JP4549259B2 - Color toner - Google Patents

Description

The present invention relates to a color toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method.

  In recent years, copying machines and printers are required to be smaller, lighter, faster, and more reliable due to demands for space saving and energy saving. As a result, the hardware configuration is configured with simple elements in various respects, and conversely, the performance required for the toner is becoming higher. Therefore, excellent hardware cannot be provided unless the toner performance can be improved. In particular, there is a demand for a toner having both transferability and fixability. By improving the transfer, advantages such as reduction in toner consumption, higher image quality, and simplification of the toner collection system can be obtained. If fixing at low temperature is possible, energy saving can be achieved.

  In recent years, as one method for increasing the transfer efficiency, the toner shape has been made closer to a spherical shape. For example, polymerized toners such as suspension polymerization and emulsion polymerization are very effective techniques for improving transfer efficiency. However, in polymerized toners, the release agent is inevitably included, so the release agent is difficult to come out on the toner surface. Fixability is inferior. In addition, when the pulverized toner is spheroidized, the release agent is likely to elute on the toner surface by a solvent or heat and easily becomes richer than necessary, and there is a problem in controlling the amount of the release agent present on the toner surface. there were. In addition, it is not necessary to simply bring the toner close to a spherical shape. If the toner is too spherical, there is a problem that the toner slips through the cleaning portion and cannot be cleaned. In order to avoid these phenomena, if all the toners are made indefinite, the fluidity of the toner is deteriorated, the transfer efficiency is lowered, and the chargeability / fluidity over time due to the movement / embedding of the external additive into the recesses is deteriorated. Changes occur.

  Therefore, in order to solve these problems, by defining the average circularity of the toner and the standard deviation of the circularity, it is possible to make the toner prepared in a uniform shape, practical without side effects such as poor cleaning and toner scattering, In addition, a toner that achieves stable image performance over a long period of time has been proposed (see, for example, Patent Document 1). Here, a toner having high circularity and low standard deviation of circularity is obtained by instantaneous heat treatment. The thermal spheroidization of the toner tends to cause the release agent to ooze out during the heat treatment and may cause a decrease in developability. In particular, bleeding of the release agent becomes remarkable when the release agent is poorly dispersed. Further, in the thermal spheronization, the small particle diameter side toner often has a higher circularity, and in this case, the high circularity small particle diameter toner may pass through the cleaning blade and cause a cleaning failure.

Therefore, when the number average particle size of the toner particles, the toner particle size distribution, and the shape index have a specific relationship, the toner fluidity, charging property, developability, transferability are satisfied simultaneously and over a long period of time, A proposal has been made to improve the problems caused by blade cleaning in a multi-color image batch transfer system used for high-speed multi-sheet copying, development, transfer, and cleaning corresponding to high image quality requirements (see, for example, Patent Document 2). Here, by mixing a plurality of toners having different particle sizes and shape factors, the average shape index of the small particle size toner is adjusted to be high, and the average shape index of the large particle size toner is adjusted to be low. . Since toners having different particle sizes and manufacturing methods are mixed, it is expected that the charge amount distribution becomes broad and selective development or the like occurs due to the difference in developability. Further, in addition to the fact that the small particle size toner has a large specific surface area and tends to increase the charge amount, it is considered that the small particle size toner is more indeterminate and thus more difficult to be transferred.
Similarly, the circularity of a predetermined particle size range is set to a specific range, excellent fluidity, stable image quality without any image defects such as fireflies and insect worms, and trying to achieve both transferability and cleanability. There is a proposal (see, for example, Patent Document 3). This is to improve transfer efficiency, and to prevent worm erosion that lowers the image density and further causes the image portion to fall out white. The evaluation method for worm-eating is not clear, but the central part of the line image on the image and the line of the character image is not transferred, but only the edge part is transferred. In other words, even if only the transfer efficiency is improved, the line image may be lost, and the dot and fine line reproducibility may deteriorate due to the scattering of the toner during transfer.
Further, the proposed toner may not be able to perform low-temperature fixing, which is desirable from the viewpoint of energy saving, or may require a load that requires considerable pressure even in the fixing configuration. Further, the charge imparting member may be contaminated with the release agent, and the image density may be lowered.
Furthermore, in particular, in a system that does not have a cleaning process and collects transfer residual toner at the same time as development, image failure or development due to charging failure due to the missing toner (remaining missing toner remaining on the electrophotographic photosensitive member). Although fogging and the like may occur due to poor collection at the part, these are not considered.

Therefore, a system that does not have a cleaning process and collects residual toner at the same time as development, considers both particle size distribution and shape in order to satisfy long-term satisfaction as well as sufficient cleaning and sufficient transferability. Must be designed.
JP 2000-003068 A JP 2004-038193 A JP 2002-278161 A

  The present invention has been made in view of the above circumstances of the prior art. That is, the object of the present invention is to satisfy the toner flowability, charging property, developability and transferability at the same time for a long period of time, and does not have a cleaning process. It is an object of the present invention to provide a full-color toner and a developer using the same. Another object of the present invention is to provide a full-color toner with improved defects in a multi-color image batch transfer system used for high-speed multi-sheet copying, development corresponding to high image quality requirements, transfer and cleaning, and a developer using the same. Is to provide.

As a result of intensive studies, the inventors have determined that when the weight average particle diameter of the toner is 3.0 μm to 7.0 μm, the equivalent circle diameter in the flow type particle image measuring device and the predetermined equivalent circle diameter range are: The inventors have found that the above requirements can be satisfied by adjusting the average circularity of the toner within the range specified in the present invention, and have reached the present invention.
That is, the present invention provides [1] a color toner having toner particles and inorganic fine particles containing at least a binder resin, a colorant and a release agent, and the toner has a weight average particle diameter (D4) of 3.0 μm to 7. 0 μm,
The transmittance (%) of light having a wavelength of 600 nm with respect to a dispersion liquid in which the toner is dispersed in an aqueous solution of 45% by volume of methanol is in the range of 30 to 70%.
The average circularity of the toner having an equivalent circle diameter of 2.00 μm or more in a flow type particle image measuring device is R, the equivalent circle diameter is 2.00 μm or more and less than 3.00 μm, 3.00 μm or more and less than 6.92 μm,
When the average circularity of the toner in each equivalent circle diameter range of 6.92 μm or more and less than 12.66 μm is r (a), r (b), r (c), R, r (a), r The relationship between (b) and r (c) is
Formula (4 )
0.940 ≦ R ≦ 0.970 (1)
R − 0.015 ≦ r (a) ≦ R + 0.015 (2)
R − 0.015 ≦ r (b) ≦ R + 0.015 (3)
R − 0.015 ≦ r (c) ≦ R + 0.015 (4)
Satisfied,
The color toner contains, as inorganic fine particles, inorganic fine particles (A) having a number average particle diameter of 60 nm or more and less than 300 nm and inorganic fine particles (B) having a number average particle diameter of 10 nm or more and less than 60 nm, The surface of the toner particles is coated with the inorganic fine particles.
And
When the coverage of the inorganic fine particles (A) is F (A) and the coverage of the inorganic fine particles (B) is F (B), the relationship between F (A) and F (B) is expressed by the formula (5).
1.0 ≦ F (B) / F (A) ≦ 10.0 (5)
Satisfied,
The inorganic fine particles (A) are externally added in an amount of 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles.
0.1 to 5.0 parts by mass of the inorganic fine particles (B) are externally added to 100 parts by mass of the toner particles;
The inorganic fine particles (A) are silica fine particles, and the inorganic fine particles (B) are silica fine particles or titanium oxide fine particles.
A color toner characterized by the above.
[2] The color toner according to [1], wherein the binder resin is a resin containing at least a polyester unit .

  According to the present invention, a color toner excellent in transfer characteristics, development characteristics, and durability stability by adjusting the average circularity for each equivalent circle diameter range in the toner flow type particle image measuring device to the range specified in the present invention. Can be provided. In addition, it has a sufficient fixable region, sufficient developability can be obtained even in continuous durability, and a high-quality image can be formed.

  The present invention is described in detail below.

The present invention relates to a color toner having toner particles and inorganic fine particles containing at least a binder resin, a colorant, and a release agent, and the toner has a weight average particle diameter of 3.0 μm to 7.0 μm,
The transmittance (%) of light having a wavelength of 600 nm with respect to a dispersion liquid in which the toner is dispersed in an aqueous solution of 45% by volume of methanol is in the range of 30 to 70%.
The average circularity of a toner having an equivalent circle diameter (number basis) of 2.00 μm or more in a flow type particle image measuring apparatus is R, the equivalent circle diameter (number basis) is 2.00 μm or more and less than 3.00 μm, 3.00 μm.
When the average circularity of the toner is r (a), r (b), and r (c) in each equivalent circle diameter range of 6.92 μm or more and 6.92 μm or more and less than 12.66 μm, respectively, R, In this color toner, the relationship between r (a), r (b), and r (c) satisfies the expressions (1) to (4).
0.940 ≦ R ≦ 0.970 (1)
R−0.015 ≦ r (a) ≦ R + 0.015 (2)
R−0.015 ≦ r (b) ≦ R + 0.015 (3)
R−0.015 ≦ r (c) ≦ R + 0.015 (4)

  A color toner that satisfies this condition (hereinafter also simply referred to as toner) has excellent transfer characteristics, development characteristics, and durability stability. Further, the toner can be fixed in a sufficient fixing temperature region. In particular, it suppresses the so-called “transfer dropout” in which only the edge portion is transferred without scattering the center portion of the line image or character image line on the image, thereby improving the reproducibility of lines and dots. be able to.

When the average circularity R of the toner having an equivalent circle diameter (number basis) of 2.00 μm or more in the toner flow type particle image measuring device is less than 0.940, external output is performed when a large number of images are output. Since the toner is deteriorated by embedding the agent, transferability may be insufficient. On the other hand, if the average circularity is greater than 0.970, the toner shape becomes too spherical, so that when the photosensitive drum is cleaned, image transfer defects may occur due to poor cleaning such as the transfer residual toner slipping through the cleaning blade. There is not preferable.

Further, the average circularity r (a) in the toner having an equivalent circle diameter of 2.00 μm or more and less than 3.00 μm is smaller than the average circularity R in color toner particles having an equivalent circle diameter of 2.00 μm or more.
In the case of (a)> R + 0.015, the shape of the particles on the fine powder side approaches a spherical shape, so that fluidity is maintained, but cleaning failure such as slipping through the cleaning blade occurs. Furthermore, the toner is easily packed in the toner container or the developing device, and the toner forms an aggregate that causes image defects, and the uniformity of the solid image tends to deteriorate, which is not preferable. Further, in a system that collects transfer residual toner simultaneously with development, the recoverability in development becomes insufficient, and the toner that cannot be collected may move around on the photosensitive drum and cause fogging.

In addition, the average circularity r (a) in the toner having an equivalent circle diameter of 2.00 μm or more and less than 3.00 μm is r (a) <R with respect to the average circularity R in a toner having an equivalent circle diameter of 2.00 μm or more.
In the case of −0.015, the circularity on the fine powder side becomes indefinite, which increases the contact area between the toner and the carrier and other members, impairs toner separation, and does not develop in the developing unit. And may continuously contaminate members such as the carrier spent and sleeve. In a system that collects untransferred toner at the same time as development, if a void occurs, a charging failure may occur at the charging portion. This is considered to be due to the fact that the residual toner remaining on the photosensitive drum cannot be immediately released when charging and entering the auxiliary charging portion, and the charger cannot uniformly charge the photosensitive drum.

Further, the average circularity r (c) in the toner having an equivalent circle diameter of 6.92 μm or more and less than 12.66 μm is r (c)> with respect to the average circularity R in a toner having an equivalent circle diameter of 2.00 μm or more.
In the case of R + 0.015, it means that the circularity of the toner on the coarse powder side is relatively high, and the toner having a high circularity has a weak adhesion to the electrophotographic photosensitive member and the transfer member. Although the transfer efficiency is improved, scattering from the developing device may occur. In addition, the coarseness of the toner on the coarse powder side is high, the adhesion between the particles is weakened, and the deposited toner transferred and formed on the recording medium is easily broken by vibration during transportation. Reproducibility may deteriorate.

Further, the average circularity r (c) of the toner having an equivalent circle diameter of 6.92 μm or more and less than 12.66 μm is r (c) <R− with respect to the average circularity R of the toner having an equivalent circle diameter of 2.00 μm or more. In the case of 0.015, the concave portion of the toner surface increases, the added external additive does not work effectively, the fluidity is lowered, the contact probability with the carrier or the sleeve is reduced, the charge amount is low, the charge amount is low. The amount distribution also widens, and selective development during development may occur. Since the circularity of the coarse powder side toner becomes relatively low and becomes more irregular, it is considered that the contact area with the drum is increased and the adhesion is increased. Due to the difference in transferability, the toner on the coarse powder side having a relatively low circularity serves as a nucleus, and the center portion of the line image on the image and the line of the character image is not transferred, and only the edge portion is transferred. It is not preferable because “transfer omission” and transfer failure may occur.

The color toner of the present invention has a weight average particle diameter of 3.0 to 7.0 μm, preferably 5.0 to 6.0 μm. When the weight average particle diameter exceeds 7.0 μm, the latent image of dots and lines cannot be faithfully developed with toner, and in particular, reproduction of photographic images or reproduction of fine lines is inferior. On the other hand, if the weight average particle size is less than 3.0 μm, it becomes difficult to control charging and toner fluidity, and a stable image cannot be obtained.
In the toner of the present invention, the light transmittance (%) at a wavelength of 600 nm with respect to a dispersion obtained by dispersing the toner in an aqueous solution of 45% by volume of methanol is preferably in the range of 30 to 70%. Is 35-50%.
The amount of the release agent in the vicinity of the toner surface is determined by measuring the transmittance of light having a wavelength of 600 nm with respect to a dispersion in which the toner is dispersed in an aqueous solution of 45% by volume of methanol as a simple and accurate method. I can grasp it. In this measurement method, the toner is forcibly dispersed once in a mixed solvent, and the characteristics of the amount of the release agent for each toner particle are easily obtained, and then the transmittance after a predetermined time is measured. It is possible to accurately grasp the amount of the release agent present in the entire toner. That is, when a large amount of hydrophobic release agent is present on the surface of the toner, it is difficult to disperse in the solvent and aggregates and precipitates, resulting in a high transmittance. Conversely, when a small amount of the release agent is present on the toner surface, a large amount of hydrophilic binder resin is present, so that it becomes easier to disperse more uniformly, and the transmittance becomes a small value such as less than 30. In other words, the transmittance (%) of the toner in a 45% by volume aqueous solution of methanol indicates the presence state of the release agent component in the toner, and by controlling this, a wide fixing region is achieved, and the release agent. It is possible to prevent the components from being detached from the toner, and to produce a toner that does not contaminate the developing member even during long-term use.
If the transmittance is less than 30%, the release agent on the toner surface is small and the releasing effect is difficult to appear at the time of fixing. Therefore, low temperature fixing desired from the viewpoint of energy saving cannot be performed. The load which requires is required. In addition, dot reproducibility may deteriorate. On the other hand, if the transmittance is greater than 70%, the release agent on the toner surface is large, and the release agent is contaminated on the charge imparting member. For example, the resistance is increased by fusing on the developing sleeve. Such an effect of the actual developing bias is lowered, which may lead to a reduction in image density. In addition, voids may occur. This is presumably because there are many release agents on the toner surface, and the adhesion force between the toners is increased by the pressure applied at the time of transfer, and the void is likely to occur.

  The color toner of the present invention may be any one as long as the weight average particle diameter, the average circularity, and the average circularity for each equivalent circle diameter are within a specified range. A mold release agent and an optional material are melt-kneaded, cooled and coarsely pulverized, finely pulverized with an airflow type or mechanical pulverizer, and further subjected to classification and surface modification treatment with a mechanical pulverizer described later. The color toner of the present invention could be obtained by treating with a surface modifying apparatus capable of mixing and mixing inorganic fine particles therein.

  The color toner of the present invention contains at least inorganic fine particles (A) having a number average particle size of 60 nm or more and less than 300 nm and inorganic fine particles (B) having a number average particle size of 10 nm or more and less than 60 nm as inorganic fine particles. Any one of the inorganic fine particles is preferably treated with silicone oil.

The number average particle diameter of the inorganic fine particles (A) is preferably 60 nm or more and less than 300 nm, and more preferably 90 nm or more and less than 150 nm. When the number average particle diameter of the inorganic fine particles (A) is 60 nm or more and less than 300 nm, the inorganic fine particles (A) are not embedded in the colored particles even if image output is continued for a long period of time, and the toner and drum Rather than being in contact with the colored particles, the state in which the inorganic fine particles and the drum are in contact with each other can be maintained, and the releasability between the toner and the drum is maintained, and as a result, a decrease in transfer efficiency can be suppressed. When the thickness is less than 60 nm, the function as a spacer is weakened, and the contribution to improving transferability is reduced. On the other hand, when it exceeds 300 nm, it becomes easier to detach from the colored particles, and it becomes difficult to stably adhere to the surface of the colored particles, and the transfer efficiency decreases. In addition, the toner may be detached from the toner during development to contaminate the developing device, or the detached fine powder may adhere to the photosensitive drum or carrier, resulting in deterioration of charging performance.

  The inorganic fine particles (B) preferably have a number average particle diameter of 10 nm or more and less than 60 nm, and more preferably 20 nm or more and less than 50 nm. If the number average particle diameter of the inorganic fine particles (B) is smaller than 10 nm, the inorganic fine particles (B) are easily embedded in the toner surface during long-term image output, and the physical adhesion of the fluid toner is increased and the fluidity is lowered. There are things to do. On the other hand, if it is larger than 60 nm, the effect of imparting fluidity is reduced, and the charging characteristics tend to be unstable.

  In addition, any one of the inorganic fine particles is preferably treated with silicone oil, and more preferably, the inorganic fine particle (B) is treated with silicone oil. By the silicone oil treatment, it is possible to prevent the occurrence of so-called “transfer omission” in which only the edge portion is transferred without transferring the central portion of the line image or character image line on the image. When the silicone oil treatment is not performed, “transfer omission” may occur.

The inorganic fine particles (A) used in the present invention have a number average particle diameter of 60 nm or more and less than 300 nm, and examples thereof include silica, alumina, and titanium oxide. The composition is not particularly limited, and in the case of silica, for example, any silica produced using a conventionally known technique such as a gas phase decomposition method, a combustion method, or a deflagration method can be used. A number average produced by a known sol-gel method that removes the solvent from the silica sol suspension obtained by hydrolyzing and condensing the alkoxysilane with a catalyst in an organic solvent in which water is present, and drying to form particles. It is particularly preferable to use particles having a particle size of 60 nm or more and less than 300 nm.
Furthermore, the silica surface obtained by the sol-gel method may be used after being hydrophobized, and a silane compound is preferably used as the hydrophobizing agent. Examples of silane compounds include monomethylsilanes such as hexamethyldisilazane, trimethylchlorosilane and triethylchlorosilane, monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane, monoaminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine, and trimethylacetoxysilane. Of monoacyloxysilane.

The inorganic fine particles (B) used in the present invention are inorganic fine particles having a number average particle diameter of 10 nm or more and less than 60 nm and having a composition different from that of the above-mentioned inorganic fine particles (A). Different compositions refer to compositions having different configurations, such as different materials or different surface treatments and shapes even if the materials are the same.
Examples of specific materials for the inorganic fine particles (B) include various metal compounds (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.) and nitrides (silicon nitride, etc.) ), Carbides (such as silicon carbide), metal salts (such as calcium sulfate, barium sulfate, and calcium carbonate), fatty acid metal salts (such as zinc stearate and calcium stearate), carbon black, and silica. In particular, silica fine particles treated with silicone oil are preferable. Silica fine particles may be used in combination with a silicone oil treatment and a surface treatment such as a silane compound, an organic silicon compound, or a titanium coupling agent. Addition of silica fine particles treated with silicone oil can provide a toner having an appropriate charge amount due to fluidity and high negative chargeability.

The surface of the toner particles is coated with the inorganic fine particles, and the ratio (coverage) of the surface of the toner particles with the inorganic fine particles is 60% or more, and the inorganic fine particles (A
) Is F (A), and the coverage of the inorganic fine particles (B) is F (B), the relationship between F (A) and F (B) satisfies the formula (5). It may be a color toner.
1.0 ≦ F (B) / F (A) ≦ 10.0 (5)

  Here, the coverage F of each inorganic fine particle can be obtained from the equation F = (√3 × Dt × ρt) / (2π × da × ρa) × C. Dt is the weight average particle diameter of the toner, ρt is the specific gravity of the toner, da is the number average particle diameter of the inorganic fine particles, ρa is the specific gravity of the inorganic fine particles, and C is the addition ratio of the inorganic fine particles to 100 parts by weight of the colored particles.

When the coverage of the inorganic fine particles with respect to the surface of the toner particles is 60% or more and the equation (5) is satisfied, transfer transfer such as a line image does not occur and high transfer efficiency can be achieved. F (B) / F (A) is preferably 1.0 ≦ F (B) / F (A) ≦ 10.0,
More preferably, 1.0 ≦ F (B) / F (A) ≦ 5.0. F (B) / F (A) is 1.
If it is smaller than 0, the size of the inorganic fine particles (A) becomes steric hindrance, the effect of adding the inorganic fine particles (B) is hindered, the fluidity is lowered, and the charging characteristics may be unstable. In addition, the line image and character quality may deteriorate. If F (B) / F (A) is greater than 10.0, the releasability of the toner from the member is lowered, and the developability and transfer efficiency are also lowered. In addition, toner charge up may occur due to long-term use.

  In the color toner of the present invention, the amount of the inorganic fine powder (A) added is 0.3 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the colored particles. is there.

  The addition amount of the inorganic fine powder (B) in the color toner of the present invention is 0.1 to 5.0 parts by mass, more preferably 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the colored particles. is there.

  Further, the color toner of the present invention contains inorganic fine particles (A) and inorganic fine particles (B) as inorganic fine particles, and further, titanium oxide having a different BET or crystal type from the inorganic fine particles (A) and inorganic fine particles (B). And one or more inorganic fine particles selected from aluminum oxide.

  The color toner of the present invention contains one or more inorganic fine particles selected from titanium oxide or aluminum oxide together with the inorganic fine particles (A) and inorganic fine particles (B) in terms of improving fluidity and chargeability. preferable. By improving the fluidity, the toner is sufficiently charged by stirring in the developing device, and the toner becomes effective against fogging and toner scattering. In general, if the toner is left in a high-temperature and high-humidity environment, the absolute charge level decreases, and after the last image is output, the image is not output for a long period of time. However, the color toner of the present invention exhibits a more remarkable effect on fogging and toner scattering, and can improve this problem.

  The color toner of the present invention further includes at least one selected from the group consisting of inorganic fine particles (A), inorganic fine particles (B), and titanium oxide or aluminum oxide as a fluidizing agent for controlling fluidity and developability. A known external additive having a composition different from that of the inorganic fine particles can be added. Various inorganic oxide fine particles, fine particles hydrophobized as necessary, vinyl polymer, zinc stearate, resin fine particles, and the like can be used. The addition amount of the external additive is preferably in the range of 0.02 to 5% by mass with respect to the total mass of the toner particles.

  The color toner of the present invention has toner particles containing at least a binder resin, a colorant, and a release agent, and various resins can be used as the binder resin according to the present invention. Specific examples of the binder resin include polyester resins, styrene resins, acrylic resins, styrene-acrylic copolymer resins, and epoxy resins.

  The binder resin preferably used includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, (c) a mixture of the hybrid resin and the vinyl polymer, (d A resin selected from any one of: a mixture of a polyester resin and a vinyl polymer; (e) a mixture of a hybrid resin and a polyester resin; and (f) a mixture of a polyester resin, a hybrid resin, and a vinyl polymer. is there.

  As the binder resin, a resin having at least a polyester unit can be easily adjusted to the equivalent circle diameter and the average circularity range for each prescribed circle diameter range in the flow particle image measuring apparatus according to the present invention, and a wide range of fixing. This is preferable in that it can be fixed at a temperature.

  In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component. The vinyl polymer unit is a vinyl monomer component, and the polyvalent carboxylic acid component and the vinyl monomer in the monomer. A monomer having a monomer or a monomer having a polyhydric alcohol component and a vinyl monomer corresponds to a polyester monomer.

The binder resin used in the color toner of the present invention has a main peak in the molecular weight range of 3500 to 35000 in the molecular weight distribution measured by gel permeation chromatography (GPC) of the resin component, It is good to have in the area | region of molecular weight 5000-20000. Moreover, it is preferable that ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 5.0 or more.
The measurement of molecular weight distribution by GPC measurement in the present invention will be described in detail later.

  When the main peak has a molecular weight of less than 3500, the high temperature offset resistance of the toner is insufficient. On the other hand, when the main peak exceeds the molecular weight of 35000, sufficient low-temperature fixability of the toner cannot be obtained, and application with a high-speed machine becomes difficult. Moreover, when Mw / Mn is less than 5.0, it becomes sharp melt and high gloss is easily obtained, but high-temperature offset resistance cannot be obtained.

  When a polyester-based resin is used as the binder resin, an alcohol component and an acid component (such as carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester) can be used as raw material monomers.

  Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2, Alkylene oxide adducts of bisphenol A such as 2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1 , 2-Propylene glycol, 1,3-propylene glycol, 1,4-butanediol Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrola, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerola, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethyl Examples include benzene.

  Examples of the acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with an alkyl group or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;

  Among these, in particular, a carboxylic acid (for example, fumaric acid) comprising a bisphenol derivative represented by the following general formula (I) as a diol component and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. , Maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.), and a polyester resin obtained by condensation polymerization of these as color components can exhibit good charging characteristics as a color toner. preferable.

〔式中、Ｒはエチレン、またはプロピレン基である。ｘ，ｙはそれぞれ１以上の整数で
あり、かつｘ＋ｙの平均値は２〜１０である。〕

[Wherein, R represents an ethylene or propylene group. x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. ]

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming the nonlinear polyester resin include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4, and the like. -Naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component used is preferably 0.1 to 1.9 mol% with respect to the total carboxylic acid monomer.

The following are mentioned as a vinyl-type monomer used when manufacturing a vinyl-type polymer. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-crawler styrene, 3, Styrene and its derivatives such as 4-dicrawler styrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinylidene chloride, vinyl bromide Vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as n-octyl acid, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate; Ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic Acid 2-crawler ethyl, acrylic esters such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N -N-vinyl compounds such as vinyl pyrollar, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the color toner of the present invention, the vinyl polymer and the vinyl polymer unit used for the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.

  Examples of the crosslinking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,5-pentanediol diacrylate. 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and diacrylate compounds linked by alkyl chain such as those obtained by replacing acrylate of the above compound with methacrylate; diethylene glycol diacrylate, triethylene glycol diacrylate, tetra Ethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and Diacrylate compounds linked by an alkyl chain containing an ether bond, such as a compound obtained by replacing acrylate with methacrylate; polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, poly Oxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and diacrylate compounds linked by a chain containing an aromatic group and an ether bond, such as those obtained by replacing acrylate of the above compound with methacrylate Kind.

Examples of polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylolethane ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds instead of methacrylate. Triallyl cyanurate, triallyl trimellitate.

  Examples of the polymerization initiator used in producing the vinyl polymer and the vinyl polymer unit according to the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′- Azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2- Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetyl Ketone peroxides such as acetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethyl Xyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, Acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaur Rate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate , Di -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  When a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved release agent dispersibility, low-temperature fixability, and offset resistance can be expected.

  The “hybrid resin” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.

  In the present invention, it is preferable that a monomer component capable of reacting with both resin components is contained in the vinyl polymer component and / or the polyester resin component. Examples of the monomer constituting the polyester resin component that can react with the vinyl polymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a hybrid resin obtained by the reaction of a vinyl polymer and a polyester resin, there is a polymer containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above. A method obtained by polymerizing one or both resins is preferred.

  A method for producing a hybrid resin used in the color toner of the present invention will be described. The hybrid resin can be produced by the production methods shown in the following (1) to (6).

  (1) A method obtained by blending after producing a vinyl polymer, a polyester resin and a hybrid resin component, and the blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. Is done. Note that the hybrid resin component is obtained by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. Synthesized ester compounds can be used.

  (2) A method obtained by reacting a polyester unit or a hybrid resin component in the presence of the vinyl polymer unit after the production thereof. The hybrid resin component is produced by a reaction between a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method obtained by reacting a vinyl polymer unit or a hybrid resin component in the presence of the polyester unit after the production thereof. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl polymer. Also in this case, an organic solvent can be appropriately used.

  (4) After producing a vinyl polymer unit and a polyester unit, a hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.

  (5) After the hybrid resin component is produced, it is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) and performing addition polymerization and / or condensation polymerization reaction. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate.

  (6) A hybrid resin component is produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate.

  By using the production methods (1) to (6) above, hybrid resins using various vinyl polymer units and polyester units having different molecular weights and different degrees of crosslinking can be produced.

  As the colorant used in the present invention, known pigments and dyes can be used alone or in combination. Examples of the colorant include the following.

  Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 16, 17; I. Acid Blue 6; I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 97, 155, 180, 185, C.I. I. Bat yellow 1, 3, 20 etc. are mentioned.

  As the black pigment, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black is used. Also, magnetic powder such as magnetite and ferrite, or yellow / magenta / cyan shown above. / The thing etc. which were toned to black using a black coloring agent are mentioned.

  The content of the colorant is preferably 1 to 15 parts by mass, more preferably 3 to 12 parts by mass, and still more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin. . When the content of the colorant is more than 15 parts by mass, the transparency is lowered, and in addition, the reproducibility of intermediate colors as typified by human skin color is likely to be lowered, and further, the chargeability of the toner is stabilized. And the low-temperature fixability becomes difficult to obtain. When the content of the colorant is less than 1 part by mass, the coloring power becomes low, and a large amount of toner must be used to obtain the density, which may be inferior in low-temperature fixability.

The release agent for the toner particles contained in the color toner of the present invention preferably has a peak temperature of the maximum endothermic peak in the endothermic peak in the range of 60 to 140 ° C. in the endothermic curve in the differential scanning calorimeter measurement. More preferably, the endothermic curve has a maximum peak in the range of 70 to 120 ° C. When the peak temperature of the maximum endothermic peak is less than 60 ° C., the release agent tends to dissolve on the toner surface when left in a high temperature environment, and the blocking resistance of the toner may deteriorate. In addition, when performing high-speed development, the toner may easily be spent on the developing sleeve and the carrier. On the contrary, when the peak temperature of the maximum endothermic peak exceeds 140 ° C, the release agent cannot quickly move to the surface of the molten toner at the time of toner fixing and melting, resulting in inferior release properties, resulting in high temperature offset. It becomes easy and fixing property will fall. In addition, low-temperature fixing cannot be performed, and it may not be applicable to high-speed development.
The endothermic peak measurement in the differential scanning calorimeter measurement in the present invention will be described in detail later.

Examples of the release agent used in the present invention include aliphatic hydrocarbons such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, microcrystalline release agents, paraffin release agents, and Fischer-Tropsch release agents. Release agents; Oxides of aliphatic hydrocarbon release agents such as oxidized polyethylene release agents; Release agents based on fatty acid esters such as aliphatic hydrocarbon ester release agents; and deoxidized carnauba release What deoxygenated one part or all part fatty acid ester like a type | mold agent is mentioned. Furthermore, a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like. Particularly preferred release agents are aliphatic hydrocarbon release agents such as paraffin release agents that have a short molecular chain, little steric hindrance, and excellent mobility.

The content of the release agent is preferably 1 to 10 parts by mass and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the binder resin. If the content of the release agent is less than 1 part by mass, the releasability may not be exhibited well at the time of oilless fixing, or the low temperature fixing property may not be satisfied. When the amount exceeds 10 parts by mass, the release agent tends to ooze out to the toner surface, and developability may deteriorate or spent resistance may deteriorate.
The release agent used in the present invention has a number average molecular weight (Mn) of preferably 200 to 2000, more preferably Mn 350 to 1000, in the molecular weight distribution by GPC measurement. The release agent preferably has a weight average molecular weight (Mw) of 200 to 2500, more preferably 350 to 1200 in the molecular weight distribution by GPC measurement. Moreover, it is preferable that ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 2.0 or less. When the release agent has a molecular weight distribution within the above range, the toner can have preferable thermal characteristics. That is, when Mn or Mw becomes smaller than the above range, it is easily affected by heat and becomes inferior in blocking resistance and developability. When Mn or Mw becomes larger than the above range, heat from the outside is effective. It is difficult to obtain excellent fixing properties and offset resistance. When Mw / Mn is greater than 2, the molecular weight distribution is wide, so that the melting behavior is not sharp against heat, and it is difficult to obtain a region satisfying both good fixability and offset resistance.

  The colored particles contained in the color toner of the present invention contain a binder resin, a colorant, and a release agent, and further contain various additives (such as a charge control agent) as necessary. Also good.

  Examples of the charge control agent include organometallic complexes, metal salts, and chelate compounds such as monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. In addition, carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic acid anhydrides and esters, and condensates of aromatic compounds are also included. In addition, phenol derivatives such as bisphenols and calixarene are also included. In the present invention, it is preferable to use a metal compound of an aromatic carboxylic acid in order to improve the rising of charging.

  The content of the charge control agent is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 0.1 parts by mass, the change in the charge amount of the toner in an environment from high temperature and high humidity to low temperature and low humidity may become large. If the amount is more than 10 parts by mass, the toner may be inferior in low-temperature fixability.

  The color toner of the present invention can be applied to both a one-component developer composed only of a toner (not including a carrier) and a two-component developer composed of a toner and a carrier. Is more preferably used as a two-component developer used by mixing with a magnetic carrier.

Examples of the magnetic carrier include surface-oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, and ferrite. Can be used.
The coated carrier obtained by coating the surfaces of the magnetic carrier particles with a resin can be particularly preferably used in a developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particle, and a method in which the magnetic carrier core particle and the coating material are mixed with powder. A conventionally known method can be applied.

  In particular, the magnetic carrier is a magnetic carrier having a magnetic fine particle dispersed resin core in which magnetic fine particles are dispersed in at least a binder resin, and a coating layer containing a coating resin that covers the surface of the magnetic fine particle dispersed resin core. It is particularly preferred.

As a method for producing a magnetic fine particle dispersed resin core constituting a magnetic carrier, there is a method of obtaining a magnetic fine particle dispersed core by mixing a monomer constituting a binder resin and magnetic fine particles and polymerizing the monomer. At this time, the monomers used for the polymerization include vinyl monomers for forming vinyl resins; bisphenols and epichlorohydrin for forming epoxy resins; phenols and aldehydes for forming phenol resins; urea Urea and aldehydes and melamine and aldehydes for forming the resin are used.
For example, as a method for producing magnetic fine particle-dispersed core particles using a curable phenolic resin, magnetic fine particles are placed in an aqueous medium, and phenols and aldehydes are polymerized in the aqueous medium in the presence of a basic catalyst. There is a method for obtaining a magnetic fine particle dispersed core.

  As another method for producing a magnetic fine particle dispersed resin core constituting a magnetic carrier, a vinyl or non-vinyl thermoplastic resin as a binder resin, a magnetic material, and other additives are sufficiently mixed by a mixer. Then, there is a method of melting and kneading using a kneader such as a heating roll, a kneader, an extruder, etc., cooling, and then crushing and classifying. At this time, the obtained magnetic fine particle dispersed resin core is preferably used after being spheroidized by thermal or mechanical treatment. As the binder resin, a thermosetting resin such as a phenol resin, a melamine resin, or an epoxy resin is preferable because it is excellent in durability, impact resistance, and heat resistance. In particular, in order to express the effects of the present invention more suitably, the binder resin is more preferably a phenol resin.

Examples of the magnetic fine particles contained in the magnetic fine particle dispersed resin core include ferromagnetic iron oxide particles such as magnetite and ferrite represented by the general formula of MO · Fe ₂ O ₃ or M · Fe ₂ O ₄ , iron Spinel ferrite particle powder containing one or more metals (Mn, Ni, Zn, Mg, Cu, etc.), magnetoplumbite type ferrite particle powder such as barium ferrite, iron or iron alloy having an oxide film on the surface Fine particle powder and the like. In the general formulas such as magnetite and ferrite, M is a divalent or monovalent metal ion (Mn, Fe, Ni, Co, Cu, Mg, Zn, Cd, Li, etc.). Metal can be used. Magnetite and maghemite can be preferably used as the magnetic fine particles, and magnetite is more preferable because it is inexpensive.

  The number average particle size of the magnetic fine particles is preferably 0.02 to 3 μm, and the number average particle size of the magnetic fine particles is 0.05 to 1 μm considering the strength of the magnetic fine particle dispersed resin core. It is preferable. The shape may be any of granular, spherical and acicular.

  The magnetic fine particle-dispersed resin core may contain nonmagnetic inorganic fine particles together with magnetic fine particles. As an example of the nonmagnetic inorganic fine particles, fine particles such as titanium oxide, silica, alumina, zinc oxide, magnesium oxide, hematite, goethite, and ilmenite can be used. Hematite, zinc oxide, titanium oxide and the like, which do not have much difference in specific gravity from magnetic fine particles, are more preferable. The number average particle diameter of the non-magnetic inorganic compound fine particles used for the production of the magnetic fine particle-dispersed resin core is preferably 0.05 to 5 μm. The number average particle diameter of the fine particles is more preferably 0.1 to 3 μm.

Examples of the coating material on the surface of the magnetic fine particle dispersed resin core include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These may be used alone or in plurality. The treatment amount of the coating material is preferably 0.1 to 30% by mass, and more preferably 0.5 to 20% by mass, based on the total mass of the magnetic fine particle dispersed resin core.
A preferred number average particle size of the magnetic carrier is 15 to 60 μm because of the relationship with the weight average particle size of the toner. More preferably, it is 25-50 micrometers. Examples of the method for preparing the magnetic carrier so as to have the above-mentioned number average particle diameter include performing classification by using a sieve. In particular, in order to classify with high accuracy, it is preferable to repeat a plurality of times using a sieve having an appropriate opening. It is also effective to use a mesh whose shape is controlled by plating or the like.

  When the two-component developer is prepared by mixing the color toner of the present invention and the magnetic carrier, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the two-component developer. % Usually gives good results. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  The toner and developer of the present invention can be applied to any image forming apparatus, but in particular, it is preferably used for an image forming apparatus having a system for collecting untransferred toner simultaneously with development.

An image forming apparatus using a general cleaning method that can use the toner and developer of the present invention will be described.
FIG. 11 is a schematic cross-sectional view of an image forming apparatus using a normal cleaning method. In FIG. 11, the surface of an electrophotographic photosensitive drum 28 as an image carrier uniformly charged by a charger 21 as a charging means is first exposed by a laser exposure device 22 as a latent image forming means, and electrostatically charged. A latent image is formed on the photosensitive drum 28. Thereafter, the electrostatic latent image on the electrophotographic photosensitive member 28 is visualized as a toner image by the developing device 11 as developing means.
After the toner image is transferred onto a recording paper 27 as a recording medium conveyed by the transfer belt 24 by a transfer electric field by the transfer charger 23, the recording paper 27 is peeled off from the transfer belt 24. Then, the transferred image is pressed and heated by the fixing device 25 to obtain a permanent image.
Residual toner and carrier remaining on the photosensitive drum 28 after the transfer are removed by a cleaner (cleaning device) 26 to prepare for the next image formation. The cleaner 26 has a blade that contacts the image forming area and the non-image forming area on the photosensitive drum 28, and electrostatically overcomes the magnetic force from the developing sleeve to the non-image forming area on the photosensitive drum 28. In this configuration, the deteriorated carrier transferred to is rubbed and removed.

In particular, the toner of the present invention uses a system that collects the transfer residual toner at the same time as the development. In addition, the charging failure due to the residual toner remaining in the system that collects the transfer residual toner at the same time as the development is solved. And more preferable.
FIG. 10 shows a system for collecting untransferred toner simultaneously with development. In FIG. 10, the electrophotographic photosensitive member 1 which is an electrostatic latent image carrier rotates in the b direction. The photosensitive member 1 is charged by a charging device 2 as a charging unit, and a laser beam L is projected onto the charged surface of the photosensitive member 1 by an exposure device 3 as an electrostatic latent image forming unit to form an electrostatic latent image. . Thereafter, the electrostatic latent image is visualized as a toner image by the developing device 4 as developing means, and is transferred to the transfer material P by the transfer device 5 as transfer means. In this transfer unit, the untransferred toner remaining on the surface of the photosensitive member without being transferred passes through the above-described charging unit and electrostatic latent image forming unit, and is again used for development or collected by the developing device.
Further, in the image forming method of the present invention, as shown in FIG. 10, the transfer residual toner on the photosensitive member is leveled after the transfer and before the charging step, and the recovery rate of the transfer residual toner in the developing device is improved. Therefore, it is preferable to further include a leveling step 6 having a bias applying means for the purpose of uniformizing the charging polarity of the transfer residual toner.
In the system that collects the transfer residual toner simultaneously with the development, the void residual toner lump remaining on the electrophotographic photosensitive member passes through the leveling step 6 having the bias applying means, and the charging device 2 as the charging means causes a charging failure. It can be a cause. In the toner of the present invention, there was no image failure due to charging failure or fogging. This is because, even when the residual toner lump remaining on the photosensitive member remains, the remaining toner lump is unraveled and rushed into the charging device 2 in a leveling process having charging means and bias applying means. It is presumed that the occurrence of defects was prevented.

  Next, a method for producing the color toner of the present invention will be described.

  This time, the present inventors melt and knead the binder resin, the colorant, the release agent and an arbitrary material, cool and coarsely pulverize them, and finely pulverize them with an airflow type or mechanical pulverizer. Thereafter, classification and surface modification treatment are performed by a mechanical pulverizer described later and a surface modification apparatus capable of performing classification and surface modification treatment described later at the same time, and inorganic fine particles are mixed therewith, whereby the color of the present invention is obtained. A toner was obtained.

  First, in the raw material mixing step, as a toner internal additive, at least a binder resin, a colorant, and a release agent are weighed and mixed and mixed. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner material blended and mixed as described above is melt-kneaded. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. A twin screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, etc. are generally used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed by a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.) or the like. After that, if necessary, the particles are classified using a classifier such as an inertia classification type elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) or a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.), and toner particles (classification). Product).

In the present invention, mechanical pulverization is performed in the pulverization step, or first-stage pulverization is performed using an air jet pulverizer, and second-stage pulverization is performed using a mechanical pulverizer. The mechanical pulverizer includes at least a rotor that is a rotating body attached to a central rotating shaft, and a stator that is arranged around the rotor while maintaining a constant distance from the rotor surface. In addition, the annular space formed by maintaining the interval is configured to be in an airtight state. The outer peripheral surface of the rotor and / or the inner peripheral surface of the stator have a plurality of convex portions and concave portions formed between the convex portions and the convex portions, and the convex portions and the convex portions. Is a distance of 2.0 mm or more and less than 3.5 mm.

The finely pulverized product obtained by the above pulverization can be prepared by introducing the coarsely pulverized product obtained by roughly pulverizing the solid material obtained by cooling the melt-kneaded product into, for example, the fine pulverization system shown in FIG. In the fine pulverization system, the coarsely pulverized product is introduced into the raw material supply machine 433, and is introduced from the raw material supply machine 433 into the air classifier 432 through the transport pipe 434. The air classifier 432 includes a center core 440 and a separate core 441 in a collector 438. In the air classifier 432, the coarsely pulverized material is classified into finely pulverized material and coarse particles by the secondary air introduced from the secondary air supply port 443. The classified finely pulverized product is discharged out of the system via a discharge pipe 442 and introduced into a raw material hopper 380 shown in FIG. The classified coarse particles are introduced into a fine pulverizer (for example, a jet mill) 431 via a main body hopper 439. In the fine pulverizer, coarse particles are supplied to a nozzle 435 into which compressed air is introduced, the coarse particles are conveyed by high-speed compressed air, collide with a collision plate 436 in the pulverization chamber 437, and finely pulverized. The finely pulverized particles are introduced into the air classifier 432 via the transport pipe 434 and classified again.

  The weight average particle size of the finely pulverized product is 3.5 to 9.0 μm, and the proportion of particles having a particle size of 4.00 μm or less is 50 to 80% by number. It is preferable for efficiently performing the surface treatment at the same time in the surface modifying apparatus.

  After the pulverization step, it is preferable to further obtain a classified product having a weight average particle size of 3.0 to 7.0 μm using an apparatus for performing surface modification using classification and mechanical impact force.

  In the present invention, a surface modification apparatus as shown in FIG. 1 capable of performing classification and surface modification treatment at the same time is preferably used. As the surface modification device, a batch-type device is preferable in which the step of classifying and removing fine powder and ultrafine powder contained in the finely pulverized product and the step of surface modification treatment of particles containing the finely pulverized product are performed simultaneously.

  The surface reforming apparatus includes a cylindrical main body casing, a charging unit for charging the finely pulverized material into the main body casing, and fine powder and ultrafine powder having a predetermined particle diameter or less from the finely pulverized material charged into the main body casing. Classification means having a classification rotor rotating in a predetermined direction for continuous removal to the outside. The fine powder and the ultra fine powder removed by the classification means are discharged from the fine powder discharge portion outside the main body casing, and the particles contained in the fine pulverized product from which the fine powder and the ultra fine powder have been removed are used by mechanical impact force. A surface modification means having a dispersion rotor that rotates in the same direction as the rotation direction of the classifying rotor for surface modification treatment is provided. Cylindrical guide means for forming a first space and a second space in the main casing. At least a toner particle discharging unit for discharging the toner particles subjected to the surface modification treatment by the dispersion rotor to the outside of the main body casing. The first space provided between the inner wall of the main body casing and the outer wall of the cylindrical guide means is a space for guiding the finely pulverized product and the surface-modified particles to the classification rotor. The second space is a space for treating the finely pulverized product from which the fine powder and the ultrafine powder have been removed and the surface-modified particles with a dispersion rotor.

In the present invention, fine particles having a predetermined particle diameter or less and ultrafine particles are removed to a predetermined amount or less and surface-modified toner particles are obtained by the following steps.
In the surface reforming apparatus, the finely pulverized material charged into the main body casing from the charging portion is introduced into the first space, and the classification means removes fine powder and ultrafine powder having a predetermined particle diameter or less to remove the fine powder. The finely pulverized product from which fine powder and ultrafine powder have been removed is moved to the second space while being continuously discharged. The surface of the finely pulverized product is subjected to surface modification treatment by the dispersion rotor, and the finely pulverized product containing the surface-modified particles is circulated through the first space and the second space. The classification and the surface modification treatment are repeated.

FIG. 1 is a schematic cross-sectional view showing a preferred example of a batch type surface reforming apparatus used in the present invention.
The batch type surface reforming apparatus shown in FIG. 1 includes a cylindrical main body casing 30, a top plate 43 installed so as to be openable and closable at the upper part of the main body casing; a fine powder discharge section 44 having a fine powder discharge casing and a fine powder discharge pipe; A cooling jacket 31 through which cooling water or antifreeze can be passed; a plurality of square disks 33 on the upper surface, which are attached to the central rotating shaft in the main body casing 30 as surface modification means, in a predetermined direction Dispersion rotor 32, which is a disk-like rotating body that rotates at high speed; liner 34 that is fixedly arranged around dispersion rotor 32 at a constant interval and that has a large number of grooves on the surface facing dispersion rotor 32 A classification rotor 35 for continuously removing fine powder and ultrafine powder of a predetermined particle size or less in the finely pulverized product; cold air inlet for introducing cold air into the main body casing 30; 6; a charging pipe having a raw material charging port 37 and a raw material supplying port 39 formed on the side surface of the main body casing 30 for introducing finely pulverized material (raw material); toner particles after the surface modification treatment are out of the main body casing 30 Product discharge pipe having a product discharge port 40 and a product extraction port 42 for discharging; openable and closable provided between the raw material input port 37 and the raw material supply port 39 so that the surface modification time can be freely adjusted A raw material supply valve 38; and a product discharge valve 41 installed between the product discharge port 40 and the product extraction port 42.

2A and 2B are views for explaining an angle θ between the input pipe of the input section and the fine powder discharge pipe of the fine powder discharge section, and is an outline of the batch type surface reforming apparatus of FIG. It is a typical top view projection (horizontal projection view).
In the top view of the surface reforming apparatus shown in FIG. 2, a straight line extending in the direction in which the finely pulverized product is charged into the first space 47 from the center position S1 of the input tube of the pulverized product input unit 37 is L1, and the fine powder discharge unit. 44, the angle θ formed by the straight line L1 and the straight line L2 is 210 to 210 with respect to the rotation direction of the classifying rotor 35. 330 degrees.

  FIG. 3 is a schematic perspective view for explaining the positional relationship between the input pipe of the input section and the fine powder discharge pipe of the fine powder discharge section of the batch type surface reforming apparatus, and FIG. It is a figure for demonstrating the positional relationship with a fine powder discharge pipe. The fine powder discharge pipe has a fine powder discharge port 45 for discharging fine powder and ultrafine powder removed by the classification rotor 35 to the outside of the apparatus.

  The surface of the liner 34 preferably has a groove as shown in FIGS. 16A and 16B in order to efficiently modify the surface of the toner particles.

  As shown in FIGS. 6A and 6B, the number of the rectangular disks 33 is preferably an even number in consideration of the rotational balance. 6A and 6B are explanatory diagrams of the rectangular disk 33. FIG. As shown in FIGS. 2A and 2B, the rotation direction of the dispersion rotor 32 is usually counterclockwise when viewed from the top surface of the apparatus.

  The classifying rotor 35 shown in FIGS. 1, 5 and 8 is preferably rotated in the same direction as the rotation direction of the dispersion rotor 32 in order to increase the efficiency of classification and the surface modification efficiency of the toner particles.

The batch type surface modification apparatus further includes, as shown in FIGS. 7A and 7B, a cylindrical guide ring 36 as a guide means having an axis perpendicular to the top plate 43. Have in. The guide ring 36 has an upper end spaced apart from the top plate by a predetermined distance, and the guide ring is fixed to the main body casing 30 by a support so as to cover at least a part of the classification rotor 36. The lower end of the guide ring 36 is provided at a predetermined distance from the rectangular disk 33 of the dispersion rotor 32.
In the batch type surface reforming apparatus, a space between the classification rotor 35 and the dispersion rotor 32 is divided into a first space 47 outside the guide ring 36 and a second space 48 inside the guide ring 36. Divided by the guide ring 36. The first space 47 is a space for guiding the finely pulverized product and the surface-modified particles to the classification rotor 35, and the second space guides the pulverized product and the surface-modified particles to the dispersion rotor. It is a space for. A gap between the plurality of rectangular disks 33 installed on the dispersion rotor 32 and the liner 34 is a surface modification zone 49, and the classification rotor 35 and a peripheral portion of the classification rotor 35 are classification zones 50. .

  The classification and surface modification treatment in the batch type surface modification apparatus will be described in detail below.

  As shown in FIG. 8, the finely pulverized product introduced into the raw material hopper 380 passes through the quantitative feeder 315, enters the apparatus from the raw material supply port 37 through the raw material supply valve 38 through the raw material supply port 37. Supplied. In the surface reforming apparatus, the cold air generated by the cold air generating means 319 is supplied into the main body casing from the cold air introduction port 46, and the cold water from the cold water generating means 320 is supplied to the cold water jacket 31, Adjust the temperature to a predetermined temperature. The supplied finely pulverized product swirls in the first space 47 outside the cylindrical guide ring 36 by the swirl flow formed by the suction air volume by the blower 364, the rotation of the dispersion rotor 32 and the rotation of the classification rotor 35. However, the classification process is performed by reaching the classification zone 50 in the vicinity of the classification rotor 35. Since the direction of the swirl flow formed in the main body casing 30 is the same as the rotation direction of the dispersion rotor 32 and the classification rotor 35, it is counterclockwise as seen from the upper surface of the apparatus as shown in FIG.

  Fine powder and super fine powder to be removed by the classification rotor 35 are sucked from the slits (see FIG. 5) of the classification rotor 35 by the suction force of the blower 364 and are passed through the fine powder discharge port 45 and the cyclone inlet 359 of the fine powder discharge pipe. 369 and bug 362. The finely pulverized product from which fine powder and ultrafine powder have been removed reaches the surface modification zone 49 in the vicinity of the dispersion rotor 32 via the second space 48, and the square disk 33 (hammer) provided in the dispersion rotor 32 and the main body. The surface modification treatment of the particles is performed by the liner 34 provided in the casing 30. The particles subjected to the surface modification reach the classification rotor 35 again while turning along the guide ring 36, and fine particles and ultrafine particles are removed from the surface-modified particles by the classification rotor 35 classification. . After the treatment for a predetermined time, the discharge valve 41 is opened, and the surface-modified toner particles from which fine powder and super fine powder having a predetermined particle diameter or less are removed are taken out from the surface reforming apparatus.

  The toner particles thus adjusted to a predetermined weight average particle diameter, adjusted to a predetermined particle size distribution, and further surface-modified to a predetermined average circularity are externally added by the toner particle transport means 321. It is transferred to the external additive process.

  The surface modification and classification may be performed separately. In such a case, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used. Further, if necessary, surface modification and spheronization treatment may be performed after using the surface modification apparatus. For the surface modification and spheronization treatment, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron Corporation is used.

  As a method of externally adding the external additive, a high-speed stirrer that gives a shearing force to the powder of a Henschel mixer, a super mixer, etc. is blended with a predetermined amount of classified toner and various known external additives. And a method of stirring and mixing.

  Below, the measuring method of the various physical properties used by this invention is demonstrated.

<Measurement of toner particle size distribution>
As a measuring device, Coulter Multisizer II (manufactured by Beckman Coulter, Inc.) is used. As the electrolytic solution, an about 1% NaCl aqueous solution is used. As the electrolytic solution, an electrolytic solution prepared using primary sodium chloride or, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan) can be used.
As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzenesulfone hydrochloric acid) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of the sample are measured for each channel by the measuring device using a 100 μm aperture as the aperture. The volume distribution and the number distribution are calculated. From these obtained distributions, the weight average particle diameter of the sample is determined. As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32-40.30 μm are used.

<Measurement of average circularity of toner and toner particles>
The average circularity of the toner and toner particles is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and is calculated using the following equation.

  Here, the “particle projected area” is the area of the binarized toner and toner particle image, and the “peripheral length of the particle projected image” is a contour obtained by connecting the edge points of the toner and toner particle image. It is defined as the length of the line. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  The average circularity in the present invention is an index indicating the degree of unevenness of the toner and toner particles. The average circularity is 1.000 when the toner and toner particles are perfectly spherical, and the average circularity becomes more complex as the surface shape becomes more complicated. Small value.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100” used for measuring the average circularity of the toner of the present invention calculates the circularity of each particle, and then calculates the average circularity. Divide 0.4 to 1.0 into equally divided classes every 0.01. The average circularity is calculated using the center value of the dividing points of each class and the number of particles divided into each class.

The number frequency cumulative value of the toner particle circularity is calculated using the data divided into the classes divided into 61 from the circularity of 0.4 to 1.0, and the number frequency cumulative value of 0.96 or more and 0.92 or less is calculated. did. In addition, the particle size distribution of the equivalent circle diameter is 2 in the range from 0.6 μm to 400 μm.
From the particle size frequency data divided into 26, the abundance of particles having a circle-equivalent diameter in the range specified in the present application was determined in number%.

As a specific method for measuring the average circularity using FPIA2100, 10 ml of ion-exchanged water from which impure solids are removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzenesulfonic acid, is used as a dispersant therein. After the salt is added, 0.02 g of toner and toner particles are further added and dispersed uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of the said dispersion liquid may not become 40 degreeC or more.
In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the in-machine temperature of the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.
At the time of measurement, the dispersion concentration is adjusted so that the concentration of toner and toner particles is 3000 to 10,000 / μl, and measurement is performed for 1000 or more particles. After the measurement, data having an equivalent circle diameter of less than 3 μm is cut using this data, and the average circularity of the toner and toner particles is obtained.

  Furthermore, the measuring device “FPIA-2100” used in the present invention improves the magnification of the processed particle image as compared with “FPIA-1000” conventionally used for calculating the shape of toner and toner particles. Further, the accuracy of the shape measurement has been improved by improving the processing resolution of the captured image (256 × 256 → 512 × 512), thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

<Measurement of maximum endothermic peak of release agent and toner, measurement of glass transition temperature of binder resin>
The glass transition temperature (Tg) of the binder resin is in accordance with ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by PerkinElmer), DSC2920 (manufactured by TA Instruments Japan) and the like. To measure. The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min within a measurement range of 30 to 200 ° C.

  In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the base line before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the binder resin.

  Further, an endothermic peak is obtained in the temperature range of 30 ° C. to 200 ° C. during this temperature raising process. Needless to say, the maximum endothermic peak is a temperature at which a maximum value is exhibited. When there are a plurality of peaks, the highest endothermic peak is the one having the highest height from the baseline in the region above the endothermic peak due to the resin.

<Molecular weight distribution of binder resin by GPC measurement>
The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.
The column was stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. About 50 to 200 μl of a THF sample solution of the resin is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. Made molecular weight 6 × 10 ² , 2.1 × 1
0 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4. It is appropriate to use 48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803 manufactured by Showa Denko KK , 804, 805, 806, and 807, and combinations of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters.

<Molecular weight distribution of release agent>
(GPC measurement conditions)
・ Apparatus: GPC-150C (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
・ Temperature: 135 ℃
Solvent: o-dichlorobenzene (0.1% ionol added)
-Flow rate: 1.0 ml / min.
-Sample: 0.4 ml injection of 0.15% sample The molecular weight calibration curve prepared from a monodisperse polystyrene standard sample was used in calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived | led-out from the Mark-Houwink viscosity formula.

<Measurement of number distribution particle size on toner particles of inorganic fine powder>
The number distribution particle size on the toner particle surface is measured using a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.). The photographing magnification is set to 100,000 times, and the photographed photograph is further doubled, and then 200 to 500 samples of each external additive particle covering the toner particle surface are randomly extracted from the photograph image. In extraction, elemental analysis is performed by EDX in advance, and after grasping what kind of particles each particle is in what shape, the maximum particle size is set as the major axis and the minimum particle size is set as the minor axis. And the distribution of the number particle diameter is obtained with the major axis as a reference.

<Measurement of transmittance in methanol 45 volume% aqueous solution>
(I) Preparation of toner dispersion An aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 20 mg of toner is impregnated on the liquid surface to cover the bottle. Thereafter, the mixture is shaken at 2.5S-1 for 5 seconds with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after 30 seconds is used as a dispersion for measurement.
(Ii) Transmittance measurement The dispersion obtained in (i) is placed in a 1 cm square quartz cell, and the transmittance at a wavelength of 600 nm of the dispersion after 10 minutes using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation) ( %).
Transmittance (%) = I / I0 × 100 (I: transmitted light beam I0: incident light beam)

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Resin A production example (hybrid resin)>
As a vinyl polymer component, 1.9 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.15 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide are put in a dropping funnel. It was. In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; 0 mol, 3.0 mol of terephthalic acid, 2.0 mol of trimellitic anhydride, 5.0 mol of fumaric acid and 0.2 g of dibutyltin oxide are put into a 4-liter 4-neck flask made of glass, a thermometer, a stirring rod, a condenser and nitrogen. The introduction tube was installed and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 150 ° C., the vinyl resin monomer and the polymerization initiator were added from the previous dropping funnel over 5 hours. And dripped. Next, the temperature was raised to 220 ° C. and reacted for 4.5 hours to obtain a hybrid resin.
Table 1 shows the results of molecular weight measurement by GPC (gel permeation chromatography). In Table 1, Mw is a weight average molecular weight, Mn is a number average molecular weight, and Mp is a peak molecular weight.

<Resin B production example (styrene acrylic resin production example)>
As a styrene acrylic resin component in 200 parts by weight of xylene, 70 parts by weight of styrene, 20 parts by weight of n-butyl acrylate, 10 parts by weight of monobutyl maleate, and 1 part by weight of di-t-butyl peroxide were thermometer and stainless steel stirred. It put into the 4-neck flask equipped with the stick | rod, the flow-down type | condenser, and the nitrogen introduction tube, and it was dripped, stirring at the temperature of 120 degreeC in the nitrogen atmosphere for 5 hours in the mantle heater. The reaction was conducted while refluxing xylene, and the solvent was distilled off under reduced pressure to obtain a styrene acrylic resin.
The results of molecular weight measurement by GPC (gel permeation chromatography) are shown in Table 1 as in the hybrid resin production example.

<Resin C production example (polyester resin production example)>
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 1.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.1 g of dibutyltin oxide are put into a 4-liter 4-neck flask made of glass, a thermometer, a stirring rod, a condenser and a nitrogen introducing tube. Was installed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 4.5 hours to obtain a polyester resin. The results of molecular weight measurement by GPC (gel permeation chromatography) are shown in Table 1 as in the hybrid resin production example.

<Toner Production Example 1>
-Hybrid resin 100 parts by mass-C.I. I. Pigment Blue 15: 3 5 parts by mass Normal paraffin wax (maximum thermal peak: 70 ° C.) 5 parts by mass Aluminum compound of di-tert-butylsalicylic acid (charge control agent) 1 part by mass They were mixed and melt kneaded at an arbitrary barrel temperature in a twin-screw extrusion kneader. After cooling, it is roughly crushed to about 1 to 2 mm using a hammer mill. In the first stage of pulverization, it is finely pulverized to a particle size of 10 μm or less at a processing speed of 40 kg per hour using a mechanical pulverizer. did. Furthermore, as a second stage, the finely pulverized product was again processed by a mechanical pulverizer at a processing speed of 80 kg per hour using a liner-rotor distance narrower than that of the first stage mechanical pulverizer. At this time, the exhaust temperature rose to 45 degrees. Subsequently, the obtained finely pulverized product is classified and spheroidized in an apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force, and is cyan-colored as toner particles having a weight average particle size distribution of 5.5 μm. Particles (classified product) were obtained. To 100 parts by mass of the obtained cyan-based colored particles (classified product), 1.5 parts by mass of the inorganic fine particles A1 shown in Table 2, 1.5 parts by mass of the inorganic fine particles B1, and 1.0 parts by mass of the inorganic fine particles C1 Were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to prepare toner 1.
The average circularity R of particles having an equivalent circle diameter (number basis) of 2.00 μm or more in this toner flow type particle image measuring device was 0.954. The weight average diameter was 5.5 μm.
In addition, the average circularity of each toner in the equivalent circle diameter range of circle equivalent diameter (number basis) of 2.00 μm or more and less than 3.00 μm, 3.00 μm or more and less than 6.92 μm, or 6.92 μm or more and less than 12.66 μm is , R (a) was 0.954, r (b) was 0.954, and r (c) was 0.957. The transmittance (%) in a 45% by volume methanol aqueous solution was 42%. In addition, Table 3 shows the coverage of external additives.

<Toner Production Example 2>
Except that the pulverization particle size by the first-stage mechanical pulverization method was adjusted to 20 μm or less, pulverization, classification, and spheroidization were performed in the same manner as in Toner Production Example 1, and cyan colored particles (
Classification product) was obtained. To 100 parts by mass of the obtained cyan-based colored particles (classified product), 1.5 parts by mass of the inorganic fine particles A1 shown in Table 2, 1.5 parts by mass of the inorganic fine particles B1, and 1.0 parts by mass of the inorganic fine particles C1 Were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to prepare toner 2. The weight average particle diameter of the toner 2 is 6.8 μm, and the physical properties of the toner such as circularity are summarized in Table 3.

<Toner Production Example 3>
Production Example 1 by adjusting the pulverization particle size by the first-stage mechanical pulverization method to 5 μm or less
On the other hand, grinding, classification, and spheronization were performed in the same manner as in Toner Production Example 1 except that the rotation speed of the classifying rotor was increased and the blower air volume was decreased in a device that simultaneously performs classification and surface modification using mechanical impact force As a result, cyan colored particles (classified product) were obtained as toner particles. The obtained cyan colored particles (classified product) were externally added and mixed in the same manner as in Toner Production Example 1 except that the inorganic fine particles C1 were changed to 2.0 parts by mass to obtain a toner 3. Table 3 summarizes the physical properties of the toner such as the particle diameter and circularity of the toner 3.

<Toner Production Example 4>
Compared with Toner Production Example 1, the rotating speed of the dispersion rotor of the apparatus that performs classification and surface modification using mechanical impact force is increased, the processing time is increased, the amount of finely pulverized material is suppressed, and the temperature of cold air is increased. Toner particles were obtained in the same manner as in Toner Production Example 1 except that the toner particles were produced under conditions that facilitated spheroidization. The obtained cyan colored particles (classified product) were externally added and mixed in the same manner as in Toner Production Example 1 except that the inorganic fine particles C1 were changed to 0.2 parts by mass to obtain a toner 4. Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 4.

<Toner Production Example 5>
Conditions for the first stage of fine pulverization using an air jet type pulverizer, lowering the rotational speed of the dispersion rotor of the apparatus that simultaneously performs classification and surface modification using mechanical impact force, and making it less likely to be spherical than Toner Production Example 1 Toner particles were obtained in the same manner as in Toner Production Example 1 except that The toner particles were instantly spheroidized with hot air to obtain cyan colored particles (classified product). The obtained cyan colored particles (classified product) were externally added and mixed in the same manner as in Toner Production Example 1 except that the inorganic fine particles C1 were changed to 1.5 parts by mass to obtain a toner 5. Table 3 summarizes the physical properties of the toner, such as the particle diameter and circularity of the toner 5.

<Toner Production Example 6>
-Preparation of resin particle dispersion 1 Styrene 370 g
30g of n-butyl acrylate
Acrylic acid 6g
24g dodecanethiol
Carbon tetrabromide 4g
A mixed solution in which the above was mixed and dissolved was obtained. This mixed solution was dispersed and emulsified in a flask in which 6 g of a nonionic surfactant and 10 g of an anionic surfactant were dissolved in 550 g of ion-exchanged water. While slowly mixing this for 10 minutes, 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thus, a resin particle dispersion 1 was prepared by dispersing resin particles having an average particle diameter of 150 nm, a glass transition point of 62 ° C., and a weight average molecular weight (Mw) of 12,000.

-Preparation of resin particle dispersion 2 280 g of styrene
120g of n-butyl acrylate
Acrylic acid 8g
A mixed solution in which the above was mixed and dissolved was obtained. This mixed solution was dispersed and emulsified in a flask in which 6 g of a nonionic surfactant and 12 g of an anionic surfactant were dissolved in 550 g of ion-exchanged water. While slowly mixing this for 10 minutes, 50 g of ion-exchanged water in which 3 g of ammonium persulfate was dissolved was added. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thus, a resin particle dispersion 2 was prepared by dispersing resin particles having an average particle diameter of 110 nm, a glass transition point of 55 ° C., and a weight average molecular weight (Mw) of 550,000.

Preparation of release agent particle dispersion 1 Polypropylene wax (melting point 85 ° C.) 50 g
Anionic surfactant 5g
200g of ion exchange water
The above was heated to 95 ° C. and dispersed using a homogenizer or the like, then dispersed with a pressure discharge type homogenizer, and a release agent particle dispersion 1 in which a release agent having an average particle diameter of 570 nm was dispersed was obtained. Prepared.

-Preparation of colorant particle dispersion 1 C.I. I. Pigment Blue 15: 3 20g
Anionic surfactant 2g
Ion exchange water 78g
The above was mixed and dispersed for 10 minutes at an oscillation frequency of 26 kHz using an ultrasonic cleaner to prepare a colorant particle dispersion (anionic) 1.

-Preparation of liquid mixture Resin particle dispersion 1 180 g
Resin particle dispersion 2 80g
Colorant particle dispersion 1 30 g
Release agent particle dispersion 1 50 g
The above was mixed in a round stainless steel flask using a homogenizer or the like and dispersed to prepare a mixed solution.

-Formation of Aggregated Particles 1.2 g of a cationic surfactant as an aggregating agent was added to the above mixed solution, and the mixture was heated to 50 ° C. while stirring the inside of the flask in a heating oil bath. After maintaining at 50 ° C. for 1 hour, it was confirmed by observation with an optical microscope that aggregated particles having a weight average particle diameter of about 4.8 μm were formed.

-Fusion Then, 3 g of anionic surfactant was added here, and then the stainless steel flask was sealed, heated to 105 ° C while continuing stirring using a magnetic seal, and held for 3 hours. Then, after cooling, the reaction product was filtered, sufficiently washed with ion exchange water, and dried to obtain cyan colored particles.
100 parts by mass of the obtained cyan colored particles (classified product), 0.3 parts by mass of the inorganic fine particles A1 shown in Table 2, 0.8 parts by mass of the inorganic fine particles B1, and 1.0 parts by mass of the inorganic fine particles C2 Were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to prepare toner 6. Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 6.

<Toner Production Example 7>
CI pigment blue 15: 3 as a pigment is changed from 5 parts by weight CI pigment yellow 74 to 8 parts by weight, and a classification rotor for an apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force on Toner Production Example 1 Yellow colored particles (classified products) were obtained as toner particles in substantially the same manner as in Toner Production Example 1 except that the rotational speed was lowered and the blower air volume was increased. 100 parts by mass of yellow colored particles (classified product), 3.0 parts by mass of the inorganic fine particles A1 and 5.0 parts by mass of the inorganic fine particles B1 shown in Table 2, Henschel mixer (FM-75 type, Mitsui Miike Chemical Industries, Ltd.) (Made by Co., Ltd.) to prepare toner 7. Table 3 summarizes the physical properties of the toner, such as the particle diameter and circularity of the toner 7.

<Toner Production Example 8>
The pigment is changed from CI pigment blue 15: 3 to CI pigmentlet 122, the binder resin is changed to resin C, and no aluminum compound (charge control agent) of di-tert-butylsalicylic acid is added. On the other hand, magenta coloration was carried out in substantially the same manner as in Toner Production Example 1 except that the speed of the classifying rotor was reduced and the blower air flow rate was increased by simultaneously performing classification and surface modification using mechanical impact force. Particles (classified product) were obtained. Henschel mixer 100 parts by mass of magenta colored particles (classified product), 0.2 parts by mass of inorganic fine particles A2 shown in Table 2, 0.08 parts by mass of inorganic fine particles B1, and 2.0 parts by mass of inorganic fine particles C2 (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to prepare toner 8. Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 8.

<Toner Production Example 9>
Except for changing the pigment from CI pigment blue 15: 3 to carbon black and lowering the rotation speed of the classification rotor for the toner manufacturing example 1 that simultaneously performs classification and surface modification using mechanical impact force. Black colored particles (classified product) were obtained in substantially the same manner as in Toner Production Example 1. Henschel mixer with 100 parts by mass of black colored particles (classified product), 1.5 parts by mass of inorganic fine particles A3 shown in Table 2, 0.1 parts by mass of inorganic fine particles B2, and 2.5 parts by mass of inorganic fine particles C1 (Toner 9 was prepared by mixing with FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). The physical properties of the toner, such as the particle size and circularity of the toner 9, are summarized in Table 3.

<Toner Production Example 10>
To 100 parts by mass of the cyan colored particles (classified product) obtained in Toner Production Example 1, 1.0 part by mass of the inorganic fine particles A4 shown in Table 2, 0.5 part by mass of the inorganic fine particles B1, and 1. Toner 10 was prepared by mixing 0 part by mass with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). Table 3 summarizes toner physical properties such as toner particle diameter and circularity.

<Toner Production Example 11>
To 100 parts by mass of cyan colored particles (classified product) in Toner Production Example 10, 2.5 parts by mass of inorganic fine particles A5 and 5.5 parts by mass of inorganic fine particles B3 shown in Table 2 were added, and a Henschel mixer (FM-75 type) was added. The toner 11 was prepared by mixing with Mitsui Miike Chemical Co., Ltd.). The physical properties of the toner, such as the particle diameter and circularity of the toner 11, are summarized in Table 3.

<Toner Production Example 12>
100 parts by mass of cyan-based colored particles (classified product) in Toner Production Example 10, 0.5 parts by mass of inorganic fine particles A6 shown in Table 2, 2.0 parts by mass of inorganic fine particles B4, and 1.5 parts by mass of inorganic fine particles D1 Toner 12 was prepared in the same manner as in Production Example 10. Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 12.

<Toner Production Example 13>
As in Production Example 10, 100 mass parts of cyan colored particles (classified product) in Toner Production Example 10 were added 5.0 mass parts of inorganic fine particles A7 and 5.0 mass parts of inorganic fine particles B5 shown in Table 2. Thus, toner 13 was prepared. Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 13.

<Toner Production Example 14>
In the same manner as in Production Example 10, adding 5.5 parts by mass of inorganic fine particles A1 and 1.2 parts by mass of inorganic fine particles B1 shown in Table 2 to 100 parts by mass of black colored particles (classified product) in Toner Production Example 9. In this way, Toner 14 was prepared. Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 14.

<Toner Production Example 15>
The cyan colored particles obtained in Toner Production Example 6 were further classified with an elbow jet classifier to obtain an intermediate powder. To 100 parts by mass of the obtained medium powder, 1.0 part by mass of inorganic fine particles A4 shown in Table 2, 0.5 part by mass of inorganic fine particles B1, and 1.0 part by mass of inorganic fine particles C1 are added, and a Henschel mixer is added. Toner 15 was prepared by mixing with FM-75 type (Mitsui Miike Chemical Co., Ltd.). Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 15.

<Toner Production Example 16>
The same procedure as in Production Example 6 was conducted except that, in Toner Production Example 6, the stirring speed during formation of the aggregated particles and the heating rate up to 50 ° C. were adjusted to obtain aggregated particles having a weight average particle diameter of 7.5 μm. Cyan colored particles were obtained. To 100 parts by mass of the obtained cyan colored particles (classified product), 1.0 part by mass of inorganic fine particles A4 shown in Table 2, 0.5 part by mass of inorganic fine particles B1, and 1.0 part by mass of inorganic fine particles C1 The toner 16 was prepared by mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 16.

<Toner Production Example 17>
The binder resin was changed to resin C, polypropylene wax (melting point 138 ° C.) was added as a release agent, kneaded and coarsely pulverized in the same manner as in Production Example 1, and finely pulverized to 10 μm or less with an air jet pulverizer. After being obtained, it was classified with an elbow jet classifier to obtain an intermediate powder. To 100 parts by mass of the obtained cyan medium powder, 1.0 part by mass of inorganic fine particles A4 shown in Table 2 and 0.5 part of inorganic fine particles B1 are shown.
Toner 17 was prepared by adding parts by mass and 1.0 part by mass of inorganic fine particles C1 and mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). Table 3 summarizes toner physical properties such as the particle diameter and circularity of the toner 17.

<Toner Production Example 18>
The mixture was kneaded and coarsely pulverized in the same manner as in Toner Production Example 1, and finely pulverized with an air jet type pulverizer. Classification was performed with an elbow jet classifier to obtain a medium powder having a weight average particle diameter of 7.5 μm. The obtained intermediate powder was spheroidized with hot air to obtain cyan colored particles (classified product).
To 100 parts by mass of the obtained cyan colored particles (classified product), 1.0 part by mass of inorganic fine particles A4 shown in Table 2, 0.5 part by mass of inorganic fine particles B1, and 1.0 part by mass of inorganic fine particles C1 The toner 18 was prepared by mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). Table 3 summarizes the physical properties of the toner, such as the particle diameter and circularity of the toner 18.

<Toner Production Example 19>
Adjusting the pulverization particle size by the first-stage mechanical pulverization method to 5 μm or less, and with respect to Production Example 3, the classification rotor rotation speed of the apparatus that simultaneously performs classification and surface modification using mechanical impact force In the same manner as in Toner Production Example 1, except that it was further increased and the blower air volume was decreased, pulverization, classification,
The toner was spheroidized to obtain cyan colored particles (classified product) as toner particles having a weight average particle diameter of 2.9 μm.
To 100 parts by mass of the obtained cyan colored particles (classified product), 1.0 part by mass of inorganic fine particles A4 shown in Table 2, 0.5 part by mass of inorganic fine particles B1, and 1.0 part by mass of inorganic fine particles C1 The toner 19 was prepared by mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). The physical properties of the toner, such as the particle diameter and circularity of the toner 19, are summarized in Table 3.

<Example of production of magnetic fine particle dispersed resin core (A)>
3.5% by mass and 2.0% by mass of silane with respect to magnetite fine particles (specific resistance 5 × 10 ⁷ (Ω · cm)) and hematite fine particles (specific resistance 3 × 10 ⁸ (Ω · cm)), respectively. A system coupling agent (3- (2-aminoethylaminopropyl) trimethoxysilane) was added, and the mixture was stirred and mixed at a high speed at 120 ° C. or higher in a container to make each fine particle lipophilic.
-Phenol 10 parts by mass-Formaldehyde solution (formaldehyde 37% by weight aqueous solution) 6 parts by mass-The above treated magnetite fine particles 74 parts by mass-The above treated hematite fine particles 10 parts by mass The above materials, 5 parts by mass of 28% by mass ammonia water and water 10 parts by mass were placed in a flask, heated and maintained at 85 ° C. over 45 minutes with stirring and mixing, and cured by polymerization reaction for 3 hours. Then, it cooled to 30 degreeC, after adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin core (A) in which magnetic fine particles were dispersed. The obtained magnetic fine particle dispersed resin core had a number average particle diameter of 35 μm and a BET specific surface area of 0.07 (m ² / g).

<Example of production of magnetic fine particle dispersed resin core (B)>
At a molar _ratio, Fe ₂ O 3 = 54 mol%, CuO = 16 mol%, were weighed such that the MgO = 30 mol%, for 8 hours mixed using a ball mill. This was calcined at 900 ° C. for 2 hours, pulverized with a ball mill, and further granulated with a spray dryer. This was sintered at 1150 ° C. for 10 hours, pulverized, and further classified to obtain a magnetic fine particle dispersed resin core (B). The obtained magnetic fine particle dispersed resin core (B) had a number average particle diameter of 35 μm and a BET specific surface area of 0.15 (m ² / g).

<Magnetic carrier production example 1>
The above-mentioned magnetic fine particle dispersed resin core (A) was put into a coater, and humidified nitrogen was introduced to adjust the moisture content to 0.3 mass%. Thereafter, 3% by mass of γ-aminopropyltrimethoxysilane diluted with a toluene solvent was applied to the core surface while continuously applying a shear stress. This is carried out while volatilizing the solvent under a dry nitrogen stream, and a mixture of 0.5% by mass of a straight silicone resin whose substituents are all methyl groups and 0.015% by mass of γ-aminopropyltrimethoxysilane is magnetically treated with toluene as a solvent. A fine particle dispersed resin core was coated. This was carried out while volatilizing the solvent under a dry nitrogen stream. Further, this magnetic coat carrier was baked at 140 ° C., and the aggregated coarse particles were cut with a 100 mesh sieve, and then fine particles and coarse particles were removed with a multi-division wind classifier to adjust the particle size distribution. The magnetic carrier 1 was then conditioned for 100 hours in a hopper maintained at 23 ° C. and 60%.

<Magnetic carrier production example 2>
20 parts of toluene, 20 parts of butanol, 20 parts of water, and 40 parts of ice are placed in a four-necked flask, and a mixture 40 of 15 moles of CH ₃ SiCl _{3 and} 10 moles of (CH ₃ ) ₂ SiCl ₂ is stirred.
Then, after further stirring for 30 minutes, a condensation reaction was performed at 60 ° C. for 1 hour. Thereafter, the siloxane was thoroughly washed with water and dissolved in a toluene-methyl ethyl ketone-butanol mixed solvent to prepare a silicone varnish having a solid content of 10%.
In this silicone varnish, 2.0 parts of ion-exchanged water and 2.0 parts of a curing agent represented by the following formula (II) and 3.0 parts of the following formula (III) with respect to 100 parts of the siloxane solid mold A carrier coating solution was prepared by simultaneously adding an aminosilane coupling agent represented by

  This carrier coating solution was applied to 100 parts of the above-described magnetic carrier core (B) with an applicator (Okada Seiko Co., Ltd .: Spiracoater) so that the resin coating amount was 1.0 part, and the magnetic carrier 2 was used as a silicone resin-coated carrier. Got.

<Example 1>
Cyan developer 1 was prepared by mixing toner 1 and magnetic carrier 1 with a V-type blender so that the toner concentration was 10% with respect to the magnetic carrier.
Two-component development evaluation was performed using Developer 1.
Developer 1 is filled in the developer, and iRC-3200 (manufactured by Canon Inc.) is used as an image forming apparatus.
At the same time, it was left overnight at room temperature and normal humidity (23 ° C., 50% RH). Thereafter, while continuously supplying the toner so that the toner density becomes constant, the copying machine plain paper (80 g / m ² ) is used as the transfer material, and the evaluation image sampling described later is performed, and the amount of toner applied on the paper is adjusted. The development contrast was adjusted to 0.55 mg / cm ^2, and 5000 images with an image area ratio of 5% were output in the monochrome mode. Next, the image forming apparatus is moved together with the developing device to a low temperature and low humidity (15 ° C., 10% RH) environment and left for one week, and an image 3000 having an image area ratio of 3% is sampled while sampling an evaluation image to be described later. Output. Furthermore, it moved to a high-temperature and high-humidity (30 ° C., 80% RH) environment together with the image forming apparatus and left to stand for one week, and 1000 images with an image area ratio of 10% were output while sampling an evaluation image described later. .

  Next, each evaluation item and evaluation method will be described.

(1) Dot reproducibility An image of an isolated dot pattern with a small diameter (45 μm) as shown in FIG. Was observed with a microscope, and dot reproducibility was evaluated as follows.
(Evaluation criteria)
A: 2 or less defects / 100 defects B: 3-5 defects / 100 defects C: 6-10 defects / 100 defects D: 11 defects / 100 defects / 100 defects

(2) Durability and stability On the 10th and 900th sheets in a high-temperature and high-humidity environment, an 80 μm × 50 μm checkered pattern image shown in FIG. 13 is output, and the number of defects in 100 solid portions is observed with a microscope. The increase in the number of defects from the 10th sheet to the 900th sheet was evaluated as follows as an index of the durability stability of the toner.
(Evaluation criteria)
A: Increase in the number of defects is 0 to 2 B: Increase in the number of defects is 3 to 5 C: Increase in the number of defects is 6 to 10 D: Increase in the number of defects is 11 or more

(3) Fine line reproducibility Striped thin line images as shown in FIG. 14 were output on the 2500th sheet in a low temperature and low humidity environment and on the 800th sheet in a high temperature and high humidity environment. (FIG. 14 is a latent image having a latent image portion width of 2 dots and a non-latent image portion width of 5 dots at a resolution of 600 dpi.)
Then, five locations were selected at random from each image, and evaluation was made based on the absolute value of the difference between the average thin line width of the image and the theoretical latent image portion width.
(Evaluation criteria)
A: 0 μm or more and less than 7 μm B: 7 μm or more and less than 15 μm C: 15 μm or more and less than 20 μm D: 20 μm or more

(4) Image density A solid image was output on the 4500th sheet in a room temperature and humidity environment, and the image density was measured. The image density was measured with the above-mentioned X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).
(Evaluation criteria)
A: Very good (over 1.60)
B: Good (from 1.40 to less than 1.60)
C: Normal (1.20 or more, less than 1.40)
D: Bad (less than 1.20)

(5) Carriage fog After the image output in the low temperature and low humidity environment is completed, a solid white image is output, the image forming apparatus is forcibly stopped during the solid white image formation, and the solid white on the electrophotographic photosensitive drum is The image portion was taped with a transparent polyester adhesive tape and attached to a white paper. Only the unused tape was stuck on the same white paper, and the whiteness of each was measured, and the fog was calculated from the difference in whiteness. The whiteness was measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku) equipped with an amber filter.
(Evaluation criteria)
A: Very good (less than 2.0%)
B: Good (2.0% or more, less than 3.0%)
C: Normal (3.0% or more and less than 5.0%)
D: Poor (5.0% or more)

(6) Transferability A solid image is output on the 2900th sheet in a low-temperature and low-humidity environment and on the 950th sheet in a high-temperature and high-humidity environment, and the transfer residual toner on the electrophotographic photosensitive drum at the time of solid image formation is transparent. The concentration difference was calculated by subtracting the concentration of the adhesive tape only on the paper from the concentration of the adhesive tape taped and peeled off with a polyester adhesive tape. And it judged as follows from the value of the density difference. The density was measured with the X-Rite color reflection densitometer described above.
(Evaluation criteria)
A: Very good (less than 0.05)
B: Good (less than 0.05 to 0.1)
C: Normal (less than 0.1-0.2)
D: Bad (over 0.2)

(7) Missing transfer The 50th sheet under normal temperature and humidity conditions is replaced with a unit in which the diameter of the intermediate transfer belt drive roller is adjusted so that there is no difference in peripheral speed between the photosensitive drum and the intermediate transfer member. A line image is formed in the A4 size center part in the paper passing direction, and the line center part on the image is not transferred and only the edge part is transferred. did. FIG. 15 shows a latent image in which the latent image portion width is 2, 4, 6, 8, and 10 dot lines at a resolution of 600 dpi, and each has a non-latent image portion width of 50 dots between the lines. Then, it was confirmed by visual observation and observation with a 20 × magnifier which dot width line of the output image was first subjected to a void.
(Evaluation criteria)
A: Very good (no voids at all)
B: Good (2 dot line, a level where a slight drop is confirmed by observation with a magnifying glass)
C: Normal (a level at which a hollow is visually confirmed with a 2-dot line)
D: Poor (at a level where it is visually confirmed that there is a void in 4 dot lines or more)

(8) Poor charging (collapse ghost) in a system that collects transfer residual toner simultaneously with development
On the 500th sheet in a high-temperature and high-humidity environment, the line image shown in FIG. Is output. Then, it is visually confirmed whether or not a line-like image due to poor charging (a hollow ghost) appears at an unexposed position after one round of the photosensitive drum from the end of the line image.
(Evaluation criteria)
A: Good (no voids at all)
B: Normal (2 dot line ghost appearance probability is less than 20%, practically no problem level)
C: Poor (2 dot line ghost appearance probability is 20% or more, which is a practical problem)

(9) Insufficient cleaning After image output under high temperature and high humidity environment, a cleaning blade is assembled in the developing device, and further 1000 images with an image area ratio of 10% are output. Was seen on the image, it was determined that a cleaning failure occurred.
(Evaluation criteria)
A: Very good (no image defects at all)
B: Good (2 to 3 spots are formed)
C: Normal (slightly spotted or streaky pattern occurs)
D: Poor (spotted, streaky pattern, density unevenness occurs)

(10) Fixable Area Using a laser jet 4100 (manufactured by Hewlett Packard) fixing machine, a fixing test was performed in a state where the fixing unit was modified so that the fixing temperature could be manually set. Developer 1 is filled in a developing device, and an image forming apparatus is iRC-3200 (manufactured by Canon Inc.). The development contrast was adjusted to ² mg / cm ² to create an unfixed image. An image is formed on A4 (TKCLA4 which is a CLC recommended paper) with an image area ratio of 25%. In a room temperature and normal humidity environment (23 ° C./60%), the temperature range was raised from 120 ° C. by 10 ° C., and the temperature range where no offset or wrapping occurred was defined as the fixable region.
(Evaluation criteria)
A: The fixing width is 50 ° C. or more.
B: The fixing width is 40 ° C. or more and less than 50 ° C.
C: The fixing width is 20 ° C. or more and less than 40 ° C.
D: The fixing width is less than 20 ° C.

<Example 2>
In the same manner as in Example 1, the toner 2 and the magnetic carrier 1 were mixed to prepare a cyan developer 2.

<Example 3>
In the same manner as in Example 1, the toner 3 and the magnetic carrier 1 were mixed to prepare a cyan developer 3.

<Example 4>
In the same manner as in Example 1, the toner 4 and the magnetic carrier 1 were mixed to produce a cyan developer 4.

<Example 5>
In the same manner as in Example 1, the toner 5 and the magnetic carrier 1 were mixed to produce a cyan developer 5.

<Example 6>
In the same manner as in Example 1, the toner 6 and the magnetic carrier 1 were mixed to prepare a cyan developer 6.

<Example 7>
In the same manner as in Example 1, toner 7 and magnetic carrier 1 were mixed to prepare yellow developer 1.

< Reference Example 1 >
In the same manner as in Example 1, the toner 8 and the magnetic carrier 1 were mixed to prepare the magenta developer 1.

< Reference Example 2 >
In the same manner as in Example 1, the black developer 1 was prepared by mixing the toner 9 and the magnetic carrier 1.

<Example 8 >
Toner 10 and magnetic carrier 1 so that the toner concentration is 10% with respect to the magnetic carrier.
Were mixed with a V-type blender to prepare cyan developer 7.

< Reference Example 3 >
In the same manner as in Example 10, the cyan developer 8 was prepared by mixing the toner 11 and the magnetic carrier 1.

< Reference Example 4 >
In the same manner as in Example 10, the toner 12 and the magnetic carrier 1 were mixed to prepare a cyan developer 9.

< Reference Example 5 >
In the same manner as in Example 10, the cyan developer 10 was prepared by mixing the toner 13 and the magnetic carrier 1.

< Reference Example 6 >
Toner 14 and magnetic carrier 2 so that the toner concentration is 10% with respect to the magnetic carrier.
Were mixed with a V-type blender to prepare a black developer 2.

<Comparative Example 1>
In the same manner as in Example 14, the toner 15 and the magnetic carrier 2 were mixed to produce a cyan developer 11.

<Comparative example 2>
In the same manner as in Example 14, the cyan developer 12 was prepared by mixing the toner 16 and the magnetic carrier 2.

<Comparative Example 3>
In the same manner as in Example 14, the cyan developer 13 was prepared by mixing the toner 17 and the magnetic carrier 2.

<Comparative example 4>
In the same manner as in Example 14, the cyan developer 14 was prepared by mixing the toner 18 and the magnetic carrier 2.

<Comparative Example 5>
In the same manner as in Example 14, the cyan developer 15 was prepared by mixing the toner 19 and the magnetic carrier 2.

In the method for producing a color toner according to the present invention, the finely pulverized product is classified and surface-modified to be used in a process for obtaining surface-modified toner particles having a suitable particle size distribution. It is a schematic sectional drawing of an example of a surface modification apparatus. (A) is a top view (horizontal projection view) of the surface modification apparatus shown in FIG. 1, and (B) is another top view. It is a partial schematic perspective view of the surface modification apparatus shown in FIG. (A) is a figure for demonstrating the position of the fine powder discharge pipe with respect to the fine powder discharge casing of the surface modification apparatus shown in FIG. 1, (B) is with respect to the fine powder discharge casing of the surface modification apparatus shown in FIG. It is a figure for demonstrating the other position of a fine powder discharge pipe. (A) is a schematic horizontal projection surface view of a classification rotor, (B) is a schematic sectional drawing of a classification rotor. (A) is a horizontal projection plane view of the distributed rotor, and (B) is a schematic vertical projection plane view of the distributed rotor. (A) is a figure for demonstrating the diameter of a guide ring, (B) is a perspective view of the support body of a guide ring and a guide ring. FIG. 4 is a partial flowchart for explaining a toner manufacturing method of the present invention. It is a figure for demonstrating an example of the flow for manufacturing a fine ground material. FIG. 2 is a schematic explanatory diagram of a system for collecting transfer residual toner simultaneously with development of the present invention. 1 is a schematic explanatory diagram of a general image forming apparatus. It is a schematic diagram which shows the isolated dot image for evaluating the dot reproducibility of the Example of this invention. It is a schematic diagram which shows the checker image for evaluating the durability stability of the Example of this invention. It is a schematic diagram which shows the fine line image for evaluating the fine line reproducibility of the Example of this invention. It is a schematic diagram which shows the fine line image for evaluating the void in the Example of this invention. (A) is a schematic horizontal projection surface view of a liner, and (B) is a partial explanatory view of the liner.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Charging roller 3 Laser beam scanner 4 Developing device 5 Transfer roller 6 Uniform means S1 to S4 of charging polarity Bias voltage application power source 11 Developing device 21 Charging device 22 Laser exposure device 23 Transfer charging device 24 Transfer belt 25 Fixing device 26 Cleaner 27 Recording paper 28 Photosensitive drum 30 Casing 31 Cooling jacket 32 Dispersing rotor 33 Square disc (hammer)
34 Liner 35 Classification rotor 36 Guide means (guide ring)
37 Raw material inlet 38 Raw material supply valve 39 Raw material supply port 40 Product discharge port 41 Product discharge valve 42 Product extraction port 43 Top plate 44 Fine powder discharge portion 45 Fine powder discharge port 46 Cooling inlet 47 First space 48 Second space 49 Surface modification zone 50 Classification zone 315 Fixed supply machine 319 Cold air generation means 320 Cold water generation means 321 Toner particle transport means 359 Cyclone inlet 362 Bug 364 Blower 369 Cyclone 380 Raw material hopper 431 Fine grinding machine 432 Pipe 435 Nozzle 436 Colliding plate 437 Grinding chamber 438 Collector 439 Main body hopper 440 Center core 441 Separate core 442 Discharge pipe 443 Secondary air supply port

Claims (2)

In a color toner having toner particles and inorganic fine particles containing at least a binder resin, a colorant, and a release agent,
The toner has a weight average particle diameter (D4) of 3.0 μm to 7.0 μm,
The transmittance (%) of light having a wavelength of 600 nm with respect to a dispersion liquid in which the toner is dispersed in an aqueous solution of 45% by volume of methanol is in the range of 30 to 70%.
The average circularity of the toner having an equivalent circle diameter of 2.00 μm or more in a flow type particle image measuring device is R, the equivalent circle diameter is 2.00 μm or more and less than 3.00 μm, 3.00 μm or more and less than 6.92 μm,
When the average circularity of the toner in each equivalent circle diameter range of 6.92 μm or more and less than 12.66 μm is r (a), r (b), r (c), R, r (a), r The relationship between (b) and r (c) is
Formula (4 )
0.940 ≦ R ≦ 0.970 (1)
R − 0.015 ≦ r (a) ≦ R + 0.015 (2)
R − 0.015 ≦ r (b) ≦ R + 0.015 (3)
R − 0.015 ≦ r (c) ≦ R + 0.015 (4)
Satisfied,
The color toner contains inorganic fine particles (A) having at least a number average particle size of 60 nm or more and less than 300 nm and inorganic fine particles (B) having a number average particle size of 10 nm or more and less than 60 nm as inorganic fine particles, The surface of the toner particles is coated with the inorganic fine particles,
When the coverage of the inorganic fine particles (A) is F (A) and the coverage of the inorganic fine particles (B) is F (B), the relationship between F (A) and F (B) is expressed by the formula (5).
1.0 ≦ F (B) / F (A) ≦ 10.0 (5)
Satisfied,
The inorganic fine particles (A) are externally added in an amount of 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles.
0.1 to 5.0 parts by mass of the inorganic fine particles (B) are externally added to 100 parts by mass of the toner particles;
The inorganic fine particles (A) are silica fine particles, and the inorganic fine particles (B) are silica fine particles or titanium oxide fine particles.
A color toner characterized by the above. The color toner according to claim 1, wherein the binder resin is a resin containing at least a polyester unit.

Images