JP4472605B2 - Toner and image forming method using the same - Google Patents

Description

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

In electrophotographic devices and electrostatic recording devices, toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a transfer material, and then fixed to the transfer material by heat to form a toner image. is doing. In addition, full-color image formation generally reproduces colors using toners of four colors, black, yellow, magenta, and cyan. Each color is developed, and each toner layer is superimposed on a transfer material. A full color image is obtained by heating the toner image and fixing it at the same time.
However, for users who are familiar with printing, the images on full-color copiers are still not at a satisfactory level, and there is a need 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 image quality.

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 the colorant, the charge control agent, and the like in the thermoplastic resin. Such uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality, and the like of the toner.

  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). 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.

  Also disclosed is a method for obtaining irregular toner particles by associating resin fine particles obtained by an emulsion polymerization method (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 is increased 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. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so that there is a variation in composition (content ratio of constituent components) and molecular weight of the constituent resin among the obtained toner particles. appear. 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, Emulsion-Aggregation method) has been proposed (see Patent Document 5). This method is a method of granulating from a polymer dissolved in an organic solvent or the like, whereas the suspension polymerization method forms particles from monomers, and has advantages such as expansion of the resin selection range and polarity controllability. In addition, there is an advantage that toner structure control (core / shell structure control) is possible. However, in this proposal, the shell structure is a resin-only layer intended to reduce the exposure of the pigment and wax to the surface, and the surface state is not particularly devised, and it is also such a structure. (See Non-Patent Document 1). Therefore, in the above proposal, although the shell structure is used, the toner surface is an ordinary resin and is not particularly devised, and when aiming at lower temperature fixing, it is not sufficient in terms of heat-resistant storage stability and environmental charge stability. Absent.

Also, in any of the above polymerization methods, styrene-acrylic resins are generally used, and polyester resins have difficulty in particle formation, and particle size, particle size distribution, and shape control are difficult. Furthermore, there is a limit to fixability when aiming at lower temperature fixing.
In addition, for the purpose of heat-resistant storage and low-temperature fixing, it has been proposed to use a polyester modified with a urea bond (see Patent Document 6). However, in this proposal, the surface is not particularly devised, and it is not sufficient in terms of environmental charging 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 fixing property are lowered, and a tendency to become a poor image is observed. On the other hand, 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, has no fluctuation in image unevenness, has excellent fluidity and charging property with little change over a long period of time, and the toner. It is an object to provide a developer using toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

Means for solving the problems are as follows. That is,
<1> The toner core and at least an external additive on the surface of the toner core, the external additive including at least a large particle size inorganic oxide having a particle size of 50 to 500 nm,
The weight average particle diameter D ₄ of the toner are observed cut surfaces of the toner maximum length Dcut particle size satisfies 0.8D ₄ above, in the TEM photographs taken at 10,000 times using a transmission electron microscope The shape of the toner is in contact with a straight line that does not intersect with the toner core at two points, and the distance between the two points has a recess of 0.1D ₄ or more
When the number of the inorganic oxides present in the region formed by the tangent and the concave portion is an average value obtained from arbitrary 10 toners, before stress application is N before, and after stress application is N after Satisfying the following formula, 1 ≦ N after / N before ≦ 5,
For applying the stress, 10 g of the toner and 20 g of the carrier are placed in a 50 ml screw vial and shaken at a vibration frequency of 400 rpm for 60 minutes using a rocking mill, and then the toner and the carrier are separated by 20 μm. The toner is characterized by being separated by using a sieve.
<2> The toner according to <1>, wherein the external additive is obtained by surface-treating silica fine particles having a BET specific surface area of 20 to 250 m ² / g with silicone oil.
<3> The toner according to <2>, wherein the content of the silicone oil in the external additive is 1 to 10% by mass.
<4> The toner according to any one of <2> to <3>, wherein the liberation rate of the silicone oil from the silica fine particles is 10 to 50% by mass.
<5> The toner according to any one of <1> to <4>, wherein the external additive is agitated at a peripheral speed of 20 to 50 m / s and externally added to the toner core.
<6> The toner according to <5>, wherein the stirring is performed at 15 to 40 ° C.
<7> The toner according to any one of <5> to <6>, wherein the external additive is stirred together with the metal oxide fine particles.
<8> The toner according to any one of <5> to <6>, wherein the external additive is added after the toner core and the metal oxide fine particles are stirred.
<9> The toner according to any one of <1> to <8>, wherein the toner material is granulated after the toner material is dissolved or dispersed in an aqueous medium to prepare an emulsion or dispersion. It is.
<10> The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The toner according to <9>, which is performed.
<11> The toner according to any one of <9> to <10>, wherein the solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in an organic solvent.

<12> A developer comprising the toner according to any one of <1> to <11>.
<13> A toner-containing container filled with the toner according to any one of <1> to <11>.
<14> 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 <11> to be a visible image And a developing means for forming a process cartridge.
<15> 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 <11> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, Fixing means for fixing the transferred image transferred to the recording medium, The image forming apparatus is characterized by having at least.
<16> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <11> 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.

The toner of the present invention comprises at least a toner core and an external additive on the surface of the toner core, and the external additive includes at least a large particle size inorganic oxide having a particle size of 50 to 500 nm,
The weight average particle diameter D ₄ of the toner are observed cut surfaces of the toner maximum length Dcut particle size satisfies 0.8D ₄ above, in the TEM photographs taken at 10,000 times using a transmission electron microscope The shape of the toner is in contact with a straight line that does not intersect with the toner core at two points, and the distance between the two points has a recess of 0.1D ₄ or more
When the number of the inorganic oxides present in the region formed by the tangent and the concave portion is an average value obtained from arbitrary 10 toners, before stress application is N before, and after stress application is N after Satisfying the following formula, 1 ≦ N after / N before ≦ 5,
For applying the stress, 10 g of the toner and 20 g of the carrier are placed in a 50 ml screw vial and shaken at a vibration frequency of 400 rpm for 60 minutes using a rocking mill, and then the toner and the carrier are separated by 20 μm. It is carried out by separating using a sieve.
The toner of the present invention can maintain good transferability and cleaning properties over a long period of time, has no fluctuations in image unevenness, and has excellent stability with little change in fluidity and chargeability over a long period of time.

In this case, it is technically difficult to attach the large particle size silica as the external additive on the toner, and (1) it is free to exist alone or agglomerate between silica, 2) Some are present on the toner surface but move on the surface (low adhesion force), and (3) some are excessively buried and buried. These are all factors that deteriorate the basic performance of the toner that is desired to be expressed (level down, adverse effects on other performances) due to the toner design concept of external addition of large particle size silica.
In the case of conventional external addition of a large particle size silica, even if a state of uniform adhesion on the surface is observed, after applying stress to the toner (especially since it needs to be charged, there is a history of stirring in the developing machine) In other words, it can be said that there is no case where the toner is not stressed), but the effect of the external additive cannot be maximized by moving the external additive on the surface of the toner core. In particular, such a situation is often observed in the case of a deformed aqueous granulated toner. As a result, the external additive attached externally to the groove formed by deforming moves due to stress and does not exhibit its function.
The present invention has developed an external addition condition in which the adhesion of an external additive, which is an inorganic oxide having a large particle diameter, functions to the maximum, and the large particle diameter silica on the toner core surface under the external addition condition. It is possible to maximize the function of burdening the external additive by making it possible to suppress the movement of the external additive, particularly the movement to the groove.

  The developer of the present invention contains the toner of the present invention. For this reason, when image formation is performed by electrophotography using the developer, as a result, good transferability and cleanability can be maintained over a long period of time, there is no fluctuation in image unevenness, fluidity, and charging. High quality images with little change over time can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. When image formation is performed by electrophotography using the toner contained in the toner-containing container of the present invention, as a result, good transferability and cleanability can be maintained over a long period of time, and there is no fluctuation in image unevenness. In addition, a high-quality image can be obtained in which fluidity and chargeability are little changed over a long period of time.

  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, it is possible to maintain good transferability and cleaning performance over a long period of time. A high-quality image can be obtained in which there is no variation in unevenness and the flowability and chargeability are less changed over a long period of time.

  The image forming apparatus of the present invention includes 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 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, there is no fluctuation in image unevenness, and high-quality electrophotographic images can be formed with little change in fluidity and chargeability over a long period of time. .

  The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make 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, there is no fluctuation in image unevenness, and high-quality electrophotographic images can be formed with little change in fluidity and chargeability over a long period of time. .

  According to the present invention, various conventional problems can be solved, good transferability and cleaning performance can be maintained over a long period of time, and fluidity and chargeability are excellent in stability with little change over a long period of time. In addition, it is possible to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method capable of improving image quality using the toner.

(toner)
The toner of the present invention has at least a toner core (hereinafter sometimes referred to as “toner base particle”) and an external additive on the surface of the toner core, and further, if necessary, a colorant and a release agent. It contains other components such as a mold agent, a plasticizer, and a charge control agent.

The external additive is an inorganic oxide having a large particle diameter, and the particle diameter is 50 to 500 nm, preferably 90 to 200 nm, and more preferably 100 to 150 nm. If the particle size is less than 50 nm, the effect of suppressing the embedding of the external additive having a small particle size in the toner base particles may not be obtained. If the particle size exceeds 500 nm, the adhesion to the toner base particles is extremely high. The external additive with a small particle size is buried in the toner base particles when the toner is exposed to stress, and the effect of suppressing this is reduced. May end up.
The inorganic oxide is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include silica fine particles, hydrophobic silica, titania, alumina, tin oxide, and antimony oxide. Among these, Silica fine particles are particularly preferred.

  As the silica fine particles, commercially available products can be used. For example, HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805 , R812 (all manufactured by Nippon Aerosil Co., Ltd.), and the like. Other suitable examples include silica and metal oxides produced by the sol-gel method or the dry flame method.

Further, the external additive is preferably a silica fine powder having a BET specific surface area of 20 to 250 m ² / g surface-treated with silicone oil.
The specific surface area can be calculated according to the BET method using a specific surface area measuring device ("Autosorb 1", manufactured by Yuasa Ionics Co., Ltd.) by adsorbing nitrogen gas on the sample surface and using the BET multipoint method.
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 modified silicone oil, methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. Can be used.
The content of the silicone oil in the external additive is not particularly limited and can be appropriately selected depending on the purpose, and is preferably 1 to 10% by mass.
10-50 mass% is preferable and, as for the liberation rate of the silicone oil from the said external additive, 20-40 mass% is more preferable. The silicone oil released from the external additive enhances the adhesive force with the toner surface, and has the effect of making it difficult to move even when stress is applied to the toner. When the release rate of the silicone oil is less than 10% by mass, the external additive easily moves on the toner surface, and easily moves to the concave portion of the toner surface due to stress, thereby suppressing the burying of other external additives. , The effect of maintaining fluidity may be lost, and if it exceeds 50% by mass, the fluidity of the toner is extremely lowered due to the presence of excessive free oil, and the developing ability is insufficient, which is satisfactory. The resulting image may not be obtained, or the performance may not be exhibited due to contamination of other members with silicone oil.

-Particle size of inorganic fine particles-
The average particle diameter of primary particles of inorganic fine particles treated with silicone oil is preferably 500 nm or less, and more preferably 200 nm or less. If it is larger than this range, the surface area of the inorganic fine particles will be reduced, the total amount of silicone oil that can be supported will be small, and even if the release rate of the silicone oil is set within the above range, the effect may not be exerted. Moreover, the average particle diameter here is a number average particle diameter. The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring device using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary aggregation of the particles after the silicone oil treatment, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. More preferably, the external additive on the toner surface is observed with a FE-SEM (field emission scanning electron microscope) at a magnification of 100,000 times. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained. When the external additive has an aggregate structure on the toner surface, the major axis of the single primary particle constituting the aggregate is determined.

-Silicone oil treatment method-
The inorganic fine particles that have been sufficiently dehydrated and dried in an oven of several hundred degrees Celsius in advance and silicone oil are uniformly contacted to adhere to the surface of the inorganic fine particles. In order to adhere, the inorganic fine particles and the silicone oil are sufficiently mixed with powder using a mixer such as a rotary blade, or the silicone oil is dissolved in a relatively low boiling point solvent capable of diluting the silicone oil, and the inorganic fine particles are put into the liquid. It can be produced by a method of impregnating and removing the solvent and drying. When the viscosity of the silicone oil is high, the treatment is preferably performed in a liquid.
Thereafter, the inorganic powder to which the silicone oil is adhered is heat-treated in an oven at 100 to several hundred degrees Celsius to form a siloxane bond between the metal and the silicone oil using the hydroxyl group on the surface of the inorganic powder. It can be further polymerized and crosslinked. A catalyst such as acid, alkali, metal salt, zinc octylate, tin octylate or dibutyltin dilaurate may be included in the silicone oil in advance to promote the reaction. In addition, the inorganic fine particles may be previously treated with a hydrophobizing agent such as a silane coupling agent before the silicone oil treatment. In addition, the amount of adsorption of silicone oil is greater in the case of inorganic powder that has been hydrophobized in advance. The amount of free silicone oil is almost determined by this heat treatment, but it does not necessarily have to be chemically bonded to the surface of the inorganic fine particles with the non-free silicone oil in the present invention. Some are included. More specifically, it is a component that comes into contact and easily desorbs from the inorganic fine particles, and is defined by a measurement method described later.

-Measurement of silicone oil release rate-
The silicone oil release rate can be measured by the following quantitative method.
--Extraction of free silicone oil--
The sample is immersed in chloroform, stirred and left to stand. Chloroform is newly added to the solid content after removing the supernatant by centrifugation, and the mixture is stirred and allowed to stand. Repeat this operation to remove the free silicone oil.
--Quantification of carbon content--
The amount of carbon was measured with a CHN element analyzer (CHN coder MT-5 type (manufactured by Yanaco)).
--Measurement of silicone oil release rate--
The silicone oil release rate can be obtained by the following formula 1.
<Formula 1>
Silicone oil release rate (%) = (C ₀ -C ₁ ) / C ₀ × 100
However, in Formula 1, C ₀ represents the amount of carbon in the sample before the extraction operation. C ₁ represents the amount of carbon in the sample after the extraction operation.

Further, it is preferable that the silica fine particles having a large particle size as the external additive are stirred together with the metal oxide fine particles. Further, the external additive is preferably added after the toner core and the metal oxide fine particles are stirred.
Examples of the metal oxide fine particles include alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, chromium oxide, cerium oxide, and bengara. , Antimony trioxide, magnesium oxide, zirconium oxide, and the like.

  The amount of the external additive added to the toner is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass.

The present invention has developed an external addition condition in which the adhesion of an external additive, which is an inorganic oxide having a large particle diameter, functions to the maximum, and the large particle diameter silica on the toner core surface under the external addition condition. It is possible to maximize the function of burdening the external additive by making it possible to suppress the movement of the external additive, particularly the movement to the groove.
Therefore, as shown in FIG. 1, the cut surface of the toner satisfying the maximum particle diameter length Dcut of 0.8D ₄ or more with respect to the weight average particle diameter D ₄ of the toner is shown by a transmission electron microscope (manufactured by JEOL Ltd.). , the shape of toner to be observed in TEM photographs taken at 10,000-fold using JEM2010), contact a straight line and two points does not intersect the toner core, the distance between the two points 0.1 D ₄ or more recesses The toner which has is selected.
As shown in FIGS. 2A, 2B, and 2C, the number of the inorganic oxides present in the region formed by the tangent and the concave portion is an average value obtained from any ten toners, and stress is applied. When N before is given and N after is given after stress, N after / N before is obtained.
The stress is applied by putting 10 g of toner and 20 g of carrier in a 50 ml screw vial, shaking the mixture at a vibration frequency of 400 rpm for 60 minutes using a rocking mill, and then opening the toner and the carrier with an opening of 20 μm. It is carried out by separating using a sieve.
After N / N before, 1 ≦ N after / N before ≦ 5, and preferably 1 ≦ N after / N before ≦ 3.
When the above (after N / before N) is less than 1, the image may be deteriorated due to contamination of the members such as the carrier and the photosensitive member due to the particles in the recesses coming out. In some cases, the external additive having a large particle size added to the concave portion is concentrated and the function of preventing the burying of the external additive having a small particle size may not be achieved.

Here, the method of externally adding the external additive to the surface of the toner core may be either a dry external addition process or a wet external addition process.
In the dry external addition process, the external additive and the toner core are mixed and the external additive adheres to the surface of the toner core.
The 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 20 to 50 m / s. When the peripheral speed is less than 20 m / s, the external additive does not adhere firmly to the surface, and when it is stressed, the external additive may move to the concave portion, and when it exceeds 50 m / s, It is observed that the external additive has already moved to the recess during the production of the toner due to excessive stirring, and the function may not be performed. Moreover, it is preferable that the said stirring is performed at 15-40 degreeC.

The wet external additive is formed by dispersing the external additive and a toner core in an aqueous medium and attaching the external additive to the toner particles.
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.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include colorants, mold release agents, fluidity improvers, cleaning property improvers, magnetic materials, metal soaps, and the like. Can be mentioned.

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 ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, 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. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method 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 organic solvent components. 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, Although it can select suitably according to the objective, The low melting-point mold release agent whose melting | fusing point is 50-120 degreeC is preferable. The low melting point release agent, when dispersed with the resin, effectively acts as a release agent between the fixing roller and the toner interface, thereby preventing oilless (release agent such as oil on the fixing roller). Even if it is not applied), the hot offset property is good.
Suitable examples of the mold release agent include waxes and waxes.
Examples of the waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and micro wax And natural waxes such as petroleum waxes such as crystallin and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate, poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used.
These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50-120 degreeC is preferable and 60-90 degreeC is more preferable.
If the melting point is less than 50 ° C., the wax may adversely affect the heat resistant storage stability, and if it exceeds 120 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

There is no restriction | limiting in particular as content in the said toner of 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 ones according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, and molybdate chelate pigments. , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid metal salts And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , Oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302 TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (Above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Japan) Ritto Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.

  The content of the charge control agent in the toner varies depending on the type of the resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be generally defined. For example, with respect to 100 parts by mass of the binder resin, 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.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

The toner of the present invention can be produced using a known method such as a suspension polymerization method, an emulsion polymerization method, or a dissolution suspension method. For example, the toner material is dissolved or dispersed in an aqueous medium. It can be obtained by granulating a toner after preparing an emulsified or dispersed liquid by dispersing.
As a preferred embodiment of the toner of the present invention, a solution or dispersion of a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium. And a toner obtained 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 to produce particles containing at least an adhesive substrate. .
Here, as a temperature at the time of manufacturing the toner of the present invention, for example, 10 to 100 ° C. is preferable, and 20 to 60 ° C. is more preferable. When the production temperature exceeds 100 ° C., the resin and the plasticizer are compatible with each other by heating, and it may be impossible to achieve both low-temperature fixability and heat-resistant storage stability.
Hereinafter, a toner according to a preferred embodiment of the present invention will be described.

-Dissolution or dispersion of toner material-
The dissolved or dispersed liquid of the toner material is obtained by dissolving or dispersing the toner material in a solvent.
The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. Examples thereof include an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. (Prepolymer) at least, preferably including the plasticizer, and further including other components such as an unmodified polyester resin, a release agent, a colorant, and a charge control agent as necessary. Become.

The solution or dispersion of the toner material is preferably prepared by dissolving or dispersing the toner material in the organic solvent. The organic solvent is preferably removed during or after the toner granulation.
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, methyl isobutyl ketone, and the like, and ester solvents 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.
In the toner production method of the preferred embodiment of the present invention, the toner material can be dissolved or dispersed in the organic solvent so that it can react with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The toner material such as a polymer, the unmodified polyester resin, the release agent, the colorant, and the charge control agent can be dissolved or dispersed in the toner material. Components other than the polymer (prepolymer) capable of reacting with the group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later, or the solution or dispersion of the toner material may be added. When added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

-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, and aliphatic diamines. 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.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be deteriorated. 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 heating medium for fixing. 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-forming group in the urea bond-forming 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, polytetramethylene ether glycol, and the like. 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 trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent 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 alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric 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, and sebacic acid. 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, an 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.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those obtained by blocking them with a phenol derivative, oxime, caprolactam or 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 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4,000 to 30,000 is more preferable. When the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

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.

-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 aqueous medium can be prepared, for example, by dispersing 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 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 resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin fine particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. 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. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", 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.

-Emulsification or dispersion-
In the dissolution or dispersion of the toner material in the aqueous medium, the dissolution or dispersion of the toner material is preferably dispersed in the aqueous medium while stirring. The dispersion method is not particularly limited and can be appropriately selected depending on the purpose. For example, the dispersion method can be performed using a known disperser, and the disperser includes the low-speed shear disperser. And the high-speed shearing disperser.

  In the method for producing a toner according to the preferable aspect of the present invention, when the emulsification or dispersion is performed, 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. An adhesive substrate (the resin) is generated.

-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, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as a glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) 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 not be sufficient.

  The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

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, and 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.

---- 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, Undenatured 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 preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. 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 preferably 35 to 70 ° C. When the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may be deteriorated, 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, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is usually 1.0 to 30.0 mgKOH / g, and preferably 5.0 to 20.0 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.
If the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated, and if it is less than 75, the low-temperature fixability and the glossiness of the image may be deteriorated. .

  As content of the said unmodified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, and 55-95 mass% is more preferable. When the content is less than 50% by mass, low-temperature fixability, fixed image strength, glossiness, and the like may be deteriorated.

  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)). A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium together with the active hydrogen group-containing compound (for example, the amines (B)) to form the oil droplets, and both in the aqueous medium. (2) A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance. It may be formed by forming droplets and subjecting both to extension reaction or crosslinking reaction in the aqueous medium, or (3) dissolving or dispersing the toner material in the aqueous medium After the addition and mixing in the system medium, the active hydrogen group-containing compound is added, the oil droplets are formed, and they are produced by subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium. Good. 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 or 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.

  Examples of 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)) in the aqueous medium include, for example, the aqueous system. In a medium, 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, and the unmodified polyester resin And the like. A method in which a solution or dispersion of the toner material prepared by dissolving or dispersing the toner material in the organic solvent is added and dispersed by shearing force.

In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
If the amount used is less than 50 parts by mass, the toner material may be poorly dispersed, and toner particles having a predetermined particle size may not be obtained. May be.

In the emulsification or dispersion, if necessary, it is preferable to use a dispersant from the viewpoint of stabilizing the oil droplets and obtaining a desired shape while sharpening the particle size distribution.
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 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) 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 (manufactured by Asahi Glass); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

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, celluloses, and the like.
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 emulsified slurry obtained by the emulsification or dispersion.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into 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 in a liquid by a cyclone, a decanter, centrifugation, or the like, 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 for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

The toner produced by the suspension polymerization method will be described below.
As described above, the toner produced by the suspension polymerization method is prepared by emulsifying or dispersing (suspending) a toner material in an aqueous medium after preparing the emulsion or dispersion (suspension). It can be obtained by granulating toner.

-Dissolution or dispersion of toner material-
In the suspension polymerization method, the solution or dispersion of the toner material is preferably a polymerizable monomer or an oil-soluble polymerization initiator, preferably the plasticizer, and if necessary, a colorant, a release agent, Other components such as a charge control agent are dissolved or dispersed. In addition, for example, in order to reduce the viscosity of the polymer produced by the polymerization reaction described later, an organic solvent, a high molecular polymer, a dispersant and the like may be added as appropriate.

--Polymerizable monomer--
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, and the like; acrylamide, methacrylic acid, The surface of toner particles by partially using amide, diacetone acrylamide, and their methylol compounds, acrylates and methacrylates having amino groups such as vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate, etc. Functional groups can be introduced into the. In addition, by appropriately selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the surface of the toner particles to introduce a functional group.
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate Acrylic acid such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Esters: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenolic methacrylate , Dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, acrylamide, and the like.

  In addition to the polymerizable monomer, a resin may be used. For example, since the polymerizable monomer is soluble in water and cannot be emulsified by dissolution in an aqueous suspension, an amino group, a carboxylic acid group, a hydroxyl group, a sulfone group, a glycidyl group, a nitrile When a hydrophilic functional group-containing polymerizable monomer such as a group is to be introduced into the toner, a random copolymer of these with a vinyl compound such as styrene or ethylene, a block copolymer, a graft copolymer, etc. A resin in the form of a copolymer, a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine can be used.

Examples of the alcohol component and the acid component that form the polyester resin include the following.
Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and the like. Polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins may be used.
Examples of the acid component include divalent carboxylic acids such as benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, and the like. Alkyl dicarboxylic acid or anhydride thereof; succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or anhydride thereof Thing; etc. are mentioned. Further, polycarboxylic acids such as trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, benzophenonetetracarboxylic acid, and anhydrides thereof may be used.
As content of the said alcohol component and the said acid component in the said polyester resin, it is preferable that the said alcohol component is 45-55 mol%, and the said acid component is 55-45 mol%.

Two or more polyester resins may be used in combination as long as the physical properties of the toner particles obtained are not adversely affected. Moreover, physical properties can be adjusted, such as modification with silicone or a fluoroalkyl group-containing compound.
Here, when using the high molecular polymer containing such a polar functional group, the average molecular weight of the high molecular polymer is preferably 5,000 or more.

Furthermore, in addition to the polymerizable monomer, the following resins can be used. Examples of the resin include homopolymers of styrene such as polystyrene and polyvinyltoluene, and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid. Methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Coalescence, styrene-vinylmethylke Copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc .; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resin, and the like. These may be used individually by 1 type and may use 2 or more types together.
As addition amount of these resin, 1-20 mass parts is preferable with respect to 100 mass parts of said polymerizable monomers, for example. When the addition amount is less than 1 part by mass, the effect of adjusting the physical properties of the toner particles due to the addition may not be exhibited, and when it exceeds 20 parts by mass, the physical property design of the toner particles may be difficult.
Further, a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the polymerizable monomer can be dissolved in the polymerizable monomer and polymerized.

--Oil-soluble polymerization initiator--
The oil-soluble polymerization initiator has a half-life of 0.5 to 30 hours during the polymerization reaction, and is added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Can give a polymer having a maximum between 10,000 and 100,000 in molecular weight, and can impart desirable strength and suitable dissolution characteristics to the toner.
The oil-soluble polymerization initiator is not particularly limited as long as it is oil-soluble, and can be appropriately selected according to the purpose. For example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyro Azo-based or diazo-based polymerization initiators such as nitriles; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butyl peroxide 2- And peroxide polymerization initiators such as ethyl hexanoate.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, a charge control agent, a crosslinking agent etc. are mentioned.

There is no restriction | limiting in particular as said colorant, It can select suitably from well-known things, For example, carbon black, a yellow colorant, a magenta colorant, and a cyan colorant are mentioned.
Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180 and the like are particularly preferable.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 and the like are particularly preferable.
Examples of the cyan colorant include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferable.
The said colorant may be used individually by 1 type, may use 2 or more types together, and can be used in the state of a solid solution. The colorant can be selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, dispersibility in the toner, and the like.
There is no restriction | limiting in particular as addition amount of the said coloring agent, According to the objective, it can select suitably, For example, 1-20 mass parts is preferable with respect to 100 mass parts of said resins.

  Examples of the release agent include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam or derivatives thereof; montan wax and derivatives thereof, hydrocarbon waxes or derivatives thereof according to the Fischer-Tropsch method, and polyolefins represented by polyethylene. And waxes or derivatives thereof, natural waxes such as carnauba wax and candelilla wax or derivatives thereof, and the like. These derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. . In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil or derivatives thereof, plant waxes, animal waxes, etc. can also be used. .

  The charge control agent is not particularly limited and may be appropriately selected from known ones. However, when the toner is produced using a direct polymerization method, the polymerization inhibitory property is low and the toner can be applied to an aqueous medium. Those having substantially no lysate are particularly preferred. Specifically, examples of the negative charge control agent include metal compounds of aromatic carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, and dicarboxylic acid; metal salts or metal complexes of azo dyes or azo pigments And polymer type compounds having a sulfonic acid or carboxylic acid group in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, and the like. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  As a method of adding the charge control agent to the toner, there are a method of adding it inside the toner base particles and a method of adding it externally. The amount of the charge control agent used is determined by the type of resin, the presence or absence of other additives, and the toner production method including the dispersion method, and is not uniquely limited. In this case, 0.1 to 10 parts by mass is preferable and 0.1 to 5 parts by mass is more preferable with respect to 100 parts by mass of the resin. In the case of the external addition method, 0.005 to 1.0 part by mass is preferable with respect to 100 parts by mass of toner, and 0.01 to 0.3 part by mass is more preferable.

The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound having two or more polymerizable double bonds can be preferably used. For example, divinyl Aromatic divinyl compounds such as benzene and divinylnaphthalene; carboxylate esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline, divinyl ether, divinyl sulfide And divinyl compounds such as divinyl sulfone; and compounds having three or more vinyl groups. These may be used individually by 1 type and may use 2 or more types together.
As addition amount of the said crosslinking agent, 0.001-15 mass parts is preferable with respect to 100 mass parts of said polymerizable monomers, for example.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water is mention | raise | lifted.
The aqueous medium preferably contains a dispersion stabilizer.
As the dispersion stabilizer, for example, known surfactants, organic dispersants, inorganic dispersants and the like can be used. Among these, harmful ultrafine particles are hardly generated, and dispersion stability is improved due to steric hindrance. Therefore, an inorganic dispersant is preferable in that it maintains a stable state even when the reaction temperature is changed, is easy to wash, and does not adversely affect the toner.
Examples of the inorganic dispersant include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metasuccinate, calcium sulfate and barium sulfate. And inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina.

The inorganic dispersant can be used as it is, but in order to obtain finer particles, the inorganic dispersant particles may be generated and used in the aqueous medium. For example, in the case of the calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed under high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At this time, a water-soluble sodium chloride salt is by-produced at the same time. However, if a water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and an ultrafine toner by emulsion polymerization is used. Is preferable because it is difficult to generate. However, since it becomes an obstacle when the remaining polymerizable monomer is removed at the end of the polymerization reaction, it is preferable to replace the aqueous medium or desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolution with an acid or alkali after completion of the polymerization.
The inorganic dispersant is preferably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the inorganic dispersant is used, it is difficult to produce ultrafine particles, but it is difficult to obtain a toner having a small particle diameter.
Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

-Suspension-
The suspension is performed by emulsifying or dispersing a solution or dispersion of the toner material in which the toner material is uniformly dissolved or dispersed in the aqueous medium. At this time, if a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used to disperse the toner particles to a desired size at once, a toner having a sharp particle size distribution can be obtained.
The oil-soluble polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or the solution or dispersion of the toner material is suspended in the aqueous medium. You may mix just before making. Further, during the granulation of the toner, the oil-soluble polymerization initiator dissolved in the polymerizable monomer or solvent may be added immediately after the granulation of the toner and before the start of the polymerization reaction.

-Granulation-
The granulation is performed by polymerizing the polymerizable monomer.
As temperature in the said polymerization reaction, it is 40 degreeC or more, for example, and generally is 50-90 degreeC. When the polymerization is performed within the temperature range, the release agent, the wax, and the like that should be present inside the toner particles are precipitated by phase separation, and can be encapsulated. In order to consume the remaining polymerizable monomer, the reaction temperature may be set to 90 to 150 ° C., but as described above, when heated above the melting point of the plasticizer, the resin and the plasticizer are In order to achieve compatibility, it is necessary to carry out the reaction at a temperature below the melting point of the plasticizer. Specifically, the reaction is preferably carried out at 100 ° C. or less.
In the granulation, it is also possible to use a seed polymerization method in which the polymerized monomer is further adsorbed on the obtained polymer particles and then polymerized using the oil-soluble polymerization initiator. At this time, a polar compound can be dissolved or dispersed in the polymerizable monomer to be adsorbed.

After completion of the polymerization reaction, it is preferable to perform stirring using a normal stirrer at a stirring speed that maintains the particle state and prevents the particles from floating and settling.
The polymer particles after completion of the polymerization reaction are filtered and washed by a known method to remove excess surfactant, dried, and further mixed with inorganic fine powder to adhere to the particle surface. Thus, toner particles are obtained. At this time, it is preferable to remove coarse powder and fine powder by classification.

The toner of the present invention is not particularly limited with respect to various physical properties such as shape and size, and can be appropriately selected according to the purpose. The weight average particle diameter (D ₄ ) and weight are as follows. It is preferable to have average particle diameter (D ₄ ) / number average particle diameter (Dn).

The weight average particle diameter (D ₄ ) of the toner is, for example, preferably 3 to 8 μm, and more preferably 4 to 6 μm.
When the weight average particle diameter (D ₄ ) is less than 3 μm, in the 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 addition, in a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. It becomes difficult to obtain a high-quality image by resolution, and when the balance of the toner in the developer is performed, fluctuations in the particle diameter of the toner may increase.

The ratio (D ₄ / Dn) of the weight average particle diameter (D ₄ ) to the number average particle diameter (Dn) in the toner is preferably 1.30 or less, and more preferably 1.00 to 1.30. .
When the ratio of the volume average particle diameter to the number average particle diameter (D ₄ / Dn) is less than 1.00, with the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device. The chargeability of the carrier may be reduced or the cleaning property may be deteriorated. Also, in the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are applied to a member such as a blade. Toner fusing is likely to occur, and if it exceeds 1.30, it becomes difficult to obtain a high-resolution and high-quality image. The particle size variation may increase.
When the ratio of the volume average particle size to the number average particle size (Dv / Dn) is 1.00 to 1.30, the storage stability, the low temperature fixability, and the hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance is maintained over a long period of time, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is used in the agent, the fluctuation of the toner particle diameter is reduced, and there is no toner filming on the developing roller and no toner fusion to the member on the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

The volume average particle diameter and the ratio (D ₄ / 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. be able to.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

  The toner of the present invention has good properties such as fluidity and fixability, and achieves both excellent low-temperature fixability and heat-resistant storage stability. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.

(Developer)
The developer of the present invention contains at least the toner of the present invention and other components appropriately selected such as the carrier. 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 service 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 according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is made thin. Therefore, 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 developing device, 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 high magnetization 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 core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  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, vinylidene fluoride And a copolymer of 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, if 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 coating method include a dipping 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.

Since the developer of the present invention contains the toner, it has excellent properties such as fluidity and fixability, and has both excellent low-temperature fixability and heat-resistant storage stability, and stable high-quality images. Can be formed.
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 is obtained by filling the container of the toner of the present invention or the developer.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body containing a toner and a cap etc. are mentioned suitably.
The size, shape, structure, material, etc. of the container body containing the toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral irregularity is formed on the inner peripheral 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. are particularly preferred.
The material of the container body containing toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, a material having good dimensional accuracy is preferable, for example, a resin is preferable. Among them, for example, polyester Preferred examples include resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride 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 of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. At least a developing means for forming the film, and other means 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 provided in various electrophotographic apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention described later.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transferring step, and a fixing step, preferably including a cleaning step, and other steps appropriately selected as necessary. For example, a static elimination process, a recycling process, a control process, etc. are included.
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 preferably includes a cleaning unit. In addition, other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like are provided.

  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 material, shape, structure, size, etc. of the electrostatic latent image carrier are not particularly limited, and can be appropriately selected from known ones. The shape is preferably a drum shape. 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.

  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. And non-contact chargers using corona discharge such as corotrons and corotrons.

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 latent electrostatic image bearing member 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 unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. 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 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 not particularly limited and can be appropriately selected from known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using the fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or may be applied to the toner of each color. On the other hand, it may be carried out simultaneously at the same time in a state of being laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. 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 ° C 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, and may be appropriately selected from known cleaners as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier. Preferred 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.

  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. 3 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and an 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 body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to 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 52 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. 3, 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 visible image (toner image). The visible image (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. 4 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. 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. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

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. A tandem image forming apparatus 100 shown in FIG. 5 is a tandem color image forming apparatus. The tandem image forming apparatus 100 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. 5. 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. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
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. The photosensitive member is exposed to each color image corresponding image (L in FIG. 6), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) 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 feeding roller 142 is rotated to feed out the sheet (recording paper) on the manual feed tray 54, separated one by one by the separation roller 58, 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 apparatus and the image forming method of the present invention, since the toner of the present invention has good characteristics such as fluidity and fixability and has both excellent low-temperature fixability and heat-resistant storage stability, 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 stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were charged 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. Next, 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 (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). 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. Further, 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 (Printtex 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 / Wax Dispersion 1].
The obtained [Pigment / Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
[Pigment / 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 Co., Ltd.). 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 then 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].

About the obtained “toner base particle 1”, the weight average particle diameter (D ₄ ), the particle size distribution (D ₄ / Dn), and the average circularity were measured as follows. The weight average particle diameter (D ₄ ) was 5.8 μm, the particle size distribution (D ₄ / Dn) was 1.15, and the average circularity was 0.950.

<Weight average particle size (D ₄ ) and particle size distribution (D ₄ / Dn)>
The weight average particle diameter (D ₄ ) 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, the particle size distribution (D ₄ / Dn) 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-
As shown in Table 1 below, surface-treated external additives A to M were prepared by a conventional method. In addition, the processing method of silicone oil, and the adjustment method of a liberation rate were performed in accordance with the following method.

<Silicone oil treatment method>
The inorganic fine particles that have been sufficiently dehydrated and dried in an oven of several hundred degrees Celsius in advance and silicone oil are uniformly contacted to adhere to the surface of the inorganic fine particles. In order to adhere, the inorganic fine particles and the silicone oil are sufficiently mixed with the powder using a mixer such as a rotary blade, or the silicone oil is dissolved in a relatively low boiling point solvent capable of diluting the silicone oil, and the inorganic fine particles are put into the liquid. It was prepared by a method of removing the solvent by impregnation and drying. In addition, when the viscosity of silicone oil is high, it is preferable to process in a liquid.
Thereafter, the inorganic powder to which the silicone oil is adhered is heat-treated in an oven at 100 to several hundred degrees Celsius to form a siloxane bond between the metal and the silicone oil using the hydroxyl group on the surface of the inorganic powder. It can be further polymerized and crosslinked.

<Measurement of silicone oil release rate>
The silicone oil release rate can be measured by the following quantitative method.
-Extraction of free silicone oil-
The sample is immersed in chloroform, stirred and left to stand. Chloroform was newly added to the solid content after removing the supernatant by centrifugation, and the mixture was stirred and allowed to stand. This operation was repeated to remove the free silicone oil.
-Quantification of carbon content-
The amount of carbon was measured with a CHN element analyzer (CHN coder MT-5 type (manufactured by Yanaco)).
-Measurement of silicone oil release rate-
The silicone oil release rate was determined by the following formula 1.
<Formula 1>
Silicone oil release rate (%) = (C ₀ -C ₁ ) / C ₀ × 100
However, in Formula 1, C ₀ represents the amount of carbon in the sample before the extraction operation. C ₁ represents the amount of carbon in the sample after the extraction operation.

* HMDS: Hexamethylene disilazane * PDMS: Silicone oil * IBMS: Isobutylmethoxysilane

(Examples 1-6 and Comparative Examples 1-6)
-Manufacture of toner-
1 part of the external additive M was added to 100 parts of the obtained “toner base particles 1”, and the mixture was mixed at a peripheral speed of 30 m / s for 5 minutes with a Henschel mixer while adjusting the internal temperature to 25 ° C. Then, 2 parts of external additives A to L were added and mixed for 10 minutes at a peripheral speed of 40 m / s with a Henschel mixer. The mixed powder was passed through a mesh with an opening of 100 μm to remove coarse particles, and toners of Examples 1 to 6 and Comparative Examples 1 to 6 were produced.

  Next, for each of the toners of Examples 1 to 6 and Comparative Examples 1 to 6, the ratio of the number of external additives before and after stress (after N / before N) was determined as follows. The results are shown in Table 2.

<Ratio of the number of external additives before and after stress (after N / before N)>
As shown in FIG. 1, a cut surface of a toner satisfying a maximum particle diameter length Dcut of 0.8 D ₄ or more with respect to the average particle diameter D ₄ of the toner is shown as a transmission electron microscope or a transmission electron microscope (JEOL Ltd.). Ltd., concave shape of toner observed in TEM photographs taken at 10,000-fold using JEM2010), contact a straight line and two points does not intersect the toner core, the distance between the two points is 0.1 D ₄ or more The toner having
As shown in FIGS. 2A, 2B, and 2C, the number of the inorganic oxides present in the region formed by the tangent and the concave portion is an average value obtained from any ten toners, and stress is applied. The ratio of the number of external additives before and after stress (after N / before N) was determined, where N before application and N after application of stress.
The stress is applied by placing 10 g of toner and 20 g of carrier in a 50 ml screw vial, shaking for 60 minutes at a vibration frequency of 400 rpm using a rocking mill, and then separating the toner and the carrier with a 20 μm mesh. The separation was carried out using an open sieve.

-Preparation of developer-
7 parts of each of the toners of Examples 1 to 6 and Comparative Examples 1 to 6 and 100 parts of the carrier were uniformly mixed and charged using a type of tumbler mixer in which the container was rolled and stirred. A developer was prepared.
The obtained developer was loaded into an image forming apparatus (IPSiO Color 8100, manufactured by Ricoh Co., Ltd.), and after 10,000 sheets of an image area ratio 0.5% chart were output, evaluation was performed as follows. The results are shown in Table 3. In the low consumption mode of 0.5%, the stress applied to the developer is the highest.

<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, to plain paper transfer paper (type 6200, manufactured by Ricoh Co., Ltd.), the image density is set to X-Rite (X-Rite). And an image density of 1.4 or more was evaluated as ◯, and less than 1.4 was evaluated as ×.

<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 white paper with a scotch tape (manufactured by Sumitomo 3M Limited), and is transferred to a Macbeth reflection densitometer RD514 type. 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.

<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 quality (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.

<Charging stability>
The change in the charge amount after the initial output and 10,000 sheets 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.

From the results in Table 3, it can be seen that Examples 1 to 6 have higher image density and superior cleaning properties, transferability, image quality, and charging stability compared to Comparative Examples 1 to 6. .

The toner of the present invention can maintain good transferability and cleaning properties over a long period of time, has no fluctuation in image unevenness, and is excellent in stability with little change in fluidity and chargeability 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 an explanatory diagram for explaining how to obtain the ratio of the number of external additives before and after stress (after N / before N). FIG. 2A is an explanatory diagram for explaining how to obtain the ratio of the number of external additives before and after stress (after N / before N). FIG. 2B is an electron micrograph for explaining how to determine the ratio of the number of external additives before and after stress (after N / before N) for toner. FIG. 2C is an electron micrograph for explaining how to determine the ratio of the number of external additives before and after stress (after N / before N) for another toner. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing another example in which the image forming method of the present invention is implemented by the image forming apparatus of the present invention. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. 6 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

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 Developing device 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 Developer 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 Corona charger 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Separating roller 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 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document transport Feeder (ADF)

Claims (12)

Comprising at least a toner core and an external additive on the surface of the toner core, the external additive including at least a large particle size inorganic oxide having a particle size of 50 to 500 nm,
The weight average particle diameter D ₄ of the toner are observed cut surfaces of the toner maximum length Dcut particle size satisfies 0.8D ₄ above, in the TEM photographs taken at 10,000 times using a transmission electron microscope The shape of the toner is in contact with a straight line that does not intersect with the toner core at two points, and the distance between the two points has a recess of 0.1D ₄ or more
When the number of the inorganic oxides present in the region formed by the tangent and the concave portion is an average value obtained from arbitrary 10 toners, before stress application is N before, and after stress application is N after Satisfying the following formula, 1 ≦ N after / N before ≦ 5,
For applying the stress, 10 g of the toner and 20 g of the carrier are placed in a 50 ml screw vial and shaken at a vibration frequency of 400 rpm for 60 minutes using a rocking mill, and then the toner and the carrier are separated by 20 μm. A toner characterized by being separated by sieving. The toner according to claim 1, wherein the external additive is obtained by surface-treating silica fine particles having a BET specific surface area of 20 to 250 m ² / g with silicone oil.   The toner according to claim 2, wherein the content of the silicone oil in the external additive is 1 to 10% by mass.   The toner according to claim 2, wherein the liberation rate of the silicone oil from the silica fine particles is 10 to 50% by mass.   The toner according to claim 1, wherein the external additive is agitated at a peripheral speed of 20 to 50 m / s and externally added to the toner core.   The toner according to claim 5, wherein the stirring is performed at 15 to 40 ° C.   The toner according to claim 5, wherein the external additive is stirred together with the metal oxide fine particles.   The toner according to claim 5, wherein the external additive is added after the toner core and the metal oxide fine particles are stirred.   9. The toner according to claim 1, wherein the toner material is granulated after the toner material is dissolved or dispersed in an aqueous medium to prepare an emulsion or dispersion. The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The toner according to claim 9, which is performed.   The toner according to claim 9, wherein the toner material is dissolved or dispersed by dissolving or dispersing the toner material in an organic solvent. An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 11 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.