized by air cooling when it was in a viscous state and stopping the reaction. The melting point of the crystalline polyester resin 1 was 68 ° C., Mn was 6200, and Mw was 15500.

<Synthesis of crystalline polyester resins 2 to 4>
Crystalline polyester resins 2 to 4 were obtained by changing the materials and blending amounts shown in Table 1 from the synthesis of the crystalline polyester resin 1. Table 1 shows the physical properties of the obtained crystalline polyester resins 2 to 4.

<Synthesis of Amorphous Polyester Resin 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Bisphenol A propylene oxide 1 mol adduct (BPA-PO 30.0 parts by mass-Bisphenol A ethylene oxide 1 mol adduct (BPA-EO) 34.0 parts by mass-Terephthalic acid 30.0 parts by mass-Fumaric acid 6 .0 parts by mass / dibutyltin oxide 0.1 parts by mass

  After the inside of the system was purged with nitrogen by depressurization, the mixture was stirred at 215 ° C. for 5 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing the stirring, and the reaction was further continued for 5 hours. The amorphous polyester resin 1 was obtained by air-cooling when it became a viscous state and stopping reaction. Amorphous polyester resin 1 had Mn of 2200, Mw of 9800, and a glass transition temperature Tg of 60 ° C.

<Synthesis of styrene acrylic resin 1>
To a 2-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, and a stirrer, 500.0 parts by mass of xylene was added, and the temperature was raised to xylene reflux temperature (about 138 ° C.).

  485.0 parts by mass of styrene and 15.0 parts by mass of butyl acrylate were added, and 50.0 parts by mass of di-t-butyl peroxide as a reaction initiator was dropped into the reaction flask over 5 hours. The reaction was further continued for 1 hour, then the temperature was lowered to 98 ° C., 2.5 parts by mass of t-butyl peroxyoctoate was added, and the reaction was carried out for 2 hours. The obtained polymerization solution was heated to 90 ° C., and the solvent was removed under reduced pressure of 8.0 kPa or less for 1 hour to obtain a styrene acrylic resin 1. The obtained styrene acrylic resin 1 had Mn of 2000, Mw of 7000, and a glass transition temperature Tg of 60 ° C.

<Synthesis of block polymer 1>
Crystalline polyester resin 1 225.0 parts by mass Diphenylmethane diisocyanate (MDI) 41.3 parts by mass Bisphenol A ethylene oxide 2 mol adduct (BPA-2EO) 33.8 parts by mass Tetrahydrofuran (THF) 300.0 Parts by mass

  The above was charged into a reaction vessel equipped with a stirrer and a thermometer while purging with nitrogen. After heating to 50 ° C. and performing a urethanization reaction over 15 hours, 3.0 parts of t-butyl alcohol was added to modify the isocyanate terminal. The solvent, THF, was distilled off to obtain block polymer 1. Table 2 shows the melting point, Mn, and Mw of the block polymer 1.

<Synthesis of block polymers 2-13>
From synthesis of block polymer 1, block polymers 2 to 13 were obtained by changing the materials and addition amounts shown in Table 2. Table 2 shows the melting points, Mn, and Mw of the obtained block polymers 2 to 13.

* 1) MDI represents diphenylmethane diisocyanate, IPDI represents isophorone diisocyanate, and XDI represents xylylene diisocyanate.
* 2) BPA-PO represents a 1 mol adduct of bisphenol A with propylene oxide, BPA-2EO represents an adduct of 2 mol of ethylene oxide with bisphenol A, and CHDM represents cyclohexanedimethanol.

  The amount of the crystalline polyester resin component indicates the content ratio of the crystalline polyester component in the block polymer.

<Synthesis of block polymer 14>
In a 4-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, and a stirrer, 500.0 parts by mass of crystalline polyester 1 and 7.2 parts by mass of maleic anhydride are placed and reacted at 150 ° C. for 2 hours. To give a maleic acid adduct. Next, 500.0 parts by mass of xylene, 490.0 parts by mass of styrene, and 10.0 parts by mass of methacrylic acid were added. After the temperature was raised to 85 ° C., 3.0 parts by mass of t-butyl peroxyoctoate was added. The reaction was performed for 4 hours. Furthermore, 1.0 part by mass of t-butyl peroxyoctoate was added, reacted for 2 hours, and this was repeated three times to obtain block polymer 14. The melting point of the block polymer 14 was 60 ° C., Mn was 20000, and Mw was 70000.

<Preparation of binder resin solution 1>
Into a beaker equipped with a stirrer, 100.0 parts by mass of acetone and 100.0 parts by mass of block polymer 1 were charged, and stirring was continued until the solution was completely dissolved at a temperature of 40 ° C. to prepare a binder resin solution 1.

<Synthesis of Binder Resin Solutions 2-15>
In the preparation of the binder resin solution 1, the binder resin solutions 2 to 15 were obtained by changing the materials and addition amounts shown in Table 3.

<Synthesis of vinyl-modified polyester monomer>
In a reaction vessel with a stir bar and thermometer set,
-Xylylene diisocyanate (XDI) 59.0 parts by mass was charged, 41.0 parts by mass of 2-hydroxyethyl methacrylate was added dropwise, and reacted at 55 ° C for 4 hours to obtain a vinyl-modified monomer intermediate.

Next, in a reaction vessel equipped with a stirring bar and a thermometer,
-Crystalline polyester 4 83.0 parts by mass-THF 100.0 parts by mass were charged and dissolved at 50 ° C. Thereafter, 10.0 parts by mass of the vinyl-modified monomer intermediate was dropped and reacted at 50 ° C. for 4 hours to obtain a vinyl-modified polyester monomer solution. The solvent, THF, was distilled off to obtain a vinyl-modified polyester monomer.

<Preparation of resin fine particle dispersion 1>
Vinyl modified organopolysiloxane (X-22-2475: molecular weight = 420, manufactured by Shin-Etsu Chemical Co., Ltd.) 15.0 parts by mass

-Vinyl-modified polyester monomer 40.0 parts by mass-Styrene (St) 35.0 parts by mass-Methacrylic acid (MAA) 10.0 parts by mass-Azobismethoxydimethylvaleronitrile 0.3 parts by mass-THF 50.0 Parts by mass

  The above was charged into a beaker, stirred and mixed at 20 ° C. to prepare a monomer solution, which was introduced into a dropping funnel previously heated and dried. Separately from this, 100 parts by mass of THF was charged into a heat-dried two-necked flask. After substituting with nitrogen, a dropping funnel was attached, and the monomer solution was added dropwise at 70 ° C. over 1 hour in a sealed state. Stirring was continued for 3 hours from the end of dropping, a mixture of 0.3 parts by mass of azobismethoxydimethylvaleronitrile and 20.0 parts by mass of THF was added again, and the mixture was stirred at 70 ° C. for 3 hours to obtain a reaction mixture. .

  Subsequently, the reaction mixture is T.W. K. A resin fine particle dispersion was obtained by dropwise addition over 10 minutes into 400.0 parts by mass of acetone adjusted to 20 ° C. while stirring at 5000 rpm with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Acetone was added to prepare a solid content concentration of 20.0% by mass to obtain resin fine particle dispersion 1. A part of the obtained resin fine particle dispersion 1 was dried, and the number average diameter of primary particles was measured using a scanning microscope. The number average particle diameter of the primary particles was 110 nm.

<Preparation of resin fine particle dispersion 2>
In a two-necked flask equipped with a dropping funnel and dried by heating, 870.0 parts by mass of normal hexane was charged. In a separate beaker, 42.0 parts by mass of normal hexane, 52.0 parts by mass of behenyl acrylate (an acrylate of an alcohol having a linear alkyl group with 22 carbon atoms), and 0.3 parts by mass of azobismethoxydimethylvaleronitrile are charged. The monomer solution was prepared by stirring and mixing at 20 ° C. and introduced into the dropping funnel. After the reaction vessel was purged with nitrogen, the monomer solution was added dropwise over one hour at 40 ° C. in a sealed state. Stirring was continued for 3 hours after the completion of dropping, and a mixture of 0.3 parts by mass of azobismethoxydimethylvaleronitrile and 42.0 parts by mass of normal hexane was added again, followed by stirring at 40 ° C. for 3 hours. Then, it cooled to room temperature and obtained the resin fine particle dispersion 2 with a volume average particle diameter of 200 nm and solid content of 20.0 mass%.

<Preparation of Colorant Dispersion 1>
・ C. I. Pigment Blue 15: 3 100.0 parts by mass, acetone 150.0 parts by mass, glass beads (1 mm) 300.0 parts by mass The above materials are put into a heat-resistant glass container, and a paint shaker (manufactured by Toyo Seiki) for 5 hours. Dispersion was performed, glass beads were removed with a nylon mesh, and a colorant dispersion 1 having a volume average particle size of 200 nm and a solid content of 40.0% by mass was obtained.

<Preparation of wax dispersion 1>
Dipentaerythritol behenate wax 16.0 parts by weight Wax dispersant (in the presence of 15.0 parts by weight of polyethylene, 50.0 parts by weight of styrene, 25.0 parts by weight of n-butyl acrylate, 10.0 parts by weight of acrylonitrile) Copolymer having a peak molecular weight of 8,500 obtained by graft copolymerization) 8.0 parts by mass / acetone 76.0 parts by mass The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the inside of the system was 70. Dipentaerythritol behenate wax was dissolved in acetone by heating to ° C. Then, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.

  This solution is put into a heat-resistant container together with 20.0 parts by weight of 1 mm glass beads, dispersed for 3 hours with a paint shaker, and a wax dispersion having a volume average particle size of 270 nm and a solid content of 16.0% by weight. 1 was obtained.

<Manufacture of toner 1>
(Manufacturing process of toner particles (before treatment) 1)
In the apparatus shown in FIG. 2, first, the valves V1 and V2 and the pressure adjustment valve V3 are closed, and the resin fine particle dispersion 1 is put in a pressure resistant granulation tank T1 having a filter and a stirring mechanism for capturing toner particles. 35.0 parts by mass were charged, and the internal temperature was adjusted to 25 ° C. Next, the valve V1 is opened, carbon dioxide (purity 99.99%) is introduced into the granulation tank T1 from the carbon dioxide cylinder B1 using the pump P1, and the valve V1 is closed when the internal pressure reaches 3.0 MPa. It was.

Charge resin solution tank T2 with 180.0 parts by weight of binder resin solution 1 31.3 parts by weight of wax dispersion 1 12.5 parts by weight of colorant dispersion 1 31.2 parts by weight of acetone, and adjust the internal temperature. Adjusted to 25 ° C.

  Next, the valve V2 is opened and the contents of the resin solution tank T2 are introduced into the granulation tank T1 using the pump P2 while stirring the inside of the granulation tank T1 at 1000 rpm. V2 was closed. After the introduction, the internal pressure of the granulation tank T1 was 5.0 MPa. The mass of the total carbon dioxide introduced was 280.0 parts by mass as measured using a mass flow meter.

  After the introduction of the contents of the resin solution tank T2 to the granulation tank T1, granulation was performed by further stirring for 10 minutes at a temperature of 25 ° C. and 2000 rpm.

  Next, the valve V1 was opened, and carbon dioxide was introduced into the granulation tank T1 from the carbon dioxide cylinder B1 using the pump P1. At this time, the pressure regulating valve V3 was set to 10.0 MPa, and carbon dioxide was further circulated while maintaining the internal pressure of the granulation tank T1 at 10.0 MPa. By this operation, carbon dioxide containing the organic solvent (mainly acetone) extracted from the granulated droplets was discharged to the solvent recovery tank T3, and the organic solvent and carbon dioxide were separated.

  The introduction of carbon dioxide into the granulation tank T1 was stopped when it reached 15 times the mass of carbon dioxide initially introduced into the granulation tank T1. At this point, the operation of replacing carbon dioxide containing the solvent with carbon dioxide containing no solvent was completed.

  Further, the pressure regulating valve V3 was opened little by little, and the internal pressure of the granulation tank T1 was reduced to atmospheric pressure, whereby the toner particles (before treatment) 1 captured by the filter were collected. The obtained toner particles (before treatment) 1 were subjected to DSC measurement, and the peak temperature (Tm) of the maximum endothermic peak derived from the binder resin was determined.

(Annealing process)
The annealing treatment was performed using a constant temperature dryer (Satake Chemical 41-S5). The internal temperature of the constant temperature dryer was adjusted to 50 ° C.

  The toner particles (before treatment) 1 were spread evenly in a stainless steel vat, placed in the constant temperature dryer, allowed to stand for 5 hours, and then taken out. Thus, annealed toner particles (after treatment) 1 were obtained. The obtained toner particles (after treatment) 1 were subjected to DSC measurement, and the peak temperature (melting point Tm) of the maximum endothermic peak derived from the binder resin was determined to be 63 ° C.

(Preparation process of toner 1)
1.8 parts by mass of hydrophobic silica fine powder treated with hexamethyldisilazane (number average diameter of primary particles: 7 nm), 10% by mass of toner particles (after treatment) 1, rutile type titanium oxide Toner 1 was obtained by dry-mixing 0.15 parts by mass of fine powder (number average diameter of primary particles: 30 nm) with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) for 5 minutes.

The toner 1 was subjected to a three-point bending test by the method described above. Table 5 shows the maximum value E _MAX of the flexural modulus E and the value of strain energy u per unit volume obtained from the obtained load-deflection curve.

  The toner 1 was measured for viscoelasticity by the method described above. The loss elastic modulus at 80 ° C. of toner 1 is shown in Table 5.

The toner 1 had a volume average particle diameter D4 of 5.7 μm and a number average particle diameter D1 of 4.8 μm. Further, the amount of the crystalline polyester resin component in the binder resin was calculated from the total amount of the additive, and was 75.0% by mass.
<Manufacture of toners 2-15>
The binder resin solution 1 and the resin fine particle dispersion 1 in the production process of the toner particles (before treatment) 1 are selected as shown in Table 4, and the annealing conditions are the same as those in the production of the toner 1 except that the conditions shown in Table 4 are used. And toners 2 to 15 were obtained.

Table 5 shows the maximum value E _MAX of the bending elastic modulus E of the toners 2 to 15, the strain energy u per unit volume, the loss elastic modulus at 80 ° C., the particle size, and the amount of the crystalline polyester resin component in the binder resin. The amount of the crystalline polyester resin component in the binder resin was calculated from the amount of the crystalline polyester resin component in the block polymer and the added crystalline polyester resin.

<Manufacture of Toner 16>
A toner 16 was obtained in the same manner as in the production of the toner 1 except that the resin fine particle dispersion 1 in the production process of the toner particles (before treatment) 1 was changed to the resin fine particle dispersion 2.

Table 5 shows the maximum value E _MAX of the bending elastic modulus E of the toner 16, the strain energy u per unit volume, the loss elastic modulus viscoelasticity at 80 ° C., the particle diameter, and the amount of the crystalline polyester resin component in the binder resin. The amount of the crystalline polyester resin component in the binder resin was calculated from the amount of the crystalline polyester resin component in the block polymer.

<Manufacture of toner 17>
Toner 17 was prepared by the following method.
Block polymer 14 50.0 parts by mass Styrene acrylic resin 1 50.0 parts by mass Pigment Blue 15: 3 5.0 parts by mass Dipentaerythritol behenate wax 5.0 parts by mass Wax dispersant (the above wax (Wax dispersant described in preparation of dispersion 1) 2.5 parts by mass

  After mixing the materials of the above-mentioned prescription with a Mitsui Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-45 type, Ikekai Tekko Co., Ltd.) set at a temperature of 140 ° C. Kneaded). The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely pulverized toner was pulverized using a collision-type airflow pulverizer using high-pressure gas. Next, the finely pulverized product obtained was finely and coarsely finely simultaneously removed with a multi-division classifier to obtain toner particles (before treatment) 17.

(Annealing process)
The annealing treatment was performed using a constant temperature dryer (Satake Chemical 41-S5). The internal temperature of the constant temperature dryer was adjusted to 50 ° C. The toner particles (before treatment) 17 were spread evenly in a stainless steel vat, placed in the constant temperature dryer, allowed to stand for 5 hours, and then taken out. Thus, annealed toner particles (after treatment) 17 were obtained.

  For 100.0 parts by mass of the toner particles (after treatment) 17, 1.8 parts by mass of hydrophobic silica fine powder treated with hexamethyldisilazane (number average diameter of primary particles: 7 nm), rutile titanium oxide Toner 17 was obtained by dry-mixing 0.15 parts by mass of fine powder (number average diameter of primary particles: 30 nm) with a Mitsui Henschel mixer for 5 minutes.

Table 5 shows the maximum value E _MAX of the bending elastic modulus E of the toner 17, the strain energy u per unit volume, the loss elastic modulus at 80 ° C., the particle diameter, and the amount of the crystalline polyester resin component in the binder resin. The amount of the crystalline polyester resin component in the binder resin was calculated from the amount of the crystalline polyester resin component in the block polymer.

<Evaluation of toner>
The obtained toners 1 to 17 were evaluated based on the following methods. The evaluation results are shown in Table 6.

<Evaluation of heat-resistant storage stability>
10 g of the toner to be evaluated was put in a 100 ml polycup and allowed to stand in a 53 ° C. environment for 3 days, and then the state of the powder was visually evaluated.

(Evaluation criteria)
A: No agglomerates are confirmed, and the state is almost the same as in the initial stage.
B: Although it seems to be agglomerated, it is in a state where it collapses by shaking the polycup lightly 5 times, and there is no particular problem.
C: Although it is agglomerated, it is in a state where it can be easily loosened when loosened with a finger.
D: Many aggregations are generated.
E: Solidified.

<Low temperature fixability>
Canon printer LBP5300 was used to evaluate low-temperature fixability. As the evaluation cartridge, the toner contained in a commercially available cartridge was extracted, the inside was cleaned by air blow, and a cartridge filled with the toner to be evaluated was used. The cartridge was allowed to stand in a normal temperature and humidity environment (23 ° C., 60% RH) for 24 hours, then mounted on the cyan station of LBP5300, and a dummy cartridge was mounted on the other stations. Next, an unfixed toner image on rough paper (Xerox 4025: 75 g / m ² ) in a single color mode, a solid image having a front end margin of 5 mm, a width of 100 mm, and a length of 28 mm (toner applied amount per unit area of 0.6 mg / cm 2) ² ) was formed.

  The fixing test was performed using a fixing unit which was removed from the color laser printer and modified so that the fixing temperature could be adjusted. The specific evaluation method is as follows.

Under a normal temperature and humidity environment (23 ° C., 60% RH), the process speed was set to 220 mm / s, the fixing temperature was set to 100 ° C., and the unfixed image was fixed. When the obtained fixed image was subjected to 10 reciprocating rubbing with sylbon paper applied with a load of 14.7 kPa (150 g / cm ² ), a density reduction rate ΔD (%) before and after rubbing represented by the following formula was calculated. It was used as an index of fixability. The image density was evaluated using a reflection densitometer (500 Series Spectrodensitometer) manufactured by X-rite. In the present invention, it was determined that A rank to C rank have good image fixability.

ΔD (%) = {(image density before rubbing−image density after rubbing) / image density before rubbing} × 100
A: ΔD is less than 3.0%.
B: ΔD is 3.0% or more and less than 5.0%.
C: ΔD is 5.0% or more and less than 8.0%.
D: ΔD is 8.0% or more and less than 10.0%.
E: ΔD is 10.0% or more.

<Evaluation of hot offset resistance>
From the evaluation of the low-temperature fixability, the paper was changed to plain paper A4 paper (“Office Planner”: 64 g / m ² , manufactured by Canon) to form a similar solid image, and the hot offset resistance was evaluated. . The fixing temperature was evaluated from 140 ° C. to 180 ° C. every 5 ° C. In the fixed image, the temperature at which hot offset was visually observed was determined as the hot offset start temperature, and the maximum temperature lower than the hot offset start temperature was determined as the high temperature fixing temperature. Incidentally, for those in which hot offset did not occur until the fixing temperature was 180 ° C., the high temperature fixing temperature was 180 ° C. In the present invention, it was judged that A rank to C rank have good fixing property at high temperature.
A: The high temperature fixing temperature is 180 ° C. or higher.
B: The high temperature fixing temperature is 170 ° C. or higher and lower than 180 ° C.
C: The high temperature fixing temperature is 160 ° C. or higher and lower than 170 ° C.
D: The high temperature fixing temperature is 150 ° C. or higher and lower than 160 ° C.
E: The high temperature fixing temperature is less than 150 ° C.

<Evaluation of increase in fine powder>
Evaluation was carried out using a commercially available Canon printer LBP9200C. The LBP 9200C employs one-component contact development and regulates the amount of toner on the developing carrier by a toner regulating member. As the evaluation cartridge, the toner contained in a commercially available cartridge was taken out, the inside was cleaned by air blow, and a cartridge filled with 260 g of the toner to be evaluated was used. The cartridge was installed in the cyan station, and evaluation was performed by installing dummy cartridges in the other stations. Under a high-temperature and high-humidity environment of 30 ° C. and 80% RH, 50,000 sheets of images with a printing rate of 2% were output continuously while supplying toner every 10,000 sheets.

  The amount of toner fine powder was measured using a flow type particle image analyzer “FPIA-3100” (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.

  As a specific measurement method, an appropriate amount of a surfactant, preferably sodium dodecylbenzenesulfonate, is added as a dispersant to 20 ml of ion-exchanged water. Thereafter, 0.02 g of a measurement sample is added, and a dispersion process is performed for 2 minutes using a tabletop ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W. To obtain a dispersion for measurement. In that case, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. The binarization threshold at the time of particle analysis was set to 85%, and the analysis particle size was determined as the fine powder amount by determining the frequency% of the number particle size of the equivalent circle diameter of 0.60 μm to 1.98 μm.

The toner in the cartridge at the time of 50,000 sheets was sampled and the amount of fine powder was evaluated.
A: The amount of fine powder is less than 3.0% by number.
B: The amount of fine powder is 3.0% by number or more and less than 5.0% by number.
C: The amount of fine powder is 5.0% by number or more and less than 10.0% by number.
D: The amount of fine powder is 10.0% by number or more and less than 15.0% by number.
E: The amount of fine powder is 15.0% by number or more.

<Examples 1 to 13 and Comparative Examples 1 to 4>
Using toners 1 to 17 and under the conditions of the image forming method according to the first aspect below, the fog on the photoconductor, the fine powder amount of the fixed charging brush, the fine powder accumulation amount of the fixed brush, the toner packing property of the fixed brush, the intermediate transfer A body cleaning test was conducted. The conditions and results are shown in Table 7.

<Examples 14 to 21>
Using toner 1, the conditions of the image forming method according to the following first aspect are changed, and the same fogging on the drum, fine powder amount of the fixed charging brush, fine powder accumulation amount of the fixed brush, toner packing of the fixed brush as described above And intermediate transfer member cleaning properties were tested. The conditions and results are shown in Table 7.

As an image forming apparatus, a commercially available laser printer CLJ-3700 (manufactured by HP) is used, and it is used in a low temperature and low humidity environment (15 ° C., 10% RH) and a high temperature and high humidity environment (30 ° C., 80% RH). went. The cleaning blade and the waste toner box installed on the intermediate transfer belt were removed, and a fixed charging brush and a charging roller were attached instead. In FIG. 4, the charging brush and the charging roller are in contact with the intermediate transfer belt where the cleaning blade is normally disposed. The fixed charging brush uses a brush member made of conductive fibers in the form according to the first aspect of the present invention. The fixed charging brush has a resistance value controlled by adding carbon to the fiber of rayon. In this embodiment, the diameter is 30 μm, 1.55 × 10 ⁸ pieces / m ² (100,000 pieces / inch ² ), the length of the bristle is 5 mm, and the resistance of the brush is 8.1 × 10 ⁷ Ω · cm. did. The fixed charging brush was brought into contact with the intermediate transfer belt so as to have an intrusion amount of 1 mm, and the width of the contact nip portion was 5 mm.

The charging roller has a three-layer structure in which a lower layer, an intermediate layer, and a surface layer are laminated around a core bar (support member). The lower layer is a foamed sponge layer, and the intermediate layer is a resistance layer for obtaining uniform resistance as the entire charging roller. The surface layer is a protective layer provided to prevent leakage even if there are defects such as pinholes. The charging roller of the present embodiment uses a stainless steel round bar having a diameter of 6 mm as a core metal, carbon is dispersed in a fluororesin as a surface layer, the outer diameter as a roller is 14 mm, and the roller resistance is 10 ⁴ Ω to 10 ^7. Ω.

(Change process cartridge)
A modified process cartridge of CLC-3700 was used as a process cartridge having a charging process, a toner layer regulating process, and a developing process. In the toner layer regulation step, the toner regulation member for regulating the toner layer and the toner carrier were attached so that the contact pressure was 30.0 N / m. Further, the toner carrier was modified so that the peripheral speed was 350 mm / s.

  The evaluation cartridge used was a cartridge filled with 260 g of toner to be evaluated after the toner contained in the cartridge was removed and the inside was cleaned by air blow. The cartridge was installed in the cyan station, and evaluation was performed by installing dummy cartridges in the other stations.

  In a high-temperature and high-humidity environment of 30 ° C. and 80% RH, an image having a printing rate of 1% was continuously output 50000 sheets while changing to a cartridge filled with toner every 5000 sheets.

<Method for measuring fog on photoconductor>
After passing 5000 sheets, a white image is output, and the image evaluation apparatus is stopped halfway through. The fog toner transferred onto the photosensitive drum is collected with an adhesive tape of a transparent substrate, and this sample tape and an unused adhesive tape to which nothing is attached as a reference tape are affixed on a white paper. Each reflectance is measured, and the reflectance of the sample tape is subtracted from the reflectance of the reference tape to obtain the fog density. The reflectance is measured with TC-6DS manufactured by Tokyo Denshoku.
A: Less than 0.7%, excellent in suppression of fog B: 0.7 or more, less than 1.2%, good suppression of fog C: 1.2 or more, less than 1.5% D: 1.5 or more, Less than 2.0%, fog suppression is slightly inferior E: 2.0% or more, fog suppression is inferior

(Evaluation of toner packing of fixed charging brush)
The fixed charging brush after passing 50,000 sheets is removed, and the state of the fixed charging brush is observed visually and with an electron microscope.
A: No toner fused to the fixed charging brush.
B: Some toner fusion is observed with an electron microscope, but there is no visual adhesion.
C: Although toner fusion is visually observed on the fixed charging brush, there is no problem in use due to the fluidity of the toner inside the fixed charging brush.
D: The toner is observed to be fused to the fixed charging brush by visual observation, and the fluidity of the toner inside the fixed charging brush is lowered.
E: The toner is fused to the fixed charging brush and the toner has no fluidity.

(Evaluation of increase in fine powder of fixed charging brush)
The amount of toner fine powder in the initial cartridge and the increase in the amount of fine powder in the fixed charging brush when 50,000 sheets were passed were evaluated.

  A sample for measuring the amount of fine powder of toner in the initial cartridge was prepared as follows. Remove the toner from the unused cartridge and use it as measurement data. A suitable amount of a surfactant, preferably sodium dodecylbenzenesulfonate, was added as a dispersant to 20 ml of ion-exchanged water. Thereafter, 0.02 g of a measurement sample is added, and a dispersion process is performed for 2 minutes using a tabletop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervo Crea)) having an oscillation frequency of 50 kHz and an electric output of 150 W. To obtain a dispersion for measurement. In that case, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.

  The sample for measuring the amount of fine powder in the fixed charging brush after passing 50,000 sheets was prepared as follows. Remove the fixed charging brush after 50,000 paper passes. A suitable amount of a surfactant, preferably sodium dodecylbenzenesulfonate, was added as a dispersant to 20 ml of ion-exchanged water. Thereafter, a part of the fixed charging brush that has been removed is put in the solution, and a dispersion process is performed for 2 minutes using a desktop ultrasonic cleaner disperser (“VS-150”) having an oscillation frequency of 50 kHz and an electric output of 150 W. The toner in the fixed charging brush was dispersed in the solution. Thereafter, the fixed charging brush was removed to obtain a dispersion for measurement. In that case, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.

  The amount of toner fine powder was measured using a flow type particle image analyzer “FPIA-3100” (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.

The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer. In the HPF measurement mode, 3000 toner particles are measured in the total count mode, the binarization threshold at the time of particle analysis is set to 85%, and the analysis particle diameter is a number with an equivalent circle diameter of 0.60 μm to 1.98 μm. The frequency% of the particle diameter was determined and used as the fine powder amount. Table 7 shows the increase in the amount of fine powder in the fixed charging brush from the fine amount of toner in the initial cartridge at the time of 50,000 sheets.
A: The amount of increase in fine powder is less than 3.0% by number.
B: The amount of increase in fine powder is 3.0% by number or more and less than 5.0% by number.
C: The amount of increase in fine powder is 5.0% by number or more and less than 10.0% by number.
D: The amount of increase in fine powder is 10.0% by number or more and less than 15.0% by number.
E: The increase amount of fine powder is 15.0% by number or more.

(Machinability of intermediate transfer belt)
The scraping property of the intermediate transfer belt was evaluated based on the following evaluation criteria by visually observing the surface of the intermediate transfer belt and further observing image defects.
A: No defects are recognized at all on the surface of the intermediate transfer belt and the image.
B: Slight scratches are observed on the surface of the intermediate transfer belt in the latter half of 50,000 sheets passing, but they do not appear in the image.
C: Some scratches are observed on the surface of the intermediate transfer belt in the latter half of 50,000 sheets passing, and some streaks appear in the halftone image.
D: There are scratches on the surface of the intermediate transfer belt in the latter half of the time when 50,000 sheets are passed, and the stripe-like unevenness occurs in the halftone image.

(Cleanability of intermediate transfer belt)
The cleaning property of the intermediate transfer belt was evaluated based on the following evaluation criteria by visually observing the surface of the intermediate transfer belt and further observing image defects.
A: No defects are recognized at all on the surface of the intermediate transfer belt and the image.
B: Slight dirt is observed on the surface of the intermediate transfer belt in the latter half of 50,000 sheets passing, but it does not appear in the image.
C: Some dirt is observed on the surface of the intermediate transfer belt in the latter half of 50,000 sheets passing, and some dirt is generated on the image.
D: In the latter half of 50,000 sheets passing, the surface of the intermediate transfer belt is very dirty, and the image is stained.

<Examples 31 to 40 and Comparative Examples 11 to 14>
The toners 1 to 5, 8 to 15, and 17 were used and evaluated under the conditions of the image forming method according to the following second aspect. First, an example of manufacturing a toner carrier used in the image forming method according to the second aspect will be described.

<Toner carrier production example 1>
The elastic layer was formed as follows.
100.0 parts of polydimethylsiloxane having vinyl ends,
Pipe-shaped gold in which 10.0 parts of carbon black and 100.0 parts of polydimethylsiloxane having silicon-bonded hydrogen atoms are kneaded with a roll until uniformly dispersed, and an axial core body coated with an adhesive is set This mixed material was injected into the mold. After that, this mold was sandwiched between hot plates at 120 ° C. for 30 minutes, crosslinked at 200 kg / cm ² , cooled and then removed from the pipe mold, and then at 200 ° C. for 4 hours in a hot air drying furnace Cured to obtain an elastic roller. In addition, as the shaft core body, a SUS rod having a surface subjected to electroless nickel plating with a thickness of 2 μm was used.

  A resin layer was formed as follows. To a methyl ethyl ketone solution prepared by adjusting the urethane resin solid content to 4.0% by mass (NCO / OH = 1.0), 15.0 parts of carbon black is stirred and dispersed with respect to 100.0 parts of the resin component. A working liquid (liquid viscosity 20 m · pa · s) was obtained. The elastic body roller obtained above was immersed in this solution, then pulled up and dried to apply the coating solution. Next, heat treatment was performed at 160 ° C. for 2 hours to obtain a toner carrier 1 in which a conductive resin layer was provided on the outer periphery of the elastic layer. The MD-1 hardness of the obtained toner carrier was allowed to stand in an environment of normal temperature and humidity (23 ° C., 55% RH) for 5 hours using a micro rubber hardness meter MD-1 type, Type A (manufactured by Polymer Design Co., Ltd.). With respect to the toner carrier thus obtained, the vicinity of the central portion was measured over five points, and the average value was obtained. Table 8 shows the physical properties of Toner Carrier 1 thus obtained.

<Toner carrier production examples 2 to 7>
In the toner carrier production example 1, toner carriers 2 to 7 were obtained in the same manner as in the toner carrier production example 1 except that the solid content of the urethane resin was changed as shown in Table 8. Table 8 shows the physical properties of Toner Carriers 2 to 7 obtained.

<Durability evaluation>
Using toners 1 to 5, 8 to 15, and 17 and using the image forming method according to the second aspect, image evaluation was performed according to the following method.

  The toner is a non-magnetic one-component developer, and the developer is used in a high temperature and high humidity condition (temperature 30 ° C., humidity 80% RH) and in a normal temperature and normal humidity environment (temperature 23 ° C., humidity 50% RH). Image evaluation was performed under the conditions (temperature 15 ° C., humidity 10% RH). An image forming apparatus that has performed image evaluation will be described below.

As the image forming apparatus, HP Color LaserJet CP6015dn (manufactured by Hewlett-Packard) was used. For the evaluation cartridge, the toner contained in the cartridge is extracted, the inside is cleaned by air blow, the conditions (a) to (b) below are changed or modified, and 120 g of the toner to be evaluated is filled. used.
(A) The process cartridge was mounted so that the contact pressure between the toner layer regulating member and the toner carrier was 35.0 N / m, and the peripheral speed of the toner carrier was changed to 550 mm / sec.
(B) The process cartridge was modified so as not to detect the service life. The supply cartridge was filled with 400 g. The evaluation cartridge and the replenishment cartridge were installed in the cyan station, and dummy cartridges were installed in the other stations.

  Under a high-temperature and high-humidity environment of 30 ° C. and 80% RH, an image having a printing rate of 1% was continuously output 60000 sheets while changing to a replenishing cartridge filled with 400 g of toner every 5000 sheets. The image evaluation shown below was performed after the output. The evaluation results are shown in Table 9.

(Development stripe)
Initially, after outputting 60,000 sheets, an HT image (toner loading: 0.6 mg / cm ² ) is printed on transfer paper (75 g / m ² , A4 size paper), and evaluated by the number of development lines did.
A: Not generated or 1 or less B: 2 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, or a line having a width of 0.5 mm or more

(Filming)
After outputting 60,000 sheets, the toner carrier was removed and the toner was blown off with air. Then, tap the toner carrier with a mending tape (manufactured by Sumitomo 3M), peel off the fused material, measure using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth), and use the value of the unused mending tape. Evaluation was made using the subtracted value (%).
A: 0.00% or more, less than 0.03% B: 0.03% or more, less than 0.06% C: 0.06% or more, less than 0.09% D: 0.09% or more

(Image density)
Initially, after the output of 60,000 sheets, evaluation was made based on the image density of the solid portion. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00. As a transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: 1.40 or more B: 1.35 or more, less than 1.40 C: 1.25 or more, less than 1.35 D: less than 1.25

(Fog)
The reflectance (%) of the non-image portion of the printout image is measured with “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using a numerical value (%) subtracted from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. The smaller the numerical value, the more image fog is suppressed. As the transfer material, LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used.
A: Less than 0.5 B: 0.5 or more, less than 1.0 C: 1.0 or more, less than 3.0 D: 3.0 or more

(gross)
The gloss value of a solid image (toner loading: 0.6 mg / cm ² ) at a fixing temperature of 170 ° C. was measured using PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.).
A: Gloss 30 or more and less than 40 B: Gloss 20 or more and less than 30 C: Gloss 15 or more and less than 20 D: Gloss 15 or less

<Examples 41 to 50 and Comparative Examples 15 and 16>
In the evaluation cartridge of the image forming apparatus, the type of the toner carrier, the contact pressure between the toner layer regulating member and the surface of the toner carrier, and the peripheral speed of the toner carrier are changed, and the toner 1 is used. Evaluation was performed. The conditions and results are shown in Table 9.

<Examples 61 to 83 and Comparative Examples 21 to 23>
Using the toner 1, 4, 5, 8 to 15, 17, the toner carrier 1 and toner supply members 1 to 5 described later, a developing device for evaluation was produced under the conditions shown in Table 11.

<Manufacture of Toner Supply Member 1>
Each component was mixed by mechanical stirring with the composition of urethane foam raw materials shown in Table 10 and the isocyanate index (NCO / OH).

  This mixture was poured into a pipe mold having an inner diameter of 16 mm into which a metal shaft having a diameter of 5 mm and a length of 290 mm was inserted, and foamed and cured by heating in a 60 ° C. oven for 30 minutes. Thereafter, the toner supply member 1 was produced by removing the mold.

  The polyether polyol B in Table 10 is obtained by block addition of propylene oxide and ethylene oxide at the chain end to glycerin. Polyether polyol B has a functional group number of 3, an ethylene oxide unit content of 15 mol%, a weight average molecular weight of 5000, a hydroxyl value of 34 mgKOH, and a total unsaturation of 0.025 (milli equivalent / g). Have ethylene oxide units.

  Polyether polyol C is EP505S (trade name of polyether polyol, manufactured by Mitsui Chemicals, Inc.), an ethylene oxide-propylene oxide random copolymer having 70 to 80 mol% of ethylene oxide units, and has a weight average molecular weight of 3000, The hydroxyl value is 50 mg KOH / g.

  The physical properties of the produced toner supply member 1 were measured by the following methods. Table 10 shows the physical properties of the obtained toner supply member.

<Load at 1 mm compression (hardness)>
As shown in FIGS. 11A and 11B, the toner supply member 12 is supported by the cored bar 15 at both ends thereof. And when the surface layer 16 made of the polyurethane foam is pressed at a speed of 10 mm / min with a jig 17 having a plate-like pressing surface of length 50 mm (roller longitudinal direction) × width 10 mm (thickness 10 mm). This is expressed as a load (g) when compressed by 1 mm. The larger the value is, the harder the surface layer 16 made of polyurethane foam is. Further, as shown in the figure, measurement was performed at three measurement points in the axial direction and four measurement points in each axial direction at 90 degrees in the circumferential direction, and the average value was shown.

<Density>
The volume of the urethane foam of the toner supply member was calculated, and the mass of the urethane foam of the toner supply member was measured to determine the density.

<Manufacture of toner supply members 2 to 5>
Except for changing the toner isocyanate index (NCO / OH) as shown in Table 10, toner supply members 2 to 5 were manufactured in the same manner as in the manufacture of the toner supply member 1. Table 10 shows the physical properties of the toner supply members 2 to 5.

<Evaluation of developing device>
In accordance with the image forming method according to the following third embodiment, a developing device for evaluation was produced and evaluated.

As an image forming apparatus, a Canon printer LBP5800 was used. In the developing device for evaluation, the toner was extracted from the cartridge for LBP5800, and the inside was cleaned by air blow. Thereafter, the toner carrier 1 and the toner supply member to be evaluated were attached, the conditions (a) to (d) below were changed or modified, and 200 g of the toner to be evaluated was filled. Table 11 shows the types of toner and toner supply member.
(A) The image forming apparatus was changed so that the contact pressure between the toner layer regulating member and the toner carrier was 20.0 N / m, and the peripheral speed of the toner carrier was 550 mm / sec.
(B) The image forming apparatus was modified so as not to detect the life of the process cartridge.
(C) The drive unit of the toner carrier 1 and the toner supply member is improved so that the surfaces of the contact portions move in opposite directions. Further, the toner carrier 1 and the toner supply member drive unit are modified so that the peripheral speed Vd of the toner carrier 1 surface, the peripheral speed Vs of the toner supply member surface, and the peripheral speed ratio Vs / of the toner carrier 1 and the toner supply member. Vd was set to the conditions shown in Table 11. However, in Comparative Example 21, the driving unit of the toner carrier 1 and the toner supply member was improved, and the surfaces of the abutting portions were set to move in the forward direction.
(D) The voltage applied to the toner supply member is set to -50V, the voltage applied to the toner carrier is set to -400V, and the voltage applied to the toner layer regulating member is set to -500V. However, no voltage is applied in Example 83 and Comparative Example 21.

  A developing device for evaluation was attached to the cyan station of LBP5800, and dummy cartridges were attached to the other stations. Under high temperature and high humidity conditions (temperature 30 ° C., humidity 80% RH), 60,000 sheets of images with a printing rate of 1% were output continuously. The image evaluation shown below was performed after the output. The evaluation results are shown in Table 11.

(Development stripe)
After the output of 60000 sheets, a monochrome halftone image was output on transfer paper (XEROX, 75 g / m ² , A4 size paper), and evaluated by the number of development stripes on the image.
A: Not generated or 1 or less B: 2 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, or a line having a width of 0.5 mm or more

(Filming)
After outputting 60000 sheets, the toner carrier was removed and the toner was blown off with air. Then, tap the toner carrier with a mending tape (manufactured by Sumitomo 3M), peel off the fused material, measure using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth), and use the value of the unused mending tape. Evaluation was made using the subtracted value (%).
A: 0.00% or more, less than 0.03% B: 0.03% or more, less than 0.06% C: 0.06% or more, less than 0.09% D: 0.09% or more

(concentration)
After outputting 60000 sheets, a solid black image with a 100% printing ratio of a single color was output on transfer paper (manufactured by XEROX, 75 g / m ² , A4 size paper), and evaluation was performed based on the image density of the solid black portion. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co.) to measure the relative density with respect to the output image of the white background portion where the document density was 0.00. As a transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: 1.40 or more B: 1.35 or more, less than 1.40 C: 1.25 or more, less than 1.35 D: less than 1.25

(Fog)
After outputting 60000 sheets, a solid white image with a single color 0% printing ratio is output on transfer paper (XEROX, 75 g / m ² , A4 size paper), and “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.) ), The reflectance (%) of the non-image portion of the output image is measured. The obtained reflectance was evaluated using a numerical value (%) subtracted from the reflectance (%) of unused transfer paper measured in the same manner. The smaller the numerical value, the more image fog is suppressed.
A: Less than 0.5 B: 0.5 or more, less than 1.0 C: 1.0 or more, less than 3.0 D: 3.0 or more

(Image density uniformity)
After outputting 60000 sheets, a solid black image with a single color 100% printing ratio was output on transfer paper (XEROX, 75 g / m ² , A4 size paper). And the density difference in the light and shade part on the image in the solid image was determined using “Macbeth reflection densitometer RD918” (manufactured by Macbeth) according to the following criteria.
A: 0.10 or more B: 0.10 or more, less than 0.15 C: 0.15 or more, less than 0.20 D: 0.20 or more

T1 granulation tank T2 resin solution tank T3 solvent recovery tank B1 carbon dioxide cylinder P1, P2 pump V1, V2 valve V3 pressure adjustment valve

Claims (20)

A charging step of charging the image bearing member with a charging means;
Exposing the charged image carrier to form an electrostatic latent image;
A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier;
A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier;
A primary transfer step for primary transfer of the toner image onto an intermediate transfer member;
A composite toner image forming step in which the steps from the charging step to the primary transfer step are performed for each color, and a composite toner image is formed by superimposing a plurality of toner images formed for each color on the intermediate transfer member;
A secondary transfer step for secondary transfer of the composite toner image to a transfer material;
A fixing process for fixing the composite toner image that has been secondarily transferred onto a transfer material to obtain a fixed toner image, and a fixed charging brush for the transfer residual toner remaining on the intermediate transfer body after the second transfer process. The transfer residual toner to which the charge is applied is reversely transferred from the intermediate transfer member onto the image carrier, and the reverse transfer residual toner is provided opposite to the image carrier. A process of collecting with a cleaning device,
An image forming method comprising:
The loss elastic modulus at 80 ° C. of the toner is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁶ Pa or less,
The distance between the fulcrums (L) of the toner sample formed by melting the toner and forming the length (l) 30.0 mm, the width (w) 13.0 mm, and the thickness (t) 4.0 mm is 15.0 mm. In the three-point bending test,
The maximum bending stress of the toner sample obtained by the following formula (1) from the maximum load F _MAX (N) measured at a temperature of 25 ° C. is σ _MAX (MPa),
When the maximum value of the bending elastic modulus E of the toner sample obtained from the slope (ΔF / Δs) of the load-deflection curve by the following equation (2) is E _MAX (MPa),
An image forming method, wherein a strain energy u per unit volume calculated from the values of σ _MAX and E _MAX by the following formula (3) is 0.20 MPa or more.
σMAX = (3 × F _MAX × L) / (2 × w × t ² ) (1)
E = L ³ / (4 × w × t ³ ) × (ΔF / Δs) (2)
u = σ _MAX ² / (2 × E _MAX ) (3)
(ΔF (N) represents the amount of change in load between any two points selected so that the amount of change in deflection Δs is 0.2 mm.) The stationary charging brush is non-rotating;
The hair density of the fixed charging brush is 1 × 10 ⁶ or more and 1 × 10 ⁹ or less (lines / m ² ),
The image forming method according to claim 1, wherein an average bristle diameter of the fixed charging brush is 5 μm or more and 200 μm or less.   The image forming method according to claim 1, wherein a contact pressure between the toner layer regulating member and the surface of the toner carrying member is 10.0 N / m or more and 50.0 N / m or less.   The image forming method according to any one of claims 1 to 3, wherein a peripheral speed of the toner carrier is 200 mm / s or more and 450 mm / s or less. A charging step of charging the image bearing member with a charging means;
Exposing the charged image carrier to form an electrostatic latent image;
A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier;
A development step of forming a toner image on the electrostatic latent image with toner on the toner carrier, and a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member;
An image forming method comprising:
MD-1 hardness of the toner carrier is 35 or more and 65 or less,
The loss elastic modulus at 80 ° C. of the toner is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁶ Pa or less,
The distance between the fulcrums (L) of the toner sample formed by melting the toner and forming the length (l) 30.0 mm, the width (w) 13.0 mm, and the thickness (t) 4.0 mm is 15.0 mm. In the three-point bending test,
The maximum bending stress of the toner sample obtained by the following formula (1) from the maximum load F _MAX (N) measured at a temperature of 25 ° C. is σ _MAX (MPa),
When the maximum value of the bending elastic modulus E of the toner sample obtained from the slope (ΔF / Δs) of the load-deflection curve by the following equation (2) is E _MAX (MPa),
An image forming method, wherein a strain energy u per unit volume calculated from the values of σ _MAX and E _MAX by the following formula (3) is 0.20 MPa or more.
σ _MAX = (3 × F _MAX × L) / (2 × w × t ² ) (1)
E = L ³ / (4 × w × t ³ ) × (ΔF / Δs) (2)
u = σ _MAX ² / (2 × E _MAX ) (3)
(ΔF (N) represents the amount of change in load between any two points selected so that the amount of change in deflection Δs is 0.2 mm.)   The image forming method according to claim 5, wherein the toner carrier has an MD-1 hardness of 40 or more and 60 or less.   The image forming method according to claim 5 or 6, wherein a contact pressure between the toner layer regulating member and the surface of the toner carrying member is 10.0 N / m or more and 50.0 N / m or less.   The image forming method according to claim 5, wherein a peripheral speed of the toner carrier is 300 mm / s or more and 600 mm / s or less. A charging step of charging the image bearing member with a charging means;
Exposing the charged image carrier to form an electrostatic latent image;
A toner layer regulating step of regulating the toner on the toner carrier with a toner layer regulating member abutted on the toner carrier;
A developing step of forming a toner image on the electrostatic latent image with toner on the toner carrier; and
A transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member;
An image forming method comprising:
A toner supply member for supplying the toner contacts the toner carrier,
The toner carrier and the toner supply member are arranged such that the surfaces of the toner carrier and the toner supply member rotate in opposite directions at the abutting portions.
The distance between the fulcrums (L) of the toner sample formed by melting the toner and forming the length (l) 30.0 mm, the width (w) 13.0 mm, and the thickness (t) 4.0 mm is 15.0 mm. In the three-point bending test,
The maximum bending stress of the toner sample obtained by the following formula (1) from the maximum load F _MAX (N) measured at a temperature of 25 ° C. is σ _MAX (MPa),
When the maximum value of the bending elastic modulus E of the toner sample obtained from the slope (ΔF / Δs) of the load-deflection curve by the following equation (2) is E _MAX (MPa),
An image forming method, wherein a strain energy u per unit volume calculated from the values of σ _MAX and E _MAX by the following formula (3) is 0.20 MPa or more.
σ _MAX = (3 × F _MAX × L) / (2 × w × t ² ) (1)
E = L ³ / (4 × w × t ³ ) × (ΔF / Δs) (2)
u = σ _MAX ² / (2 × E _MAX ) (3)
(ΔF (N) represents the amount of change in load between any two points selected so that the amount of change in deflection Δs is 0.2 mm.)   10. The image forming method according to claim 9, wherein a ratio Vs / Vd between a peripheral speed Vs of the toner supply member and a peripheral speed Vd of the toner carrier is 0.50 or more and 3.00 or less.   The image forming method according to claim 9 or 10, wherein a peripheral speed of the surface of the toner carrier is 300 mm / s or more.   The image forming method according to claim 9, wherein an electric field is formed between the toner supply member and the toner carrier.   The image forming method according to claim 9, wherein an electric field is formed between the toner layer regulating member and the toner carrier. The toner supply member is a toner supply member having a cored bar and a roller-shaped surface layer made of a foamed elastic body formed on the outer periphery of the cored bar,
The image forming method according to any one of claims 9 to 13, wherein a load when the toner supply member is compressed by 1 mm is 200 g or more and 400 g or less. The image forming method according to claim 1, wherein the toner sample has an E _MAX of 100 MPa or more and 650 MPa or less. The image forming method according to claim 15, wherein the toner sample has an E _MAX of 200 MPa to 450 MPa.   The image forming method according to claim 1, wherein the toner has toner particles containing a binder resin containing a crystalline polyester resin.   The image forming method according to claim 17, wherein the binder resin contains a block polymer in which a crystalline polyester resin portion and an amorphous polyurethane resin portion are chemically bonded.   The image forming method according to claim 17 or 18, wherein the binder resin contains 50.0% by mass or more and 85.0% by mass or less of a component derived from the crystalline polyester resin. The toner is a toner having toner particles having a core-shell structure in which a shell phase is formed on the surface of the core;
The image forming method according to claim 1, wherein the shell phase contains a resin having an organic polysiloxane structure.

Images