JP4602880B2 - Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method. .

In an electrophotographic apparatus, an electrostatic recording apparatus, etc., a toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a recording medium, and then fixed on the recording medium by heat to form a toner image. Is forming. Also, full-color image formation generally involves color reproduction using four color toners of black, yellow, magenta, and cyan. Each color is developed, and each toner layer is superimposed on a recording medium. The toner image is heated and fixed at the same time, thereby forming a full-color image.
However, from the viewpoint of users who are familiar with printing, in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-resolution, and high resolution. It is known that a toner having a small particle size and a narrow particle size distribution is effective for improving the quality of a photographic image.

Conventionally, an electrical or magnetic latent image has been developed with toner. The toner used for this electrostatic image development is generally colored particles containing a colorant, a charge control agent, and other additives in a binder resin. The toner production methods are roughly classified into a pulverization method and a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and dispersed uniformly in a thermoplastic resin, and the resulting toner composition is pulverized and classified to produce toner. is doing.
According to the pulverization method, it is possible to produce a toner having excellent properties to some extent, but there are limitations on the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be made sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and if an attempt is made to obtain a copy image with good resolution and gradation, for example, A fine powder having a diameter of 5 μm or less and a coarse powder having a diameter of 20 μm or more must be removed by classification, which has a disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse additives such as a colorant and a charge control agent in the thermoplastic resin. Such non-uniform dispersion of additives adversely affects toner fluidity, developability, durability, image quality, and the like.

  In recent years, in order to overcome these problems in the pulverization method, for example, toner particles are obtained by a suspension polymerization method (see Patent Document 1). However, the toner particles obtained by this suspension polymerization method are spherical, but have the disadvantage of poor cleaning properties. In development and transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not become a problem. However, untransferred images were formed due to high image area ratios such as photographic images, as well as poor paper feed. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Furthermore, the low-temperature fixability is not sufficient, and a lot of energy required for fixing is required.

  On the other hand, a method of obtaining irregular toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 2). However, in the toner particles obtained by this emulsion polymerization method, the surfactant remains in a large amount not only on the surface but also inside the particles even after the water washing step, and the environmental stability of toner charging is impaired. The charge amount distribution is widened, and the background stain of the obtained image becomes poor. Further, the remaining surfactant may contaminate the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability may not be exhibited.

  Further, in a fixing process by a contact heating method performed using a heating member such as a heat roller, the toner particles are required to be releasable from the heating member (hereinafter sometimes referred to as “offset resistance”). Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, in Patent Document 3 and Patent Document 4, there is a method in which not only the resin fine particles are contained in the toner particles but also the resin fine particles are unevenly distributed on the surface of the toner particles, thereby improving the offset resistance. Proposed. However, this proposal has a problem that the fixing lower limit temperature rises and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

  In addition, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method. That is, when the release agent fine particles are associated with each other in order to improve the offset resistance, the release agent fine particles are taken into the toner particles. As a result, the offset resistance cannot be sufficiently improved. This is because toner particles are formed by randomly fusing resin fine particles, release agent fine particles, colorant fine particles, etc., so the composition (content ratio of constituent components) and the molecular weight of the constituent resin among the obtained toner particles Variation occurs. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Furthermore, in a low-temperature fixing system that requires low-temperature fixing, there is a problem in that fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface, and a sufficient fixing temperature range cannot be secured.

  Recently, a new production method called an emulsion aggregation method (EA method, Emulsion-Aggregation method) has been proposed (see Patent Document 5). This emulsion aggregation method is a method of granulating from a polymer dissolved in an organic solvent or the like, while the suspension polymerization method forms particles from a monomer. There is an advantage that toner structure control (core / shell structure control) is possible. However, in this proposal, the shell structure is intended to reduce the exposure of the pigment and wax to the surface with a resin-only layer. In particular, the surface state is not devised, and such a structure is also obtained. (See Non-Patent Document 1). As described above, in the above proposal, although the shell structure is used, the toner surface is a normal resin, and there is no particular ingenuity. When aiming at lower temperature fixing, in terms of heat-resistant storage stability and environmental charge stability. Not enough.

In addition, the suspension polymerization method, emulsion polymerization method, and emulsion aggregation method generally use a styrene-acrylic resin. If a polyester resin is used, it is difficult to form a particle. It is difficult to control the particle size distribution and shape. Furthermore, there is a limit to fixability when aiming at lower temperature fixing.
Therefore, it has been proposed to use a polyester modified with a urea bond for the purpose of heat-resistant storage stability and low-temperature fixing (see Patent Document 6). However, in this proposal, the toner surface is not particularly devised, and it is not sufficient in terms of environmental charge stability which is more severe.

Recently, in the field of electrophotography, high image quality has been studied from various angles, and among them, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, as the diameter of the toner is reduced, the transferability and the fixability are lowered, and a tendency to become a poor image is observed. Further, it is known that transferability is improved by making the toner spherical (Patent Document 7). Under such circumstances, in the field of color copiers and color printers, higher speed image formation is desired. The “tandem method” is effective for speeding up (see Patent Document 8).
The “tandem method” is a method for obtaining a full-color image on a transfer sheet by sequentially superimposing and transferring the image formed by the image forming unit on a single transfer sheet conveyed to a transfer belt. A tandem color image forming apparatus has a variety of transfer papers that can be used, has high quality of a full color image, and has excellent characteristics that a full color image can be obtained at a high speed. In particular, the characteristic that a full color image can be obtained at a high speed is a characteristic that is not found in other color image forming apparatuses.

  Attempts have also been made to achieve high speed while improving image quality using spherical toner. For example, a spherical toner such as a chemical toner forms a developed toner image on the photoreceptor densely, so that the transfer pressure at the time of transfer is evenly applied to the toner layer. There are few occurrences of transfer abnormalities such as transfer rate and transfer image dropout. However, when used over time, the fluidity modifier added externally to improve the transferability and fluidity of the toner, compared to the pulverized toner, is buried in the toner surface rapidly. The change of becomes large. In particular, when the image area is small, that is, when images with low toner consumption are output continuously, the external additive in the toner is buried with the passage of time of use, and the fluidity improvement effect cannot be obtained. At present, there are problems such as fluctuations and unevenness on the image due to the fluctuations.

Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A Japanese Patent No. 3141784 Japanese Patent Laid-Open No. 11-133667 JP 9-258474 A JP-A-5-341617 Takao Ishiyama and two others "Characteristics and Future Prospects of New Toner" (4th Joint Imaging Society of Japan Society of Electrostatics (2000.7.29))

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention can maintain good transferability and cleaning properties over a long period of time, prevent the occurrence of photoconductor filming, no fluctuation in image unevenness, and external addition by stirring the developer during use. Toner having excellent stability with no change in fluidity and chargeability over a long period of time, developer, toner-containing container, process cartridge, image forming apparatus, and image forming method using the toner The purpose is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, it is possible to effectively exert the toner performance even if the external additive aggregates in the toner are too much or too little. Unfavorably, by controlling the number of aggregates of the external additive to be within a certain range, it is possible to maintain good transferability and cleaning properties over a long period of time, prevent the occurrence of photoconductor filming, and image quality It has been found that there can be obtained a toner having excellent stability with no variation in unevenness, no embedding of the external additive by stirring of the developer at the time of use, and little change in fluidity and chargeability over a long period of time.

This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is,
<1 > A toner having at least an external additive, wherein the external additive is a large particle having a volume average particle diameter of 100 to 150 nm and a small particle having a smaller volume average particle diameter than the large particle. Then, 0.2 g of the toner was air blown on a sieve having a 635 mesh and a mesh area of 452 cm ² with air blowing at a suction pressure of 5 mmHg and a blow pressure of 0.2 MPa from a height of 160 mm above the sieve. The toner is characterized in that the number of aggregates of the external additive remaining on the sieve is 4,500 or less and 5 or more when air suction is performed at a suction pressure of 20 mmHg. .
<2> The toner according to <1>, wherein the number of aggregates of the external additive remaining on the sieve is 4,500 or less and 20 or more.
<3> The toner according to any one of <1> and <2>, wherein the number of aggregates of the external additive remaining on the sieve is 3,000 or less and 30 or more .
<4 > The toner according to any one of <1> to < 3 >, wherein the large particle is externally added before the small particle.
< 5 > The toner according to any one of <1> to < 4 >, wherein the large particle is a silica particle, and the small particle is at least one of a titanium oxide particle and a hydrophobic silica particle.
< 6 > The toner according to any one of <1> to < 5 >, wherein the toner has a volume average particle diameter of 3 to 8 μm.
< 7 > The toner according to any one of <1> to < 6 >, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.25 or less.
< 8 > The toner according to any one of <1> to < 7 >, wherein the toner has an average circularity of 0.900 to 0.980.
< 9 > The toner according to any one of <1> to < 8 >, wherein an external additive and toner particles are mixed and the external additive is attached to the toner particles.
< 10 > The toner according to any one of <1> to < 8 >, wherein the external additive and toner particles are dispersed in an aqueous medium, and the external additive is attached to the toner particles.
< 11 > From the above <1>, in which an external additive, an aggregate obtained by aggregating large-diameter particles, and toner particles are mixed, and the external additive and the aggregate are adhered to the toner particles. The toner according to any one of < 8 >.
< 12 > The toner according to any one of <1> to < 11 >, wherein the content of large-diameter particles is smaller than the content of small-diameter particles.
< 13 > A toner solution containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is dissolved or dispersed in an organic solvent to prepare a toner solution, and then the toner solution is placed in an aqueous medium. A dispersion is prepared by emulsifying or dispersing in the aqueous medium, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form an adhesive substrate in the form of particles. The toner according to any one of <1> to < 12 >, which is produced by removing the organic solvent.
< 14 > A developer comprising the toner according to any one of <1> to < 13 >.
< 15 > A toner-containing container filled with the toner according to any one of <1> to < 13 >.
< 16 > An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to < 13 > to be a visible image. And a developing means for forming a process cartridge.
< 17 > An electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of <1> to < 13 >. An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
< 18 > An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <1> to < 13 > At least development means for forming a visible image by developing with toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium An image forming apparatus comprising:

The toner of the present invention has at least an external additive, and the external additive comprises a large particle and a small particle having a volume average particle size smaller than that of the large particle. the 2 g, 635 mesh, on a sieve of a mesh area 452Cm ^2, after air blow at a blow pressure 0.2MPa than on the sieve while the air suction by the suction pressure 5mmHg height 160 mm, air suction by the suction pressure 20mmHg In this case, the number of aggregates of the external additive remaining on the sieve is 4,500 or less, and 5 or more.
According to the toner of the present invention, good transferability and cleanability can be maintained for a long time, the occurrence of photoconductor filming is prevented, there is no fluctuation in image unevenness, and the developer agitation during use It is possible to obtain a high-quality image in which the external additive is not buried and the fluidity and chargeability are little changed over a long period of time.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, as a result, good transferability and cleanability can be maintained over a long period of time, the occurrence of photoconductor filming can be prevented, and image unevenness can be prevented. In addition, a high-quality image can be obtained in which the external additive is not buried by stirring the developer at the time of use, and the flowability and chargeability are little changed over a long period of time.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when an image is formed by electrophotography using the toner contained in the toner-containing container, good transferability and cleaning properties can be maintained over a long period of time, and photoconductor filming occurs. Thus, there is no fluctuation in image unevenness, and there is no burying of the external additive by stirring the developer at the time of use, and a high-quality image with little change in fluidity and chargeability over a long period of time can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. As a result, good transferability and cleaning performance can be maintained over a long period of time. High-quality images that prevent body filming, have no fluctuations in image unevenness, and have no external additives buried by stirring the developer during use, and have little change in fluidity and chargeability over a long period of time. Is obtained.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, good transferability and cleanability can be maintained over a long period of time, photoconductor filming can be prevented, image irregularity does not fluctuate, and external additives can be buried by stirring the developer during use. Therefore, it is possible to form a high-quality electrophotographic image with little change in fluidity and chargeability over a long period.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image is developed using the toner of the present invention to be visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, good transferability and cleanability can be maintained over a long period of time, photoconductor filming can be prevented, image irregularity does not fluctuate, and external additives can be buried by stirring the developer during use. Therefore, it is possible to form a high-quality electrophotographic image with little change in fluidity and chargeability over a long period.

  According to the present invention, conventional problems can be solved, good transferability and cleaning properties can be maintained over a long period of time, the occurrence of photoconductor filming is prevented, and there is no fluctuation in image unevenness. Toner having excellent stability in which the external additive is not buried by developer agitation at the time of use and the flowability and chargeability are little changed over a long period of time, and the developer, toner-containing container, process cartridge, An image forming apparatus and an image forming method can be provided.

(toner)
The toner of the present invention has at least an external additive, and the external additive includes large-sized particles and small-sized particles having a volume average particle size smaller than that of the large-sized particles, and other components as necessary. It contains.

The toner of the toner 0.2 g, 635 mesh, on a sieve of a mesh area 452Cm ^2, after air blowing from the oversize height 160mm with air suction at blowing pressure 0.2MPa at suction pressure 5mmHg When the air is sucked at a suction pressure of 20 mmHg, the number of aggregates of the external additive remaining on the sieve is 4,500 or less, and 5 or more, and 4,500 or less. And 20 or more, preferably 3,000 or less, more preferably 30 or more, 2,500 or less, and even more preferably 40 or more.

Here, (1) an external additive, particularly an external additive having a large average particle size of 80 to 250 nm, can be produced with a sharp particle size distribution, especially when it is produced by a wet process. There are many aggregates that appear to be. Since the aggregate of the external additive is present away from the toner, it is rubbed and stretched mainly on the photosensitive member by the cleaning blade, which causes filming. Such inorganic particles absorb polar substances in the air, become a leak source of latent image potential, and have a problem of blurring the image.
Therefore, in the present invention, by using a toner that is controlled so that the number of aggregates of the external additive remaining on the sieve is 4,500 or less, it is possible to prevent the occurrence of filming, and to achieve a clear high A quality image is obtained.

On the other hand, (2) agglomerates of external additives, particularly external additives derived from large-sized particles having a volume average particle size of 80 to 250 nm are mixed in a small amount of toner, whereby agglomerates of large-sized particles in the toner are obtained. According to the stirring time of the developer, it is gradually crushed and adheres to the toner surface. As a result, the large-diameter particles are slightly buried, and the fluidity of the toner changes or moves inside the toner. Is supplied to the toner, and the transferability can be maintained for a long time, and a uniform image can be obtained regardless of the image area of the output image.
Therefore, in the present invention, by controlling the number of aggregates of the external additive remaining on the sieve to be 5 or more, good transferability and cleaning properties can be maintained over a long period of time.

Therefore, in the toner of the present invention, 0.2 g of the toner is air-sucked at a suction pressure of 5 mmHg on a sieve having a 635 mesh and a mesh area of 452 cm ^{2 and} a blow pressure of 0.2 MPa from a height of 160 mm on the sieve. After air blowing, when the air is sucked at a suction pressure of 20 mmHg, the number of aggregates of the external additive remaining on the sieve is controlled to be 4,500 or less and 5 or more. As a result, good transferability and cleanability can be maintained over a long period of time, the occurrence of photoconductor filming can be prevented, there is no fluctuation in image unevenness, and external additives can be buried by stirring the developer during use. Thus, a toner having excellent stability with little change in fluidity and chargeability over a long period of time can be obtained.

Here, as a method for measuring the number of aggregates of the external additive, for example, 0.2 g of toner is weighed on a V-blowing cell (635 mesh, sieve having a mesh area of 452 cm ² ). While air is sucked at a suction pressure of 5 mmHg, air is blown from a height of 160 mm above the cell at a blow pressure of 0.2 MPa to remove the toner, and then the toner is removed by air suction at a suction pressure of 20 mmHg. When toner removal is incomplete, these operations are continuously performed to remove the toner. The residue remaining on the sieve is observed at 150 times with a digital microscope (KEYENCE VHX-100). The number of external additive aggregates (white aggregate particles of about 30 μm) remaining on the sieve is counted. This is measured for 4 to 20 visual fields, and the amount of aggregates of the external additive contained in the toner is determined.

The large diameter particles preferably have a volume average particle size of 80 to 250 nm, more preferably 90 to 200 nm, and particularly preferably 100 to 150 nm. When the volume average particle size is less than 80 nm, the external additive tends to be buried in the toner, and it may not work effectively for reducing non-electrostatic adhesion. Therefore, it may be easy to shift to the contact member.
Further, the volume average particle diameter of the small-diameter particles is not particularly limited and can be appropriately selected according to the purpose, and is preferably 5 to 50 nm.
In the present invention, by using the external additive particles having different particle diameters as described above, even if the shape of the toner is substantially spherical, the rotational movement of the toner is suppressed and the toner is excessively packed. Therefore, it is possible to maintain good cleaning and transferability. In addition, it is possible to prevent the fine powder having a small diameter from being selectively embedded in the toner by long-term developer agitation, so that stable fluidity can be obtained over a long period.
Of these two types of fine particles, large particles have relatively little effect on improving the fluidity of the toner. For example, in a toner in which the same amount of small-diameter particles and large-diameter particles are added, a much higher fluidity is obtained when the small-diameter particles are added. However, with only small-diameter particles, the additive is buried in the toner when used over time, and the fluidity tends to decrease. In contrast, the addition of large-diameter particles can suppress a decrease in fluidity over time, but many large-particles cause the large-diameter particles to be detached from the toner when the developer is agitated. Even if large particles are mixed, there is a problem such that the large particles do not adhere properly to the toner, so the transferability variation over time of use is slightly improved compared to when only small particles are used. Although not enough. In particular, when outputting images with different image areas, the transferability varies depending on the stirring time of the developer and the retention of toner in the developer. This is because large particles are gradually embedded in the toner in the same manner as small particles in the toner, and at that time, large particles that are uniformly mixed in advance on the toner surface are unevenly distributed. This is because it accumulates in uneven surfaces and the effect expected for large particles cannot be expressed.

  Since the large-diameter particles are externally added before the small-diameter particles, the large-diameter particles have a lower fluidity development effect than the small-diameter particles, and therefore, the crushing effect of the aggregates of the large-diameter particles can be promoted. This is preferable in that a large amount of large-diameter particles can be prevented from being liberated and the external additive of large-diameter particles can be uniformly dispersed on the toner surface.

It is preferable that the external additive and toner particles are mixed and the external additive is adhered to the toner particles, that is, a dry external addition treatment is performed. The dry-type external addition treatment generally has a feature that the external additive has a large true specific gravity and is more likely to be peeled off than the toner base particles because it exists as an aggregate. The effect becomes more significant depending on the particle size. In other words, the small-diameter particles are easily attached to the toner base particles, and the large-diameter particles are difficult to adhere and easily peel off. Therefore, when these external additives are added simultaneously, the small-diameter particles adhere to the selective tip first, and the large-diameter particles tend to exist as free components, which is not preferable. In the mixing process, the aggregated external additive is first crushed, and then the crushed external additive is dispersed and adhered to the surface of the toner base particles. The adhering external additive is presumed to be fixed by rubbing between the toners and colliding with the wall of the device. Therefore, if the small particle is added first, the fluidity of the toner particle becomes very good, so the large particle is attached. It is not preferable because it is difficult to take a share for making it into a free state. As a result of various investigations on the addition method, it is effective to first mix the toner base particles and the large diameter particles. It is also effective to mix the toner base particles after stirring only the external additive. It is also effective to add external additives little by little. Mixing can be performed by a known mixer such as a V-type blender, a Henschel mixer, or a hybridizer.
The peripheral speed of the rotating body of these devices is preferably 10 to 150 m / s. When the peripheral speed is less than 10 m / s, the aggregate of the external additive cannot be completely crushed and requires a lot of time for pulverization, which may not be efficient. The external additive may adhere to the toner base particles too much and lose the function as the external additive.

It is preferable that the external additive and the toner particles are dispersed in an aqueous medium and the external additive is attached to the toner particles, that is, a wet external addition treatment is performed. According to this wet external addition, the aggregate of large particles can be crushed (disaggregated) by dispersing it in a liquid, compared to external addition in gas (dry external addition). Thus, the aggregation can be easily unwound and can be easily broken into the number of aggregates of the external additive of the present invention.
In the case of dry toner, the wet external addition treatment is performed by dispersing toner base particles before dry external addition in water using a surfactant or the like if necessary. When the toner particles are formed in water, it is preferable to perform a wet external addition step after removing the used surfactant and the like by washing. Excess surfactant present in water is removed by solid-liquid separation such as filtration and centrifugation, and the resulting cake and slurry are redispersed in an aqueous medium. Further, inorganic fine particles are added and dispersed in the slurry. It is also possible to previously disperse the inorganic fine particles in the aqueous dispersion. At that time, if the dispersion is made by using a surfactant having a polarity opposite to that of the surfactant prepared in the aqueous dispersion of the toner base, the adhesion to the toner particle surface is more efficiently performed. In addition, when the inorganic fine particles have been hydrophobized and are difficult to disperse in the aqueous dispersion, the inorganic fine particles may be dispersed after the interfacial tension is lowered by using a small amount of alcohol or the like to facilitate wetting.
Thereafter, an aqueous surfactant solution having a reverse polarity is gradually added with stirring. The reverse polarity surfactant is preferably used in an amount of 0.01 to 1% by mass based on the solid content of the toner particles. By adding a surfactant having a reverse polarity, the charge of the inorganic fine particle dispersion in water is neutralized, and the inorganic fine particles can be aggregated and adhered to the surface of the toner particles. The inorganic fine particles are preferably used in an amount of 0.01 to 5% by mass based on the solid content of the toner particles.
In addition, instead of gradually adding an aqueous surfactant solution having a reverse polarity with stirring, the inorganic fine particles can be adhered by changing the pH of the dispersion to the acid or alkali side.
The inorganic fine particles adhered to the toner surface can be fixed to the toner surface by heating the slurry and then prevented from being detached. At that time, it is desirable to heat at a temperature higher than the glass transition temperature (Tg) of the resin constituting the toner. Further, heat treatment after drying may be performed while preventing aggregation.
Further, for the purpose of further enhancing the chargeability, the charge control agent fine particle dispersion may be present in the redispersed slurry. The charge control agent is usually in the form of a powder. However, the surfactant used when the toner particles are produced in the aqueous medium and the reverse polarity surfactant added for the purpose of imparting the charge are separately used in the aqueous medium. A fine particle dispersion can be obtained by dispersing in. By adding a surfactant having a reverse polarity, the charge of the charge control agent fine particle dispersion in water can be neutralized and agglomerated and adhered to the surface of the toner particles.
The charge control agent is preferably a dispersion having a particle size of 0.01 to 1 μm, and can be used in an amount of 0.01 to 5% by mass based on the solid content of the toner particles.
Further, for the purpose of further reinforcing the chargeability, the resin fine particle dispersion can be present in the redispersed slurry. The resin fine particle dispersion is preferably obtained by emulsion polymerization. By adding a surfactant having a reverse polarity, the charge in the resin fine particle dispersion in water can be neutralized and can be aggregated and adhered to the toner particle surface. The resin fine particles can be used in an amount of 0.01 to 5% by mass based on the solid content of the toner particles.

As the external additive composed of the large particles and the small particles, fine particles that have been used for the purpose of imparting fluidity and chargeability can be used. For example, oxide fine particles, inorganic fine particles, hydrophobic treated inorganic fine particles , Etc.
The external additive is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), Examples thereof include metal oxides (titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, etc. Among these, the large-diameter particles are silica fine particles having a volume average particle diameter of 80 to 150 nm, and the small-diameter particles are It is preferably at least one of titanium oxide fine particles and hydrophobic silica fine particles.

Examples of the silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, and HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, and R812 (all Nippon Aerosil Co., Ltd.) Company-made).
Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); There are MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation) and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF- 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.); IT-S (manufactured by Ishihara Sangyo Co., Ltd.).

In order to obtain the hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, the hydrophilic fine particles are converted into silane coupling agents such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. Can be obtained by processing. Further, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. can be used. .
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Other polymer fine particles include, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polycondensation system such as methacrylate ester, acrylate ester copolymer, silicone, benzoguanamine, nylon, heat Examples thereof include polymer particles made of a curable resin.

Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  The content of the large particle in the toner is preferably 0.1 to 5% by mass. The content of the small diameter particles in the toner is preferably 0.5 to 5% by mass. The content of the large particle is preferably smaller than the content of the small particle.

  The toner of the present invention is not particularly limited as long as the production method and material satisfy the above conditions, and can be appropriately selected from known ones according to the purpose. For example, a high-quality and high-definition image is output. Therefore, it is preferable that the toner has a small particle diameter and a nearly spherical shape. As a method for producing such a toner, there are a pulverization classification method, a suspension polymerization method, an emulsion polymerization method, a polymer suspension method, etc. in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. is there.

  The pulverization method is, for example, a method of obtaining the toner base particles by melting and kneading the toner material, pulverizing, classifying and the like. In the case of the pulverization method, for the purpose of setting the average circularity of the toner in the range of 0.97 to 1.0, the shape is controlled by applying a mechanical impact force to the obtained toner base particles. May be. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

The suspension polymerization method is an oil-soluble polymerization initiator, emulsification described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersant are contained. Emulsified and dispersed by the method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, By using a part of acrylate or methacrylate having amino groups such as methacrylamide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate, etc. on the toner particle surface. Functional groups can be introduced.
Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

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

In the present invention, among these, since the selectivity of the resin is high, the low-temperature fixability is high, the granulation property is excellent, and the particle size, the particle size distribution, and the shape can be easily controlled. A toner solution containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is dissolved or dispersed in an organic solvent to prepare a toner solution, and then the toner solution is emulsified in an aqueous medium. A dispersion is prepared by dispersing, and in the aqueous medium, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive substrate in the form of particles. Those obtained by removing the organic solvent are preferred.
Examples of the toner material include an adhesive base obtained by reacting an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a binder resin, a release agent, and a colorant. And other components such as resin fine particles and a charge control agent.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

The storage elastic modulus of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² , Usually, it is 100 ° C. or higher, and preferably 110 to 200 ° C. When the (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
The viscosity of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (Tη) at which a poise of 1,000 at a measurement frequency of 20 Hz is usually 180 ° C. or less. Yes, 90-160 degreeC is preferable. When the (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
Therefore, from the viewpoint of achieving both hot offset resistance and low-temperature fixability, the (TG ′) is preferably higher than the (Tη). That is, the difference (TG′−Tη) between (TG ′) and (Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The larger the difference, the better.
Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the (TG′−Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20 to 80 ° C.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred examples include polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the 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. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When 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) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
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 the 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 depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) 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). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
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 the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be 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. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
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 will be low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride 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 the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said 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 isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  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 what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said 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 A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. 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 the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, etc. 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 trihydric or higher polyol (TO) is preferably a trihydric or higher polyhydric alcohol, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, or a trihydric or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-100: 10 are preferable and 100: 0.01-100: 1 are more preferable.

There is no restriction | limiting in particular as said 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 tricarboxylic or higher polycarboxylic acid.
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 DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, sebacic acid, and the like. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said 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 (TO) is preferably a trivalent to octavalent or higher one, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

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

  The mixing ratio for 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, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), 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 especially preferable.
When 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, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

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, Examples include tetramethylhexane 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- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
These can 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-containing group are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
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. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. 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 count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weight made by Tosoh Corporation 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 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

--Binder resin--
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Unmodified polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

The weight average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferred. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, the content of the component having the weight average molecular weight (Mw) of less than 1,000 as described above. Is required to be 8 to 28% by mass. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 70 ° C, still more preferably 35 to 50 ° C, and particularly preferably 35 to 45 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, more preferably 1.0 to 45.0 mgKOH / g, and still more preferably 15.0 to 45.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
As content of the said non-modified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, 70-95 mass% is more preferable, 80-90 mass% is still more preferable. When the content is less than 50% by mass, the low-temperature fixability and the glossiness of the image may be deteriorated.

-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.

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

The content of the colorant in the toner 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 is less than 1% by mass, a reduction in the coloring power of the toner is observed, and when the content exceeds 15% by mass, a poor dispersion of the pigment in the toner occurs. The characteristics may be degraded.

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

  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 An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. The so-called flushing method is also preferable in that the wet cake of the colorant can be used as it is, and it does not need to be dried.
The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and the organic solvent component. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Among these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferable.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability.
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 1000 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 the said 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 charge control agent is not particularly limited and may be appropriately selected from known materials according to the purpose. However, since a color tone may change when a colored material is used, a material that is colorless to nearly white is used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. 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 quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added when directly dissolving or dispersing in the organic solvent together with the components of the toner, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content 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, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be 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. Examples of the resin include vinyl resins. Among these, vinyl resins are particularly preferable.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin in that an aqueous dispersion of fine spherical resin resin 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. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. "; Manufactured by Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A 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 or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

  Examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, etc., and can react with an active hydrogen group-containing compound and the active hydrogen group-containing compound. The toner material containing the polymer is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing solution is prepared in the aqueous medium. A toner obtained by reacting a compound with a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in the form of particles and removing the organic solvent is preferred.

-Toner solution-
The toner solution can be prepared by dissolving the toner material in the organic solvent.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. 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 toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and may be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch method, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

As an example of the method for producing the toner, a method for obtaining the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive base material in the form of particles, for example, the preparation of an aqueous medium phase, the preparation of the toner solution, the preparation of the dispersion, the addition of the aqueous medium, etc. Synthesis of a polymer (prepolymer) capable of reacting with an active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by adding, in the organic solvent, the active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, the charge control agent, and the unmodified. A toner material such as a polyester resin 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 are added when the resin fine particles are dispersed in the aqueous medium in the preparation of the aqueous medium phase. The toner solution may be added and mixed in the aqueous medium, or may be added to the aqueous medium phase together with the toner solution when the toner solution is added to the aqueous medium phase.

The dispersion can be prepared by emulsifying and dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The toner solution is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The toner solution is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and in the aqueous medium phase (3) The toner solution may be added to and mixed with the aqueous medium, and then the active hydrogen group-containing material may be formed. The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification / dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, the unmodified Examples thereof include a method in which the toner solution prepared by dissolving or dispersing the toner material such as polyester resin in the organic solvent is added and dispersed by shearing force. The details of the dispersion method are as described above.

In preparing the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets composed of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and those having a fluoroalkyl group are preferable. 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- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate ester and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), Megafuck F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant 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.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
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 Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water, or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). 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. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture with a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board, etc. are mentioned. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and a pulverization air pressure are lowered, a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  The toner has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), average circularity, shape factors SF-1 and SF-2, and the like. It is preferable.

The volume average particle diameter (Dv) of the toner is, for example, preferably 3 to 8 μm, more preferably 4 to 7, and still more preferably 5 to 6. Here, the volume average particle diameter is defined as Dv = [(Σ (nD ³ ) / Σn) ^1/3 (where n is the number of particles and D is the particle diameter).
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the 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, and if it exceeds 8 μm, the resolution is high and the resolution is high. It becomes difficult to obtain an image having an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.25 or less, more preferably 1.00 to 1.20. .10 to 1.20 is more preferable.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.25 or less, the particle size distribution of the toner is relatively sharp and the fixability is improved. If it is less than the above, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be deteriorated or the cleaning property may be deteriorated. In the case of the agent, toner filming on the developing roller and toner fusion to the member such as a blade are likely to occur because the toner is thinned. It becomes difficult to obtain a high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles, and is preferably 0.900 to 0.98, for example, 0.940 to 0 .98 is more preferred.
When the average circularity is less than 0.900, the toner becomes an irregular shape separated from the spherical shape, and a satisfactory transfer property and a high-quality image free from dust may not be obtained, and exceeds 0.98. In an image forming system that employs blade cleaning or the like, defective cleaning occurs on the photosensitive member and the transfer belt, and in the case of image formation with high image area ratio such as dirt on the image, for example, a photographic image. The toner on which an untransferred image is formed due to a paper feed failure or the like may become a transfer residual toner on the photosensitive member, resulting in background smearing of the image, or the charging roller for contact charging the photosensitive member Etc., and the original charging ability may not be exhibited.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

The shape factors SF-1 and SF-2 are obtained by, for example, randomly sampling 300 SEM images of the toner obtained by measuring with an FE-SEM (S-4200) manufactured by Hitachi, and using the image information as an interface. And introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco Corp., and the values obtained from the following formulas 1 and 2 were defined as shape factors SF-1 and SF-2. In addition, although the value calculated | required by Luzex is preferable as the value of SF-1 and SF-2, if the same analysis result is obtained, it will not be specifically limited to the said FE-SEM apparatus and an image analysis apparatus.
<Formula 1>
SF-1 = (L ² / A) × (π / 4) × 100
<Formula 2>
SF-2 = (P ² / A) × (1 / 4π) × 100
In Equations 1 and 2, L represents the absolute maximum length of the toner, A represents the projected area of the toner, and P represents the maximum circumferential length of the toner.
In addition, if it is a true sphere, both SF-1 and SF-2 will be 100, and will become an indefinite form from a spherical shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.

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

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm.
When the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
The mixing ratio of the toner and the carrier of the two-component developer is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, the developer of the present invention is excellent in offset resistance and heat-resistant storage stability and can stably form a clear and high-quality image.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge according to the present invention forms a visible image by developing an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using toner. And at least a developing unit for selecting the charging unit, an exposing unit, a developing unit, a transferring unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other members as necessary. It has. In FIG. 1, reference numeral 103 denotes an exposure unit, which uses a light source capable of writing with high resolution. Reference numeral 105 denotes a recording medium.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 102.

  The image forming apparatus of the present invention is constructed by integrally combining the electrostatic latent image carrier and the components such as a developing device and a cleaning device as a process cartridge, and this unit can be attached to and detached from the apparatus main body. It may be configured. In addition, a process cartridge is formed by integrally supporting at least one of a charging device, a developing device, a transfer device, and a cleaning device together with an electrostatic latent image carrier to form a single unit that is detachable from the device body. It is good also as a structure which can be attached or detached using guide means, such as this rail.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further, other steps appropriately selected as necessary, for example, a static elimination step, It includes a cleaning process, a recycling process, a control process, and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image bearing member (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. . Among these, amorphous silicon or the like is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used by a film forming method such as the above. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may be any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the electrophotographic apparatus. When the magnetic brush is used, the magnetic brush is made up of various ferrite particles such as Zn-Cu ferrite as a charging member, a nonmagnetic conductive sleeve for supporting the ferrite member, and a magnet roll included in the nonmagnetic conductive sleeve. Or when using a brush, for example, as the material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound or attached to a metal or other conductive core. To make a charger.
Of course, the charger is not limited to the contact type charger as described above, but an image forming apparatus in which ozone generated from the charger is reduced can be obtained. Is preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, 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.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes 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. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. When the volume resistance is set to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, (1) a material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery of the belt. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

For the intermediate transfer belt, fluorine resin, polycarbonate resin, polyimide resin and the like have been conventionally used. However, in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. . The transfer of a color image using a resin belt has the following problems. A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.
The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.

  Examples of the resin in the elastic belt include polycarbonate resin, fluorine resin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-α-methylstyrene resin, styrene-butadiene copolymer, and styrene-vinyl chloride copolymer. Styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic) Acid butyl copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-methacrylic acid) Ethyl copolymer, styrene-me Styrene-based resins (styrene or styrene-substituted monopolymers or copolymers) such as phenyl crylate copolymer), styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate ester copolymer, etc. Coalesced), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (eg, silicone-modified acrylic resin, vinyl chloride resin-modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride Resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, io Mer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins.

  Examples of the elastic rubber or elastomer include butyl rubber, fluorine-based rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, Ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, ricone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, Hydrogenated nitrile rubber, thermoplastic elastomer (eg, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) And the like.

The conductive material for adjusting the resistance value is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, oxidation Conductive metal oxides such as indium, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO), and the conductive metal oxides are barium sulfate and magnesium silicate. Further, it may be coated with insulating fine particles such as calcium carbonate.
Surface layer materials and surface layers are required to prevent contamination of the photoreceptor by elastic materials, reduce surface friction resistance to the surface of the transfer belt, reduce toner adhesion, and improve cleaning properties and secondary transfer properties. . For example, materials that use one or a combination of two or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide Such powders and particles can be used by dispersing one type, two or more types, or a combination of particles having different particle sizes. Further, it is also possible to use a material having a reduced surface energy by forming a fluorine-rich layer on the surface by performing a heat treatment like a fluorine-based rubber material.
The manufacturing method of the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid paint is sprayed to form a film, a cylindrical mold is used. Examples include, but are not limited to, a dipping method in which the material is dipped in a solution of the material, a casting method in which it is injected into the inner mold and the outer mold, a method in which a compound is wound around a cylindrical mold and vulcanized and polished. In general, a belt is manufactured by combining a plurality of manufacturing methods.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into a core layer, and the like, but the method is limited to a specific production method is not.
The material constituting the core layer for preventing elongation includes, for example, natural fibers such as cotton and silk; polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, Synthetic fibers such as polyurethane fiber, polyacetal fiber, polyfluoroethylene fiber and phenol fiber; inorganic fibers such as carbon fiber, glass fiber and boron fiber; one or two kinds selected from metal fibers such as iron fiber and copper fiber By using the above combination, a woven fabric or a yarn may be used.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, a single twisted yarn, various twisted yarns, a double yarn, or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment. On the other hand, as the woven fabric, any woven fabric such as knitted fabric can be used. Interwoven woven fabric can also be used and naturally conductive treatment can be performed.
The production method for providing the core layer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a woven fabric woven in a cylindrical shape is covered with a mold or the like, and a coating layer is formed thereon. A method of providing, a method of providing a coating layer on one or both sides of a core layer by immersing a woven fabric woven in a cylindrical shape in a liquid rubber, etc., winding a thread spirally around a mold or the like at an arbitrary pitch, Examples thereof include a method of providing a coating layer.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur on the surface layer. Also, it is not preferable that the thickness is too large (approximately 1 mm or more) because the amount of expansion and contraction becomes large and the image is stretched.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. 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 is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. 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 pressing means is usually preferably 80 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. 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. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and also for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion 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 the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

In the tandem type electrophotographic apparatus in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention, the image on each photoconductor 1 is transferred by the transfer device 2 by the sheet conveying belt 3 as shown in FIG. As shown in FIG. 5, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer body 4 by the primary transfer device 2 as shown in FIG. There is an indirect transfer type in which an image on the transfer body 4 is collectively transferred to a sheet s by a secondary transfer device 5. The transfer device 5 is a transfer conveyance belt, but there are also roller shapes and methods.
Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. Due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt, there is a drawback that the fixing device 7 tends to affect image formation on the upstream side. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 hardly affects the image formation.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.
In this type of color electrophotographic apparatus, as shown in FIG. 5, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

A tandem image forming apparatus 100 shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus 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, and can be rotated clockwise in FIG. 6. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 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 transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. An exposure device that exposes the photoconductor for each color image corresponding image (L in FIG. 7) and forms an electrostatic latent image corresponding to each color image on the photoconductor; Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoreceptor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . 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 synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, good transferability and cleanability can be maintained over a long period of time, the occurrence of photoconductor filming is prevented, there is no fluctuation in image unevenness, and Since the toner is not buried by the stirring of the developer and the toner has excellent stability with little change in fluidity and chargeability over a long period of time, a high-quality image can be obtained efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts of styrene, methacrylic acid When 83 parts, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. This was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain an aqueous vinyl resin (a copolymer of methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle diameter of the fine particles contained in the obtained [fine particle dispersion 1] was measured by a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. there were. Moreover, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 58 ° C., and the weight average molecular weight (Mw) was 130,000.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, 208 parts terephthalic acid, 46 parts adipic acid, and 2 parts of dibutyltin oxide was charged and reacted at 230 ° C. for 7 hours under normal pressure. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours to obtain [Low molecular weight polyester 1].
The obtained [low molecular weight polyester 1] had a glass transition temperature (Tg) of 43 ° C., a weight average molecular weight (Mw) of 6700, a number average molecular weight of 2300, and an acid value of 25.

-Synthesis of prepolymer-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 7 hours under normal pressure. Further, the reaction was carried out under reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate polyester 1].
The obtained [Intermediate polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, a glass transition temperature (Tg) of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained.
The obtained [Prepolymer 1] had a free isocyanate mass% of 1.53%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 417.

-Preparation of masterbatch (MB)-
1200 parts of water, 540 parts of carbon black (Printex 35, manufactured by Degussa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of a polyester resin (manufactured by Sanyo Chemical Industries, Ltd., RS801) are added, and a Henschel mixer is added. (Mitsui Mining Co., Ltd.) The resulting mixture was kneaded at 110 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a carbon black masterbatch. This is designated as [Masterbatch 1].

-Preparation of oil phase-
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of [low molecular weight polyester 1], 100 parts of carnauba wax, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining the time, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a reaction vessel and mixed for 1 hour to obtain a dissolved product. This is referred to as [Raw material solution 1].
Next, 1324 parts of [Raw Material Solution 1] was transferred to a reaction vessel, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed: 1 kg / hr, disk peripheral speed: 6 m / sec, 0.5 mm Carbon black and wax were dispersed under the conditions of zirconia bead filling amount: 80% by volume and pass number: 3 times.
Next, 1324 parts of a 65% ethyl acetate solution of [low molecular polyester 1] was added, and a dispersion was obtained using a bead mill under the same conditions as described above, with a pass number of 2 times. This is designated as [Pigment and Wax Dispersion 1].
The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
[Pigment and wax dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and [Ketimine compound 1] 2.9 parts are placed in a reaction vessel, and 5 using a TK homomixer (manufactured by Tokushu Kika). 2,000 rpm for 2 minutes. Thereafter, 1200 parts of [Aqueous Phase 1] was added to the reaction vessel, and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 25 minutes to obtain an aqueous medium dispersion. This is designated as [Emulsified slurry 1].

-Deorganic solvent-
[Emulsion slurry 1] is put into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging is performed at 45 ° C. for 4 hours, and the organic solvent is distilled off. A dispersion was obtained. This is designated as [Dispersion Slurry 1].

-Cleaning and drying-
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure, and washed and dried as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4) Add 100 parts of ion-exchanged water to the filter cake of (3), add an aqueous solution in which a fluorine-based surfactant equivalent to 0.1% of the solid content of the cake is dissolved, and mix with a TK homomixer (at 12000 rpm). Filtered for 10 minutes).
(5) 300 parts of ion-exchanged water was added to the filter cake of (4), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to prepare a filter cake.
Next, the obtained filter cake was dried at 45 ° C. for 48 hours with a circulating drier, and sieved with a mesh having an opening of 75 μm to obtain toner base particles. This is designated as [toner base particle 1].

  The obtained “toner base particle 1” was measured for volume average particle size (Dv), particle size distribution (Dv / Dn), and average circularity as follows. The volume average particle diameter (Dv) was 5.8 μm, the particle size distribution (Dv / Dn) was 1.15, and the average circularity was 0.950.

<Volume Average Particle Size (Dv) and Particle Size Distribution (Dv / Dn)>
The volume average particle size and particle size distribution of the toner were measured using a particle size measuring device (“Coulter Counter TAII”; manufactured by Coulter Electronics Co., Ltd.) under the condition of an aperture diameter of 100 μm. From these results, (volume average particle diameter / number average particle diameter) was calculated.

<Average circularity>
The average circularity of the toner was measured using a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of water from which impure solids have been removed in advance, and each toner is further added. 0.1 to 0.5 g was added and dispersed. The obtained dispersion was dispersed for about 1 to 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), and the shape and distribution of the toner were measured at a dispersion concentration of 3000 to 10,000 / μl. The average circularity was calculated from these measurement results.

-Carrier manufacturing-
200 parts of toluene, 200 parts of silicone resin (SR2400, manufactured by Toray Dow Corning Silicone Co., Ltd., nonvolatile content 50%), 7 parts of aminosilane (SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.), and 4 parts of carbon black A coating solution was prepared by dispersing with a stirrer for 10 minutes.
Coating which coats the obtained coating liquid and 5000 parts of Mn ferrite particles (weight average particle size = 35 μm) as a core material while forming a swirling flow having a rotating bottom plate disk and stirring blades in a fluidized bed The coating liquid was applied to the core material after being put in the apparatus. The obtained coating was fired in an electric furnace at 250 ° C. for 2 hours to prepare a carrier.

-Preparation of external additives-
Surface-treated external additives A to L as shown in Table 1 below were prepared by a conventional method.
The external additive J *, the external additive K *, and the external additive L * are external additives that themselves contain a large amount of aggregates.

-Production of externally added aggregates-
100 parts of water: methanol = 10: 90 mixed solution is added to 100 parts of external additive F (Table 1), this is left to dry in a beaker for 24 hours, and then dried under reduced pressure for 24 hours. The body was made. This was pulverized in a mortar, sieved with a stainless mesh having an opening of 45 μm, and the sieve passage was designated as external additive aggregate H.
Further, the external additive G (Table 1) was subjected to the same treatment as described above to produce an external additive aggregate I.

( Reference Examples 1 to 4, Examples 5 and 6, and Comparative Example 1)
-Manufacture of toner-
External additives 1 to 3 and aggregates were added in the prescribed amounts shown in Table 2 to 100 parts of the obtained “toner base particles 1” and mixed with a Henschel mixer. The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse particles, thereby preparing toners A to G.

Next, with respect to the obtained toners of Reference Examples 1 to 4, Examples 5 and 6, and Comparative Example 1, the number of aggregates of external additives in the toner was measured as follows. The results are shown in Table 3.
<Measurement of the number of aggregates of external additives>
0.2 g of each toner is weighed on a V-blowing cell (635 mesh, mesh area of 452 cm ² ), and air is sucked into the cell at a suction pressure of 5 mmHg. After air blowing at 0.2 MPa to remove the toner, the toner is removed by air suction at a suction pressure of 20 mmHg. When toner removal is incomplete, these operations are continuously performed to remove the toner. The residue remaining on the sieve is observed at 150 times with a digital microscope (KEYENCE VHX-100). The number of external additive aggregates (white aggregate particles of about 30 μm) remaining on the sieve is counted. This was measured for 4 to 20 visual fields, and the number of aggregates of external additives contained in the toner was determined.

( Reference Example 7)
-Preparation of toner-
One part of the external additive F was added to 100 parts of the obtained “toner base particles 1”, and mixed for 10 minutes at a peripheral speed of 40 m / s using a Henschel mixer. Next, 0.5 part of external additive A and 0.5 part of external additive D were added to the mixture, and mixed for 10 minutes at a peripheral speed of 60 m / s with a Henschel mixer. The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse particles, whereby toner H of Reference Example 7 was obtained.

(Example 8)
-Preparation of toner-
One part of the external additive K was added to 100 parts of the obtained “toner base particles 1”, and mixed for 10 minutes with a Henschel mixer at a peripheral speed of 40 m / s. Next, 0.5 part of external additive J and 0.5 part of external additive D were added to the mixture, and mixed for 10 minutes at a peripheral speed of 40 m / s with a Henschel mixer. The powder after mixing was passed through a mesh having an opening of 100 μm to remove coarse particles, whereby toner I of Example 8 was obtained.

Example 9
-Preparation of toner-
One part of the external additive L was added to 100 parts of the obtained “toner base particles 1”, and mixed for 10 minutes with a Henschel mixer at a peripheral speed of 45 m / s. Next, 1 part of the external additive B and 0.5 part of the external additive C were added to the mixture, and the mixture was mixed with a Henschel mixer at a peripheral speed of 40 m / s for 10 minutes. The powder after mixing was passed through a mesh having an opening of 100 μm to remove coarse particles, whereby toner J of Example 9 was obtained.

(Comparative Example 2)
-Preparation of toner-
1 part of the external additive J and 1 part of the external additive D were added to 100 parts of the obtained “toner base particle 1”, and mixed for 8 minutes with a Henschel mixer at a peripheral speed of 30 m / s. The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse particles, whereby a toner K of Comparative Example 2 was obtained.

(Comparative Example 3)
-Preparation of toner-
1 part of the external additive J and 0.5 part of the external additive D were added to 100 parts of the obtained “toner base particles 1”, and mixed for 10 minutes at a peripheral speed of 30 m / s using a Henschel mixer. Next, 1 part of the external additive L was added to the mixture, and mixed for 5 minutes at a peripheral speed of 40 m / s with a Henschel mixer. The mixed powder was passed through a mesh having a mesh size of 100 μm to remove coarse particles, whereby the toner L of Comparative Example 3 was obtained.

(Comparative Example 4)
Toner M of Comparative Example 4 was prepared in the same manner as Example 1 of JP-A-2001-66820.

(Example 10)
-Preparation of toner-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 138 parts of styrene, methacrylic acid When 138 parts of acid and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to disperse the vinyl resin (styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) organic fine particle emulsion in an aqueous dispersion. A liquid was obtained. The volume average particle diameter measured by LA-920 (manufactured by Horiba Seisakusho) was 0.14 μm. A portion of this was dried to isolate the resin content. The glass transition temperature (Tg) of the resin component was 152 ° C.

Next, 200 parts of an ethyl acetate solution of the polyester resin, 5 parts of carnauba wax, and 4 parts of copper phthalocyanine blue pigment are charged into a sealed pot, and ball mill dispersion is performed for 24 hours using zirconia beads having a diameter of 5 mm. It was. Thereafter, 20 parts of the isocyanate-containing polyester in terms of solid content was added and mixed by stirring to obtain a toner composition. Next, 600 parts of ion-exchanged water in a beaker, 48 parts of an aqueous dispersion of an organic fine particle emulsion, 24 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 36 parts of ethyl acetate was mixed and stirred to obtain a milky white liquid.
Next, after maintaining the beaker internal temperature at 20 ° C. and stirring at 12000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), an oil phase was prepared by mixing 1 part of the ketimine compound with the toner composition immediately before emulsification. The mixture was stirred and emulsified for 3 minutes. Next, this mixed solution was transferred to a flask equipped with a stirring bar and a thermometer, and the solvent was removed at 30 ° C. under reduced pressure of 50 mmHg for 8 hours.
It was confirmed by gas chromatography that ethyl acetate in the dispersion was 100 ppm or less. Thereafter, the dispersion was separated by filtration, and the obtained cake was redispersed in distilled water and filtered, and washed three times. The obtained cake was redispersed in distilled water so as to have a solid content of 10% to obtain a dispersion of toner base particles.
The obtained toner base particles had a volume average particle diameter (Dv) of 5.8 μm, Dv / Dn = 1.15, SF-1 = 110, and SF-2 = 115.

  Next, silica particles A to C having characteristics shown in Table 4 obtained by the metal alkoxide hydrolysis polycondensation method were prepared.

Next, 3 parts of silica particles A were mixed with N, N, N, -trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (product name: Footage 310, manufactured by Neos). The mixture was gradually added to a solution of 2 parts, 70 parts of ion exchange water and 30 parts of methanol with stirring to obtain a dispersion of silica fine particles. The obtained silica fine particle dispersion was mixed with the above base particle dispersion, and then stirred at room temperature for 1 hour, filtered and separated, and the resulting cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner particles. Obtained. According to SEM (scanning electron microscope), each silica fine particle was uniformly attached to the surface of the obtained base particle. This is designated as toner particle A.
To 100 parts of the obtained toner particles A, 0.5 part of hydrophobic silica R972 (manufactured by Nippon Aerosil Co., Ltd.) and 0.5 part of hydrophobic titanium oxide MT150AI (manufactured by Titanium Industry Co., Ltd.) are mixed with a Henschel mixer, and the toner is mixed. N was produced.

(Example 11)
-Preparation of toner-
In Example 10, a toner O of Example 11 was produced in the same manner as in Example 10 except that the silica particles B shown in Table 4 were used instead of the silica particles A.

(Example 12)
-Preparation of toner-
In Example 10, a toner P of Example 12 was produced in the same manner as in Example 10 except that the silica particles C shown in Table 4 were used instead of the silica particles A.

Next, with respect to the obtained toners of Reference Example 7, Examples 8 to 12 and Comparative Examples 2 to 4, external additives were obtained in the same manner as Reference Examples 1 to 4, Examples 5 and 6, and Comparative Example 1. The number of aggregates was measured. The results are shown in Table 5.

-Preparation of developer-
A type in which a container rolls and stirs 7 parts of each of the obtained toners of Reference Examples 1 to 4 and 7, Examples 5, 6, 8 to 12 and Comparative Examples 1 to 4 and 100 parts of the carrier. Were mixed uniformly using a tumbler mixer and charged to prepare a developer.
The obtained developer was loaded into an image forming apparatus (IPSiO Color 8100, manufactured by Ricoh Co., Ltd.), an image was output, and evaluated as follows. The results are shown in Table 6.

<Image density>
After outputting a solid image with an adhesion amount of 0.3 ± 0.1 mg / cm ² , which is a low adhesion amount on plain paper transfer paper (Ricoh Co., Ltd., type 6200), the image density is set to X-Rite (X-Rite). Manufactured) and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Image density is 1.4 or more.
X: The image density is less than 1.4.

<Cleanability>
Transfer residual toner on the photosensitive member that has passed the cleaning process after outputting 1,000 sheets of an image area ratio 95% chart is transferred to a white paper with Scotch tape (manufactured by Sumitomo 3M Limited), and measured with a Macbeth reflection densitometer RD514 type. The evaluation was made according to the following criteria.
〔Evaluation criteria〕
A: The difference from the blank is less than 0.005.
(Circle): The difference with a blank is 0.005-0.010.
(Triangle | delta): The difference with a blank is 0.011-0.02.
X: The difference with a blank exceeds 0.02.

<Transferability>
After the image area ratio 20% chart is transferred from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before cleaning is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.). Measured and evaluated according to the following criteria.
〔Evaluation criteria〕
A: The difference from the blank is less than 0.005.
(Circle): The difference with a blank is 0.005-0.010.
(Triangle | delta): The difference with a blank is 0.011-0.02.
X: The difference with a blank exceeds 0.02.

<Image graininess, sharpness>
A photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated according to the following criteria.
〔Evaluation criteria〕
A: Same as offset printing.
○: Slightly worse than offset printing.
Δ: It is considerably worse than offset printing.
X: Very bad at the level of conventional electrophotographic images.

<Fog>
In an environment of a temperature of 10 ° C. and a humidity of 15% RH, an image forming apparatus (Ricoh Co., Ltd., IPSiO Color 8100) was remodeled to an oil-less fixing system and tuned to an evaluation machine. The degree of toner contamination on the transfer paper upper surface after the endurance test for outputting 100,000% charts continuously was evaluated visually (loupe) according to the following criteria.
〔Evaluation criteria〕
A: The toner is not observed at all and is in a good state.
○: Slight dirt is observed, and there is no problem.
Δ: Slightly dirty.
X: Very dirty and out of the allowable range.

<Toner scattering>
In an environment of a temperature of 40 ° C. and a humidity of 90% RH, an image forming apparatus (Ricoh Co., Ltd., IPSiO Color 8100) was remodeled to an oil-less fixing system and tuned to an evaluation machine. The toner contamination state in the image forming apparatus after the endurance test for outputting 100,000% charts continuously was visually evaluated according to the following criteria.
〔Evaluation criteria〕
A: The toner is not observed at all and is in a good state.
○: Slight dirt is observed, and there is no problem.
Δ: Slightly dirty.
X: Very dirty and out of the allowable range.

<Charging stability>
Using each toner, an endurance test for outputting 100,000 sheets continuously was performed using a character image pattern having an image area ratio of 12%, and the change in the charge amount at that time was evaluated. A small amount of developer was collected from the sleeve, the change in charge amount was determined by the blow-off method, and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Change in charge amount is less than 5 μc / g.
Δ: Change in charge amount is 5 μc / g or more and 10 μc / g or less.
X: Change in charge amount exceeds 10 μc / g.

<Filming properties>
Filming on the developing roller after outputting 1,000 sheets of band charts with image area ratios of 100%, 75%, and 50% and filming on the photoreceptor were observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Filming does not occur at all.
○: The occurrence of filming can be confirmed slightly.
Δ: Filming occurs in streaks.
X: Filming has occurred on the entire surface.

The toner of the present invention can maintain good transferability and cleaning properties for a long period of time, prevent the occurrence of photoconductor filming, no fluctuation in image unevenness, and external addition by stirring the developer during use. Since the agent is not buried and fluidity and chargeability are excellent in stability with little change over a long period of time, it is suitably used for high-quality image formation.
The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic configuration diagram showing an example of a process cartridge of the present invention. FIG. 2 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 4 is a partial schematic view showing an example of the tandem type image forming apparatus of the present invention. FIG. 5 is a partial schematic view showing another example of the tandem type image forming apparatus of the present invention. FIG. 6 is an overall schematic diagram showing an example of the tandem type image forming apparatus of the present invention. FIG. 7 is a partially enlarged view of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer body cleaning device 10 Photoconductor (photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 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 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure Means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Belt type image fixing device 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed capacity Set 145 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 400 Automatic document feeder (ADF)

Claims (18)

A toner comprising at least an external additive, wherein the external additive is a large particle having a volume average particle size of 100 to 150 nm and a small particle having a volume average particle size smaller than the large particle; Then, 0.2 g of the toner was air blown at a suction pressure of 5 mmHg on a sieve of 635 mesh and a mesh area of 452 cm ² , and then air blown at a blow pressure of 0.2 MPa from a height of 160 mm above the sieve, followed by suction pressure. The toner, wherein when the air is sucked at 20 mmHg, the number of aggregates of the external additive remaining on the sieve is 4,500 or less and 5 or more.   The toner according to claim 1, wherein the number of aggregates of the external additive remaining on the sieve is 4,500 or less and 20 or more.   The toner according to claim 1, wherein the number of aggregates of the external additive remaining on the sieve is 3,000 or less and 30 or more. The toner according to claim 1, wherein the large diameter particles are externally added before the small diameter particles. The toner according to claim 1, wherein the large-diameter particles are silica fine particles, and the small-diameter particles are at least one of titanium oxide fine particles and hydrophobic silica fine particles. The toner according to claim 1, wherein the toner has a volume average particle diameter of 3 to 8 μm. The toner according to claim 1, wherein the volume average particle diameter (Dv) / number average particle diameter (Dn) of the toner is 1.25 or less. The toner according to claim 1, wherein the toner has an average circularity of 0.900 to 0.980. The toner according to claim 1, wherein an external additive and toner particles are mixed, and the external additive is attached to the toner particles. The toner according to claim 1, wherein the external additive and toner particles are dispersed in an aqueous medium, and the external additive is attached to the toner particles. The external additive, an aggregate obtained by aggregating large-diameter particles, and toner particles are mixed, and the external additive and the aggregate are attached to the toner particles. Toner. The toner according to claim 1, wherein the content of large-sized particles is smaller than the content of small-sized particles. A toner solution containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is dissolved or dispersed in an organic solvent to prepare a toner solution, and then the toner solution is emulsified in an aqueous medium. A dispersion is prepared by dispersing, and in the aqueous medium, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive substrate in the form of particles. The toner according to claim 1, obtained by removing the organic solvent. A developer comprising the toner according to claim 1. A toner-filled container filled with the toner according to claim 1. An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 13 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using toner according to any one of claims 1 to 13 And developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. Image forming apparatus.