JP2010217619A - Image forming apparatus and electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which hardly causes oozing-out of wax to a toner surface due to agitation of a developer, does not increase an attachment force between toner and carrier, and suppresses defective drawing-up thereof and a void image, and also to provide an image forming apparatus using the toner. <P>SOLUTION: A two-component developer for electrostatic charge image development including a carrier composed of toner prepared by aqueous granulation and a magnetic particle is characterized in that, with respect to the wax amount on toner surface before and after agitation when agitating the developer made by mixing the toner and carrier at toner concentration of 9% with a magnet roller for 90 min, a change amount of FTIR-ATR measurement falls into the following range: (1) P(A)≤0.20, (2) 0.03≤P(B)≤0.25, (3) P(A)≤P(B), therein, P(A) is surface wax amount [peak(2850 cm<SP>-1</SP>) originated from wax/peak(828 cm<SP>-1</SP>) originated from binder resin] before vacant agitation for 90 min with a magnet roller, and P(B)is surface wax amount after vacant agitation for 90 min with the magnet roller. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used as a developer and an image forming apparatus using the toner when developing an electrostatic image formed by electrophotography, electrostatic recording, or the like.

The image forming apparatus includes a charging step for uniformly charging an image forming area on the surface of the image carrier, an exposure step for writing on the image carrier, a development step for forming an image with toner that is frictionally charged on the image carrier, The image is fixed on the printing paper after a transfer process in which the image on the image carrier is transferred directly to the printing paper or indirectly via an intermediate transfer body. Further, the untransferred toner remaining without being transferred onto the image carrier is scraped off from the image carrier by the cleaning process, and enters the next image forming process.
As the developer used, there are a two-component developer composed of a toner and a carrier, and a one-component developer composed of only a magnetic or non-magnetic toner. The production of these toners is generally a kneading and pulverizing method in which a resin, a pigment, a charge control agent, and a release agent are melt-kneaded, cooled and then pulverized and classified, but the particle size and shape are not uniform. It is difficult to control.
Under such circumstances, recently, there has been an attempt to control the particle size of toner particles intentionally to solve the above-mentioned problems, and polymerized toner methods such as emulsion polymerization method and dissolution suspension method as aqueous granulation. Became popular.

  In recent years, there has been an increasing demand for higher image quality, and in particular, in order to realize high-definition images in color image formation, there has also been an increasing demand for toner diameter reduction and particle size uniformity. When an image is formed using a toner having a wide particle size distribution, the problem that fine powder toner contaminates the developing roller, charging roller, charging blade, photoconductor, carrier, etc., and toner scattering increases, resulting in high image quality. And it was difficult to achieve high reliability at the same time. On the other hand, when the particle size is uniform and the particle size distribution is sharp, the development behavior of the individual toner particles is uniform, and the reproducibility of minute dots is greatly improved.

Recently, many copiers are also provided with a printer function, and the output of only one copy or print has increased, and the developer agitation time has increased with respect to the number of copies and prints. . In the developing device, the stirring of the developer greatly affects the deterioration of the developer. The developer is pumped up to the developing roller, and the carrier and the toner are rubbed at the doctor portion. As a result, the temperature of the developer rises, and the toner component locally adheres to the carrier. In the oilless toner, wax is dispersed in order to ensure fixing releasability. When a thermal stress or pressure stress is applied to the developer, the wax comes out on the toner surface, the wax becomes excessive, and the wax adheres to the carrier surface. As a result, when the toner polarity is negative, the same negative polarity wax adheres to the carrier, thereby reducing the charge amount of the developer.
Furthermore, the toner on which the wax is excessively deposited on the surface is kept in contact with the carrier, thereby increasing the non-electrostatic adhesion between the toner and the carrier and making it difficult for the toner to be separated from the carrier. An image may be generated, or image density unevenness may occur due to poor pumping.

Therefore, for example, in Patent Document 1, it has been studied to solve the above-mentioned problem by defining the amount of wax existing in the initial surface layer of toner (hereinafter referred to as surface wax amount). Among these, the value defining the amount of the wax existing in the depth region from the surface of the toner particles to 0.3 μm is a peak derived from the wax obtained by FTIR-ATR (total reflection absorption infrared spectroscopy) method. A method is known in which the intensity ratio with the peak derived from the binder resin is defined as a range of 0.01 to 0.40. However, this only prescribes the initial surface wax amount of the toner, and does not consider the temperature rise and stress due to stirring with the carrier, so the amount of wax deposited on the surface due to toner deterioration There is no mention of the resulting deterioration.
In Patent Document 2, the amount of surface wax before and after heating is defined in consideration of the temperature rise of the toner. However, even in the present invention, no consideration has been given to the exudation of wax from the toner surface due to contact with the carrier, and there is a concern that the quality problem cannot be solved reliably.
Further, regarding the seepage of the wax to the toner particle surface during fixing, the toner described in Patent Documents 1 and 2 is not subjected to the surface treatment as in the present invention. According to Patent Documents 1 and 2, “exudation of wax to the toner particle surface by agitation” has not been known in the past, and the “agitation of wax by agitation” is also not considered. It cannot be said that it has been publicly known at least what influence the degree of “bleeding to the toner particle surface” can be washed in the image forming process.

The subject of this invention is as follows.
That is, the present invention provides a toner that suppresses poor pumping and white-out images, does not increase the adhesion between the toner and the carrier, and does not increase the adhesion between the toner and the carrier due to the stirring of the developer, and image formation using the toner. An object is to provide an apparatus.

The above problems are solved by (1) to (17) of the present invention.
(1) A two-component developer for developing an electrostatic image comprising a toner prepared by aqueous granulation and a carrier comprising magnetic particles,
Regarding the toner surface wax amount before and after stirring when the developer in which the toner and the carrier are mixed at a toner concentration of 9% is stirred with a mag roll for 90 minutes, the amount of change in the FTIR-ATR measured value is within the following range. A two-component developer characterized by being.
P (A) ≦ 0.20 (1)
0.03 ≦ P (B) ≦ 0.25 (2)
P (A) ≦ P (B) (3)
(P (A); amount of surface wax before air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]).
P (B): Amount of surface wax after air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]).
(2) The toner includes at least a binder resin, a colorant, a release agent, and a modified layered inorganic mineral. The modified layered inorganic mineral has at least a part of interlayer ions in the layered inorganic mineral modified with organic ions. The two-component developer as described in (1) above, wherein
(3) The toner contains at least an organic solvent containing a binder resin, a prepolymer made of a modified polyester resin, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and interlayer ions in a layered inorganic mineral. A modified layered inorganic mineral that is at least partially modified with organic ions is dissolved or dispersed to prepare a solution or dispersion, and the solution or dispersion is emulsified or dispersed in an aqueous medium, and then a crosslinking reaction or elongation reaction. The two-component developer as described in (2) above, which is obtained by removing the solvent from the dispersion obtained.
(4) The toner according to (3), wherein the modified layered inorganic mineral is contained in an amount of 0.05 mass% to 10 mass% in a solid content in a solution or dispersion. The two-component developer according to item).
(5) The toner has a small particle size silica adhered thereto, and the BET specific surface area of the small particle size silica is in the range of 50 [m ² / g] to 400 [m ² / g]. The two-component developer according to any one of (1) to (4), wherein the average circularity A is in the range of 0.94 ≦ A ≦ 0.99.
(6) The volume average particle diameter of the toner is 3 [μm] to 8 [μm], and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00. The two-component developer according to any one of (1) to (5), which is in a range of ˜1.30.
(7) The two-component developer according to any one of (1) to (6), wherein the toner has a particle size of 2 [μm] or less of 1 [number%] to 10 [number%].
(8) a developer carrier that carries a developer to be supplied to the image carrier on the surface, a developer supply member that supplies the developer to the surface of the developer carrier, a developer container that contains the developer, A developing means comprising: the two-component developer according to any one of (1) to (7).
(9) charging means for charging the surface of the image carrier, exposure means for forming a latent image on the image carrier by exposing the surface of the image carrier, and developing toner on the latent image Development means for forming a visible image, transfer means for transferring the visible image to a recording medium or intermediate transfer member, fixing means for fixing the transferred image transferred to the recording medium, and recording medium to the intermediate An image forming apparatus comprising: a cleaning unit that cleans transfer residual toner on the image bearing member that has not been completely transferred to the transfer member; and the developing unit according to the item (8) is provided as the developing unit. apparatus.
(10) At least one selected from a developing device, a charging device for charging the latent image carrier, and a cleaning device for cleaning the surface of the development carrier after transfer, and the latent image carrier are integrally supported, and the process The image forming apparatus according to (9), wherein the cartridge is configured to be detachable from the main body of the image forming apparatus as a cartridge.
(11) An electrostatic charge image developing toner, wherein the base particles of the toner are produced by aqueous granulation,
The amount of change in the FTIR-ATR measured value for the toner surface wax amount before and after stirring when the developer in which the two-component electrostatic charge image developing carrier and the toner are mixed at a toner concentration of 9% is stirred for 90 minutes with a mag roll is as follows: A toner for developing an electrostatic charge image, characterized by being in the range.
P (A) ≦ 0.20 (1)
0.03 ≦ P (B) ≦ 0.25 (2)
P (A) ≦ P (B) (3)
(P (A); amount of surface wax before air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )])
P (B): Amount of surface wax after air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]).
(12) At least a binder resin, a colorant, a release agent, and a modified layered inorganic mineral, wherein the modified layered inorganic mineral has at least part of interlayer ions in the layered inorganic mineral modified with organic ions. The toner for developing an electrostatic charge image according to item (11).
(13) At least a part of interlayer ions in a binder polymer, a modified polyester resin, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and a layered inorganic mineral, at least in an organic solvent The modified layered inorganic mineral modified with organic ions is dissolved or dispersed to prepare a solution or dispersion, and the Casson yield value at 25 ° C. of the solution or dispersion is 1 [Pa] to 100 [Pa]. The solution or dispersion obtained by emulsifying or dispersing the dispersion or dispersion in an aqueous medium and removing the solvent from the dispersion obtained by crosslinking reaction or elongation reaction, Item 12) is an electrostatic image developing toner.
(14) The electrostatic image development according to the above (13), wherein the modified layered inorganic mineral is contained in an amount of 0.05 [% by mass] to 10 [% by mass] in the solid content of the solution or dispersion. Toner.
(15) Small particle size silica is adhered to the toner particles, and the BET specific surface area of the small particle size silica is in the range of 50 [m ² / g] to 400 [m ² / g]. The toner for developing an electrostatic charge image according to any one of (11) to (14), wherein the average circularity A is in a range of 0.94 ≦ A ≦ 0.99.
(16) The volume average particle diameter is 3 [μm] to 8 [μm], and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1. 30. The image forming method according to any one of (11) to (15), which is in a range of 30.
(17) The electrostatic image developing toner according to any one of (11) to (16), wherein particles having a particle size of 2 [μm] or less are 1 [number%] to 10 [number%].

  As will be apparent from the following detailed and specific invention, according to the present invention, in an aqueous granulated toner, the inorganic fine particles are strongly fixed on the toner surface, so that the degree of toner irregularity is not increased. It is possible to obtain a toner and an image forming apparatus that can ensure performance, obtain good transferability, obtain high image quality with excellent microdot reproducibility, and obtain high reliability. It has an excellent effect.

It is a schematic explanatory drawing which shows an example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. FIG. 4 is a schematic explanatory view showing a part of the image forming apparatus shown in FIG. 3. It is a figure which shows the result by this invention toner analysis method.

The present invention is an image forming apparatus having at least an image carrier, a charging step, an exposure step, a development step, a transfer step, a fixing step, and a cleaning step, and the developer used for image formation is produced by aqueous granulation. A developer for developing a two-component electrostatic image comprising a carrier comprising toner and magnetic particles, wherein the toner is obtained by stirring a developer obtained by mixing the toner and the carrier at a toner concentration of 9% with a mag roll for 90 minutes. The toner surface wax amount before and after stirring is a toner in which the amount of change in the FTIR-ATR measured value is within the following range.
P (A) ≦ 0.20 (1)
0.03 ≦ P (B) ≦ 0.25 (2)
P (A) ≦ P (B) (3)
P (A): amount of surface wax before air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]
P (B): Amount of surface wax after air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]

As shown by the formula (1), the amount of surface wax before stirring is desirably 0.20 or less. When the amount of surface wax exceeding 0.20 is present in the initial toner, there is no margin in storage stability. It is conceivable that the surface wax easily oozes out by storage at a high temperature and forms a toner aggregate. More preferably, it is 0.18 or less.
As indicated by the formula (2), the amount of surface wax after stirring is preferably between 0.03 and 0.25. Basically, the wax present on the toner surface after stirring plays its role (release ability or hot offset prevention ability) in the fixing process. If the amount of wax is less than 0.03, the amount of wax in the vicinity of the surface is insufficient, and sufficient releasability cannot be obtained, causing an abnormal image due to hot offset. On the other hand, if the amount of the surface wax exceeds 0.25, the amount of wax in the vicinity of the surface is excessively present, so that there is a concern that the blocking resistance and glossiness may be reduced. More preferably, the surface wax amount is in the range of 0.05 to 0.20 in order to improve the compatibility with hot offset resistance, developability, blocking resistance and the like during fixing.
Regarding the formula (3), the amount of surface wax before stirring needs to be larger than the amount of surface wax after stirring. The larger amount of surface wax before stirring means that the wax existing on the toner surface after stirring may move to the carrier side due to stirring in the developing container and impair the charging ability of the carrier. It is to be done. Furthermore, in the developer container, the non-electrostatic adhesion between the developer and the developer increases due to the wax movement to the carrier, and stirring is not sufficiently performed. It is possible to cause defects.
From the above, it is required that the amount of surface wax before and after agitation exists within the entire range of the above-described equations (1), (2), and (3).

  The image forming apparatus of the present invention includes an electrostatic latent image forming process (charging process and exposure process), a developing process, a transfer process, a fixing process, and a cleaning process. You may further have processes, such as a process and a control process.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming means. The electrostatic latent image forming unit preferably has a charger (charging unit) that uniformly charges the surface of the image carrier and an exposure unit (exposure unit) that exposes the surface of the image carrier.
Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.
The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be employed.

The development step is a step of forming a visible image by developing the electrostatic latent image using the toner of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing unit that accommodates the toner of the present invention and can apply the toner to the electrostatic latent image in a contact or non-contact manner. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used.
In the developing device, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and is held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image with toner is formed on the surface of the image carrier.

The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used is usually two or more colors, and it is preferable to use a full-color toner. For this reason, it is more preferable to have a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto a recording medium.
The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.
The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be fixed each time the toner of each color is transferred to the recording medium, or each color toner is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.

  The cleaning step is a step of removing the toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used. It is preferable to use a blade cleaner.

The recycling process is a process in which the toner removed in the cleaning process is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.
A control process is a process of controlling each process, and can be performed using a control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  The process cartridge of the present invention is used in the image forming apparatus of the present invention, and integrally supports an image carrier and at least one unit selected from a charging unit, a developing unit, and a cleaning unit to form the image of the present invention. It is detachable from the main body.

FIG. 1 shows an example of an image forming apparatus used in the present invention. The image forming apparatus (100A) includes a drum-shaped photosensitive member (10) as an image carrier, a charging roller (20) as a charging unit, an exposure device (30) as an exposure unit, and development as a developing unit. An apparatus (40), an intermediate transfer member (50), a cleaning device (60) as a cleaning means, and a static elimination lamp (70) as a static elimination means are provided.
The intermediate transfer member (50) is an endless belt, and is stretched by three rollers (51) so as to be movable in the direction of the arrow. A part of the three rollers (51) also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member (50). A cleaning device (90) having a cleaning blade is disposed in the vicinity of the intermediate transfer member (50). Further, a transfer roller (80) as a transfer means capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to a recording paper (95) as a recording medium is opposed to the recording paper (95). Has been placed. Around the intermediate transfer member (50), there is a corona charger (58) for applying a charge to the toner image on the intermediate transfer member (50) in the rotational direction of the intermediate transfer member (50). 10) and the intermediate transfer member (50) and the contact portion between the intermediate transfer member (50) and the transfer paper (95).
The developing device (40) includes a developing belt (41) as a developer carrying member, a black developing device (45K), a yellow developing device (45Y), and a magenta developing device (45M) provided around the developing belt (41). And a cyan developing unit (45C). The black developing device (45K) includes a developer accommodating portion (42K), a developer supply roller (43K), and a developing roller (44K), and the yellow developing device (45Y) includes a developer accommodating portion (42Y). ), A developer supply roller (43Y), and a development roller (44Y). The magenta developer (45M) includes a developer accommodating portion (42M), a developer supply roller (43M), and a development roller (44M). The cyan developing device (45C) includes a developer container (42C), a developer supply roller (43C), and a developing roller (44C). Further, the developing belt (41) is an endless belt, is stretched by a plurality of belt rollers so as to be movable in the direction of the arrow, and a part thereof is in contact with the photoreceptor (10).

  In the image forming apparatus (100A), the charging roller (20) uniformly charges the photoconductor (10), and then exposes the photoconductor (10) using the exposure device (30), thereby electrostatic latent. Form an image. Next, the electrostatic latent image formed on the photoconductor 10 is developed by supplying a developer from the developing device (40) to form a toner image. Further, the toner image is transferred (primary transfer) onto the intermediate transfer member (50) by the voltage applied by the roller (51), and further transferred (secondary transfer) onto the recording paper (95). As a result, a transfer image is formed on the recording paper (95). The toner remaining on the photoconductor (10) is removed by a cleaning device (60) having a cleaning blade, and the charged charge on the photoconductor (10) is removed by a static elimination lamp (70).

  FIG. 2 shows another example of the image forming apparatus used in the present invention. The image forming apparatus (100B) does not include the developing belt (41), and a black developing unit (45K), a yellow developing unit (45Y), a magenta developing unit (45M), and a cyan developing unit are provided around the photoreceptor (10). Except that (45C) is arranged to face each other, it has the same configuration as that of the image forming apparatus (100A) and exhibits the same functions and effects. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

FIG. 3 shows another example of the image forming apparatus used in the present invention. The image forming apparatus (100C) is a tandem color image forming apparatus. The image forming apparatus (100C) includes a copying apparatus main body (150), a paper feed table (200), a scanner (300), and an automatic document feeder (400). The copying machine main body (150) is provided with an endless belt-like intermediate transfer member (50) at the center. The intermediate transfer member (50) is stretched around the support rollers (14), (15) and (16) so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device (17) for removing toner remaining on the intermediate transfer body (50) is disposed in the vicinity of the support roller (15). The intermediate transfer member (50) stretched by the support rollers (14) and (15) is opposed to image forming means (18) of four colors of yellow, cyan, magenta, and black along the conveyance direction. A tandem developing device (120) juxtaposed in parallel is arranged. An exposure device (21) is disposed in the vicinity of the tandem developing unit (120). A secondary transfer device (22) is arranged on the opposite side of the intermediate transfer member (50) from the side where the tandem developing device (120) is arranged. In the secondary transfer device (22), a secondary transfer belt (24), which is an endless belt, is stretched between a pair of rollers (23), and the recording paper conveyed on the secondary transfer belt (24) is intermediate to the recording paper. The transfer bodies (50) can contact each other. A fixing device (25) is disposed in the vicinity of the secondary transfer device (22). The fixing device (25) includes a fixing belt (26) that is an endless belt, and a pressure roller (27) that is arranged to be pressed against the fixing belt (26).
In the image forming apparatus (100C), a sheet reversing device (28) for reversing the transfer paper is disposed in the vicinity of the secondary transfer device (22) and the fixing device (25). Thereby, images can be formed on both sides of the recording paper.

Next, full color image formation (color copying) using the tandem developing device (120) will be described. First, the document is set on the document table (130) of the automatic document feeder (400), or the automatic document feeder (400) is opened and the document is set on the contact glass (32) of the scanner (300). The automatic document feeder (400) is closed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is conveyed on the contact glass (32) and then on the contact glass (32). When is set, the scanner (300) is immediately driven, and the first traveling body (33) and the second traveling body (34) travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body (33) is reflected by the mirror of the second traveling body (34) and passes through the imaging lens (35) to the reading sensor (36). Received light. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. The image information of each color is transmitted to the image forming means (18) for each color in the tandem developing device (120), and a toner image for each color is formed.
The toner image on the black photoconductor (10K), the toner image on the yellow photoconductor (10Y), the toner image on the magenta photoconductor (10M), and the toner image on the cyan photoconductor (10C) are intermediate. Transfer (primary transfer) is sequentially performed on the transfer body (50). Then, the toner images of the respective colors are superimposed on the intermediate transfer member (50) to form a composite color image (color transfer image).

  As shown in FIG. 4, each color image forming means (18) in the tandem developing device (120) includes a photoreceptor (10) and a charger (59) for uniformly charging the photoreceptor (10). And an exposure device (21) that forms an electrostatic latent image on the photoconductor (10) by exposing the photoconductor (10) based on image information of each color ((L) in the figure), and each color. The electrostatic latent image is developed using the toner of the developer, and a developing device (61) that forms a toner image of each color on the photoreceptor (10), and the toner image of each color is transferred onto the intermediate transfer member (50). A transfer charger (62), a photoreceptor cleaning device (63), and a static eliminator (64).

  On the other hand, in the paper feed table (200), one of the paper feed rollers (142a) is selectively rotated to feed the recording paper from one of the paper feed cassettes (144) provided in multiple stages in the paper bank (143). The sheet is separated one by one by the separation roller (145a), sent to the sheet feeding path (146), conveyed by the conveying roller (147) and guided to the sheet feeding path (148) in the copying machine main body (150), and the registration roller Stop at (49). Alternatively, the recording paper on the manual feed tray (52) is fed out by rotating the paper feed roller (142b), separated one by one by the separation roller (145b), and put into the manual paper feed path (53). 49) and stop. The registration roller (49) is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller (49) is rotated in time with the color transfer image formed on the intermediate transfer member (50), and the recording paper is interposed between the intermediate transfer member (50) and the secondary transfer device (22). , A color transfer image is formed on the recording paper. The toner remaining on the intermediate transfer body (50) after the transfer is cleaned by the intermediate transfer body cleaning device (17).

  The recording paper on which the color transfer image is formed is conveyed to the fixing device (25) by the secondary transfer device (22), and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw (55), discharged by the discharge roller (56), and stacked on the discharge tray (57). Alternatively, the sheet is switched by the switching claw (55), reversed by the sheet reversing device (28) and led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller (56) and discharged by the discharge tray (57). ) Is stacked on top.

[Toner characteristics measurement method]
<Casson yield measurement method>
The Casson yield value can be measured using a high shear viscometer or the like.
The measurement conditions are as follows.
Device: AR2000 (TA Instruments)
Shear stress: 120 Pa / 5 min Geometry: 40 mm steel plate Geometry gap: 1 mm
Analysis software: TA DATA ANALYSIS (TA Instruments)

<Weight average particle diameter (Dw), volume average particle diameter (Dv), and number average particle diameter (Dn)>
The weight average particle diameter (Dw), volume average particle diameter (Dv), and number average particle diameter (Dn) of the toner are measured using a particle size measuring device (“Multisizer III” manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. It measured and analyzed with the analysis software (Beckman Coulter Multisizer 3 Version3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was mixed with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Average circularity>
The average circularity of the toner is defined by an average circularity SR = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. Measurement was performed using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analysis was performed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the concentration of 5000 to 15000 / μl was obtained. In this measurement method, it is important that the dispersion concentration is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. Similar to the measurement of the toner particle size described above, the required amount of the surfactant varies depending on the hydrophobicity of the toner. If it is added in a large amount, noise due to bubbles is generated. It will be enough. Further, the toner addition amount differs from the particle size, and is small when the particle size is small and needs to be increased when the particle size is large. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

<Measurement of toner wax amount>
In the toner of the present invention, the dispersion state of the wax can be defined by the following measurement based on the total amount of wax in the toner particles and the amount of wax in the vicinity of the toner particle surface. The total amount of wax in the toner particles is obtained by a DSC (Differential Scanning Calorimeter) method. Each of the toner sample and the single wax sample is measured by the following measuring device and conditions, and each is obtained from the ratio of the endothermic amounts of the waxes obtained.
・ Measurement device: DSC device (DSC60; manufactured by Shimadzu Corporation)
-Sample amount: about 5mg
-Temperature rising temperature: 10 ° C / min
Measurement range: room temperature to 150 ° C
・ Measurement environment: In nitrogen gas atmosphere
The total amount of wax was calculated by the following (Formula 1).
Total amount of wax (% by mass) = (Endothermic amount of wax of toner sample (J / g)) × 100) / (Endothermic amount of single wax (J / g)) (Formula 1)
As described above, the total amount of wax in the toner particles can be effectively defined by the above analysis even when the wax flows out during the toner manufacturing process and all the charged wax is not contained in the toner.

<Measurement of toner surface wax amount>
The amount of wax in the vicinity of the toner particle surface can be obtained by FTIR-ATR (total reflection absorption infrared spectroscopy). From the measurement principle, the analysis depth is about 0.3 μm, and this analysis makes it possible to obtain the relative amount of wax in a depth region of 0.3 μm from the surface of the toner particles. The measurement method is as follows.
First, as a sample, 3 g of toner was pressed with an automatic pellet molding machine (Type M No. 50 BRP-E; manufactured by MAEKAWA TESTING MACHINE CO.) For 1 minute under a load of 6 t to produce 40 mmφ (about 2 mm thick) pellets. . The toner pellet surface was measured by the FTIR-ATR method. The micro FTIR apparatus used was a Perscope ELMER Spectrum One with a MultiScope FTIR unit installed, and was measured with a micro ATR of a germanium (Ge) crystal having a diameter of 100 μm. Measurement was performed with an infrared incident angle of 41.5 °, a resolution of 4 cm −1, and a total of 20 times.
The intensity ratio (P2850 / P828) between the obtained wax-derived peak (2850 cm ⁻¹ ) and the binder resin-derived peak (828 cm ⁻¹ ) was defined as the relative amount of wax near the toner particle surface. The average value after measuring four times by changing the measurement location was used.

<Agitating developer with mag roll>
Stirring with a mag roll in the present invention is carried out by the following method. First, a magnet is attached to the lower part of the roll mill container, which is a mag roll, and a stirring device comprising a sealed container that can be stirred while applying a load to the magnetic carrier of the developer in the container by the magnetic force of the magnet, 7 g of developer mixed with a toner concentration of 9% is put into the stirring device. Next, the developer is stirred for 90 minutes at a rotational speed of 280 rpm while applying a magnetic force of 3000 G. The toner surface wax amount after stirring is measured by the above-described surface wax measurement method after sieving using a sieve having an opening of 25 μm and forcibly removing the carrier and the toner.

  The ratio (Dw / Dn) of the weight average particle diameter (Dw) to the number average particle diameter (Dn) in the toner manufactured by the manufacturing method of the present invention is preferably 1.30 or less, for example, 1.00 to 1 .30 is more preferred. When the ratio of the weight average particle diameter to the number average particle diameter (Dw / Dn) is less than 1.00, in the two-component developer, the toner is fused to the surface of the carrier during long-term agitation in the developing device, and the carrier It tends to lead to a decrease in charging ability and deterioration in cleaning performance. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. Further, if Dw / Dn exceeds 1.30, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter increases. Sometimes.

  Further, when the ratio (Dw / Dn) of the weight average particle diameter to the number average particle diameter of the toner is 1.00 to 1.30, any of storage stability, low-temperature fixability, and hot offset resistance can be obtained. Also tends to be an excellent toner. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. Even if the toner balance for a long time is carried out with a two-component developer, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even with long-term stirring in the developing device. With toner balance, the toner particle size fluctuations are reduced, and there is no toner filming on the developing roller and no toner fusion to a member such as a blade for thinning the toner. Good and stable developability can be obtained even during long-term use (stirring) of the apparatus, and high-quality images can be obtained.

  On the other hand, the inorganic fine particles are used for imparting fluidity, developability, chargeability and the like to the toner particles. The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Silicon, silicon nitride, or the like can be used.

As the particle size of the inorganic fine particles, large particle size inorganic fine particles having a primary average particle size of 50 to 500 nm can be preferably used. In particular, hydrophobic silica and / or hydrophobic titanium oxide are preferred. The primary average particle diameter of the inorganic fine particles is preferably 100 to 400 nm, and particularly preferably 120 to 360 nm. Moreover, it is preferable that the specific surface area by BET method is 20-35 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.

Hereinafter, an example of a method for producing the toner of the present invention will be specifically described.
[Raw materials used for producing the toner of the present invention]
(Resin fine particles (A))
The resin fine particles (A) used in the present invention are not particularly limited as long as they can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose. The resin for the resin fine particles (A) may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin Melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to form at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin because an aqueous dispersion of fine spherical resin fine particles can be easily obtained. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer, Examples thereof include a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.

  The resin fine particles (A) are required to be anionic. This is because they do not aggregate when used together with the anionic surfactant shown above. The resin fine particles (A) can also be prepared by using an anionic activator by a production method described later, or by introducing an anionic group such as a carboxylic acid group or a sulfonic acid group into the resin. As the particle size, an average particle size of primary particles of 5 to 50 nm is important for controlling the particle size and particle size distribution of the emulsified particles, and more preferably 10 to 25 nm. The particle diameter can be measured by SEM, TEM, light scattering method or the like. Preferably, LA-920 manufactured by HORIBA, Ltd. using a laser scattering measurement method may be used after diluting to an appropriate concentration so as to enter the measurement range. The particle diameter is determined as a volume average diameter.

The resin fine particles (A) can be obtained by polymerization according to a known method appropriately selected according to the purpose, but are preferably obtained as an aqueous dispersion of the resin fine particles (A). As a method for preparing the aqueous dispersion of the resin fine particles (A), for example, the following methods are preferably exemplified.
(1) In the case of a vinyl resin, the resin fine particles (A) are directly formed by any polymerization reaction selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material. A method for producing an aqueous dispersion.
(2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof was dispersed in an aqueous medium in the presence of an appropriate dispersant. Then, heating or adding a hardening | curing agent and making it harden | cure, and manufacturing the aqueous dispersion liquid of resin microparticles | fine-particles (A).
(3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid. It may be liquefied by heating). A method in which a suitable emulsifier is dissolved therein and then water is added to perform phase inversion emulsification.
(4) Resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) After the resin fine particles (A) are obtained by pulverizing using, and then classified, they are dispersed in water in the presence of an appropriate dispersant.
(5) A spray of a resin solution prepared by previously dissolving a resin prepared in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. A method of dispersing the resin fine particles in water in the presence of an appropriate dispersant after obtaining the resin fine particles (A).
(6) A poor solvent is added to a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Or by precipitating resin fine particles (A) by cooling a resin solution previously dissolved in a solvent by heating, and then removing the solvent to obtain resin fine particles, and then adding the resin fine particles (A) to an appropriate dispersant. A method of dispersing in water in the presence.
(7) A resin solution prepared by previously dissolving a resin prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is appropriately dispersed. A method in which the solvent is removed by heating or decompression after being dispersed in an aqueous medium in the presence of an agent.
(8) A suitable emulsifier in a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. There is a method of phase inversion emulsification by adding water after dissolving.

(Resin fine particles (B))
The resin fine particles (B) can be prepared by the same method as the resin fine particles (A). The average particle size of primary particles is 50 to 500 nm as the particle size, which is important for controlling the particle size and particle size distribution of the emulsified particles, and more preferably 100 to 250 nm. The particle size and particle size distribution of the resin fine particles (B) can be measured by the same method as that for the resin fine particles (A). Those having the property of being unstable and aggregating when mixed with the anionic surfactant solution mentioned above are more likely to adhere to the droplet surface of the toner material. For that purpose, it can be prepared by using a nonionic surfactant, an amphoteric surfactant or a cationic surfactant in the production method described above, or by introducing a cationic group such as an amine group or an ammonium base into the resin.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of amine salt type surfactants include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. It is done. Among cationic surfactants, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, and the like are preferable.

  Commercially available cationic surfactants include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Kogyo Co., Ltd.), MegaFuck F -150, F-824 (Dainippon Ink Co., Ltd.); Xtop EF-132 (Tochem Products Co., Ltd.);

  Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.

  Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

  The resin component for the fine resin particles (B) is preferably a styrene-acrylic resin that is incompatible with the resin constituting the toner, such as a styrene-methyl acrylate copolymer, a styrene-ethyl acrylate copolymer, or a styrene-acrylic acid. Butyl copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Preferred examples include polymers, styrene-acrylonitrile copolymers, and styrene-acrylonitrile-indene copolymers. Examples of copolymers with styrene-other resins include styrene-p-chlorostyrene copolymers and styrene-propylene. Copolymer, styrene-vinyltoluene copolymer, styrene Vinylnaphthalene copolymer, styrene - vinyl methyl ketone copolymer, styrene - butadiene copolymer, styrene - isoprene copolymer, styrene - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.

  The resin fine particles (B) are preferably cross-linked polymers so that they do not dissolve when adhering to the emulsified droplets and are immobilized on the surface, and are co-polymerized with a monomer having at least two unsaturated groups. A polymerized one is preferred. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the purpose. For example, a sodium salt of methacrylic acid ethylene oxide adduct sulfate (“Eleminol RS-30”) Manufactured by Sanyo Chemical Industries), divinyl compounds such as divinylbenzene, and diacrylate compounds such as 1,6-hexanediol acrylate.

(Anionic surfactant)
Examples of the anionic surfactant used in the production method of the present invention include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, etc., and anionic surfactants having a fluoroalkyl group are preferred. Listed. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (having 6 to 6 carbon atoms). 11) Sodium oxy] -1-alkyl (3 to 4 carbon atoms) sulfonic acid, sodium 3- [ω-fluoroalkanoyl (6 to 8 carbon atoms) -N-ethylamino] -1-propanesulfonic acid, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate and the like.

  Examples of commercially available anionic surfactants having a fluoroalkyl group include Surflon S-111, S-112, and S-113 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 ( Dainippon Ink, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Etc.).

(Binder Resin: For convenience of explanation, the material from the binder resin to the magnetic material described below may be called a toner material.)
The binder resin used in the method for producing the toner of the present invention is not particularly limited, and preferably contains at least two kinds of resins, such as polyester resins, silicone resins, styrene / acryl resins, styrene resins, acrylic resins, Known binder resins such as epoxy resins, diene resins, phenol resins, terpene resins, coumarin resins, amideimide resins, butyral resins, urethane resins, ethylene / vinyl acetate resins can be used.
Among these, the resin phase for the toner production method of the present invention is preferably a polyester resin that has sufficient flexibility even when the molecular weight is lowered, in that it can sharply melt during fixing and smooth the image surface. Further, other resins may be used in combination with the polyester resin.
The polyester resin used in the present invention is one or more polyols represented by the following general formula (1),
A- (OH) m (1)
[Wherein, A represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. m represents an integer of 2 to 4. ]
One or two or more polycarboxylic acids represented by the following general formula (2) are polyesterified.
B- (COOH) n (2)
[Wherein, B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. n represents an integer of 2 to 4. ]

  Specific polyols represented by the general formula (1) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2, 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl Propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide addition Products, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

  Specific polycarboxylic acids represented by the general formula (2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid. Azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, Isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5 -Hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxyprop 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, Examples include butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and ethylene glycol bis (trimellitic acid).

(Active hydrogen group-containing compound)
By including an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the compound in the toner material of the present invention, the mechanical strength of the obtained toner is increased, and the resin fine particles (B) and external additives are buried. Can be suppressed. When the active hydrogen group-containing compound has a cationic polarity, the resin fine particles (B) can be attracted electrostatically. Further, the fluidity of the toner during heat fixing can be adjusted, and the fixing temperature range can be widened. It can be said that the active hydrogen group-containing compound and the modified polyester resin capable of reacting with the compound are binder resin precursors.
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium. The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group and can be appropriately selected according to the purpose. For example, a polymer that can react with the active hydrogen group-containing compound contains an isocyanate group. In the case of the polyester prepolymer (A), the amines (B) are preferable because they can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A).

  The active hydrogen group is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), amino group, carboxyl group, mercapto group , Etc. can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

  There is no restriction | limiting in particular as amines (B), According to the objective, it can select suitably, For example, diamine (B1), trivalent or more polyamine (B2), amino alcohol (B3), amino mercaptan (B4) ), Amino acids (B5), amino acids of (B1) to (B5) blocked (B6), and the like can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, aliphatic diamines, and the like. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan, aminopropyl mercaptan, and the like.
In addition, examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
(B6) obtained by blocking the amino group of (B1) to (B5), for example, obtained from any of the amines of (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And ketimine compounds, oxazolidone compounds, and the like.

A reaction terminator is used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. The use of a reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. As the reaction terminator, monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking them (ketimine compounds) can be used.
As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), an isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and an amino group [in the amines (B) [ The mixing equivalent ratio of NHx] ([NCO] / [NHx]) is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and more preferably 1 / 1.5 to Particularly preferred is 1.5 / 1. This is because if the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is low. This is because the hot offset resistance may deteriorate.

(Polymer capable of reacting with active hydrogen group-containing compound)
The polymer that can react with the active hydrogen group-containing compound (hereinafter referred to as “prepolymer”) is not particularly limited as long as it has at least a site that can react with the active hydrogen group-containing compound. For example, a polyol resin, a polyacrylic resin, a polyester resin, an epoxy resin, a derivative resin thereof, or the like can be used. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting. In addition, these may be used individually by 1 type and may use 2 or more types together.
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and can be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, an acid chloride can be selected. Group, and the like. These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable. Among prepolymers, it is easy to adjust the molecular weight of the polymer component, ensuring oil-free low-temperature fixing characteristics in dry toners, especially good release and fixing properties even when there is no release oil application mechanism to the fixing heating medium. In view of the ability, a urea bond-forming group-containing polyester resin (RMPE) is particularly preferable.

  As a urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the polyester resin (RMPE) is particularly preferably an isocyanate group-containing polyester prepolymer (A). The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), and Examples include those obtained by reacting an active hydrogen group-containing polyester resin with polyisocyanate (PIC). There is no restriction | limiting in particular as a polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol ( TO) and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, diol (DIO) alone or a mixture of diol (DIO) and a small amount of a trivalent or higher polyol (TO) is preferable. Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.

  As the alkylene glycol, those having 2 to 12 carbon atoms are preferable, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. It is done. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of bisphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols. Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, an alkylene of a trihydric or higher polyphenol. And oxide adducts. Examples of the trivalent or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and the like. Examples of the trihydric or higher polyphenols include trisphenol bodies (such as Trisphenol PA manufactured by Honshu Chemical Industry Co., Ltd.), phenol novolacs, cresol novolacs, and the like. Examples of the alkylene oxide adduct of trihydric or higher polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to trihydric or higher polyphenols.
The mixing mass ratio (DIO: TO) of the diol (DIO) and the trihydric or higher polyol (TO) in the mixture of the diol (DIO) and the trihydric or higher polyol (TO) is 100: 0.01 to 10 Is preferable, and 100: 0.01-1 is more preferable.

  There is no restriction | limiting in particular as polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) And a mixture of trivalent or higher valent polycarboxylic acids. These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of dicarboxylic acid (DIC) and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.

  Examples of the dicarboxylic acid (DIC) include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like. Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. Moreover, as alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. Moreover, as aromatic dicarboxylic acid, a C8-C20 thing is preferable, for example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned. Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

  The trivalent or higher polycarboxylic acid (TC) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids. Moreover, as an aromatic polycarboxylic acid, a C9-C20 thing is preferable, for example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  The polycarboxylic acid (PC) is any one selected from dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), and a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid. These acid anhydrides or lower alkyl ester compounds can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  As a mixing mass ratio (DIC: TC) of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC) in a mixture of dicarboxylic acid (DIC) and higher or lower polycarboxylic acid (TC), There is no restriction | limiting, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio in the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the hydroxyl group in the polyol (PO) [ OH] and the equivalent ratio ([OH] / [COOH]) of the carboxyl group [COOH] in the polycarboxylic acid (PC) are usually preferably 2/1 to 1/1, and 1.5 / The ratio is more preferably 1-1 / 1, and particularly preferably 1.3 / 1-1.02 / 1.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of a polyol (PO), Although it can select suitably according to the objective, 0.5-40 mass% is preferable, for example. -30 mass% is more preferable, and 2-20 mass% is especially preferable. This is because if the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. This is because the low temperature fixability may be deteriorated if the temperature exceeds.

The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3 -Methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These may be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group in the hydroxyl group-containing polyester resin [ The mixing equivalent ratio with [OH] ([NCO] / [OH]) is usually preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. It is particularly preferably 1 to 1.5 / 1. This is because when the isocyanate group [NCO] exceeds 5, the low-temperature fixability may deteriorate, and when it is less than 1, the offset resistance may deteriorate.
There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable, 1-30 mass% is more preferable, and 2-20 mass% is further more preferable. This is because, when the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability, and exceeds 40% by mass. This is because the low-temperature fixability deteriorates.

  As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable. This is because if the average number of isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with a urea bond-forming group becomes low, and the hot offset resistance deteriorates.

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is preferably 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 4,000 to 30,000 are more preferable. This is because when the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

Measurement of molecular weight distribution by gel permeation chromatography (GPC) can be performed, for example, as follows. That is, first, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) was flowed as a column solvent at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a tetrahydrofuran sample solution of the resin. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Or the molecular weights made by Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

(Other ingredients)
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Materials, metal soaps, and the like.

(Coloring agent)
The colorant for the toner used in the present invention is not particularly limited and can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa Yellow (10G, 5G, G), Cadmium Yellow, Yellow Iron Oxide, Ocher, Yellow Lead, Titanium Yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Sand, Red Zhu , Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Par Nent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Chi Indigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue Phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, Zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Examples include lean gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type and may use 2 or more types together.
The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content of the colorant is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion occurs in the toner, resulting in a reduction in the coloring power, and the toner. The electrical characteristics may be degraded.

The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, polyester, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate, polybutyl Methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic Examples include hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene N-acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.
The master batch can be produced by mixing or kneading a master batch resin and a colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used. The colorant can be arbitrarily contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two resins. It is well known that the colorant deteriorates the charging performance of the toner when present on the toner surface. Therefore, the charging performance (environmental stability, charge retention ability, charge amount, etc.) of the toner can be improved by selectively containing a colorant in the first resin phase present in the inner layer.

(Release agent)
There is no restriction | limiting in particular as a mold release agent, Although it can select suitably according to the objective, A low melting-point mold release agent whose melting | fusing point is 50-120 degreeC is preferable. The low melting point release agent, when dispersed with the resin, effectively works as a release agent between the fixing roller and the toner interface. Even if it is not applied, the hot offset property is good.
Preferable examples of the release agent include waxes and waxes. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and microcrystalline And natural waxes such as petroleum waxes such as Petrolatum; In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as melting | fusing point of a mold release agent, Although it can select suitably according to the objective, 50-120 degreeC is preferable and 60-90 degreeC is more preferable. When the melting point is less than 50 ° C., the wax may adversely affect the heat-resistant storage stability. When the melting point exceeds 120 ° C., a cold offset may easily occur during fixing at a low temperature. The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained. There is no restriction | limiting in particular as content in the said toner of a mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.
The release agent can be arbitrarily contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two resins. By selectively including in the second resin phase present in the outer layer of the toner, the release of the release agent occurs sufficiently even in a short heating time during fixing, so that sufficient release properties can be obtained. Further, by selectively including the release agent in the first resin phase present in the inner layer, it is possible to suppress the spent of the release agent to other members such as a photoreceptor and a carrier. In the present invention, the arrangement of the release agent may be designed relatively freely, and an arbitrary arrangement can be taken according to each image forming process.

(Charge control agent)
The charge control agent is not particularly limited and may be appropriately selected from known materials according to the purpose. For example, a nigrosine dye, a triphenylmethane dye, a chromium-containing metal complex dye, a molybdate chelate pigment, Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, metal salts of salicylic acid, And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include Nitronine-based dye Bontron 03, Quaternary ammonium salt Bontron P-51, Metal-containing azo dye Bontron S-34, O-naphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 ( As mentioned above, manufactured by Hoechst Co., Ltd.), LRA-901, LR-147 (Japanese car) which is a boron complex Tsu DOO Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent can be used in any of the resin phase in the toner particle body and the resin phase of the resin particle (B) by utilizing the difference in affinity between the resin in the toner particle body and the resin fine particle (B). Can be included. By selectively containing it in the resin phase of the resin fine particles (B) present on the toner surface, it becomes easier to obtain an effect against power failure with a smaller amount of charge control agent. Further, by selectively containing the charge control agent in the resin phase in the toner particle main body existing in the inner layer, the spent of the charge control agent on other members such as a photoreceptor and a carrier can be suppressed. In the toner manufacturing method of the present invention, the arrangement of the charge control agent may be designed relatively freely, and an arbitrary arrangement may be taken according to each image forming process.
The content of the charge control agent with respect to the toner varies depending on the type of the resin, the presence or absence of the additive, the dispersion method, and the like, and cannot be generally specified. For example, the content is 0.1% with respect to 100 parts by mass of the binder resin. -10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content of the charge control agent is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, By reducing the effect, the electrostatic attraction force with the developing roller may increase, leading to a decrease in developer fluidity and a decrease in image density.

(Inorganic fine particles)
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles. The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Silicon, silicon nitride, or the like can be used. These may be used individually by 1 type and may use 2 or more types together.
As the inorganic fine particles for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, in addition to the large-sized inorganic fine particles having a primary average particle diameter of 80 to 500 nm, small particles Inorganic fine particles having a diameter can be preferably used. In particular, hydrophobic silica and / or hydrophobic titanium oxide are preferred. The primary average particle diameter of the inorganic fine particles is preferably 5 to 50 nm, and particularly preferably 10 to 30 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.

(Fluidity improver)
A fluidity improver is an agent that increases surface hydrophobicity by surface treatment and prevents deterioration of flow characteristics and charging characteristics even under high humidity. And silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. Silica and titanium oxide are particularly preferably surface treated with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

(Cleaning improver)
The cleaning improver is an agent added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as metal salts, polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

[Method for Producing Toner of the Present Invention]
In the toner production method of the present invention, a solution or dispersion formed by dissolving or dispersing a binder resin or a toner material mainly composed of a binder resin raw material and a colorant in an organic solvent is used as an aqueous medium. A desired toner is produced by preparing an emulsified or dispersed liquid by emulsifying or dispersing in, and adhering the granulated resin fine particles (B) to a toner precursor containing the emulsified or dispersed toner material. Preferably, a solution or dispersion of a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium, and the active hydrogen is contained in the aqueous medium. By reacting a group-containing compound with a polymer capable of reacting with an active hydrogen group-containing compound to produce toner precursor particles containing at least an adhesive substrate, and attaching the granulated resin fine particles (B) A desired toner is produced.

(Dissolution or dispersion of toner material)
The solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in a solvent. The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. For example, the active hydrogen group-containing compound and a polymer (pre-polymer capable of reacting with the active hydrogen group-containing compound) can be selected. Any of the above-mentioned other components such as an unmodified polyester resin, a mold release agent, a colorant, and a charge control agent. The toner material dissolved or dispersed liquid is preferably prepared by dissolving or dispersing the toner material in an organic solvent. The organic solvent is preferably removed during or after the toner granulation.

(Organic solvent)
The organic solvent for dissolving or dispersing the toner material is not particularly limited as long as it is a solvent capable of dissolving or dispersing the toner material, and is a relatively polar material, a relatively non-polar material such as the wax in the present invention, etc. These can be appropriately selected according to each purpose, and a plurality of miscible solvents having different SP values and HLB values suitable for each material can be mixed and used. Those having a boiling point of less than 150 ° C. are preferable from the viewpoint of easy removal after granulation, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene. In addition to water-immiscible solvents such as chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, etc. Hydrophilic organics such as alcohols such as methanol and ethylene glycol, ethers such as THF and dioxane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, and nitrogen-containing organic solvents such as DMH A solvent can be preferably used. Ester solvents are preferred, and ethyl acetate is particularly preferred. These may be used individually by 1 type and may use 2 or more types together. The amount of the organic solvent used is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, based on 100 parts by weight of the toner material. -120 mass parts is more preferable. The toner material is dissolved or dispersed in an organic solvent containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, an unmodified polyester resin, a release agent, a colorant, and charge control. The toner material such as an agent can be dissolved or dispersed. In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later. When the dissolved or dispersed liquid of the toner material is added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

(Aqueous medium)
There is no restriction | limiting in particular as an aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with water, a mixture thereof, etc. can be used, Among these, water Is particularly preferred. The solvent miscible with water is not particularly limited as long as it is miscible with water. For example, alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and the like can be used. Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium is prepared, for example, by dispersing the resin fine particles (A) in the aqueous medium in the presence of an anionic surfactant. The addition amount of the anionic surfactant and the resin fine particles (A) in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. . The resin fine particles (B) are then added to the aqueous medium. When the resin fine particles (B) are cohesive with the anionic surfactant, the aqueous medium is preferably dispersed with a high-speed shearing disperser before emulsification.

(Emulsification or dispersion)
The dissolution or dispersion of the toner material in the aqueous medium is preferably carried out by dispersing the toner material dissolution or dispersion in the aqueous medium while stirring. There is no restriction | limiting in particular as a dispersion method, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser. In this toner production method, an adhesive base material is formed when an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction during emulsification or dispersion. . The resin fine particles (B) may be added to the aqueous medium during or after emulsification. It is carried out while dispersing with a high-speed shearing disperser, or by switching to low-speed agitation after emulsification, or appropriately while checking the adhesion of the resin fine particles (B) to the toner and the immobilization state.

(Adhesive substrate)
The adhesive base material is an adhesive polymer that exhibits an adhesive property to a recording material such as paper and is obtained by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. It is preferable to contain. Note that a binder resin appropriately selected from known binder resins may be included. There is no restriction | limiting in particular as a weight average molecular weight of an adhesive base material, Although it can select suitably according to the objective, 3,000 or more are preferable, 5,000-1,000,000 are more preferable, 7, 000 to 500,000 is particularly preferred. This is because if the weight average molecular weight is less than 3,000, the hot offset resistance may deteriorate.
There is no restriction | limiting in particular as glass transition temperature (Tg) of an adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. This is because if the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and if it exceeds 70 ° C., the low-temperature fixability may not be sufficient. In the electrophotographic toner of this embodiment, since a polyester resin subjected to a cross-linking reaction and an extension reaction coexists, good storability is exhibited even when the glass transition temperature is lower than that of a conventional polyester-based toner.
The glass transition temperature (Tg) is measured by the following method using, for example, a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. To do.

  There is no restriction | limiting in particular as resin for adhesive base materials, Although it can select suitably according to the objective, A polyester-type resin etc. are especially suitable. There is no restriction | limiting in particular as a polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned as a particularly suitable thing. The urea-modified polyester resin comprises an amine (B) as an active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound in an aqueous medium. Obtained by reaction. The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the content molar ratio of the urea bond and the urethane bond (urea bond / urethane bond) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100/0 to 10/90. Preferably, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. This is because if the urea bond is less than 10, the hot offset resistance may be deteriorated.

Preferable specific examples of the urea-modified polyester resin include the following.
(1) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid Mixture with polycondensate.
(2) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2-mole adduct and terephthalic acid Mixture with polycondensate.
(3) A bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polyester prepolymer obtained by reacting a polycondensate of terephthalic acid with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene Mixture of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and polycondensate of terephthalic acid.
(4) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate, and bisphenol A propylene Mixture of oxide 2 mol adduct and terephthalic acid polycondensate.
(5) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2-mole adduct, and terephthalate Mixture with acid polycondensate.
(6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A Mixture of propylene oxide 2 mol adduct and polycondensate of terephthalic acid.
(7) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate with urea and ethylenediamine 2 mol adduct and terephthalic acid Mixture with condensate.
(8) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with diphenylmethane diisocyanate, and urethanized with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture with the polycondensate.
(9) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate was uread with hexamethylenediamine. And a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid.
(10) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with toluene diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture with the polycondensate.

The adhesive substrate (for example, a urea-modified polyester resin) is, for example, (1) a toner material containing a polymer (for example, an isocyanate group-containing polyester prepolymer (A)) that can react with an active hydrogen group-containing compound. A dispersion is emulsified or dispersed in an aqueous medium together with an active hydrogen group-containing compound (for example, amines (B)), oil droplets are formed, and both are subjected to an extension reaction or a crosslinking reaction in the aqueous medium. (2) A solution or dispersion of the toner material is emulsified or dispersed in an aqueous medium to which an active hydrogen group-containing compound has been added in advance to form oil droplets, and both are elongated in the aqueous medium. It may be produced by a reaction or a crosslinking reaction. Alternatively, (3) a toner material solution or dispersion is added and mixed in an aqueous medium, then an active hydrogen group-containing compound is added to form oil droplets, and both extend from the particle interface in the aqueous medium. It may be produced by a reaction or a crosslinking reaction. In the case of (3), the modified polyester resin is preferentially produced on the surface of the toner to be produced, and it becomes possible to provide a concentration gradient on the toner particles.
The reaction conditions for producing an adhesive substrate by emulsification or dispersion are not particularly limited, and are appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. be able to. In addition, as reaction time, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.

Examples of a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)) in an aqueous medium include, for example, an activity in an aqueous medium. Dissolve or disperse a toner material such as a polymer capable of reacting with a hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)), a colorant, a release agent, a charge control agent, and an unmodified polyester resin in an organic solvent. For example, a method of adding a solution or dispersion of a toner material prepared in such a manner and dispersing the toner material by shearing force may be used.
In emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material. This is because if the amount used is less than 50 parts by mass, the toner material is in a poorly dispersed state and toner particles having a predetermined particle size may not be obtained. Because it becomes.
In addition to the anionic surfactant and resin fine particles (A) described above, the following inorganic compound dispersants and polymer protective colloids can be used in combination with the aqueous medium. Examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

Examples of polymeric protective colloids include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers with vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amide compounds Alternatively, homopolymers or copolymers such as those having methylol compounds, chlorides, nitrogen atoms or heterocycles thereof, polyoxyethylenes, celluloses, and the like can be given. Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, Examples include glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like.
Examples of vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of esters of a compound containing vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Moreover, as an amide compound or these methylol compounds, acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds etc. are mentioned, for example.

Examples of chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine.
Examples of the polyoxyethylene type include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples include ethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
When using a dispersion stabilizer that is soluble in acids or alkalis such as calcium phosphate, remove the calcium phosphate from the fine particles by dissolving the calcium phosphate with an acid such as hydrochloric acid and then washing with water or decomposing with an enzyme. It becomes possible to do.

(Removal of organic solvent)
The organic solvent is removed from the emulsified slurry obtained by emulsification or dispersion. The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.
When the organic solvent is removed, toner particles are formed. The formed toner particles are washed, dried, etc., and then classified as desired. The classification is performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like. The classification operation may be performed after obtaining the powder after drying.
The toner particles thus obtained are mixed with particles such as a colorant, a release agent, and a charge control agent, and further a mechanical impact force is applied to the particles such as a release agent from the surface of the toner particles. Can be prevented from desorbing. As a method of applying a mechanical impact force, for example, a method of applying an impact force to a mixture with a blade rotating at high speed, a mixture of particles in a high-speed air stream and acceleration to accelerate or a composite particle to an appropriate collision plate And the like. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery). Mfg. Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

Hereinafter, the carrier used in the present invention will be specifically described.
As the basic structure of the carrier in the present invention, the basic structure of the carrier in the present invention is composed of core material particles having magnetism and a resin layer covering the surface thereof. The selection of the particle size is important. The carrier used in the developing method of the present invention has a weight average particle diameter Dw in the range of 20 to 45 μm. When the weight average particle diameter Dw is larger than the above range, carrier adhesion is less likely to occur, but the toner is not developed faithfully with respect to the electrostatic latent image, and the variation in the dot diameter increases and graininess (roughness). Decreases.
In addition, when a carrier having a weight average particle diameter Dw smaller than 20 μm is used, particles with small magnetization are present everywhere in the magnetic brush, and the carrier adhesion is rapidly deteriorated.

  Further, in the carrier particles having a weight average particle diameter Dw of 22 to 32 μm, sharp particles in which particles smaller than 36 μm are 80% by weight or more, more preferably 82% by weight or more and the content of particles smaller than 44 μm are 90% by weight or more. A carrier coated with a resin having a particle size distribution has a small variation in magnetization of each carrier particle, and carrier adhesion can be greatly improved by a developing method in which a DC bias is applied.

In particular, the content of particles having a particle size smaller than 20 μm is in the range of 0-7 wt%, the content of particles smaller than 36 μm is 80-100 wt%, and the content of particles smaller than 44 μm is 90-100 wt%. A carrier coated with a resin having a sharp particle size distribution becomes smaller in variation in magnetization of each carrier particle, and can greatly improve carrier adhesion.
Further, in the carrier particles having a weight average particle diameter Dw of 22 to 32 μm, sharp particles in which particles smaller than 36 μm are 80% by weight or more, more preferably 82% by weight or more and the content of particles smaller than 44 μm are 90% by weight or more. A carrier coated with a resin having a particle size distribution has a small variation in magnetization of each carrier particle, and carrier adhesion can be greatly improved by a developing method in which a DC bias is applied.

  Further, the carrier used in the present invention is preferably a carrier having a sharper particle size distribution and uniform particle size, and in addition to the above-mentioned regulation of the weight average particle diameter Dw, the carrier and the carrier regulated by the number average particle diameter Dp. Preferably, core material particles are used.

As a particle size analyzer for measuring the particle size distribution in the present invention, a Microtrac particle size analyzer (model HRA9320-X100: manufactured by Honeywell) was used.
In addition, the carrier according to the present invention requires a predetermined magnetization because of the need to form a magnetic brush. The amount of magnetization of such a carrier is the amount of magnetization when a magnetic field of 1000 oersted (Oe) is applied. 40-100 emu / g, more preferably 50e-90 mu / g. When it becomes less than 40 emu / g, carrier adhesion tends to occur, and when it becomes 100 emu / g or more, the head trace of the magnetic brush becomes strong.

The amount of magnetization can be measured as follows. A BH tracer (BHU-60 / manufactured by Riken Denshi Co., Ltd.) is used, and 1 g of carrier core particles are packed in a cylindrical cell and set in an apparatus. The magnetic field is gradually increased and changed to 3000 oersted, then gradually reduced to zero, and then the opposite magnetic field is gradually increased to 3000 oersted. Further, after gradually reducing the magnetic field to zero, a magnetic field is applied in the same direction as the first. In this way, a BH curve is drawn, and a magnetic moment of 1000 Oersted is calculated from the figure.
The amount of magnetization of such carriers is basically determined by the magnetic material that becomes the core particles. Examples of the core particles that are 40 emu / g or more when a 1000 oersted magnetic field used in the carrier of the present invention is applied include, for example, ferromagnetic materials such as iron and cobalt, magnetite, hematite, Li-based ferrite, and MnZn-based materials. Examples thereof include ferrite, CuZn ferrite, NiZn ferrite, Ba ferrite, and Mn ferrite.

The core particles used in the carrier of the present invention are crushed particles of magnetic material, or in the case of core materials such as ferrite and magnetite, the primary granulated product before classification is classified, and the sintered particles are classified. It can be obtained by mixing a plurality of particle powders after classification into particle powders having different particle size distributions by treatment.
As a method of classifying the core particles, conventionally known classification methods such as a sieving machine, a gravity classifier, a centrifugal classifier, and an inertia classifier can be used, but the productivity is easy and the classification point can be easily changed. Therefore, it is preferable to use an air classifier such as a gravity classifier, a centrifugal classifier, or an inertia classifier.

  In the carrier of the present invention, the electrical resistivity (log R) is preferably in the range of 11.0 to 17.0 Ω · cm, and more preferably in the range of 11.5 to 16.5 Ω · cm. When the resistivity logR of the carrier is less than 11.0 Ω · cm, when the developing gap (the closest distance between the photosensitive member and the developing sleeve) is narrowed, charges are induced in the carrier and carrier adhesion is likely to occur. When it is larger than 17.0 Ω · cm, the edge effect becomes strong and the image density of the solid image portion becomes low. On the other hand, when LogR is greater than 17.0 Ω · cm, charges having the opposite polarity to the toner are likely to be accumulated, and the carrier is charged and carrier adhesion is likely to occur.

The resistivity of the carrier can be adjusted by adjusting the resistance of the coating resin on the core particles and controlling the coating layer thickness. Moreover, it is also possible to add conductive fine powder to the coating resin layer for carrier resistance adjustment. Examples of the conductive fine powder include conductive metals such as ZnO and Al, or cerium oxide, alumina, for example, metal oxides such as SiO ₂ and TiO ₂ having a hydrophobic surface, SnO ₂ prepared by various methods, and various _{SnO 2, TiB 2, ZnB 2} , borides such as MoB ₂ that doped with elements, silicon carbide, polyacetylene, polyparaphenylene, poly (para - phenylene sulfide) polypyrrole, a conductive polymer such as polyethylene, furnace black, Examples thereof include carbon black such as acetylene black and channel black.

  These conductive fine powders can be obtained by the following methods: a dispersing machine using a medium such as a ball mill or a bead mill after the conductive fine powder is put into a solvent used for coating or a resin solution for coating, or a blade rotating at high speed. The dispersion for forming a coating layer is prepared by uniformly dispersing by using a stirrer equipped with, and the carrier can be prepared by applying the dispersion for forming a coating layer to the core material particles.

As the resin used for the carrier coating layer, various conventionally known resins can be used, and a silicone resin is preferably used.
In the present invention, a straight silicone resin can be used as the silicone resin. Examples thereof include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2406 (manufactured by Toray Dow Corning Silicone).

In the present invention, a modified silicone resin can be used as the silicone resin. Examples of such a resin include epoxy-modified silicone, acrylic-modified silicone, phenol-modified silicone, urethane-modified silicone, polyester-modified silicone, and alkyd-modified silicone. Specific examples of the modified silicone resin include epoxy modified product: ES-1001N, acrylic modified silicone: KR-5208, polyester modified product: KR-5203, alkyd modified product: KR-206, urethane modified product: KR-305 ( As mentioned above, Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.
Furthermore, in this invention, it is also possible to use the resin shown below individually or in mixture with the said silicone resin.

  Polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, Styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer) Polymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylate copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, Styrene-phenyl methacrylate copolymer, etc.) Styrenic resins such as styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, epoxy resin, polyester resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, ketone resin, ethylene -An ethyl acrylate copolymer, a xylene resin, a polyamide resin, a phenol resin, a polycarbonate resin, a melamine resin, a fluorine resin, or the like can be suitably mixed with the silicone resin.

In the present invention, a carrier having good durability can be obtained by adding an aminosilane coupling agent to the coating layer made of the silicone resin.
The aminosilane coupling agent used in the present invention is preferably 0.001 to 30% by weight.
As a method for forming the resin coating layer on the surface of the carrier core material particles, a known method such as a spray drying method, a dipping method or a powder coating method can be used. In particular, the method using a fluidized bed type coating apparatus is effective for forming a uniform coating layer.
The thickness of the coating layer on the surface of the carrier core particles is usually 0.02-1 μm, preferably 0.03-0.8 μm. Since the thickness of the coating layer is extremely small, the carrier having the coating layer formed on the surface of the core particle and the carrier core particle have substantially the same particle size.
In this case, the carrier bulk density affects the carrier adhesion, but the carrier bulk density recommended in the present invention is 2.15 to 2.70 g / cm ³ , more preferably 2.25 to 2.60 g / cm ³ . When the carrier is porous, or the surface irregularities are large and the bulk density is less than 2.15, the substantial magnetization per particle is increased even if the amount of magnetization (emu / g) of 1 KOe of the core particle is large. Since the value is small, it is disadvantageous for carrier adhesion.
To increase the bulk density, it is possible to increase the firing temperature. However, it is preferable that the core particles are less than 2.7 g / cm ³ because the core particles are easily fused and difficult to disintegrate. More preferably, it is less than 6 g / cm ³ .
According to the metal powder-apparent density test method (JIS-Z-2504), the carrier according to the present invention has a bulk density of 25 cm ³ made of stainless steel, which is allowed to flow naturally from an orifice having a diameter of 2.5 mm. After pouring the carrier into the cylindrical container until it overflows, the upper surface of the container is scraped flat with a single operation along the upper end of the container using a nonmagnetic horizontal spatula. If it is difficult to flow with an orifice having a diameter of 2.5 mm, the carrier naturally flows out from the orifice having a diameter of 5 mm. By this operation, the weight of the carrier per cm ^{3 is} obtained by dividing the weight of the carrier flowing into the container by the volume of the container 25 cm ³ . This is defined as the bulk density of the carrier.

In the following examples, the production of the toner of the present invention will be described in detail. The change in the amount of surface wax due to the heating and carrier contact history shown in the range of the above formulas (1) to (3) of the present invention is controlled. This state is preferably achieved by aqueous granulation.
In the method of granulating the toner by dispersing the oil phase and the toner composition primary particles in the aqueous medium, the polarity of the aqueous medium, the polarity of each material of the toner composition, and the solvent or monomer that forms the oil phase are used. Existence and uneven distribution of each material inside the toner are largely controlled.
For example, when the binder resin and the release agent are compared, the release agent often has a lower polarity tendency. Although the tendency varies depending on the solvent species and monomer species forming the oil phase, generally, a material having a polarity similar to that of the aqueous medium tends to be relatively unevenly distributed on the surface side of the toner particles.
In the case of a binder resin, major factors governing polarity include an acid value and a hydroxyl value, and by selecting these, the state of affinity between the aqueous medium and the wax is determined.
In contrast, waxes are often less polar than binder resins. Therefore, in the case of wax, not only in terms of polarity, but also a wax dispersant (for example, styrene / polyethylene polymer (Tg = 72 ° C., number average) added to improve the dispersibility and affinity for the binder resin. (The molecular weight of 7100 can be preferably used), and the dispersion state can be suitably formed in the binder resin, and the dispersibility in the binder resin is governed by the type and amount of the wax dispersant.
In order to increase the wax inclusion, there are an increase in the amount of the wax dispersant, an increase in the acid value of the binder resin, and a decrease in the polarity of the wax.
Thus, although the amount existing on the surface of the wax can be controlled to some extent, it is difficult to keep it within the range defined in the present invention, and it is necessary to produce the toner by the above-described toner manufacturing method.

  The method for producing a toner of the present invention includes a step of dissolving or dispersing a toner material containing at least a binder resin or a binder resin precursor in an organic solvent to prepare a toner material dissolved or dispersed liquid, and dissolving the toner material Alternatively, the dispersion is added to an aqueous medium containing an anionic fine resin particle (A) having an average particle diameter of 5 to 50 nm and an anionic surfactant, and emulsified or dispersed to prepare an emulsified or dispersed liquid. And a step of removing the organic solvent from the emulsified or dispersed liquid. Moreover, the step of preparing the emulsification or dispersion includes a step of adding resin fine particles (B) having an average particle size of 50 to 500 nm in the aqueous medium. The resin fine particles (B) may be added to the aqueous medium before or after the addition of the anionic resin fine particles (A) or the anionic surfactant, or the toner material is further dissolved or dispersed in the aqueous medium. Or after further emulsification of this aqueous medium by stirring or the like. That is, in the next step of removing the organic solvent, the resin fine particles (B) may be added so as to adhere to the surface of the toner particle main body having the toner material as a core. In the toner manufactured by the above manufacturing method, the resin fine particles (A) and the resin fine particles (B) are attached to the surface of the toner particle main body having the toner material mainly including the colorant and the binder resin as the core. However, since the resin fine particles (A) have a small particle diameter, they are buried in the toner particle main body or adhered between the toner particle main body and the resin fine particle (B). Therefore, if the toner is not observed very finely, the toner appears to have resin fine particles (B) attached to the surface of the toner particle main body. The average particle size of the toner is adjusted by emulsification or dispersion conditions such as stirring of the aqueous medium in the emulsification step.

  In the toner produced by the production method of the present invention, fine particles having a large particle size (resin fine particles (B)) are attached to the toner surface, and the large particle size fine particles have a certain degree of hardness. Thus, the non-electrostatic adhesion force of the toner particles is reduced, and even when the transfer time is shortened as in a high-speed machine, sufficient transfer efficiency can be obtained without impairing the fixing property. Furthermore, since the large particle size has sufficient hardness, the large particle size particles adhering to the surface of the toner are contained in the toner even when the mechanical stress with time is large as in a high-speed machine. Since it can continue to exist without being buried, it is possible to maintain a sufficient transfer efficiency even in the long term. At the same time, it is possible to prevent the external additive from adhering to the toner surface from being buried.

According to this production method, the resin fine particles (B) are added before or after emulsification. At this timing, since the organic solvent is present in the toner composition droplets, the resin fine particles (B) enter the droplet surface to some extent after adhering to the droplet surface, and adhere to the toner surface after the organic solvent is removed. A desirable form such as being fixed can be realized.
The anionic resin fine particles (A) adhere to the toner surface, and are fused and fused to form a relatively hard surface. Therefore, there is an effect of preventing the resin fine particles (B) adhered and fixed from being buried or moved due to mechanical stress. Further, since the resin fine particles (A) have an anionic property, the resin fine particles (A) have an effect of adsorbing to the droplets containing the toner material and suppressing coalescence of the droplets, and are important for controlling the particle size distribution of the toner. Furthermore, negative chargeability of the toner can be given. In order to exert these effects, the anionic resin fine particles (A) are preferably made smaller than the resin fine particles (B) and the average particle diameter is 5 to 50 nm.

It is preferable that at least a large fine particle (resin fine particle (B)) having a primary average particle diameter of 50 to 500 nm is adhered and solidified on the surface of the toner, and in particular, a large particle diameter of 100 to 400 nm is adhered and solidified. It is preferable. As a result, the non-electrostatic adhesion force of the toner particles can be reduced by the spacer effect, and even when the mechanical stress with the passage of time is large as in a high-speed machine, the static particles are buried by the surface of the toner. It is possible to suppress an increase in the electric adhesion force, and it is possible to maintain a sufficient transfer efficiency over a long period. In particular, the toner produced by the production method of the present invention is very effective when it has a primary transfer process, a secondary transfer process, and two transfer processes in the intermediate transfer system. The effect can be exerted particularly greatly in a relatively high-speed image forming process (transfer linear speed 300 to 1000 mm / sec, transfer time at the secondary nip portion 0.5 to 20 msec). In a process with a lower linear speed and a shorter secondary transfer time than this, the difference between the present invention and a toner not having resin fine particles (B) on the surface is not large. Further, when the speed is higher than this, the transfer efficiency tends to be prevented from being lowered.
When the primary average particle diameter of the resin fine particles (B) is smaller than 50 nm, the spacer effect cannot be sufficiently obtained, so that the non-electrostatic adhesion force of the toner particles cannot be reduced. As described above, when the mechanical stress with time is large, the resin fine particles (B) and the external additive are easily buried in the toner surface, and there is a possibility that sufficient transfer efficiency cannot be maintained over a long period of time. Further, when the primary average particle diameter of the resin fine particles (B) is larger than 500 nm, the fluidity of the toner is deteriorated, and the uniform transferability may be hindered.

  The binder resin is preferably a polyester resin. The polyester resin has little compatibility with the resin fine particles (B), and is particularly compatible when the resin fine particles (B) are fine particles of a crosslinked resin containing a styrene polymer, an acrylate polymer, or a methacrylic ester polymer. There is no. In the emulsification step, when the resin fine particles (B) are added before or after emulsification, the organic fine particles are present in the droplets of the toner material, so that the resin fine particles (B) are dissolved after adhering to the droplet surfaces. May end up. When the resin component constituting the toner is a polyester resin and the resin fine particles (B) are fine particles of a crosslinked resin containing a styrene polymer, an acrylate polymer, or a methacrylic ester polymer, the compatibility between the resins is Since it is bad, the resin fine particles (B) are present in a state where they are incompatible with the droplets of the toner material. Accordingly, it is possible to achieve a desirable form in which the ink enters to some extent from the surface of the droplet and is adhered and fixed to the toner surface after the organic solvent is removed.

The resin fine particles (B) preferably have a property of forming aggregates in the aqueous anionic surfactant solution. In the production method of the present invention, when the resin fine particles (B) are added before or after emulsification in the emulsification step, the resin fine particles (B) do not adhere to the droplets of the toner material and exist independently and stably. That is not preferable. Since the resin fine particles (B) have the property of forming aggregates in an aqueous medium containing an anionic surfactant, the resin fine particles present on the aqueous phase side during or after emulsification are droplets of toner material. It moves to the surface and can easily adhere to the droplet surface of the toner material. That is, in an aqueous medium containing an anionic surfactant, the resin fine particles (B) are unstable and usually aggregate, and if there is a droplet of toner material, the attractive force with the droplet of toner material is present. When it is strong, a complex of different particles is formed.
The resulting composite exhibits a strong adhesive force as it is, but after emulsification the resin fine particles move to the surface of the toner material droplets and adhere to the surface of the toner material droplets, and then become stronger by a heating process. Can be fixed on the toner surface. The fixing temperature is preferably higher than the glass transition point of the resin used for the toner.
The toner material preferably contains an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the compound. By containing an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the compound in the droplets of the toner material, the mechanical strength of the resulting toner is increased and the embedding of the resin fine particles (B) and external additives is suppressed. I can do it. When the active hydrogen group-containing compound has a cationic polarity, the resin fine particles (B) can be attracted electrostatically. Further, the fluidity of the toner during heat fixing can be adjusted, and the fixing temperature range can be widened.

The amount of the resin fine particles (B) added is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight, based on 100% by weight of the toner. When the added ratio is less than 0.5% by weight, the spacer effect cannot be sufficiently obtained, and the non-electrostatic adhesion force of the toner particles cannot be reduced. In such a case, the fluidity of the toner is deteriorated, the uniform transferability is hindered, the fine particles cannot be sufficiently fixed to the toner and are easily detached, and the toner adheres to the carrier or the photoconductor to contaminate the photoconductor. There is a risk.
In general, the toner filled in the developing machine is attached to the toner particles mainly by mechanical stress inside the developing machine because the resin particles on the toner surface are embedded in the toner or moved to the recesses on the surface of the toner particle main body. The effect of reducing the wearing force is lost. Further, when the external additive is exposed to the same stress, it is buried inside the toner, and the adhesion force of the toner is increased. Further, when the toner has a large amount of surface wax, there is a concern that mechanical stress promotes an increase in non-electrostatic adhesion to the carrier and leads to poor development.
However, in the toner according to the manufacturing method of the present invention, the resin fine particles (B) are relatively large and difficult to be embedded in the toner particle main body, and the layer of the resin fine particles (A) suppresses the exudation of wax near the surface. It is possible to suppress an increase in toner adhesion due to mechanical stress inside. Even if the wax in the vicinity of the surface oozes out, the resin fine particles (B) exhibit a spacer effect with the carrier and thus do not directly adhere to the carrier.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to the Example and comparative example which are illustrated here. In addition, the part in an Example represents a mass part unless there is particular description.

[Production of toner]
A specific preparation example of the toner used for evaluation will be described. The toner used in the present invention is not limited to these examples.
(Preparation of solution or dispersion of toner material)
~ Synthesis of unmodified polyester (low molecular weight polyester) ~
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

-Preparation of masterbatch (MB)-
1000 parts by mass of water, 540 parts by mass of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by mass of the unmodified polyester were combined with a Henschel mixer (Mitsui Mine). Mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

~ Preparation of wax dispersion ~
In a reaction vessel equipped with a stirrer and a thermometer, 378 parts of unmodified polyester resin (1), 110 parts of carnauba wax, salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.)
22 parts and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 [° C.] with stirring. The temperature was maintained at 80 [° C.] for 5 [hours], and then cooled to 30 [° C.] over 1 [hour]. Next, 500 parts of master batch (1) and 500 parts of ethyl acetate were charged into the reaction vessel, and mixed for 1 [hour] to obtain a raw material solution (1).
1324 parts of the obtained raw material solution (1) was transferred to a reaction vessel and filled with 80 [volume%] of 0.5 mm zirconia beads using an ultraviscomil (made by Imex Co., Ltd.), a bead mill. [Kg / hour], disk pass speed is 6 [m / sec], 3 passes, C
. I. Pigment Red and carnauba wax were dispersed to obtain a wax dispersion (1).

~ Preparation of dispersion of toner material ~
Next, 1324 parts of a 65% by weight ethyl acetate solution of the unmodified polyester resin (1) was added to the wax dispersion (1). A layered inorganic mineral montmorillonite (Clayton APA Southern) modified at least partly with a quaternary ammonium salt having a benzyl group was added to 200 parts of a dispersion obtained by one pass using Ultraviscomyl under the same conditions as above.
1.0 part of Cray Products) was added. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 30 minutes to obtain a toner material dispersion (1).

-Preparation of resin fine particles (A)-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 16 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours. A dispersion [resin fine particle (A) dispersion 1] was obtained. The volume average particle size of the [resin fine particle (A) dispersion 1] (measured with LA-920 manufactured by Horiba, Ltd.) was 9 nm.

-Preparation of resin fine particles (B)-
A reaction vessel equipped with a stir bar and thermometer was charged with 683 parts of water, 10 parts of distearyldimethylammonium chloride (cation DS, manufactured by Kao), 138 parts of styrene, 138 parts of methyl methacrylate, and 1 part of ammonium persulfate, and rotated 400 times. The mixture was stirred for 15 minutes at / min, and a white emulsion was obtained. The system was heated to raise the temperature in the system to 65 ° C. and reacted for 10 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous dispersion (resin fine particle (B) dispersion 1) of a vinyl resin (styrene-methyl methacrylate). The volume average particle size of the [resin fine particle dispersion 1] (measured with LA-920 manufactured by Horiba, Ltd.) was 42 nm.

(Manufacture of toner a)
-Preparation of aqueous medium phase-
660 parts by weight of water, 25 parts by weight of the resin fine particle (A) dispersion 1, 25 parts by weight of an aqueous solution of 48.5% by weight of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 60 parts by mass of ethyl acetate was mixed and stirred to obtain a milky white liquid (aqueous phase). Further, 50 parts by weight of resin fine particles 1 were added. When observed with an optical microscope, several hundred μm aggregates were observed.

~ Emulsification or preparation of dispersion ~
150 parts by mass of the aqueous medium phase and 1.0 part by weight of inorganic fine particles are put in a container and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 100 parts by mass of the solution or dispersion of the mixture was added and mixed for 10 minutes to prepare an emulsion or dispersion (emulsified slurry).

~ Removal of organic solvent ~
Into a flask equipped with a degassing pipe, a stirrer, and a thermometer, 100 parts by mass of the emulsified slurry was charged, and the solvent was removed under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. did. Thereafter, the dispersion was heated to 60 ° C. to fix the fine particles B1 adhering to the toner surface.

~Washing~
After filtering the whole amount of the solvent removal slurry A under reduced pressure, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer, redispersed (at 12,000 rpm for 10 minutes) and then filtered. . To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered three times.

~ Dry ~
After the heat treatment, the cake was dried at 45 ° C. for 48 hours in a forward air dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner particles a.
[Carrier production]
[Carrier coating layer]
・ Silicon resin solution [solid content: 23% by weight
(SR2410: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 132.2 parts by weight / aminosilane [solid content: 100% by weight
(SH6020: manufactured by Toray Dow Corning Silicone Co.)] 0.66 parts by weight of aluminum oxide
Particle size: 0.40 μm, true specific gravity: 3.9 145 parts by weight / 300 parts by weight of toluene were dispersed with a homomixer for 10 minutes to obtain a silicon resin coating film forming solution. Spiral coater (Okada Seiko Co., Ltd.) using 5000 parts by weight of an average particle size of 35 μm sintered ferrite powder (true specific gravity 5.5) as the core material, and having the coating film forming solution on the surface of the core material to a thickness of 0.15 μm. Applied to the coater at a temperature of 40 ° C. and dried. The obtained carrier was baked by standing in an electric furnace at 240 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 63 μm, D / h: 2.3, volume resistivity: 15.9 [Log (Ω · cm)], magnetization: 68 Am ² / kg [ Career].
The toner a obtained above was evaluated as follows.
As evaluation items, the image density unevenness and hot offset state were evaluated from the image.

<Evaluation of uneven image density>
1. All toners and devices used for evaluation are left in an environment room at 25 ° C. and 50% for one day.
2. All toner on the PCU of the image forming apparatus is removed, leaving only the carrier in the developing device.
3. 36 g of black toner serving as a sample is put into a developing device including only a carrier, and 400 g of a developer having a toner concentration of 9% is prepared.
4). The developing device is mounted on the image forming apparatus main body, and only the developing device is idled for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
5). Both the developing sleeve and the photosensitive member were rotated by trailing at a target linear velocity, and the charging potential and the developing bias were adjusted so that the toner on the photosensitive member was 0.6 ± 0.05 mg / cm ² .
6). The cleaning blade was only one cleaning blade mounted on a commercially available Imagio neo C600 PCU, its elastic modulus was 70%, the thickness was 2 mm, and the contact angle with the image carrier at the counter was 20 °.
7). Under the above development conditions, the transfer current is adjusted so that the transfer rate is 96 ± 2%.
8). Using the set values, 1000 halftone images were output.
9. The 1000th image was ranked by visual evaluation.

Judgment criteria ○: Density unevenness is not visible at visual level
Δ: Some density unevenness is observed, but it is not noticeable and does not cause a problem
X: Vivid density unevenness is observed, which causes a problem on an image.

<Fixing separation evaluation>
1. Using an externally added toner (developer), Ricoh's ipsio CX2500, an unfixed image in which a solid belt image (adhesion amount 9 g / m ² ) having a width of 36 mm is printed on the tip 3 mm with A4 longitudinal paper. To do.
2. This unfixed image is fixed at a fixing temperature in increments of 10 ° C. in the range of 130 ° C. to 190 ° C. using the following fixing device, and a separable / non-offset temperature range is obtained. The temperature range refers to a fixing temperature range in which the paper is satisfactorily separated from the heating roller, no offset phenomenon occurs, and image peeling does not easily occur. The paper used and the paper passing direction were 45 g / m ² of Y-long vertical paper that is disadvantageous in separability. The peripheral speed of the fixing device was 120 mm / sec. The fixing device is of a soft roller type having a fluorine surface layer composition. Specifically, the heating roller has an outer diameter of 40 mm, an aluminum core metal having a thickness of 1.5 mm made of silicone rubber, and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer. It has a heater inside the aluminum core. The pressure roller has an outer diameter of 40 mm, and has an elastic body layer made of silicone rubber and a PFA surface layer made of silicone rubber on an aluminum core. Note that the paper on which the unfixed image is printed is passed.

Judgment criteria ○: Separable / non-offset temperature range was 50 ° C or higher
Δ: Separable / non-offset temperature range was 30 ° C or higher and lower than 50 ° C
X: The separable / non-offset temperature range was less than 30 ° C.

  Example 1 Toner b was obtained in the same manner as in Example 1 except that the amount of wax in the production process of toner a was changed from 4 parts by weight to 6 parts by weight with respect to the total toner weight.

  Example 1 Toner c was obtained in the same manner as in Example 1 except that the amount of wax in the production process of toner a was changed from 4 parts by weight to 2 parts by weight with respect to the total toner weight.

  Example 1 Toner d was obtained in the same manner as in Example 1 except that the wax type was changed from carnauba wax to paraffin wax in the production process of toner a.

  Example 4 A toner e was obtained in the same manner except that the amount of wax in the production process of the toner d was changed from 4 parts by weight to 6 parts by weight with respect to the total weight of the toner.

  Example 4 A toner f was obtained in the same manner except that the amount of wax in the production process of the toner d was changed from 4 parts by weight to 2 parts by weight with respect to the total weight of the toner.

  Example 1 Toner g was obtained in the same manner as in Example 1 except that carnauba wax was changed to microcrystalline wax in the production process of toner a.

  Example 7 Toner h was obtained in the same manner as in Example 7 except that the amount of wax in the production process of toner g was changed from 10 parts by weight to 15 parts by weight.

  Example 7 Toner i was obtained in the same manner as in Example 7 except that the amount of wax in the production process of toner g was changed from 4 parts by weight to 6 parts by weight with respect to the total toner weight.

(Comparative Example 1)
In Comparative Example 1, a toner prepared by the following production method was used.
(Adjustment of resin emulsion)
The following monomers are mixed uniformly to prepare a monomer mixture.
Styrene monomer 71 parts n-butyl acrylate 25 parts acrylic acid 4 parts The following aqueous solution mixture is placed in a reactor and heated to 70 ° C under stirring. While stirring the liquid temperature at 70 ° C., 5 parts of the monomer mixture and 1% aqueous solution of potassium persulfate were added dropwise simultaneously over 4 hours, and further polymerized at 70 ° C. for 2 hours to obtain a solid content of 50%. A resin emulsion was obtained.
Water 100 parts Nonionic emulsifier (Emulgen 950) 1 part Anionic emulsifier (Neogen R) 1.5 parts

(Preparation of wax emulsion)
The following aqueous solution mixture was put in a reactor, heated under stirring at 70 ° C. until the wax particles were completely dissolved, and cooled by cooling to obtain a wax emulsion.
Carnauba wax 100 parts Nonionic emulsifier 20 parts
380 parts of water

(Toner particle adjustment)
The following mixture was stirred for 2 hours at 25 ° C. using a disper.
Pigment 20 parts Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) 1 part Anionic emulsifier (Neogen R) 0.5 part Wax emulsion 15 parts Water 310 parts Next, 188 parts of the above emulsion was added to this dispersion, and After stirring for 2 hours, the mixture was heated to 60 ° C. and adjusted to pH 7.0 with ammonia. Further, this dispersion was heated to 90 ° C. and maintained at this temperature for 2 hours to obtain dispersion slurry 1.
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 10% hydrochloric acid was added to the filter cake of (1) to prepare a pH of 2.8, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(3): Add 300 parts of ion-exchanged water to the filter cake of (2), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1]. It was.
[Filter cake 1] was dried with a circulating dryer at 45 ° C. for 48 hours and sieved with a mesh having a mesh size of 75 μm to obtain a toner having a weight average particle diameter of 5.9 μm. Further, R972 (silica manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 0.016 μm) was externally added as a fluidity imparting agent at a ratio of 1.2 parts to 100 parts of toner to obtain toner j.

(Comparative Example 2)
Comparative Example 1 Toner k was obtained in the same manner except that the amount of wax in the production process of toner j was changed from 15 parts by weight to 5 parts by weight and the wax was changed to paraffin.

(Comparative Example 3)
Comparative Example 1 Toner l was obtained in the same manner except that the amount of wax in the production process of toner j was changed from 6 parts by weight to 2 parts by weight with respect to the total weight of the toner, and the wax was changed to microcrystalline.

(Comparative Example 4)
Comparative Example 1 Toner m was obtained in the same manner except that the amount of wax in the production process of toner j was changed from 6 parts by weight to 4 parts by weight with respect to the total toner weight.

(Comparative Example 5)
Comparative Example 1 Toner n was obtained in the same manner except that the wax in the production process of toner j was changed to paraffin.

(Comparative Example 6)
Comparative Example 1 Toner o was obtained in the same manner except that the amount of wax in the production process of toner j was changed from 6 parts by weight to 4 parts by weight with respect to the total toner weight, and the wax was changed to microcrystalline.

In FIG. 5 (however, in FIGS. 5A and 5B, ● represents a toner having excellent image unevenness and fixing separation property, and ◆ represents a toner having a problem in image unevenness and fixing separation property. Further, the black frame range is a preferable range within the present invention range and the white frame range (no black frame and no white frame).
From this result, it was revealed that the toner within the scope of the present invention is a toner excellent in image quality and fixing separation property.

  Table 1 shows the physical property values of the toners of Examples and Comparative Examples of the present invention, and Table 2 shows the evaluation results of image unevenness and fixing separation of the toners of Examples and Comparative Examples of the present invention.

(Figures 1 and 2)
DESCRIPTION OF SYMBOLS 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developing apparatus 41 Developing belt 42K Developer accommodating part 42Y Developer accommodating part 42M Developer accommodating part 42C Developer accommodating part 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller 44Y Development roller 44M Development roller 44C Development roller 45K Black developer (black development unit)
45Y Yellow development unit (Yellow development unit)
45M Magenta Developer (Magenta Developer Unit)
45C cyan developer (cyan development unit)
50 Intermediate transfer member 51 Roller 58 Corona charger 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Recording paper (transfer paper)
100A Image forming apparatus 100B Image forming apparatus

(Figs. 3 and 4)
7 endless belt-like 10 photoconductor 10K photoconductor for black 10Y photoconductor for yellow 10M photoconductor for magenta 10C photoconductor for cyan 11 intermediate transfer member cleaning device 14 support roller 15 support roller 16 support roller 17 intermediate transfer member cleaning device 18 image Forming means 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading Sensor 49 Registration roller 50 Intermediate transfer body 52 Manual feed tray 53 Manual feed path 55 Switching claw 56 Ejection roller 57 Ejection tray 59 Charger 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 100C Image forming device 120 Tandem Type developer 30 Document platen 142a Paper feed roller 142b Paper feed roller 143 Paper bank 144 Paper cassette 145a Separation roller 145b Separation roller 146 Paper feed path 147 Carriage roller 148 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder L exposure

JP 2004-246345 A JP 2007-249082 A

Claims (11)

A two-component developer for developing an electrostatic charge image comprising a carrier made of toner and magnetic particles prepared by aqueous granulation,
Regarding the toner surface wax amount before and after stirring when the developer in which the toner and the carrier are mixed at a toner concentration of 9% is stirred with a mag roll for 90 minutes, the amount of change in the FTIR-ATR measured value is within the following range. A two-component developer characterized by being.
P (A) ≦ 0.20 (1)
0.03 ≦ P (B) ≦ 0.25 (2)
P (A) ≦ P (B) (3)
P (A): amount of surface wax before air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]
P (B): Amount of surface wax after air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]   The toner includes at least a binder resin, a colorant, a release agent, and a modified layered inorganic mineral, and in the modified layered inorganic mineral, at least a part of interlayer ions in the layered inorganic mineral is modified with organic ions. The two-component developer according to claim 1.   The toner includes at least a part of an interlayer ion in a prepolymer made of a binder resin, a modified polyester resin, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and a layered inorganic mineral in at least an organic solvent. Obtained by dissolving or dispersing a modified layered inorganic mineral modified with organic ions to prepare a solution or dispersion, emulsifying or dispersing the solution or dispersion in an aqueous medium, and causing a crosslinking reaction or elongation reaction. The two-component developer according to claim 2, wherein the two-component developer is obtained by removing the solvent from the obtained dispersion.   4. The toner according to claim 3, wherein the modified layered inorganic mineral is contained in an amount of 0.05 mass% to 10 mass% in a solid content of the solution or dispersion. Two component developer. The toner has small particle size silica attached thereto, and the BET specific surface area of the small particle size silica is in the range of 50 [m ² / g] to 400 [m ² / g], and the average circularity of the toner is The two-component developer according to claim 1, wherein A is in the range of 0.94 ≦ A ≦ 0.99.   The volume average particle diameter of the toner is 3 [μm] to 8 [μm], and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1.n. The two-component developer according to any one of claims 1 to 5, which is in the range of 30.   7. The two-component developer according to claim 1, wherein particles having a particle diameter of 2 μm or less are 1 [number%] to 10 [number%].   Development comprising: a developer carrier that carries a developer to be supplied to the image carrier on the surface; a developer supply member that supplies the developer to the surface of the developer carrier; and a developer container that contains the developer. A developing means characterized in that the two-component developer according to any one of claims 1 to 7 is accommodated.   A charging means for charging the surface of the image carrier; an exposure means for forming a latent image on the image carrier by exposing the surface of the image carrier; and developing a visible image by developing toner on the latent image. A developing unit for forming the visible image, a transfer unit for transferring the visible image to a recording medium or an intermediate transfer member, a fixing unit for fixing the transfer image transferred to the recording medium, and the recording medium to the intermediate transfer member. 9. An image forming apparatus, comprising: a cleaning unit that cleans transfer residual toner on the image carrier that has not been completely transferred; and the developing unit according to claim 8 as the developing unit.   At least one selected from a developing device, a charging device for charging the latent image carrier, and a cleaning device for cleaning the surface of the development carrier after transfer, and the latent image carrier are integrally supported, and an image is formed as a process cartridge. The image forming apparatus according to claim 9, wherein the image forming apparatus is configured to be detachable from the forming apparatus main body. An electrostatic charge image developing toner, the toner is produced by aqueous granulation,
The amount of change in the FTIR-ATR measured value for the toner surface wax amount before and after stirring when the developer in which the two-component electrostatic charge image developing carrier and the toner are mixed at a toner concentration of 9% is stirred for 90 minutes with a mag roll is as follows: A toner for developing an electrostatic charge image, characterized by being in the range.
P (A) ≦ 0.20 (1)
0.03 ≦ P (B) ≦ 0.25 (2)
P (A) ≦ P (B) (3)
P (A): amount of surface wax before air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]
P (B): Amount of surface wax after air stirring with mag roll for 90 minutes [peak derived from wax (2850 cm ⁻¹ ) / peak derived from binder resin (828 cm ⁻¹ )]

Images