JP2014063189A - Toner, two-component developer, process cartridge, image forming device, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner which exhibits stable cleaning performance even after repeated use in low-temperature/low-humidity and high-temperature/high-humidity environments, and forms an image having improved photoreceptor filming (contamination) resistance and environment resistance, two-component developer using the toner, a process cartridge, an image forming device, and an image forming method.SOLUTION: Toner includes toner base particles having colorant and resin, and one or more kinds of oxide fine particles, and has a weight average particle diameter Dof 2-7 μm and circularity of 0.95-1.00. The oxide fine particles contain at least a silicon element and have a number average particle diameter Dn of 30-150 nm when sticking to the toner base particles. A standard deviation ratio DL (%) of a number average particle diameter in a particle size distribution is 0≤DL≤20 (DL=σ/Dn×100, σ is standard deviation). A shape factor SF1 is 131-180. A shape factor SF2 is 126-180. A standard deviation ratio SF1L (%) of SF1 is 0≤SF1L≤20 (SF1L=σ/SF1×100, σ is standard deviation). A standard deviation ratio SF2L (%) of SF2 is 0≤SF2L≤20 (SF2L=σ/SF2×100, σ is standard deviation).

Description

  The present invention relates to a toner, a two-component developer, a process cartridge, an image forming apparatus, and an image forming method.

  A typical image forming process using electrophotography or electrostatic printing is to uniformly charge a photoconductive insulating layer, expose the insulating layer, and then dissipate the charge on the exposed portion. A development process for forming an electrical latent image and visualizing the latent image by attaching a finely charged toner to the latent image; a transfer process for transferring the obtained visible image to a transfer material such as transfer paper; It consists of a fixing step for fixing by heating or pressing (usually using a heat roller).

  The toner used in such an electrophotographic method or electrostatic printing method contains a binder resin and a colorant as main components, and further contains additives such as a charge control agent and an offset preventive agent as necessary. Various performances are required in each of the above steps. For example, in the development process, in order to attach toner to an electrical latent image, the toner and the binder resin for toner are charged appropriately for a copier or printer without being affected by the surrounding environment such as temperature and humidity. You must keep the amount. Further, in the fixing step by the heat roller fixing method, the non-offset property that does not adhere to the heat roller that is usually heated to a temperature of about 100 to 230 ° C. and the fixing property to paper must be good. Furthermore, blocking resistance that prevents toner from blocking during storage in a copier is also required.

  In recent years, in the field of electrophotography, high image quality has been studied from various angles, and in particular, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, there is a problem that the transferability is lowered as the toner diameter is reduced, resulting in a poor image. Further, it is known that transferability is improved by making the toner spherical (see Patent Document 1), but there is a problem that the cleaning characteristics of the toner are lowered when the toner is made spherical.

  On the other hand, for the purpose of improving toner cleaning characteristics, flow characteristics, charging characteristics, etc., a method of mixing toner particles with various oxide fine particles has been proposed. It is called an agent. Examples of the oxide fine particles include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, and tin oxide. The shape of the oxide fine particles is generally indefinite, and it has been desired to have an appropriate shape and an appropriate adhesion state on the toner surface in order to effectively exert the function of the external additive on the toner surface. Further, there is a demand for an image forming apparatus with high so-called robustness that can cope with various user usage environments and use image modes in recent years. On the other hand, the oxide fine particles have a problem of adversely affecting the fixing characteristics of the toner due to their physical and chemical characteristics, and oxide fine particles that do not cause fixing problems are desired.

  Furthermore, recently, there is a demand for an apparatus capable of forming a stable image even in a severer temperature and humidity environment, and there is a problem that an apparatus showing sufficient stability cannot be provided.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is not only low-temperature and low-humidity, but also has a stable cleaning characteristic even when it is repeated in a high-temperature and high-humidity environment, and has improved resistance to photoconductor filming (contamination). And a two-component developer, a process cartridge, an image forming apparatus, and an image forming method using the toner.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by using oxide fine particles obtained by performing predetermined shape control, and the present invention has been completed. It came. That is,
<1> A toner having a toner base particle having a colorant and a resin, and one or more kinds of oxide fine particles, having a weight average particle diameter D4 of ₂ to 7 μm and a circularity of 0.95 to 1.00. ,
The oxide fine particles are composed of oxide fine particles containing at least silicon element,
The number average particle diameter Dn of the oxide fine particles in a state where the oxide fine particles adhere to the toner base particles is 30 nm to 150 nm, and the standard deviation rate DL (%) of the number average particle diameter of the particle size distribution is 0. ≦ DL ≦ 20 (DL = σ / Dn × 100 σ; standard deviation), the shape factor SF1 is 131 to 180, the shape factor SF2 is 126 to 180, and the standard deviation rate of the SF1 SF1L (%) is 0 ≦ SF1L ≦ 20 (where SF1L = σ / SF1 × 100 σ; standard deviation), and the standard deviation rate SF2L (%) of the SF2 is 0 ≦ SF2L ≦ 20 (where SF2L = σ / SF2 × 100 σ; standard deviation).
<2> The toner according to <1>, wherein the oxide fine particles are oxide fine particles produced by a sol-gel method.
<3> The toner according to any one of <1> to <2>, wherein the oxide fine particles are hydrophobized with hexamethyldisilazane.
<4> The toner according to any one of <1> to <3>, further including at least one oxide fine particle having a number average particle size of less than 30 nm.
<5> The toner, wherein the toner is obtained by dispersing and / or emulsifying an oil phase and / or monomer phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium and granulating the toner phase. The toner according to any one of <1> to <4>.
<6> The toner according to any one of <1> to <5>, wherein the resin includes a polyester resin.
<7> A toner composition containing a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent is crosslinked and / or in the presence of resin fine particles in an aqueous medium. The toner according to any one of <1> to <6>, wherein the toner is subjected to an elongation reaction.
<8> A two-component developer comprising the toner according to any one of <1> to <7> and a carrier.
<9> The two-component developer according to <8>, wherein the carrier is magnetic particles.
<10> A process cartridge that integrally supports the electrostatic image carrier and the developing unit and is detachable from the main body of the image forming apparatus, wherein the developing unit is any one of <1> to <7> A process cartridge having the toner described in 1 above.
<11> An electrostatic charge image carrier, an electrostatic charge image forming unit for forming an electrostatic charge image on the electrostatic charge image carrier, and an electrostatic charge on a surface of the electrostatic charge image carrier on which the electrostatic charge image is formed. A developing unit that develops the toner image with a developer for image development; and a transfer unit that is in contact with the surface of the electrostatic charge image carrier via the transfer material and electrostatically transfers the toner image to the transfer material. In the image forming apparatus,
The toner used in the image forming apparatus is the image forming apparatus according to any one of <1> to <7>.
<12> an electrostatic charge image forming step of forming an electrostatic charge image on the surface of the electrostatic charge image carrier;
A developing step of developing a toner image with a developer for developing an electrostatic image on the surface of the electrostatic image carrier on which the electrostatic image is formed;
A transfer step of transferring the toner image developed on the surface of the electrostatic image carrier to a transfer material by electrostatic transfer;
In an image forming method having
In the image forming method, the toner used in the image forming method is the toner according to any one of <1> to <7>.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and not only low temperature and low humidity but also stable cleaning characteristics even when repeated in a high temperature and high humidity environment, and Toner capable of forming an image with excellent anti-environmental stability with improved photoconductor filming (contamination), and two-component developer, process cartridge, image forming apparatus and image forming method using the toner Can be provided.

FIG. 1 is a schematic configuration diagram showing an example of an embodiment of the present invention. FIG. 2 is a schematic configuration diagram illustrating an example of an embodiment of the present invention. FIG. 3 is a schematic configuration diagram illustrating an example of an embodiment of the present invention. FIG. 4 is a schematic configuration diagram illustrating an example of an embodiment of the present invention. FIG. 5 is a schematic configuration diagram showing an example of an embodiment of the present invention. FIG. 6 is a schematic diagram showing a configuration of an image forming apparatus including the process cartridge of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described. The following description is an example of the best mode of the present invention, and it is easy for a person skilled in the art to make other embodiments within the scope of the claims by making changes and modifications within the scope of the claims. However, this does not limit the scope of the claims.

(toner)
The toner according to the present invention includes toner base particles having a colorant and a resin and at least one kind of oxide fine particles, and other components as necessary.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have used a toner having oxide fine particles, which will be described later, as an external additive having a predetermined shape and adhesion state for image formation, and thus the stress resistance of the toner. Improves the cleaning characteristics due to the moderate release of fine oxide particles, reduced non-electrostatic adhesion of the toner, and improved photoconductor filming (contamination). Even when the process is repeated, it is possible to provide an image forming apparatus having excellent environmental stability and stable cleaning characteristics and improved photoconductor filming (contamination). When the fine oxide particles as external additives adhere to the surface of the toner base particles with appropriate strength, and the oxide fine particles are released from the toner base particles, the dam effect between the photosensitive blades improves the cleaning performance. It is done. When the toner is spherical, the function is not sufficient because it passes between the photoreceptor and the blade, but by having the above-mentioned predetermined shape, the oxide fine particles can be appropriately prevented from rolling and the dam effect is further improved. The function can be exhibited with a small amount of free oxide fine particles, which is considered to be more preferable. The present invention can effectively exhibit the dam effect (cleaning) by reducing the amount of free oxide fine particles as much as possible in terms of suppressing side effects other than cleaning such as photoconductor filming and carrier spent. This effect is considered to be superior to the prior art.

The mechanism as described above is currently being elucidated, but the following was presumed from some analysis data. The weight average particle diameter _{D 4} is 2-7 [mu] m (preferably 4 to 6 [mu] m), circularity 0.95 (more preferably from 0.96 to 0.98) be small particle size, nearly spherical shape In general, the number average particle diameter Dn of oxide fine particles, which will be described later, is 30 nm to 150 nm when attached to toner base particles that are very difficult to clean, and the standard deviation of the particle size distribution of the oxide fine particles is small and the particle size distribution is sharp. (The standard deviation rate DL (%) of the particle size distribution is 0 ≦ L ≦ 20 (DL = σ / Dn × 100 σ; standard deviation), and the shape distribution is small and the shape is not spherical (the shape factor SF1 is 131). ˜180, the shape factor SF2 is 126˜180, and the standard deviation rate SF1L (%) of SF1 is 0 ≦ SF1L ≦ 20 (where SF1L = σ / SF1 × 100 σ; standard deviation), and SF2 The standard deviation rate SF2L (%) of 0 ≦ SF2L ≦ 20 (where SF2L = σ / SF2 × 100 σ; standard deviation)) oxide fine particles are contained, so that the appropriate particle size, The diameter distribution, shape, and shape distribution appropriately prevent the oxide fine particles from being buried in the toner, and at the same time exert the effect of imparting fluidity as an external additive.

  Further, the non-electrostatic adhesion force of the toner is reduced by the particle size, particle size distribution and shape, and shape distribution, and the release of the oxide fine particles themselves is also reduced, so that the filming (contamination) property to the photoconductor is improved. .

The shape, size, and structure of the toner according to the present invention are not particularly limited as long as the above conditions are satisfied, and may be appropriately selected according to the purpose. Hereinafter, the toner according to the present invention, the weight average particle diameter D ₄ and circularity of the toner, and, in a state adhering to the toner base particles, the number average particle size Dn of the oxide particles, the particle size distribution of the oxide particles standard deviation The rate DL, the shape factors SF1 and SF2 of the oxide fine particles, and the standard deviation rates SF1L and SF2L of SF1 and SF2 will be described.

[Weight average particle diameter D ₄ ]
The weight average particle diameter _{D 4} of the toner according to the present invention, a 2-7 [mu] m, preferably, is 4 to 6 [mu] m. D ₄ is less than 2 [mu] m, the development of the toner particles, transferring, cleaning property becomes difficult, and when it exceeds 7 [mu] m, image quality of the image granularity, etc. is reduced. In particular, when D ₄ is less than 4 μm, the cleaning property is particularly insufficient in a severe environment such as low-temperature and low-humidity environment or high image area printing, and when it exceeds 6 μm, development stability is particularly stable in a high-temperature and high-humidity environment. And the image quality margin such as image granularity decreases.

A method for measuring the weight average particle diameter (D ₄ ) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter) And a method of measuring using a particle size distribution measuring apparatus such as the above. In the present invention, Coulter Multisizer II is used. The measurement method is described below.

First, 0.1 to 5 mL of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is prepared by preparing about 1% NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample (here, the toner according to the present invention) is further added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles or toner are measured with the measuring device using a 100 μm aperture as the aperture, Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D ₄ ) and number average particle diameter of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

[Toner circularity]
The circularity of the toner according to the present invention is 0.95 to 1.00, preferably 0.96 to 0.98. If the circularity is less than 0.95, the image granularity decreases, which is not preferable. In particular, when the circularity is less than 0.96, the image particle size margin in a high-temperature and high-humidity environment decreases, and when it exceeds 0.98, the rolling property of the toner is improved, so the cleaning margin decreases. To do.

  The circularity of the toner according to the present invention is defined as circularity = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. In the present invention, measurement was performed using a flow particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analysis was performed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Specifically, 0.1 to 0.5 mL of 10% by mass of a surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 mL beaker, and each toner 0.1 ˜0.5 g was added and stirred with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (Honda Electronics). The shape and distribution of the toner were measured using the FPIA-2100 until the concentration of the dispersion reached 5,000 to 15,000 / μL. In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. Further, the amount of toner added varies depending on the particle size, and it is small for small particle sizes and needs to be increased for large particle sizes. When the toner particle size is 2 to 7 μm, the toner amount is 0.1 to 0.00. By adding 5 g, the dispersion concentration can be adjusted to 5,000 to 15,000 / μL.

[Number average particle diameter Dn]
In the toner of the present invention, the number average particle diameter Dn of the oxide fine particles described later in a state of adhering to the toner base particles is 30 nm to 150 nm, preferably 50 nm to 130 nm, and more preferably 80 nm to 120 nm. . Within this range, it is possible to sufficiently exhibit a spacer effect for preventing aggregation of toners having oxide fine particles, and to prevent the oxide fine particles from being buried when the toner is stored at a high temperature or when the toner is strongly stirred and deteriorated. If the number average particle diameter Dn is less than 30 nm, the spacer effect on the toner surface is not sufficient, and if it exceeds 150 nm, it becomes difficult to impart sufficient fluidity to the toner, resulting in high image quality and high stability. It becomes a problem in maintaining. Further, oxide fine particles are detached from the toner surface and easily act as a cause of photoconductor filming.

  In the toner of the present invention, the method for measuring the number average particle diameter Dn of the oxide fine particles in the state of adhering to the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a scanning electron microscope (FE-SEM) is used to measure the surface image of the toner. Among the images obtained by such measurement, an image derived from oxide fine particles is used using image processing software such as Image-Pro Plus. The method of evaluating may be used.

[Standard deviation rate DL of particle size distribution of oxide fine particles]
In the toner of the present invention, the standard deviation rate DL of the particle size distribution of the oxide fine particles described later in a state of adhering to the toner base particles is 0 ≦ DL ≦ 20. Here, DL is σ / Dn × 100, and σ is a standard deviation. When DL satisfies this range, the particle size distribution of the oxide fine particles becomes extremely sharp, and the spacer effect by the oxide fine particles on the toner surface is more exhibited, which is preferable. When DL> 20, particles having different particle size distributions are mixed, and the adhesion force between the toner, the adhesion force between the toner and the photoconductor, and the adhesion force between the toner and the carrier become non-uniform and oxidize. The effect of the fine particles is not sufficiently exhibited.

  In the toner of the present invention, the method for measuring the standard deviation rate DL of the particle size distribution of the oxide fine particles in a state of adhering to the toner base particles is not particularly limited and may be appropriately selected depending on the purpose. Similar to the measurement of the number average particle diameter Dn of the oxide fine particles, the surface image of the toner is measured using a scanning electron microscope (FE-SEM). The image derived from the image may be evaluated using image processing software such as Image-Pro Plus.

[Shape factor SF1, shape factor SF2, and standard deviation rates SF1L and SF2L of SF1 and SF2]
In the toner of the present invention, the shape factor SF1 of the oxide fine particles to be described later in the state of adhering to the toner base particles is 131 to 180, and the shape factor SF2 of oxide fine particles to be described later in the state of adhering to the toner base particles. Is 126-180. The standard deviation rates SF1L and SF2L of SF1 and SF2 are 0 ≦ SF1L ≦ 20 and 0 ≦ SF2L ≦ 20. Within such a range, the shape of the oxide fine particles is not a perfect sphere, but is appropriately ovalized or a shape having surface irregularities. In particular, SF1 is an ellipticity index, and SF2 is a surface roughness index. Here, it has been found that the stability of the cleaning and the like is remarkably improved even when a low temperature and low humidity environment and a high temperature and high humidity environment are repeated by being appropriately indeterminate, not completely spherical. Since this is not spherical, the oxide fine particles are not easily detached from the toner surface due to the multi-faceted contact surface, and the spacer effect on the toner surface is more exerted. At the same time, the oxide fine particles even when detached from the toner surface. However, it is considered that the toner can be prevented from rolling and the dam effect by the oxide fine particles can be more effectively exhibited to improve the cleaning property. At this time, even when the toner surface becomes soft under a high temperature and high humidity environment, the shape of the toner can be slightly deformed from a spherical shape to prevent the oxide fine particles from being trapped. Even if it becomes, rolling can be prevented by the effect of deforming. Furthermore, when the standard deviation rate DL of the particle size distribution of the oxide fine particles is within the above-mentioned range, the distribution of the oxide fine particles is sharper, the adhesion state on the toner surface becomes more uniform, and both cleaning properties and filming properties are achieved. Is more preferable.

  In the toner according to the present invention, it is particularly important that the fine oxide particles control the particle size of the fine oxide particles in the state of being adhered to the toner base particles. The reason is that no matter how much the particle size distribution of the oxide fine particles is specified, the toner adheres to the toner base particles, for example, agglomerates and adheres to the toner base particles, or adheres only to the concave portion of the toner with low adhesion to the toner. Because there is also. Conversely, when the primary particle size sufficient as oxide fine particles can be controlled, even if there is secondary aggregation, the aggregate can be crushed or loosened under the stirring conditions of the toner, and the oxide fine particles can be mixed. It is important to control the optimal toner surface condition including the conditions.

  In the toner of the present invention, the method for measuring the shape factor SF1 and the shape factor SF2 of the oxide fine particles in the state of adhering to the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. A method for directly obtaining a particle size, a particle size distribution, a shape, and a shape distribution from an image obtained by an electron microscope (FE-SEM) can be mentioned. When FE-SEM is used, the original shape may be damaged by platinum deposition or the like. Therefore, even when the deposition is performed, the deposition thickness is reduced to about 1 nm, or even if the acceleration voltage is decreased, the resolution is high. Using a high-resolution FE-SEM (for example, Ultra 55 manufactured by Zeiss Co., Ltd.) or the like, measurement is performed with a low acceleration voltage (several eV to 10 keV) on an object to be measured (here, toner with fine oxide particles adhered). Is more preferable. At least 100 oxide fine particles or more may be observed, and the particle size distribution, shape counts SF1 and SF2, and SF1L and SF2L may be statistically calculated by image processing software such as Image-Pro Plus. In particular, analysis was performed using Image-Pro Plus 4.5.1 manufactured by Media Cybernetics, and values obtained from the following formulas were defined as SF1 and SF2. The values of SF1 and SF2 are preferably values obtained by the above software, but are not particularly limited to the above FE-SEM device, image analysis device, and software as long as similar analysis results can be obtained.

SF1 = (L ² / A) × (π / 4) × 100
SF2 = (P ² / A) × (1 / 4π) × 100
SF1L = σ / SF1 × 100 σ; standard deviation of SF1 SF2L = σ / SF2 × 100 σ; standard deviation of SF2 where
The absolute maximum length of the oxide fine particles is L
The projected area of the oxide fine particles is A
The maximum perimeter of the oxide fine particles is P
And

  Each of SF1 and SF2 is 100 if it is a true sphere, and the value changes from spherical to indefinite as the value becomes larger than 100. In particular, SF1 is an index indicating the shape of the entire toner (such as an ellipse or a sphere), and SF2 is an index indicating the degree of unevenness on the surface.

<Oxide fine particles>
In the toner according to the present invention, the oxide fine particles are made of oxide fine particles containing at least silicon element, and the number average particle diameter Dn, standard deviation rate DL (%), shape factor SF1, shape factor SF2, and standard deviation rate SF1L. As long as (%) and the standard deviation rate SF2L (%) of SF2 are as described above, there is no particular limitation, and it may be appropriately selected according to the purpose.

  The oxide fine particles are preferably oxide fine particles produced by a sol-gel method described later in that they can be produced with higher reproducibility of the aforementioned particle diameter and shape. Further, it is preferable that the oxide fine particles have been subjected to a hydrophobic treatment with at least hexamethyldisilazane. In this case, the above-mentioned number average particle diameter Dn of 30 nm to 150 nm and a relatively large oxide fine particle that is easily affected by the external environment can be sufficiently treated to ensure hydrophobicity as a toner. . As a result, it leads to the environmental stability of the developer and the stability of the image quality.

The oxide fine particles are preferably hydrophobized spherical silica fine particles in which R ¹ ₃ SiO _1/2 units are introduced on the surface in order to improve environmental charging stability. Here, R ¹ is the same or different monovalent hydrocarbon group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples include a cyclohexyl group, a phenyl group, a vinyl group, and an allyl group, and a methyl group is particularly preferable.

The introduction of the R ¹ ₃ SiO _1/2 unit may be performed according to a known surface modification method for silica fine powder. That is, the silazane compound represented by the general formula R ¹ ₃ SiNHSiR ¹ ₃ is contacted at 0 to 400 ° C. in the gas phase, liquid phase or solid phase in the presence of water, and then heated at 50 to 400 ° C. This can be done by removing the silazane compound.

Examples of the silazane compound represented by the general formula R ¹ ₃ SiNHSiR ¹ ₃ include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyl. Examples thereof include disilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, and the like. In particular, hexamethyldisilazane is preferable from the viewpoint of hydrophobicity after modification and easy removal thereof.

  The amount of the oxide fine particles in the toner according to the present invention is not particularly limited and may be appropriately selected depending on the purpose. The silica fine particles may be obtained by external addition. However, if the amount is less than 0.01 parts by mass with respect to 100 parts by mass of the toner, the fluidity of the toner becomes insufficient. Adversely affects the performance and fixability. For this reason, the content of the oxide fine particles in the toner is preferably in the range of 0.01 to 20 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner. The oxide fine particles may be mixed with the toner base particles by any method. For example, the oxide fine particles may adhere to the surface of the toner particles by using a V blender, a Henschel mixer, a ribbon blender, or a reiki machine. The toner may be fused, or may be contained in the toner.

[Production Method of Oxide Fine Particles]
The method for producing oxide fine particles is not particularly limited as long as the above configuration can be obtained, and may be appropriately selected depending on the purpose. Examples thereof include a sol-gel method and a combustion method. Of these, the sol-gel method is preferable in terms of uniformity of particle size distribution and manufacturability of spherical oxide fine particles.

-Sol-gel method-
The sol-gel method is a method of obtaining silica fine particles by hydrolyzing and condensing an organosiloxane such as tetraalkoxysilane in a water-alcohol mixed solvent in the presence of an acid or an alkali catalyst.

  This method is excellent in that fine spherical particles with a monodisperse particle size can be obtained, that there are very few impurities derived from raw materials, solvents and catalysts, the operation of hydrolysis condensation, the equipment is simple and the productivity is high. ing. In particular, in the process of the sol-gel method, SF1 and SF2 fall within the following ranges by partially melting and binding the primary particles of the sol by controlling the alkali concentration, etc. Fine particles can be formed. Further, the particle size can be controlled by controlling the dropping speed and the like.

  As a method for producing oxide fine particles, for example, an alkoxysilane is hydrolyzed in an alcohol (ethanol) solvent in the presence of an acidic catalyst to synthesize a silica sol, which is gelled, dried, calcined, sintered Thus, a method for producing oxide fine particles may be used.

The aforementioned alkoxysilane is represented by the general formula R ² _a Si (OR ³ ) _4-a (where R ² and R3 are monovalent hydrocarbon groups having 1 to 4 carbon atoms, a is an integer of 0 to 4) ), For example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane Diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane , Trimethylbutoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, tripropylmethoxysilane, tripropylethoxysilane, tributylmethoxysilane, tributylethoxysilane, etc. Tetramethoxysilane and methyltrimethoxysilane are more preferable in terms of particle diameter, particle size distribution, and particle shape control.

<Other ingredients>
<< External additive >>
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include inorganic fine particles and hydrophobized inorganic fine particles in addition to the oxide fine particles described above. It is more desirable to include at least one kind of inorganic fine particles having a number average particle size of 1 to 100 nm, more preferably a number average particle size of less than 30 nm, which has been subjected to hydrophobic treatment. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

  Any of them can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  In particular, the toner according to the present invention preferably further includes at least one other oxide fine particle having a number average particle size of less than 30 nm in addition to the above oxide fine particles. In this case, the effect of improving the fluidity is further exhibited, and the image stability at a higher level can be ensured.

  Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above Hoechst) and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.

  In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  The silicone oil is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil , Polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, methacryl modified silicone Oil, α-methylstyrene-modified silicone oil, etc. can be used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred. The addition amount may be 0.1 to 5% by mass, preferably 0.3 to 3% by mass, based on the toner.

<< surface treatment agent >>
The surface treatment agent is not particularly limited as long as it treats the surface of the external additive containing the above oxide fine particles, and may be appropriately selected according to the purpose. For example, dialkyl dihalogenated silane, trialkyl halogen Silane coupling agents such as fluorinated silanes, alkyltrihalogenated silanes, hexaalkyldisilazanes, silylating agents, silane coupling agents having alkyl fluoride groups, organic titanate coupling agents, aluminum coupling agents, silicones Examples thereof include oil and silicone varnish. More preferred are organosilicon compound surface treatment agents and hydrophobic treatment agents.

<Toner base particles>
In the toner according to the present invention, the toner base particles include a colorant and a resin, and optionally other components.
<< Resin >>
In the toner according to the present invention, the resin (binder resin) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the weight of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the substitution product thereof. Copolymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, 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-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrenic copolymers such as ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, Examples thereof include rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax, which can be used alone or in combination. In particular, a polyester resin is more preferable.

-Polyester resin-
There is no restriction | limiting in particular as a polyester resin, What is necessary is just to select suitably according to the objective, Although the thing of various types can be used, Especially the thing of the following (I)-(III) is mentioned.

(I) At least one selected from divalent carboxylic acids and their lower alkyl esters and acid anhydrides (II) A diol component represented by the following general formula (2)

(In the formula, R ¹ and R ² may be the same or different and each is an alkylene group having 2 to 4 carbon atoms, and x and y are the number of repeating units, each being 1 or more, and x + y = 2-16.)

  (III) At least one selected from any of trivalent or higher polyvalent carboxylic acids, lower alkyl esters and acid anhydrides thereof, and trivalent or higher polyhydric alcohols

  Among these, a polyester resin obtained by reacting these (I), (II) and (III) is preferable.

  Here, the divalent carboxylic acid (I) and its lower alkyl ester and acid anhydride are not particularly limited and may be appropriately selected depending on the intended purpose. For example, terephthalic acid, isophthalic acid, sebacic acid, There are decyl succinic acid, maleic acid, fumaric acid and their monomethyl, monoethyl, dimethyl and diethyl esters, and phthalic anhydride, maleic anhydride, etc. Especially, terephthalic acid, isophthalic acid and their dimethyl esters have blocking resistance and cost. This is preferable. These divalent carboxylic acids and their lower alkyl esters and acid anhydrides greatly affect the fixability and blocking resistance of the toner. That is, although depending on the degree of condensation, if a large amount of aromatic terephthalic acid, isophthalic acid or the like is used, the blocking resistance is improved, but the fixing property is lowered. Conversely, if a large amount of sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid or the like is used, the fixing property is improved, but the blocking resistance is lowered. Accordingly, these divalent carboxylic acids are appropriately selected according to the other monomer composition, ratio and degree of condensation, and used alone or in combination.

  The diol component represented by the general formula (2) in (II) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyoxypropylene- (n) -polyoxyethylene- (n ′ ) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (n) -2,2-bis ( 4-hydroxyphenyl) propane and the like, and in particular, polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane in which 2.1 ≦ n ≦ 2.5 and 2.0 ≦ Polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane where n ≦ 2.5 is preferred. Such a diol component has the advantage of improving the glass transition temperature and making it easier to control the reaction.

  In addition, it is also possible to use aliphatic diols such as ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, propylene glycol as the diol component. is there.

  The trivalent or higher polyvalent carboxylic acid (III) and its lower alkyl ester and acid anhydride are not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2,4-benzenetricarboxylic acid (Trimellitic acid), 1,3,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthylenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2 , 4-butanetricarboxylic acid, 1,2,5-hexatricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octane Examples thereof include tetracarboxylic acid, empole trimer acid, and monomethyl, monoethyl, dimethyl, and diethyl esters thereof.

  The trihydric or higher polyhydric alcohol (III) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan , Pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1, Examples include 2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, and the like.

  Here, the blending ratio of the trivalent or higher polyvalent monomer is suitably about 1 to 30 mol% of the whole monomer composition. When it is 1 mol% or less, the offset resistance of the toner is lowered, and the durability is likely to deteriorate. On the other hand, when the amount is 30 mol% or more, toner fixability tends to deteriorate.

  Of these trivalent or higher polyvalent monomers, benzenetricarboxylic acids such as benzenetricarboxylic acid and anhydrides or esters of these acids are particularly preferable. That is, by using benzenetricarboxylic acids, both fixability and offset resistance can be achieved.

  Moreover, the manufacturing method of these binder resin is not specifically limited, Any of block polymerization, solution polymerization, emulsion polymerization, suspension polymerization, ester polymerization, etc. can be used.

<< Colorant >>
In the toner according to the present invention, the colorant is not particularly limited and may be appropriately selected depending on the purpose, and all known dyes and pigments can be used, 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, 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, Anslagen Yellow BGL, Isoindolinone Yellow, Bengala, Red Red, Lead Zhu, Cado Muum Red, Cadmium Mercury Red, Antimon Zhu, Permanentre 4R, Para Red, Fire Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scalate VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol 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, Thioindigolet B, Thioindigo , Oil Red, Quinacridone Red, Pyrazolone 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, Dioxazine Violet, Anthraquinone Violet, Chrome Green, Zinc Green, chromium oxide, pyridian emerald green, pigment green B, naphthol green B, green gold, acid grits Enlake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof. The amount used is generally 0.1 to 50 parts by mass with respect to 100 parts by mass of the binder resin.

-Masterbatch pigment-
In the toner according to the present invention, for the purpose of improving the affinity between the resin and the pigment, a master batch pigment in which the resin and the pigment are mixed and kneaded in a ratio of about 1: 1 can be used. More preferably, a master batch pigment having excellent environmental charge stability can be obtained by heating and kneading a resin and pigment having a low polar solvent-soluble component amount without using an organic solvent. Furthermore, dispersibility can be further improved by using dry powder pigment and using water as a method of wetting with the resin. Organic pigments that are generally used as colorants are hydrophobic, but in the manufacturing process, they are washed with water and dried, so if some force is applied, water is soaked into the pigment aggregate. It is possible. When a mixture of a pigment in which water is soaked into the aggregate and a resin is kneaded at a set temperature of 100 ° C. or higher with an open type kneader, the water inside the aggregate instantaneously reaches the boiling point and expands in volume. Therefore, a force is applied to break up the aggregate from the inside of the aggregate. The force from the inside of the aggregate can disintegrate the aggregate very efficiently compared to the force applied from the outside. Furthermore, at this time, since the resin is heated to a temperature higher than the softening point, the viscosity is lowered and the aggregate is efficiently wetted. By being replaced by the effect, a master batch pigment in which the pigment is dispersed in a state close to primary particles can be obtained. Furthermore, in the process of evaporating water, the heat of vaporization accompanying water evaporation is taken away from the kneaded product, so the temperature of the kneaded product is kept at a relatively low temperature and high viscosity of 100 ° C. or less, so the shearing force is effective. In addition, it has the effect of being added to the pigment aggregate. As an open type kneading machine for producing master batch pigments, a method using a Banbury mixer as an open type, a continuous two roll kneader manufactured by Mitsui Mining Co. Can do.

  In the present invention, the softening point is a temperature obtained by measuring the softening temperature and the outflow start temperature at a heating rate of 1 ° C./min using a softening point measuring device (FP90, manufactured by Mettler). is there.

<< Other ingredients >>
In the toner according to the present invention, the other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a charge control agent for controlling the chargeability of the toner, a fixing member and a recording medium such as paper Wax applied to promote winding and fixing release, cleaning property improver to remove toner after transfer remaining on the photoreceptor and primary transfer medium, shape control agent for controlling toner shape, toner particle size Examples thereof include a particle size controlling agent to be controlled.

-Charge control agent-
The toner of the present invention may contain a charge control agent as necessary. The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, and all known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and salicylic acid And metal salts of derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt. In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.

-Wax-
There is no restriction | limiting in particular as a wax, What is necessary is just to select suitably according to the objective. For example, a wax may be contained in the toner or the developer described later. In particular, when an oilless fixing machine that does not apply oil to the image fixing unit is used, it is preferable that the toner contains wax. The wax has a melting point of 40 to 120 ° C., and preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be obtained by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant rate of temperature rise, for example, (10 ° C./min) is defined as the melting point. The content of the wax is preferably 0 to 20 parts by mass, and more preferably 0 to 10 parts by mass.

  Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial kenne. And fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. In particular, polyolefins and esters having a softening point by the ring-and-ball method of 60 to 150 ° C are preferable, and polyolefins and esters having a softening point of 70 to 120 ° C are more preferable. More preferably, at least one kind of wax selected from a deliberate fatty acid type carnauba wax having an acid value of 5 or less, a montan ester wax, an oxidized rice wax having an acid value of 10 to 30 and a sazol wax is used. The de-free fatty acid type carnauba wax is obtained by removing free fatty acid from carnauba wax as a raw material. Therefore, the acid value is 5% or less, and it becomes finer than conventional carnauba wax, resulting in a binder resin. The dispersion average particle diameter becomes 1 μm or less, and dispersibility is improved. The montan-based ester wax is refined from a mineral, becomes microcrystalline like the carnauba wax, has a dispersion average particle size of 1 μm or less in the binder resin, and improves dispersibility. In the case of montan ester wax, the acid value is particularly preferably 5 to 14.

  The dispersion diameter of the wax is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 3 μm or less, more preferably 2 μm or less, and particularly preferably 1 μm or less. When the dispersion diameter is 3 μm or more, the wax outflow property and the transfer material peelability are improved, but the high-temperature and high-humidity durability as a toner, the charging stability and the like are lowered.

  Oxidized russian wax is air-oxidized rice bran wax. The acid value is preferably 10 to 30, and if it is less than 10, the minimum fixing temperature increases and the low temperature fixability becomes insufficient. If it exceeds 30, the cold offset temperature increases and the low temperature fixability becomes insufficient. As the sazol wax, Sazol wax H1, H2, A1, A2, A3, A4, A6, A7, A14, C1, C2, SPRAY30, SPRAY40, etc. can be used, among which H1, H2, SPRAY30, SPRAY40. Is preferable because of low temperature fixing and storage stability. Further, the above wax may be used alone or in combination, and it is 1 to 15 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Results are obtained.

-Cleaning improver-
The cleaning property improving agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is more preferable that it be contained in the toner or added to the toner surface, or contained in the developer or added to the surface. Examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles, polystyrene fine particles, and the like. . The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm. The content of the cleaning improver is preferably 0.001 to 5 parts by mass, and more preferably 0.001 to 1 part by mass.

-Magnetic material-
The magnetic material is not particularly limited as long as it can be used for the toner according to the present invention and can obtain the magnetic toner, and may be appropriately selected according to the purpose. In this case, the toner particles may contain magnetic fine particles. Such a magnetic material includes ferrite, magnetite and other irons, nickel, cobalt and other metals or alloys exhibiting ferromagnetism or compounds containing these elements, but do not contain ferromagnetic elements, but are subjected to appropriate heat treatment. An alloy that exhibits ferromagnetism, for example, a seed alloy called Heusler alloy containing manganese and copper such as manganese copper aluminum and manganese-copper-tin, chromium dioxide, and the like. It is preferable that the magnetic material is contained in a uniformly dispersed form in the form of fine powder having an average particle size of 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by mass, and particularly preferably 20 to 50 parts by mass with respect to 100 parts by mass of the obtained toner.

[Toner Production Method]
The toner production method according to the present invention is not particularly limited as long as it can obtain the above-described colorant and resin, and may be appropriately selected according to the purpose. And chemical methods (polymerization method, melting method, capsule method, etc.).

-Grinding method-
As a pulverization method for producing the toner according to the present invention, starting from a colorant, a resin, and other components, particles that can become toner base particles are formed, and then pulverized to have desired physical properties (particle diameter). If there is, there is no particular limitation, and it may be appropriately selected according to the purpose. For example, a step of mechanically mixing at least a binder component (binder), a developer component containing a main charge control agent and a pigment, and melt-kneading It may be a method having a process, a pulverizing process, and a classification process. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles that become the product obtained in the pulverization or classification step is returned and reused.

  The powders (sub-products) other than the particles used as the product referred to here are fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and the subsequent classification step. It means fine particles and coarse particles other than the components that become products of a desired particle size generated in (1). It is preferable that such a by-product is mixed in the mass ratio of the other raw material 50 to the sub-product 50 from the other raw material 99 to the sub-product 1 in the mixing step and the melt-kneading step.

  The mixing step of mechanically mixing developer components including at least a binder resin, a main charge control agent and a pigment, and a by-product may be performed under normal conditions using a normal mixer using a rotating blade, and the like. There is no.

  When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader or the like is preferably used.

  It is important that this melt-kneading is performed under appropriate conditions so as not to break the molecular chain of the binder resin. Specifically, the melt-kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed. When controlling the amount of volatile components in the toner, it is more preferable to set optimum conditions for the melt-kneading temperature, time, and atmosphere while monitoring the amount of residual volatile components at that time.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

  After this pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner (toner base particle) having a predetermined particle size and a volume average particle size of 2 to 7 μm. The volume average particle diameter can be measured using, for example, COULTERTA-II (COULTER ELECTRONICS, INC).

  Further, when preparing the toner, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the oxide fine particles of the present invention listed above in addition to the toner produced as described above, Inorganic fine particles such as hydrophobic silica fine powder may be added and mixed. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.

  Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

-Polymerization method-
[Aspect 1 of polymerization method]
As one aspect of the polymerization method, first, a polymerizable monomer, and if necessary, a polymerization initiator, a colorant, a wax, and the like are granulated in an aqueous dispersion medium, and the granulated monomer composition particles have an appropriate particle size. Classify. Thereafter, the monomer composition particles having a prescribed inner particle diameter obtained by this classification are polymerized. An example of the method is to obtain toner base particles by subjecting the polymer obtained in this manner to an appropriate treatment to remove the dispersant and then filtering, washing and drying the polymerized product obtained as described above.

[Aspect 2 of polymerization method]
In one embodiment of the polymerization method, a toner composition containing at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent in an aqueous medium in the presence of fine resin particles. Examples of the method include crosslinking and / or elongation reaction.

  There is no restriction | limiting in particular as this aspect, What is necessary is just to select suitably according to the objective, for example, it has the following process (1)-(5).

(1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
(2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
(3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
(4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
(5) The toner base particles obtained above are charged with a charge control agent or adhered / reacted on the toner surface to fix them, and the inorganic fine particles such as oxide fine particles, silica fine particles and titanium oxide fine particles are removed. Add to obtain toner.

-Step (1)-
In this process, a colorant, an unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent are dispersed in an organic solvent to form a toner material liquid.

  The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. The usage-amount of an organic solvent is 0-300 mass parts normally with respect to 100 mass parts of polyester prepolymers, Preferably it is 0-100 mass parts, More preferably, it is 25-70 mass parts.

-Step (2)-
In this step, the toner material liquid obtained in step (1) is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.

  The aqueous medium may be water alone, or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.

  The amount of the aqueous medium used relative to 100 parts by mass of the toner material liquid is usually 50 to 2,000 parts by mass, preferably 100 to 1,000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20,000 parts by mass, it is not economical.

  Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.

  As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

  The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 μm and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao), SGP (manufactured by Soken), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).

  In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Steal, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and carboxyl groups Such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, Nitrogen compounds such as ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Reoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited and may be appropriately selected depending on the purpose. Known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

-Step (3)-
At the same time as the preparation of the emulsion, amines (B) are added to react with the polyester prepolymer (A) having an isocyanate group.

  This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

-Step (4)-
After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.

  In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

-Step (5)-
In this step, a charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain toner.

  The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.

  Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

  The toner according to the present invention is a toner obtained by granulating by dispersing and / or emulsifying an oil phase and / or a monomer phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium. Also good. Thus, it is more preferable that oxide fine particles having a number average particle diameter Dn of 30 nm to 150 nm and a relatively large particle size can be held on the toner surface in an appropriate adhesion state, and the effect thereof is more easily exhibited.

  Further, the toner is obtained by crosslinking a toner composition containing at least a polymer capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent in an aqueous medium in the presence of resin fine particles. Alternatively, the image forming apparatus is characterized in that an elongation reaction is performed, so that oxide particles having a relatively large number average particle diameter Dn of 30 nm to 150 nm can be held on the toner surface in an appropriate adhesion state. Is more preferable because it is easier to exhibit.

[Mode 3 of polymerization method]
As one aspect of the polymerization method, first, a low molecular weight resin, a high molecular weight resin, a colorant, a wax, a wax dispersant, and a charge control agent, if necessary, are dispersed in an oil layer dispersion medium using a solvent such as ethyl acetate. Let Next, it is dropped into water containing organic fine particles and an extender, and emulsified and converged. There is a method in which the obtained dispersion is heated, polymerized, desolvated, aged in water, washed, collected and dried to obtain base particles.

-Capsule method-
The capsule method is not particularly limited and may be appropriately selected depending on the purpose.For example, after kneading a resin, if necessary, a colorant or the like with a kneader or the like to obtain a molten toner core material, The toner core material is put in water and stirred vigorously to form a fine particle core material. Thereafter, the core material fine particles are put in a shell material solution, and a poor solvent is dropped while stirring, and the core material surface is covered with a shell material to encapsulate. A method of filtering the capsule obtained as described above and drying it to obtain base particles is exemplified.

(Two-component developer)
The two-component developer according to the present invention includes the above-described toner according to the present invention and a carrier, and other members as necessary.

<Career>
The carrier is not particularly limited as long as it can be used as one member of the developer, and may be appropriately selected according to the purpose. Examples thereof include a magnetic carrier and a resin carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. The carrier to toner content ratio in the developer is preferably 1 to 10 parts by mass of toner with respect to 100 parts by mass of carrier.

  The carrier may be coated with a suitable coating material, and examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, and silicone resins. Moreover, the film thickness of these coating materials is 0.01-3 micrometers, More preferably, it is 0.1-0.3 micrometers. When the thickness is 0.01 μm or less, film control is difficult and the function as a coat film cannot be exhibited. Further, if it is 3 μm or more, conductivity cannot be obtained, which is not preferable. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  Although it has been described that the toner can be used as one member of the two-component developer, the toner according to the present invention can be used as a one-component magnetic toner or a non-magnetic toner without using a carrier.

(Process cartridge)
As shown in FIG. 6, the process cartridge that can be attached to and detached from the image forming apparatus according to the present invention includes a photoreceptor 702, a charging unit 704, a developing unit 706, and a cleaning unit 708. In the present invention, a plurality of components such as the photosensitive member 702, the charging unit 704, the developing unit 706, and the cleaning unit 708 are integrally combined as a process cartridge, and the process cartridge is configured as a copying machine or a printer. It is configured to be detachable from the main body of the image forming apparatus.

  In the image forming apparatus having the process cartridge of the present invention, the photosensitive member 702 is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member 702 is uniformly charged at a predetermined positive or negative potential on its peripheral surface by the charging unit 704, and then receives image exposure light from an image exposure unit such as slit exposure or laser beam scanning exposure. Thus, electrostatic latent images are sequentially formed on the peripheral surface of the photosensitive member 702, and the formed electrostatic latent image is then developed with toner by the developing means 706. The developed toner image is transferred from the paper supply unit to the photosensitive member 702. And transfer means are sequentially transferred by a transfer means to a recording material (including an intermediate transfer member) fed in synchronism with the rotation of the photosensitive member. The recording material that has undergone image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing toner remaining after transfer by a cleaning unit, and after being further neutralized, it is repeatedly used for image formation.

(Image forming device)
The image forming apparatus according to the present invention includes an electrostatic charge image carrier, an electrostatic charge image forming unit, a developing unit, and a transfer unit, and other members as necessary. FIG. 1 is a schematic configuration diagram of an example of the image forming apparatus. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 110 as an image carrier, a charging roller 120 as a charging device, an exposure device 130, a cleaning device 160 having a cleaning blade, a static elimination lamp 170 as a static elimination device, and development. An apparatus 140 and an intermediate transfer member 150 as an intermediate transfer member are provided. The intermediate transfer member 150 is suspended by a plurality of suspension rollers 151 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller 151 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device 190 having a cleaning blade for the intermediate transfer member 150 is also provided. Further, a transfer roller 180 is provided as a transfer means for transferring the developed image onto the transfer sheet 1100 as the final transfer material, facing the intermediate transfer body 150. The transfer roller 180 is applied with a transfer bias by a power supply device (not shown). Supplied. Around the intermediate transfer member 150, a corona charger 152 as a charge applying unit is provided.

  The developing device 140 includes a developing belt 141 as a developer carrying member, a black (hereinafter referred to as “Bk”) developing unit 45K, a yellow (hereinafter referred to as “Y”) developing unit 45Y, and a magenta (hereinafter referred to as “below”). The developing unit 45M includes a magenta developing unit 45M and a cyan developing unit 45C (hereinafter referred to as C). The developing belt 141 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Move at almost the same speed.

  Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit 45K, and the other Y developing units 45Y, 45M, and 45C will be shown in the portions corresponding to those in the Bk developing unit 45K in the drawing. In the unit, Y, M, and C are added after the numbers given to the units, and the description is omitted. The Bk developing unit 45K is disposed so that a developing tank 42K containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component and a lower part are immersed in the liquid developer in the developing tank 42K. And a coating roller 44K that thins the developer pumped from the pumping roller 43K and applies it to the developing belt 141. The application roller 44K has conductivity, and a predetermined bias is applied from a power source (not shown).

  In addition to the apparatus configuration as shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment is an apparatus configuration in which development units 145 of the respective colors are provided around the photoconductor 110 as shown in FIG. It may be.

  Subsequently, the operation of the image forming apparatus according to the present embodiment will be described. In FIG. 1, the photosensitive member 110 is uniformly charged by the charging roller 120 while being driven to rotate in the direction of the arrow, and then the reflected light from the original is imaged and projected onto the photosensitive member 110 by the exposure device 130 using an optical system (not shown). An electrostatic latent image is formed. This electrostatic latent image is developed by the developing device 140 to form a toner image as a visible image. The developer layer on the developing belt 141 is peeled off from the developing belt 141 in a thin layer state by contact with the photoconductor in the developing region, and moves to a portion where a latent image is formed on the photoconductor 110. The toner image developed by the developing device 140 is transferred to the surface of the intermediate transfer member 150 at the contact portion (primary transfer region) between the photosensitive member 110 and the intermediate transfer member 150 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 150.

  A corona charger 152 for applying a charge to the superimposed toner image on the intermediate transfer member is provided downstream of the contact facing portion between the photosensitive member 110 and the intermediate transfer member 150 in the rotation direction of the intermediate transfer member 150, and It is installed at a position upstream of the contact facing portion between the intermediate transfer member 150 and the transfer paper 1100. The corona charger 152 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and the charge is sufficient for good transfer to the transfer paper 1100. To the toner image. The toner image is charged by a corona charger 152 and then transferred to a transfer paper 1100 conveyed in the direction of an arrow from a paper supply unit (not shown) by a transfer bias from a transfer roller 180 (secondary transfer). . Thereafter, the transfer paper 1100 onto which the toner image has been transferred is separated from the photoreceptor 110 by a separation device (not shown), and after being subjected to a fixing process by a fixing device (not shown), is discharged from the device. On the other hand, the untransferred toner is collected and removed by the cleaning device 160 on the photosensitive member 110 after the transfer, and the residual charge is discharged by the discharging lamp 170 in preparation for the next charging. A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer passes through primary transfer (transfer from the photosensitive member to the intermediate transfer belt) and secondary transfer (transfer from the intermediate transfer belt to the sheet).

-Tandem type color image forming device-
The image forming apparatus according to the present invention can also be used as a tandem color image forming apparatus. An example of an embodiment of a tandem type color image forming apparatus will be described. As shown in FIG. 3, the tandem type electrophotographic apparatus includes a direct transfer system in which an image on each photoconductor 1 is sequentially transferred onto a sheet s conveyed by a sheet conveying belt 3 by a transfer apparatus 2; As shown in FIG. 4, the images on the respective photoconductors 1 are once sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2, and then the images on the intermediate transfer member 4 are transferred to the sheet s by the secondary transfer device 5. There are indirect transfer systems that perform batch transfer. The secondary transfer device 5 is a transfer conveyance belt, but there is also a roller shape method.

  Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The paper feeding device 6 and the fixing device 7 can be disposed so as to overlap the tandem type image forming apparatus T, and there is an advantage that downsizing is possible.

  In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. There is a drawback that the fixing device 7 tends to affect image formation on the upstream side due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt.

  On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 can hardly affect the image formation.

  In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.

  In this type of color electrophotographic apparatus, as shown in FIG. 4, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

  FIG. 5 shows an embodiment of the present invention, which is a tandem indirect transfer type electrophotographic apparatus. In the figure, reference numeral 100 is a copying apparatus main body, reference numeral 200 is a paper feed table on which the copying apparatus is placed, reference numeral 300 is a scanner mounted on the copying apparatus main body 100, and reference numeral 400 is an automatic document feeder (ADF) mounted thereon. ). The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.

  Then, as shown in FIG. 5, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so that it can be rotated and conveyed clockwise in the figure.

  In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.

  Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.

  An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.

  A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.

  The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.

  In the illustrated example, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. Is provided.

  Now, when making a copy using this color electrophotographic apparatus, a document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.

  When a start switch (not shown) is pressed, when a 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 other contact glass 32. Immediately drives the scanner 300 and travels through the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15, and 16 is driven to rotate by a drive motor (not shown), and the other two support rollers are driven to rotate to convey the intermediate transfer member 10. To do. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying apparatus main body 100, and abutted against the registration roller 49 and stopped.

  Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.

  Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

  On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.

  Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

(Image forming method)
The image forming method according to the present invention includes at least an electrostatic charge image forming step, a developing step, and a transfer step, and includes other steps as necessary.

<Static charge image forming step>
The electrostatic charge image forming step is not particularly limited as long as it can form an electrostatic charge image on the surface of an electrostatic charge image carrier such as the above-mentioned photoreceptor, and may be appropriately selected according to the purpose. And a process using the above charging device.

<Development process>
The development step is not particularly limited as long as the toner image can be developed with the developer having the toner according to the present invention on the surface of the electrostatic image bearing member on which the electrostatic image is formed. For example, a process using the above-described developing device can be given.

<Transfer process>
The transfer step is not particularly limited as long as the toner image developed on the surface of the electrostatic image bearing member can be transferred to a transfer material by electrostatic transfer, and may be appropriately selected according to the purpose. For example, a process using the above-mentioned transfer means can be mentioned.

<Other processes>
The other steps are not particularly limited and may be appropriately selected depending on the purpose. For example, in the cleaning step and the cleaning step for cleaning the surface of the electrostatic charge image carrier after the toner image is transferred to the transfer material. There is a charge eliminating step for removing charges on the surface of the cleaned electrostatic charge image carrier.

<< Cleaning process >>
There is no restriction | limiting in particular as a cleaning process, What is necessary is just to select suitably according to the objective, For example, the process using a photoconductor cleaning apparatus is mentioned.

<< Static elimination process >>
There is no restriction | limiting in particular as a static elimination process, What is necessary is just to select suitably according to the objective, For example, the process using a static elimination apparatus is mentioned.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example. In the following examples, parts and% are based on mass unless otherwise specified. The obtained characteristics, the evaluation machine used, and the evaluation results are shown in Table 1. In the examples, physical properties and evaluation of the toner were performed as follows.

<Physical properties>
- Measurement of weight average particle diameter D ₄ -
The weight average particle diameter D ₄ of the toner, using a Coulter Multisizer II, was measured as follows. First, 0.1 to 5 mL of alkylbenzene sulfonate was added as a dispersant to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution was prepared by preparing about 1% NaCl aqueous solution using primary sodium chloride, and ISOTON-II (manufactured by Coulter) was used. Next, 2 to 20 mg of the obtained toner was added to this liquid. The electrolytic aqueous solution in which the toner is suspended is dispersed with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles or toner are determined by a measuring device (Coulter Multisizer II) using a 100 μm aperture as an aperture. Measurements were made to calculate the volume distribution and the number distribution to obtain a weight average particle diameter (D ₄ ). In addition, as a channel, it is less than 2.00-2.52 micrometer; 2.52-3.17 micrometer; 3.17-4.00 micrometer; 4.00-5.04 micrometer; 5.04-6.35 micrometer 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Particles with a particle size of 2.00 μm or more and less than 40.30 μm were used using 13 channels of less than 25.40 μm; 25.40 to less than 32.00 μm;

-Circularity-
The circularity of the toner is measured using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 0.1 to 0.5 mL of 10% by mass of a surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 mL beaker, and each toner 0.1 ˜0.5 g was added and stirred with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The degree of circularity was calculated by measuring the shape and distribution of the toner using the FPIA-2100 until the density of the dispersion reached 5,000 to 15,000 / μL.

-Number average particle diameter Dn-
The number average molecular weight Dn of the oxide fine particles adhered to the toner base particles in the obtained toner was measured as follows. That is, the measurement object was measured without vapor deposition at a low acceleration voltage (several eV to 10 keV) using an ultra high resolution FE-SEM (for example, Ultra 55 manufactured by Zeiss Co., Ltd.) At least 100 oxides or more. The fine particles were observed, and the number average molecular weight Dn was calculated by image processing software (Image-Pro Plus).

-Standard deviation rate DL of particle size distribution-
The standard deviation rate DL of the particle size distribution of the oxide fine particles adhered to the toner base particles in the obtained toner was measured as follows. That is, the measurement object was measured without vapor deposition at a low acceleration voltage (several eV to 10 keV) using an ultra high resolution FE-SEM (for example, Ultra 55 manufactured by Zeiss Co., Ltd.) At least 100 oxides or more. The fine particles were observed, and the standard deviation rate DL of the particle size distribution was calculated by image processing software (Image-Pro Plus).

-Standard deviation rates SF1L and SF2L of shape counts SF1 and SF2 and SF1 and SF2-
The shape counts SF1 and SF2 of the oxide fine particles adhered to the toner base particles and the standard deviation rates SF1L and SF2L of SF1 and SF2 are measured using an ultra-high resolution FE-SEM (for example, Ultra 55 manufactured by Zeiss Co., Ltd.) The object to be measured was measured without vapor deposition at a low acceleration voltage (several eV to 10 keV), and at least 100 oxide fine particles were observed, and statistical processing was performed according to the following formula using image processing software (Image-Pro Plus). Specifically, the particle size distribution, the shape counts SF1 and SF2, and the standard deviation rates SF1L and SF2L of SF1 and SF2 were calculated.

SF1 = (L ² / A) × (π / 4) × 100
SF2 = (P ² / A) × (1 / 4π) × 100
SF1L = σ / SF1 × 100 σ; standard deviation of SF1 SF2L = σ / SF2 × 100 σ; standard deviation of SF2 where
The absolute maximum length of the oxide fine particles is L
The projected area of the oxide fine particles is A
The maximum perimeter of the oxide fine particles is P
And

-Molecular weight-
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by GPC (gel permeation chromatography) as follows. A sample solution is prepared by dissolving 80 mg of a sample in 10 mL of THF, filtered through a 5 μm filter, 100 μL of this sample solution is injected into the column, and the retention time is measured under the following conditions. Moreover, the retention time was measured using polystyrene having a known average molecular weight as a standard substance, and the number average molecular weight of the sample was determined in terms of polystyrene from a calibration curve prepared in advance.

・ Column: Guard column + GLR400M + GLR400M + GLR400
(All manufactured by Hitachi, Ltd.)
-Column temperature: 40 ° C
-Mobile phase (flow rate): THF (1 mL / min)
・ Peak detection method: UV (254 nm)

-Glass transition point (Tg)-
In the present invention, the glass transition point Tg was measured under the following conditions using the following differential scanning calorimeter.

・ Differential scanning calorimeter: SEIKO1DSC100
SEIKO1SSC5040 (Disk Station)
-Measurement conditions Temperature range: 25-150 ° C
Temperature increase rate: 10 ° C / min Sampling time: 0.5 seconds Sample amount: 10mg

<Evaluation machine>
In this invention, it evaluated using the following evaluation machines.
Evaluation was performed using an evaluation machine in which a part of a full color copier, imagio MP C6000 SP, manufactured by Ricoh Co., Ltd., which has a four-color non-magnetic two-component developing unit and a four-color photoreceptor, was tuned. The printing speed was evaluated by high-speed printing (60 sheets / min / A4).

<Evaluation items>
1) Evaluation of cleaning performance in a low-temperature, low-humidity, high-temperature, high-humidity repeated environment After outputting 10,000 5% image area density charts in a temperature-humidity environment at a temperature of 10 ° C and a relative humidity of 15%, the temperature is 38 ° C and the relative humidity After outputting 10,000 sheets of 5% image area density chart in an 80% environment, and further outputting 10,000 sheets of 5% image area density chart in a temperature and humidity environment at a temperature of 10 ° C. and a relative humidity of 15%, The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and measured with an X-Rite 938 (manufactured by X-Rite). Evaluations were evaluated as ◎ for less than 0.005, “◯” for 0.005 or more and less than 0.010, “Δ” for 0.010 or more and less than 0.02, and “×” for 0.02 or more. In addition, what was evaluated as “◯” and “Δ” is a level at which there is no practical problem in terms of cleaning performance.

2) Filming property in a low-temperature, low-humidity, high-temperature, high-humidity repeated environment In a temperature-humidity environment where the temperature is 10 ° C. and the relative humidity is 15%, after outputting 10,000 5% image area density charts, the temperature is 38 ° C. and the relative humidity. Photosensitivity after printing 10,000 sheets of 5% image area density chart in 80% environment and further outputting 10,000 sheets of 5% image area density chart in a temperature and humidity environment of 10 ° C. and 15% relative humidity. The amount of adhering components adhering to the body was visually evaluated. The case where no adhesion was observed was evaluated as ◎, the case where a slightly cloudy trace was observed was evaluated as ◯, the case where a cloudy streak could be confirmed was evaluated as △, and the case where a cloudy area was large was evaluated as ×. In addition, what was evaluated as “◯” and “Δ” is a level at which there is no practical problem with respect to filming property.

<Two-component developer evaluation>
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin with an average thickness of 0.3 μm is used as follows, and each color toner 7 is added to 100 parts by mass of the carrier. The developer was prepared by uniformly mixing and charging the parts by mass using a tumbler mixer of the type in which the container rolls and stirs.

(Carrier production)
・ Core material Cu—Zn ferrite particles (weight average diameter: 35 μm) 5,000 mass parts ・ Coating material Toluene 450 mass parts Silicone resin SR2400 450 mass parts (made by Toray Dow Corning Silicone, nonvolatile content 50%)
Aminosilane SH6020 10 parts by mass (made by Toray Dow Corning Silicone)
10 parts by mass of carbon black

  The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, and the coating solution and the core material are coated while forming a swirling flow in which a rotating bottom plate disk and a stirring blade are provided in a fluidized bed. The coating liquid was applied to the core material. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier 1.

(Oxide fine particles 1)
Into a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 624 g of methanol, 41 g of water and 50 g of 50% aqueous ammonia solution were added and mixed. The mixed solution was adjusted to 28 ° C., and while stirring, 1,143 g of tetramethoxysilane and 418 g of 5.2 mass% aqueous ammonia were simultaneously started and dropped over 8 hours. Stirring was continued for 2 hours after completion of dropping, and a co-hydrolysis and condensation reaction was performed to obtain a dispersion of oxide fine particles. After adding 242 g of hexamethyldisilazane to this dispersion at room temperature, the dispersion was heated to 60 ° C. and reacted for 6 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain a fine powder aggregate. The obtained powder was pulverized by a jet mill and collected by a bag filter to obtain oxide fine particles 1. The production conditions are summarized in Table 2.

(Oxide fine particles 2 to 5)
Production of oxide fine particles 1 was performed in the same manner as oxide fine particles 1 except that the production conditions were individually changed as shown in Table 2, and oxide fine particles 2 to 5 were obtained.

(Oxide fine particles 6)
In the production of oxide fine particles 1, oxide fine particles 6 were obtained in the same manner as the production of oxide fine particles 1 except that the steps after the treatment of the dispersion of oxide fine particles were changed as follows.

  After adding 200 g of hexamethyldisilazane to the dispersion of oxide fine particles at room temperature, the dispersion was heated to 60 ° C. and reacted for 3 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain fine particles. Thereafter, the fine particles, 30 g of polydimethylsiloxane having a viscosity of 350 cs, and 500 g of toluene were dispersed by ultrasonic irradiation while stirring. After visually confirming that there was no aggregate, the solvent was distilled off under reduced pressure to obtain a fine powder aggregate. The obtained powder was crushed by a jet mill and collected by a bag filter to obtain oxide fine particles 6.

(Oxide fine particles 7)
The oxide fine particles 1 were produced in the same manner as the oxide fine particles 1 except that the steps after the treatment of the oxide fine particle dispersion were changed as follows.

  After adding 180 g of hexamethyldisilazane to the dispersion of oxide fine particles at room temperature, the dispersion was heated to 60 ° C. and reacted for 6 hours to trimethylsilylate the silica fine particles. Thereafter, 100 g of dimethyldichlorosilane was further added and reacted for 1 hour. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain a fine powder aggregate. The obtained powder was crushed by a jet mill and collected by a bag filter to obtain oxide fine particles 7.

(Oxide fine particles 8-13)
Production of oxide fine particles 1 was performed in the same manner as oxide fine particles 1 except that the production conditions were individually changed as shown in Table 2, and oxide fine particles 8 to 13 were obtained.

(Oxide fine particles 14)
Distilled and purified methyltrimethoxysilane was heated, nitrogen gas was bubbled therein, and methyltrimethoxysilane was introduced into an oxyhydrogen flame burner with a stream of nitrogen gas, and burned and decomposed in the oxyhydrogen flame. At this time, the methyltrimethoxysilane addition amount is 980 g / hour, the oxygen gas addition amount is 2.3 Nm ³ / hour, the hydrogen gas addition amount is 1.8 Nm ³ / hour, and the nitrogen gas addition amount is 0.43 Nm ³ / hour. Yes, the generated fine oxide powder was collected by a bag filter. 1 kg of the oxide fine powder was charged into a 5 liter planetary mixer, 8 g of pure water was added with stirring, and after sealing, the mixture was further stirred at 55 ° C. for 8 hours. Next, after cooling to room temperature, 5 g of hexamethyldisilazane was added with stirring, and after sealing, the mixture was further stirred for 12 hours. The temperature was raised to 115 ° C., the remaining raw material and generated ammonia were removed while a nitrogen gas was passed, and a fine powder aggregate was obtained. The obtained powder was crushed by a jet mill and collected by a bag filter to obtain oxide fine particles 14.

Example 1
~ Synthesis of organic fine particle emulsion ~
Production Example 1
The following components were charged in a reaction vessel equipped with a stir bar and a thermometer, and stirred at 3,800 rpm for 30 minutes to obtain a white emulsion.

Water 683 parts by weight Sodium salt of methacrylic acid ethylene oxide adduct sulfate 11 parts by weight (Eleminol RS-30, manufactured by Sanyo Chemical Industries)
166 parts by weight of methacrylic acid 110 parts by weight of butyl acrylate 1 part by weight of ammonium persulfate

  The obtained emulsion was heated to raise the system temperature to 75 ° C. and reacted for 3 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 70 ° C. for 5 hours to obtain an aqueous dispersion of a vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). A liquid [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 75 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 60 ° C., and the weight average molecular weight was 110,000.

~ Preparation of aqueous phase ~
Production Example 2
The following components were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

990 parts of water [fine particle dispersion 1] 83 parts by weight sodium dodecyl diphenyl ether disulfonate 37 parts by weight ((Eleminol MON-7), 48.3% aqueous solution, manufactured by Sanyo Chemical Industries)
90 parts by mass of ethyl acetate

~ Synthesis of low molecular weight polyester ~
Production Example 3
The following components were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, reacted at 230 ° C. at normal pressure for 7 hours, and further reacted at 5 to 15 mm Hg for 5 hours. 44 parts of trimellitic anhydride was added and reacted at 180 ° C. and normal pressure for 5 hours to obtain [Low molecular weight polyester 1].

Bisphenol A ethylene oxide 2-mole adduct 229 parts by mass Bisphenol A propylene oxide 3-mole adduct 529 parts by mass Terephthalic acid 208 parts by mass Adipic acid 46 parts by mass Dibutyltin oxide 2 parts by mass

  The obtained [Low molecular weight polyester 1] had a number average molecular weight of 3,200, a weight average molecular weight of 8,900, a Tg of 49 ° C., and an acid value of 26.

~ Synthesis of intermediate polyester ~
Production Example 4
The following components were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg [intermediate polyester 1 ] Was obtained.

Bisphenol A ethylene oxide 2-mole adduct 682 parts by mass Bisphenol A propylene oxide 2-mole adduct 81 parts by mass Terephthalic acid 283 parts by mass Trimellitic anhydride 22 parts by mass Dibutyltin oxide 2 parts by mass

  The obtained [Intermediate polyester 1] had a number average molecular weight of 2,200, a weight average molecular weight of 9,700, 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 pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] obtained had a free isocyanate mass% of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
600 parts of water, Pigment Blue 15: 3 water-containing cake (solid content 50%) 2,400 parts, polyester resin 1,200 parts are added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), and the mixture is used with two rolls The mixture was kneaded at 120 ° C. for 45 minutes, rolled and cooled, and pulverized with a pulverizer to obtain [Master batch 1].

~ Creation of oil phase ~
Production Example 7
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 80 parts of Carnauba WAX, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw material solution 1] 1,324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / second, and 0.5 mm zirconia beads are 80 The pigment and WAX were dispersed under the conditions of volume% filling and 3 passes. Next, 1,324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was passed through a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1,200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion Slurry 1]. [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure and then subjected to the following steps (1) to (4) to obtain [Filter Cake 1].

(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide 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: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.

  The obtained [filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, in the aqueous solvent phase in which the fluorine compound of the following formula (21) is dispersed at a concentration of 1% by mass, the following fluorine compound is mixed with the toner base so that the following fluorine compound becomes 0.1% by mass, and the following fluorine compound is adhered. After (bonding), it was dried at 45 ° C. for 48 hours with a circulating drier, and further dried on a shelf at 30 ° C. for 10 hours. Thereafter, sieved with a mesh of 75 μm, [Toner Base Particle 1] was obtained.

  Thereafter, 100 parts of [toner base particle 1] were allowed to stand in an environment of 50 ° C. for 24 hours to age the particle surface, and 1.0 part of oxide fine particles 1 were then added using a Henschel mixer (FM20C manufactured by Mitsui Mining Co., Ltd.). The toner was obtained by mixing. The mixing conditions were a peripheral speed of 30 m / sec, a set of 120 sec rotation and 60 sec rotation stop was repeated 7 times and mixed to obtain a toner.

  100 parts by mass of the carrier 1 with respect to 7 parts by mass of the obtained toner was uniformly mixed and charged using a type of tumbler mixer in which the container was rolled and stirred to prepare a developer. Table 1 shows the physical properties of the obtained toner and developer, and Table 3 shows the evaluation results.

(Example 2)
In Example 1, a toner and a developer were prepared and evaluated in the same manner as in Example 1 except that toner base particles 2 obtained by changing the steps after the oil phase preparation step of the toner as described below were used. . The physical properties of the obtained toner and developer are shown in Table 1, and the evaluation results are shown in Table 2.

<Method for Producing Toner Base Particle 2>
~ Creation of oil phase ~
Production Example 10
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 80 parts of Carnauba WAX, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw material solution 1] 1,324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / second, and 0.5 mm zirconia beads are 80 The pigment and WAX were dispersed under the conditions of volume% filling and two passes. Next, 1,324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was passed twice with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 2]. The solid content concentration of [Pigment / WAX Dispersion 2] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 11
[Pigment / WAX Dispersion 2] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1,200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 15 minutes to obtain [Emulsion slurry 2]. [Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 5 hours to obtain [Dispersion slurry 2].

~ Washing⇒Drying ~
Production Example 12
[Dispersion Slurry 2] 100 parts were filtered under reduced pressure and then subjected to the following steps (1) to (4) to obtain [Filter Cake 1].

(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide 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: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 2]. It was.

  [Filter cake 2] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, in a water solvent phase in which the fluorine compound of the above formula (2) is dispersed at a concentration of 1% by mass, the fluorine compound is mixed to 0.1% by mass with respect to the toner base, and the fluorine compound is adhered. After (bonding), it was dried at 45 ° C. for 48 hours with a circulating drier, and further dried on a shelf at 30 ° C. for 10 hours. Thereafter, the mixture was sieved with a mesh of 75 μm to obtain [Mother toner particles 2].

(Examples 3 to 8)
In Examples 3 to 8, toners were produced and evaluated in the same manner as in Example 1 except that the oxide fine particles 1 added to the toner were changed to oxide fine particles 2 to 7 in Example 1. Table 1 shows the physical properties of the obtained toner and developer, and Table 3 shows the evaluation results.

Example 9
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the steps after the mixing step of the toner and the oxide fine particles were changed as follows.

  [Toner Base Particle 1] 100 parts were left in an environment of 50 ° C. for 24 hours and the particle surface was aged, then 1.0 part of oxide fine particles 1 and hydrophobic silica RX200 (primary particle size 12 nm, Nippon Aerosil Co., Ltd.) 1.0 part) was mixed with a Henschel mixer (FM20C manufactured by Mitsui Mining Co., Ltd.) to obtain a toner. The mixing conditions were a peripheral speed of 30 m / sec, a 120-second rotation and a 60-second rotation stop set were repeated four times and mixed to obtain a toner. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 3.

(Example 10)
In Example 1, evaluation was performed in the same manner as in Example 1 except that toner base particles 3 shown below were used instead of toner base particles 1. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 3.

<Method for Producing Toner Base Particle 3>
<< First Step >>
-Preparation of dispersion (1)-
The following ingredients were mixed and dissolved.

Styrene 370g
n-butyl acrylate 30g
Acrylic acid 8g
24g dodecanethiol
Carbon tetrabromide 4g

  From the obtained solution, 6 g of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) and 10 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) are dissolved in 550 g of ion-exchanged water. This was dispersed in a flask and emulsified. While slowly mixing this for 10 minutes, 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added thereto to perform nitrogen substitution. Thereafter, the contents in the flask were heated with an oil bath until the contents reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. As a result, a dispersion (1) was prepared by dispersing resin particles having an average particle size of 155 nm, a glass transition point of 59 ° C., and a weight average molecular weight (Mw) of 12,000.

-Preparation of dispersion (2)-
The following components were mixed and dissolved.

280 g of styrene
n-butyl acrylate 120g
Acrylic acid 8g

  From the obtained solution, 6 g of nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 12 g of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) are dissolved in 550 g of ion-exchanged water. This was dispersed in a flask and emulsified. While slowly mixing this for 10 minutes, 50 g of ion-exchanged water in which 3 g of ammonium persulfate was dissolved was added thereto to perform nitrogen substitution. Thereafter, the contents in the flask were heated with an oil bath until the contents reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. As a result, a dispersion liquid (2) was prepared by dispersing resin particles having an average particle diameter of 105 nm, a glass transition point of 53 ° C., and a weight average molecular weight (Mw) of 550,000.

-Preparation of colorant dispersion (1)-
The following components were mixed and dissolved.

Carbon black 50g
(Cabot Corporation: Mogal L)
Nonionic surfactant 5g
(Sanyo Kasei Co., Ltd .: Nonipol 400)
200g of ion exchange water

  The obtained solution was dispersed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and a colorant dispersion (1) obtained by dispersing a colorant (carbon black) having an average particle size of 250 nm was obtained. Prepared.

-Preparation of release agent dispersion (1)-
The following components are heated to 95 ° C. and dispersed using a homogenizer (IKA: Ultra Turrax T50), and then dispersed with a pressure discharge type homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion (1) was prepared.

40 g paraffin wax
(Nippon Seiwa Co., Ltd .: HNP-9, melting point 75 ° C.)
Cationic surfactant 7g
(Manufactured by Kao Corporation: Sanizol B50)
200g of ion exchange water

--Preparation of aggregated particles--
The following components were mixed and dispersed in a round stainless steel flask using a homogenizer (manufactured by IKA: Ultra Turrax T50).

Dispersion (1) 120g
Dispersion (2) 80g
Colorant dispersion (1) 30g
Release agent dispersion (1) 40 g
Cationic surfactant 1.5g
(Manufactured by Kao Corporation: Sanizol B50)

  Then, it heated to 40 degreeC, stirring the inside of a flask in the oil bath for heating. After maintaining at 40 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5 μm were formed.

<Second step>
-Preparation of adhered particles-
To this, 60 g of the dispersion liquid (1) as the resin-containing fine particle dispersion liquid was gradually added. In addition, the volume of the resin particle contained in the dispersion liquid (1) is 25 cm ³ . And the temperature of the heating oil bath was raised to 50 degreeC, and was hold | maintained for 1 hour.

<Third step>
Then, after adding 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel flask was sealed, and stirring was continued using a magnetic seal up to 105 ° C. Heated and held for 3 hours. Then, after cooling, the reaction product was filtered, washed thoroughly with ion exchange water, and dried to obtain toner base particles 3.

(Comparative Example 1)
In Example 1, toner 4 was obtained and evaluated in the same manner as in Example 1 except that toner base particles 4 shown below were used instead of toner base particles 1. Table 1 shows the physical properties of the obtained toner and developer, and Table 3 shows the evaluation results.

  The following components were thoroughly stirred with a flasher.

Water 1,200 parts by weight Phthalocyanine green water-containing cake (solid content 30%) 200 parts by weight Carbon black (MA60 manufactured by Mitsubishi Chemical Corporation) 540 parts by weight

  Here, 1,200 parts by mass of polyester resin (acid value; 3, hydroxyl value; 25, number average molecular weight Mn; 48,000, weight average molecular weight Mw / Mn; 4.0, glass transition point Tg; 60 ° C.) In addition, after kneading at 150 ° C. for 30 minutes, 1,000 parts of xylene was added and further kneaded for 1 hour, after removing water and xylene, rolling and cooling, and grinding with a pulverizer to obtain a master batch pigment.

  Next, the following components were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled.

100 parts by mass of polyester resin (acid value; 3, hydroxyl value; 25, Mn; 48,000, Mw / Mn; 4.0, Tg; 60 ° C.)
5 parts by mass of the above master batch 2 parts by mass of charge control agent (Orient Chemical Co., Ltd. Bontron E-84)

  Thereafter, an impingement plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow were used to obtain toner base particles 4. .

(Comparative Example 2)
In Example 1, evaluation was performed in the same manner as in Example 1 except that toner base particles 5 shown below were used instead of toner base particles 1. Table 1 shows the physical properties of the obtained toner and developer, and Table 3 shows the evaluation results.

  Stir the following ingredients well with a flasher.

600 parts by weight of water Pigment Blue 15: 3 1,200 parts by weight of water-containing cake (50% solid content)

  Here, 1,200 parts of polyester resin (acid value; 3, hydroxyl value; 25, Mn; 48,000, Mw / Mn; 4.0, Tg; 60 ° C.) was added, and after kneading at 150 ° C. for 30 minutes, After adding 1,000 parts of xylene, the mixture was further kneaded for 1 hour, water and xylene were removed, rolled and cooled, pulverized with a pulverizer, and further passed with a three-roll mill to obtain a master batch pigment.

  Next, the following components were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled.

100 parts by mass of polyester resin (acid value; 3, hydroxyl value; 25, Mn; 48,000, Mw / Mn; 4.0, Tg; 60 ° C.)
3 parts by mass of the above master batch 4 parts by mass of charge control agent (Orient Chemical Co., Ltd. Bontron E-84)

  Thereafter, an impingement plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow were performed. Thereafter, the toner surface was left on a shelf in an environment of 65 ° C. for 24 hours to spheroidize the toner surface. Again, the particle size distribution was adjusted by air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain toner base particles 5.

(Comparative Example 3)
In Example 1, a toner was produced and evaluated in the same manner as in Example 1 except that the mixing conditions of the toner base particles 1 and the oxide fine particles 1 were changed as follows. Table 1 shows the physical properties of the obtained toner and developer, and Table 3 shows the evaluation results.

  [Toner base particle 1] 100 parts (without aging the particle surface) and 1.0 part of oxide fine particles 1 were mixed with a Henschel mixer (FM20C manufactured by Mitsui Mining Co., Ltd.) to obtain a toner. The mixing conditions were a peripheral speed of 20 m / sec, a set of 60 second rotation and 30 second rotation stop was repeated twice and mixed to obtain a toner. The physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

(Comparative Examples 4 to 10)
In Comparative Examples 4 to 10, toners were produced and evaluated in the same manner as in Example 1 except that the oxide fine particles 1 added to the toner in Example 1 were changed to oxide fine particles 8 to 14. Table 1 shows the physical properties of the obtained toner and developer, and Table 3 shows the evaluation results.

  As is apparent from the results in Table 3, the toner according to the present invention has a stable cleaning characteristic not only in a low temperature and low humidity environment but also in a high temperature and high humidity environment, and also improves the resistance to photoconductor filming (contamination). It was revealed that the environmental stability is extremely excellent.

  The image forming apparatus of the present invention can be widely used in, for example, a laser printer, a direct digital plate making machine, a full color copying machine using a direct or indirect electrophotographic multicolor image developing system, a full color laser printer, and a full color plain paper fax machine.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer apparatus 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer apparatus 6 Paper feed apparatus 7 Fixing apparatus 8 Photoconductor cleaning apparatus 9 Intermediate transfer body cleaning apparatus 10 Intermediate transfer body 14 Support roller 15 Support roller 16 Support roller DESCRIPTION OF SYMBOLS 17 Intermediate transfer body cleaning device 18 Image forming means 20 Tandem image forming device 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 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photoconductor 40C Photoconductor 40K Photoconductor 40M Photoconductor 40Y Photoconductor 42Y Photoconductor 42 Feed roller 42C Developer tank 42K Developer tank 42M Developer tank 42Y Developer tank 43 Paper bar 43C pumping roller 43K pumping roller 43M pumping roller 43Y pumping roller 44 paper feed cassette 44C coating roller 44K coating roller 44M coating roller 44Y coating roller 45 separation roller 45C C developing unit 45K Bk developing unit 45M M developing unit 45Y Y developing unit 46Y Paper path 47 Conveying roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separating roller 53 Manual paper feed path 55 Switching claw 56 Ejection roller 57 Ejection tray 100 Copier main body 110 Photoconductor 120 Charging roller 130 Exposure apparatus 140 developing device 141 developing belt 142 developing tank 143 pumping roller 144 coating roller 145 developing unit 150 intermediate transfer member 151 suspension roller 152 corona belt 153 Constant current source 160 Cleaning device 170 Static elimination lamp 180 Transfer roller 190 Cleaning device 200 Paper feed table 300 Scanner 400 Automatic document feeder 700 Process cartridge 702 Photoconductor 704 Charging means 706 Developing means 708 Cleaning means 1100 Transfer paper s Sheet T Tandem Type image forming apparatus

JP 9-258474 A

Claims (12)

A toner having a toner base particle having a colorant and a resin and one or more kinds of oxide fine particles, having a weight average particle diameter D4 of ₂ to 7 μm and a circularity of 0.95 to 1.00,
The number average particle diameter Dn of the oxide fine particles in a state where the oxide fine particles adhere to the toner base particles is 30 nm to 150 nm, and the standard deviation rate DL (%) of the number average particle diameter of the particle size distribution is 0. ≦ DL ≦ 20 (DL = σ / Dn × 100 σ; standard deviation), the shape factor SF1 is 131 to 180, the shape factor SF2 is 126 to 180, and the standard deviation rate of the SF1 SF1L (%) is 0 ≦ SF1L ≦ 20 (where SF1L = σ / SF1 × 100 σ; standard deviation), and the standard deviation rate SF2L (%) of the SF2 is 0 ≦ SF2L ≦ 20 (where SF2L = σ / SF2 × 100 σ; standard deviation).   The toner according to claim 1, wherein the oxide fine particles are oxide fine particles produced by a sol-gel method.   The toner according to claim 1, wherein the oxide fine particles are hydrophobized with hexamethyldisilazane.   The toner according to claim 1, further comprising at least one oxide fine particle having a number average particle diameter of less than 30 nm.   2. The toner obtained by granulating by dispersing and / or emulsifying an oil phase and / or a monomer phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium. 4. The toner according to any one of 4 above.   The toner according to claim 1, wherein the resin contains a polyester resin.   A toner composition containing a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent is crosslinked and / or extended in an aqueous medium in the presence of resin fine particles. The toner according to any one of claims 1 to 6.   A two-component developer comprising the toner according to claim 1 and a carrier.   The two-component developer according to claim 8, wherein the carrier is magnetic particles.   A process cartridge that integrally supports an electrostatic charge image carrier and a developing unit and is detachable from a main body of the image forming apparatus, wherein the developing unit includes the toner according to claim 1. A process cartridge characterized by that. An electrostatic charge image carrier, an electrostatic charge image forming means for forming an electrostatic charge image on the electrostatic charge image carrier, and an electrostatic charge image developing unit on the surface of the electrostatic charge image carrier on which the electrostatic charge image is formed An image forming apparatus comprising: a developing unit that develops a toner image with a developer; and a transfer unit that is in contact with the surface of the electrostatic charge image carrier via a transfer material and electrostatically transfers the toner image to the transfer material. In
The image forming apparatus according to claim 1, wherein the toner used in the image forming apparatus is the toner according to claim 1. An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the electrostatic charge image carrier;
A developing step of developing a toner image with a developer for developing an electrostatic image on the surface of the electrostatic image carrier on which the electrostatic image is formed;
A transfer step of transferring the toner image developed on the surface of the electrostatic image carrier to a transfer material by electrostatic transfer;
In an image forming method having
The image forming method according to claim 1, wherein the toner used in the image forming method is the toner according to claim 1.