JP2001318487A - Toner, method for manufacturing toner, method for forming image and device for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which does not cause melt sticking on a latent image carrying body or a rough appearance of a halftone image in a low humidity environment, which does not produce a dot-like defect due to aggregation of the toner even when the toner is stored in a high humidity environment or which does not cause image failure by contamination of an electrifying member. SOLUTION: The toner contains toner particles containing at least a binder resin and a coloring agent and the following particles [1], [2], [3] mixed with the toner particles. The particles are [1] metal oxide inorganic fine particles (1) where the metal is selected from titanium, aluminum, zinc and zirconium and having 80 to 800 nm average primary particle size, [2] inorganic fine particles (2) except for silica having <80 nm average primary particle size, and [3] silica fine particles having <30 nm average primary particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, or the like. More specifically, the present invention relates to a toner used in a copying machine, a printer, and a facsimile, which forms a toner image on an electrostatic latent image carrier in advance and then transfers the image onto a transfer material to form an image, a method for manufacturing the toner, and a method for manufacturing the toner. The present invention relates to an image forming method and an image forming apparatus used.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Numerous methods are known as described in Japanese Patent Application Laid-Open Publication No. Hei. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor, and then the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper. The image is fixed by heating, pressure, heating / pressing or solvent vapor to obtain a final image. The toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such a copying apparatus has begun to be used not only in a general business copying machine for copying an original document but also in a field of a printer as a computer output or a personal copy for an individual. .

[0004] For this reason, specifications such as small size, light weight, high speed and low power consumption have been pursued for copiers, printers and the like, and machines have been constructed with simpler elements in various points.

For example, as a method of developing an electrostatic latent image,
A two-component developing method using a mixture of a toner and a carrier,
A magnetic one-component developing method using only a magnetic toner is generally known.

The two-component developing method uses a carrier and a so-called AT that adjusts the mixing ratio of the toner and the carrier.
Considering the necessity of the R mechanism, it contradicts demands for downsizing and weight reduction.

[0007] The magnetic one-component developing method has a drawback that it is difficult to cope with a color toner because it uses a magnetic toner.

On the other hand, Japanese Patent Application Laid-Open Nos. Sho 58-116559, Sho 60-120368 and Sho 63
The non-magnetic one-component developing method disclosed in JP-A-271371 is attracting attention as a developing method for solving the above problems. In the non-magnetic one-component developing method, a toner is coated on a toner carrier by a layer thickness controlling means such as a blade. The toner is charged by friction with the blade or the surface of the toner carrier, but when the coating layer is thick, there is a toner that cannot be sufficiently charged, and this causes fogging and scattering, so the toner must be coated in a thin layer. . Therefore, the blade must be pressed against the toner carrier with a sufficient pressure. At this time, the force received by the toner is smaller than the force received by the toner in the two-component developing method or the one-component developing method using the magnetic toner. large. For this reason, deterioration of the toner is apt to occur, and image deterioration such as fogging and density reduction occurs.

As a problem associated with the deterioration of the toner, there is a drop of the toner which occurs when printing a large number of sheets. This is a phenomenon in which when a large number of sheets are printed, the toner aggregates in the developing device and appears as dots on an image.

When the printing speed of the apparatus is increased, the deterioration of the toner is apt to occur as the printing speed is increased, and the above-mentioned problem caused by the deterioration of the toner becomes more prominent.

On the other hand, cases of use in various severe environments are increasing. Some of the problems that can occur in harsh environments include:

As one of them, in recent years, these electrophotographic copiers, printers, and facsimile machines have been used in various countries of the world. There has been an increasing demand for similar high-quality images for various recording materials.

Another point is a fog phenomenon.

In order to obtain a color image, a color image is formed by superimposing images formed by a plurality of color toners. At this time, if there is fog, the image is mixed with other color image portions and the image quality is degraded. Cause a decrease. This fogging phenomenon is particularly problematic when outputting many images having a very low color printing ratio under a low humidity environment such as an office.

Still another point is the fusion of the toner to the latent image carrier which occurs in a low-temperature and low-humidity environment. This is a phenomenon that appears as a dot-like defect on an image due to the effect of the toner fused on the latent image holding member. In particular, this phenomenon occurs when printing an image with a high color printing ratio.

Further, as another point, there is a phenomenon of "roughness" of a halftone image in a low humidity environment. This is a phenomenon in which the image becomes rough due to the difficulty in developing the toner. This may degrade the image quality of a halftone portion such as a photographic image.

Still another point is a phenomenon in which the toner drops when exposed to a high temperature. When the toner is exposed to a high temperature during storage, the toner aggregated at the start of use appears as dots on an image. With the spread of color printers, the use environment and the storage environment of the toner are diversified, and there is a demand for a toner that does not cause such a phenomenon even under a severer high temperature environment than before.

In the case where the printing speed of the apparatus is increased, the above problem becomes more remarkable because it becomes difficult to sufficiently obtain the toner charging property with the increase in the printing speed.

In recent years, the demand for image quality of an image output by a copying machine, a printer, or the like using an electrophotographic system has been higher than ever. In particular, color copiers / printers have a high demand for image quality. In addition, as color copiers / printers have become more widespread due to their networking and lower prices, the use of high-color images, such as photographs and graphics, has increased from professional use to color printing ratios. As the uses have been diversified toward office use, which produces a large number of low-output images, it has been required to meet more diverse demands. Some of the demands for higher performance than before are as follows.

Further improvements are required to satisfy all of the recent high demands described above.

Another point is a retransfer phenomenon. As described above, a color image is formed by sequentially transferring images of a plurality of colors onto a transfer material such as an intermediate transfer member / paper, and is superimposed. This is a phenomenon of returning to the latent image holding member during transfer. When this phenomenon occurs, the color of the previously transferred toner becomes lighter, and the color of the final image changes, which causes deterioration in image quality.

When the printing speed of the apparatus is increased, the above-mentioned problem tends to appear more remarkably.

Various improvements have been made for these problems. For example, Japanese Patent Application Laid-Open No. H11-143188 discloses a method for preventing retransfer and changing fog by changing development conditions in a plurality of times of image formation. Japanese Patent Application Laid-Open No. 9-114126 discloses a method for preventing fog and retransfer by improving the toner.

However, even with these proposals, it has been difficult to satisfy all of the above-mentioned problems and the recent high demands for high image quality.

Further improvements are required to satisfy all of the recent high demands described above.

Another point is "image failure due to contamination of the charging member" which charges the latent image holding member. This is a phenomenon in which high-resistance silica fine particles / toner particles externally added to the toner adhere to the charging member, hinder uniform charging of the latent image holding member, and cause streak-like image unevenness in a halftone image or the like. .

In Japanese Patent Application Laid-Open No. 10-48872,
There is a proposal for a toner to which an inorganic fine particle having a specific average particle diameter is externally added and which has a differential thermal analysis endothermic peak in a specific temperature range. Although retransfer in single transfer is effective, other problems including retransfer in multiple transfer cannot satisfy all recent high demands.

[0028]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above-mentioned problems of the prior art, a method for producing the toner, an image forming method using the toner, and an image forming apparatus.

An object of the present invention is to provide a toner which does not cause a phenomenon of fusing of toner on a latent image holding member in a low humidity environment, a method of manufacturing the toner, an image forming method and an image forming apparatus using the toner. To provide.

An object of the present invention is to provide a toner which does not cause "roughness" of a halftone image in a low humidity environment, a method for producing the toner, an image forming method using the toner, and an image forming apparatus. .

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that does not cause toner dropping even when stored in a high-temperature environment or when printing a large number of sheets, a method for manufacturing the toner, and an image forming method using the toner. A method and an image forming apparatus are provided.

An object of the present invention is to provide a toner free from fogging even when a large number of images having a low color printing ratio are printed in a low humidity environment, a method for producing the toner, an image forming method using the toner, and an image. An object of the present invention is to provide a forming apparatus.

An object of the present invention is to provide a toner which does not cause a phenomenon of fusing of toner to a latent image holding member even when an image having a high color printing ratio is printed in a low humidity environment, a method of manufacturing the toner, An object of the present invention is to provide an image forming method and an image forming apparatus using a toner.

An object of the present invention is to provide a toner having no retransfer phenomenon, a method for producing the toner, an image forming method and an image forming apparatus using the toner.

An object of the present invention is to provide an image forming method and an image forming apparatus in which the image quality is not degraded due to the quality and condition of the recording material.

[0036]

According to the present invention, toner particles containing at least a binder resin and a colorant, and an average primary particle size mixed with the toner particles is 80 to 800 nm.
m, an inorganic oxide fine particle of a metal selected from the group consisting of titanium, aluminum, zinc and zirconium (1), inorganic fine particles other than silica having an average primary particle size of less than 80 nm (2), and an average primary particle 30n diameter
m, which has silica fine particles of less than m.

The present invention also provides a first mixing and dispersing step of mixing and dispersing toner particles containing at least a binder resin and a colorant and inorganic fine particles (1) to obtain a toner precursor; In the method for producing a toner having a second mixing and dispersing step of mixing and dispersing a toner precursor, inorganic fine particles (2) and silica fine particles to obtain a toner, the inorganic fine particles (1) have an average primary particle size of 80 to 80%. 800 nm, which is an oxide of a metal selected from the group consisting of titanium, aluminum, zinc and zirconium. The inorganic fine particles (2) are inorganic fine particles other than silica having an average primary particle diameter of less than 80 nm. The present invention relates to a method for producing a toner, wherein the silica fine particles have an average primary particle size of less than 30 nm.

Further, the present invention provides (I) a step of supplying a non-magnetic toner onto a toner carrier by a supply roller; (II) an electrostatic latent image formed on the latent image carrier is placed on the toner carrier. Developing the formed toner layer with the non-magnetic toner to form a developed image; (III) pressing the non-magnetic toner on the toner carrier with a toner application blade to form a toner layer on the toner carrier An image forming method comprising the steps of: applying a charge to the non-magnetic toner by rubbing the non-magnetic toner; (IV) transferring a developed image to a transfer material; and (V) fixing the transferred developed image. And an image forming method using the toner having the above configuration as the non-magnetic toner.

Further, the present invention provides (I) a latent image carrier for carrying an electrostatic latent image, a charging device for primary charging the latent image carrier, and a device for charging the latent image carrier with a primary charge. A plurality of image forming units including an exposure unit for forming an electrostatic latent image and a developing device for developing the electrostatic latent image with a non-magnetic toner to form a toner image; and (II) each of the images An image forming apparatus having a transfer device for sequentially transferring a toner image formed by a forming unit onto a transfer material, wherein the non-magnetic toner is a toner having the above-described configuration.

The present invention also relates to (I) a latent image carrier for carrying an electrostatic latent image; (II) a charging device for primary charging the latent image carrier; and (III) a primary charged carrier. Exposure means for forming an electrostatic latent image on the latent image carrier; (IV) a plurality of developing devices for developing the electrostatic latent image with non-magnetic toner to form a toner image; An intermediate transfer member for sequentially transferring toner images formed by the developing device; and (VI) an image having a transfer device for collectively transferring the multiple toner images transferred on the intermediate transfer member to a transfer material The present invention relates to an image forming apparatus, wherein each of the non-magnetic toners is a toner having the above configuration.

Further, the present invention provides (I) a latent image carrier for carrying an electrostatic latent image; (II) a charging device for primary charging the latent image carrier; and (III) a primary charged carrier. An exposure unit for forming an electrostatic latent image on the latent image carrier; (IV) a plurality of developing devices for developing the electrostatic latent image with a non-magnetic toner to form a toner image; The present invention relates to an image forming apparatus having a transfer device for sequentially transferring a toner image formed by each developing device to a transfer material, wherein each non-magnetic toner is a toner having the above configuration.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The phenomenon of fusing toner on a latent image holding member in a low humidity environment is caused by the fact that excessively charged toner particles strongly adhere to the latent image holding member in a low humidity environment. Is thought to be the cause. In the present invention, titanium, aluminum having an average primary particle size of 80 to 800 nm,
By mixing inorganic fine particles 1 selected from oxides of zinc and zirconium with toner particles, the inorganic fine particles 1 control the charge of the toner, suppress excessive charging, and firmly adhere to the latent image holding member. Inorganic fine particles other than silica having an average primary particle size of less than 80 nm, and silica fine particles having an average primary particle size of less than 30 nm.
Increases the toner charge control effect to a level previously unattainable. As a result, the occurrence of excessively charged toner in a low-humidity environment can be prevented, and the phenomenon of toner fusing on a latent image holding member in a low-humidity environment Can be solved.

Further, regarding the phenomenon of "graining" of a halftone image in a low humidity environment, a toner particle excessively charged in a low temperature environment fills the developing potential on the latent image holding member with a small amount of toner. It is considered that this phenomenon may hinder the development of the toner having an appropriate charge amount. For the same reason as described above, the toner of the present invention suppresses the generation of an excessively charged toner, so that "half-toned image"
The phenomenon can be solved.

Further, the fogging phenomenon is a phenomenon in which a toner that cannot be provided with an appropriate charge amount develops into a non-image area on a latent image holding member. Part of the toner particles strongly adheres to the developing sleeve / developing carrier / toner regulating member, which is the charging member, and inhibits the charging of the newly supplied toner.
It is considered that the fog phenomenon occurs. The toner of the present invention can be solved by suppressing the generation of excessively charged toner for the same reason as described above.

It is considered that fog generated in a high-humidity environment is caused by the effect of moisture adsorbed on the surface of the toner, thereby hindering the charging of the toner. The toner of the present invention comprises inorganic fine particles 1, inorganic fine particles 2, and
The fog phenomenon can be solved by the silica fine particles having a primary particle diameter of less than 30 nm promoting the charging of the toner.

Regarding the re-transfer phenomenon, a transfer current is injected into the toner once transferred onto the transfer material through the transfer material at the time of the next color transfer, and the charge of the toner that did not have an appropriate charge amount is reduced. This is considered to be a phenomenon in which the toner whose charge has been inverted is returned to the latent image holding member from the transfer material. The toner of the present invention can solve this problem by suppressing the generation of a toner that cannot be provided with an appropriate charge amount for the same reason as described for the fogging phenomenon.

Regarding the phenomenon of toner dripping when exposed to a high temperature, a fluidity-imparting agent such as silica on the toner surface is embedded by storing the toner in a high-temperature environment, and the toner surface is hardly charged. This is considered to be a phenomenon in which toner agglomeration occurs and is developed by the latent image holding member without being loosened by the regulating member of the developing device. The toner of the present invention solves this phenomenon by giving appropriate charge to the toner that has become difficult to be charged for the same reason as described in the fogging phenomenon and preventing toner aggregation. Can be.

Regarding image defects due to contamination of the charging member, the toner of the present invention has an average primary particle size of 80 to 800 n.
m, inorganic fine particles 1 selected from oxides of any of titanium, aluminum, zinc, and zirconium, and inorganic fine particles 2 other than silica having an average primary particle diameter of less than 80 nm selectively adhere to the charging member; Since the adhesion of the silica fine particles which causes the image failure due to the contamination of the charging member is prevented, the image failure due to the contamination of the charging member can be prevented.

Further, the fogging phenomenon that occurs when printing a large number of low-printing-rate images is a phenomenon in which the toner that cannot be provided with an appropriate charge amount adheres to the non-image portion on the latent image holding member. Conceivable. In particular, when printing a large number of images with a low printing ratio, many toners are repeatedly circulated in the developing device without being developed, so that the mechanical stress applied to the toners becomes extremely large. Therefore, among the fine particles contained in the toner, particles having a relatively large particle diameter are gradually separated from the toner particles by the mechanical impact. The detached particles have different particle properties such as chargeability, particle size, specific gravity, and adhesion from toner particles, and thus behave differently from toner particles in each image forming process. Therefore, the ratio of the particles present in the toner changes during the process of printing a large number of sheets, and the charging performance of the toner decreases. Further, since particles having a relatively small particle diameter gradually become buried in the surface of the toner particles, the fluidity of the toner gradually decreases. It is considered that the fogging phenomenon occurs due to a decrease in the chargeability and fluidity of the toner due to the detachment or burial of the fine particles. In particular, in a low humidity environment where excessive charging of the toner tends to occur, a more severe fog phenomenon is likely to occur. In the method for producing a toner according to the present invention, the toner charge control effect of the inorganic fine particles 1 for controlling the charge of the toner is improved by the presence of the inorganic fine particles 2 and the silica fine particles. By mixing strongly, the toner charge control effect is synergistically improved to a level that could not be obtained conventionally, and it is possible to impart proper charge to the toner even in a use environment where mechanical impact is repeatedly applied to the toner. Further, it is possible to prevent the generation of excessively charged toner in a low humidity environment, and to suppress fog.

From the above findings, in the method for producing a toner of the present invention, fine particles to be added are specified in the first mixing and dispersing step (step A) and the second mixing and dispersing step (step B). It is doing.

That is, in the method for producing a toner of the present invention, a first mixing and dispersing step of mixing and dispersing toner particles containing at least a binder resin and a coloring agent and inorganic fine particles (1) to obtain a toner precursor. And a second mixing and dispersing step of mixing and dispersing the obtained toner precursor, inorganic fine particles (2) and silica fine particles to obtain a toner, wherein the inorganic fine particles (1) have an average primary particle diameter. Is 80 to 800 nm, an oxide of a metal selected from the group consisting of titanium, aluminum, zinc and zirconium, wherein the inorganic fine particles (2) have an average primary particle size of less than 30 nm. .

Hereinafter, the components of the present invention will be described in detail.

In the present invention, the average primary particle size is 80 to 800.
The inorganic fine particles 1 selected from oxides of any of titanium, aluminum, zinc, and zirconium having a diameter of nm are mixed with the toner particles. The average primary particle size of the inorganic fine particles 1 is 80n
If it is less than m, the effect of controlling the charge of the toner and the prevention of image defects due to contamination of the charging member cannot be obtained. If the average primary particle size of the inorganic fine particles 1 exceeds 800 nm, the surface of the latent image holding member is likely to be finely scratched, the toner fusing phenomenon is deteriorated, and a sufficient charge control effect cannot be obtained.

The oxide of any of titanium, aluminum, zinc and zirconium is white and can be used for color toners, has a high effect of controlling the charge of the toner, and causes minute scratches on the surface of the latent image holding member. It is difficult to prevent image defects due to contamination of the charging member.

Inorganic fine particles other than oxides of any of titanium, aluminum, zinc and zirconium solve all the problems of the present invention in terms of color, charge controllability, and easiness of damaging the latent image holding member surface. Can not do.

In particular, it is more preferable to use an oxide of either titanium or aluminum from the viewpoints of charge controllability, difficulty in damaging the surface of the latent image holding member, and prevention of image defects due to contamination of the charging member.

The average primary particle size of the inorganic fine particles 1 is preferably 100 to 500 nm for the purpose of further enhancing the above effects.

The charge amount of the inorganic fine particles 1 is 10 m in absolute value.
C / kg or less is preferable because the charge controllability of the toner becomes higher. The inorganic fine particles 1
The effect of controlling the charge of the toner and the effect of preventing an image defect due to contamination of the charging member are particularly high as compared with the others.

As the inorganic fine particles 1, those whose surfaces have been subjected to a hydrophobic treatment with an organic compound such as a coupling agent or an oil can be used. Is preferably used because it becomes low.

The inorganic fine particles 1 may be used in combination of two or more kinds.

The addition amount of the inorganic fine particles 1 is preferably 0.05 to 5% by mass, more preferably 0.06 to 3% by mass, based on the toner particles. 0.05
If the amount is less than 5% by mass, the effect of the present invention is hardly obtained, and
Exceeding the range lowers the toner fixability.

In the present invention, inorganic fine particles 2 other than silica having an average primary particle size of less than 80 nm are mixed with toner particles.
When the average primary particle size is 80 nm or more, the effect of controlling the charge of the inorganic fine particles 1 cannot be sufficiently obtained, and the effect of preventing image defects due to contamination of the charging member cannot be obtained.

The inorganic fine particles 2 preferably have an average primary particle diameter of preferably 70 nm or less, more preferably 25 to 70 nm, for further enhancing the above effects.

The inorganic fine particles 2 include magnesium, zinc, aluminum, titanium, cobalt, zirconium,
Oxide powders such as manganese, cerium and strontium; composite metal oxide powders such as calcium titanate, magnesium titanate, strontium titanate and barium titanate; boron, silicon, titanium, vanadium, zirconium, molybdenum and tungsten And carbides such as magnesium, calcium, strontium and barium, and inorganic metal salt powders such as sulfates and phosphates.

Among them, the inorganic fine particles 2 are titanium,
Preferably, it is any oxide of aluminum. Titanium and aluminum have particularly high effects of enhancing the charge control effect of the inorganic fine particles 1 and preventing image defects due to contamination of the charging member, as compared with other materials.

The surface of the inorganic fine particles 2 is a coupling agent,
It is preferable to use those that have been subjected to a hydrophobic treatment with an organic compound such as oil.

When the hydrophobic particles and the non-hydrophobic particles are used in combination as the inorganic fine particles 2, the effect of suppressing the generation of excessively charged toner particles in a low humidity environment is enhanced. Obtained and preferred.

The inorganic fine particles 2 may be used in combination of two or more kinds.

The amount of the inorganic fine particles 2 added is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.7% by mass, based on the toner particles.
When the amount is less than 0.01% by mass, the effect is hardly obtained, and when the amount exceeds 1.0% by mass, the fixability of the toner is reduced.

According to the present invention, the average primary particle size is 30n.
m and silica particles are mixed with the toner particles. When the average primary particle size is 30 nm or more, the charge control effect of the inorganic fine particles 1 cannot be sufficiently obtained, and all the problems of the present invention cannot be solved. It is considered that the high negative chargeability of the silica fine particles enhances the charge control effect of the inorganic fine particles 1.

The average primary particle size of the silica fine particles is preferably 20 nm or less, more preferably 8 to 20 nm, for the purpose of further enhancing the above effects. In this case, a higher charge control effect of the inorganic fine particles 1 can be obtained.

The addition amount of the silica fine particles is preferably 0.2 to 5.0% by mass, and more preferably 0.4 to 3.0% by mass based on the toner particles.
It is preferably 0% by mass. If the amount is less than 0.2% by mass, the effect of improving the problem is hardly obtained. If the amount exceeds 5.0% by mass, the fixability of the toner is reduced.

As the silica fine particles, both a so-called dry method produced by the vapor phase oxidation of a silicon halide and a so-called fumed silica, and a so-called wet silica produced from water glass or the like can be used. .

[0074] As the base of the small oil-treated silica particles having a particle diameter less silanol groups on the inner surface and fine silica powder, also Na ₂ O, of dry silica with no manufacturing residue of SO ₃ ^2-like Is more preferred.

In the case of fumed silica, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide in the production process. And also includes them.

The silica fine particles used in the present invention are preferably treated in advance with a silane coupling agent and / or silicone oil.

The silane coupling agent is represented by the following general formula

[0078]

Embedded image For example, typically, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxy Examples thereof include propyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

The silane coupling agent treatment of the silica fine powder may be a dry treatment in which a vaporized silane coupling agent is reacted with a cloud of silica fine powder by stirring, or a silane coupling agent in which silica is dispersed in a solvent. The treatment can be carried out by a generally known method such as a wet method in which a ring agent is dropped.

The silicone oil is generally represented by the following formula.

[0081]

Embedded image R: C ₁ alkyl group -C ₃ R ': alkyl, halogen-modified alkyl, silicone oil modified group R is selected from phenyl or modified phenyl ": an alkyl group or a C ₁ -C ₃ alkoxy group C ₁ -C ₃

Examples of such silicone oils include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil.

A known technique is used for the method of treating the silicone oil. For example, fine silica powder and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or the silicone oil may be sprayed on the base silica. Depending on the method. Alternatively, it may be prepared by dissolving or dispersing silicone oil in an appropriate solvent, mixing with a base silica fine powder, and removing the solvent.

In the present invention, the content ratio by mass of the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles mixed with the toner particles in the toner is preferably as follows: inorganic fine particles (1): inorganic fine particles (2): silica fine particles =
1: (0.01 to 1): (0.1 to 6), and more preferably, the following conditions: inorganic fine particles (1): inorganic fine particles (2): silica fine particles =
1: (0.02 to 0.9): (0.2 to 5.6)

When the content ratio of the inorganic fine particles (2) to the inorganic fine particles (1) is less than 0.01, the effect of the present invention is hardly obtained. ), It is difficult to sufficiently obtain the charge control effect, and it is difficult to solve all the problems of the present invention.

When the content ratio of the silica particles to the inorganic fine particles (1) is less than 0.1, the effect of the present invention is hardly obtained, and when it is more than 6, the charging of the inorganic fine particles (1) becomes difficult. It is difficult to obtain a sufficient control effect, and it is difficult to solve all the problems of the present invention.

In the present invention, the toner has a weight average particle diameter of 4 to
More preferably, the toner particles having a particle size of 8 μm and 4 μm or less are 3 to 20% by number.

When the weight average particle diameter of the toner is less than 4 μm, the toner tends to be excessively charged in a low humidity environment.
Problems such as fusion of the toner to the latent image holding member, roughening of the halftone image, and dropping of the toner during high-temperature storage are likely to occur. When the weight average particle diameter of the toner exceeds 8 μm, image defects due to retransfer, fog and contamination of the charging member are likely to occur.

When toner particles having a particle size of 4 μm or less are less than 3% by number, reproducibility of fine dots in a high humidity environment tends to be low. When the number of toner particles having a particle size of 4 μm or less exceeds 20% by number, the toner tends to be excessively charged in a low-humidity environment. And other problems are likely to occur.

The method of mixing the inorganic fine powders 1, 2 and the silica fine particles with the toner particles can be achieved by stirring and mixing the toner particles, the inorganic fine powders 1, 2 and the silica fine particles with a mixer such as a Henschel mixer.

In the above-described method for producing a toner for producing the toner of the present invention, the average primary particle size is 80 nm.
Inorganic fine particles 1 selected from oxides of any of titanium, aluminum, zinc, and zirconium having a thickness of 800 nm
Is mixed and dispersed with toner particles to obtain a toner precursor. Then, the toner precursor is mixed with inorganic fine particles 2 other than silica having an average primary particle size of less than 80 nm and silica fine particles having an average primary particle size of less than 30 nm. It is preferable to produce a toner by mixing and dispersing.

According to the above-described production method, the produced toner has a high level of charge control effect which could not be obtained conventionally.

The toner of the present invention preferably has at least one endothermic peak in the range of 60 to 90 ° C. in the endothermic curve at the time of temperature rise in the differential thermal analysis. 60-9
In a toner having an endothermic peak at 0 ° C., the toner charge control by the external additive composition of the present invention works more effectively, and more preferable results are obtained. Results are obtained.

The endothermic peak is not in the range of 60 to 90 ° C.
When the temperature is lower than 0 ° C., storage stability is impaired, and problems such as blocking are likely to occur. Even if the endothermic peak is not in the range of 60 to 90 ° C. and has an endothermic peak at a temperature exceeding 90 ° C., it is difficult to obtain the effect of further improving the charge controllability of the toner. If there is an endothermic peak at 60 to 90 ° C, an endothermic peak may be further present in a temperature range exceeding 90 ° C.

In the present invention, 60 to 60 in differential thermal analysis
The half width of the endothermic peak in the temperature range of 90 ° C. is preferably 10
C. or lower, more preferably 6 ° C. or lower.
If the half-value width exceeds 10 ° C., the effect of preventing fusion of the toner to the latent image holding member, fogging, dropping of the toner when left at high temperatures, and image defects due to contamination of the charging member cannot be further enhanced.

The endothermic peak in the differential thermal analysis was 60 to 9
As a means for forming the toner at 0 ° C., a method of internally adding a compound having an endothermic peak at 60 to 90 ° C. in differential thermal analysis to the toner is preferable.

The endothermic peak in the differential thermal analysis was 60 to 9
As a substance having one or more at 0 ° C., wax is preferably used.

As the wax, paraffin wax,
Petroleum waxes such as microcrystalline wax and petrolactam and derivatives thereof; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof by the Fischer-Tropsch method; polyolefin waxes and derivatives thereof represented by polyethylene; carnauba wax and candelilla wax. Natural waxes and their derivatives, alcohol waxes of higher aliphatic alcohols; fatty acids and their compounds such as stearic acid and palmitic acid; acid amides and their derivatives; esters and their derivatives; ketones and their derivatives; hydrogenated castor oil and their derivatives Vegetable waxes; and animal waxes. Derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products.

In the present invention, a wax having an endothermic peak at 60 to 90 ° C. in differential thermal analysis is preferably used.

The wax content of the toner particles is from 0.3 to
It is preferably 30% by mass, more preferably 0.5 to 20% by mass.

Examples of the binder resin usable in the present invention include the following. For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and substituted products thereof; styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer Styrene-maleic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-maleic acid copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl methyl ether copolymer,
Styrene-vinyl ethyl ether copolymer, styrene-
Styrene copolymers such as vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile indene copolymer; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin Modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, tempen resin, cumarone indene resin, petroleum resin Can be used.

In the present invention, among the above binder resins, a styrene polymer or a styrene copolymer containing a styrene polymer is particularly preferable. The styrene-based polymer has a low polarity of the main chain of the styrene-based polymer itself, and thus, the charge control of the toner by the constitution of the external additive of the present invention is more effective, so that it is preferable.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Double bonds such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide Or a substituted product thereof; acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid and crotonic acid and α- or β-alkyl derivatives thereof; and non-carboxylic acids such as fumaric acid, maleic acid and citraconic acid. Saturated dicarboxylic acids and their monoester derivatives or acid anhydrides can be mentioned. Such a monomer can be used alone or as a mixture and copolymerized with another monomer to produce a desired polymer.

As the cross-linking agent, compounds having two or more polymerizable double bonds are mainly used, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate, ethylene glycol Glycol dimethacrylate, 1,
Carboxylic acid esters having two double bonds such as 3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinylether, divinylsulfide and divinylsulfone; and compounds having three or more vinyl groups, alone or as a mixture. Can be used.

In the toner of the present invention, the GP soluble in THF is used.
Those having a peak molecular weight of 15,000 to 30,000,000 in the C measurement are preferable. When the THF-soluble component has a peak molecular weight of 15,000 to 30,000,000 in GPC measurement, the generation of excessively charged toner in a low-temperature and low-humidity environment is suppressed and the toner is Is suppressed, the toner charge control by the external additive composition of the present invention works more effectively, and more preferable results are obtained. When the peak molecular weight is less than 15,000, it is difficult to obtain the effect of improving the charge controllability of the toner and the effect of preventing an image failure due to contamination of the charging member. If the peak molecular weight exceeds 30,000, fixability tends to be impaired.

The toner of the present invention preferably has an acid value of 10
mgKOH / g or less, more preferably 1 to 9 mgKOH
/ G. When the acid value is 10 mgKOH / g or less, the generation of excessively charged toner in a low humidity environment is suppressed, and the toner charge control by the external additive composition of the present invention works more effectively, and more preferable results are obtained. Further, the effect of preventing image defects due to contamination of the charging member is high.

In the present invention, the absolute value of the charge amount of the toner is preferably from 40 to 80 mC / kg, more preferably from 42 to 75 mC / kg. If the absolute value of the charge amount of the toner is less than 40 mC / kg, image defects due to retransfer, fog, and contamination of the charging member are likely to occur. When the absolute value of the charge amount of the toner exceeds 80 mC / kg, fusion of the toner to the latent image holding member, roughening of the halftone image, and dropping of the toner during high-temperature storage are likely to occur.

The toner of the present invention is particularly effective when it is a non-magnetic toner.

Non-magnetic toner tends to generate excessively charged toner in a low-humidity environment as a toner base as compared with magnetic toner containing magnetic powder having relatively low electric resistance. Therefore, the effect of the external additive composition of the present invention appears more remarkably in the non-magnetic toner than in the magnetic toner. Further, non-magnetic toner has high electric resistance,
Image defects are also likely to occur due to contamination of the charging member. Therefore, the effect of the present invention is more remarkable in the non-magnetic toner than in the magnetic toner. A non-magnetic toner is also preferable in that it can easily handle colors.

In the toner of the present invention, the shape factor SF-
The value of 1 is preferably 100 to 170, more preferably 1
00 to 120, and its shape factor SF-2
Is preferably 100 to 140, more preferably 10
It is preferably 0 to 115. Shapes in the above range are
The toner surface is relatively smooth, the toner charge control by the external additive composition of the present invention works more effectively, and a higher effect is obtained. High effects can be obtained.

When SF-1 exceeds 170, and S
When F-2 exceeds 140, it is difficult to obtain an effect of further improving the charge control property of the toner and the ability to prevent image defects due to contamination of the charging member.

In the present invention, in step A, a metal complex compound, a metal salt or a mixture of a metal complex compound and a metal salt of a low-crystalline or amorphous aromatic compound is mixed with toner particles and inorganic fine particles. It is preferred to mix and disperse together with (1). At this time, the charging characteristics of the toner are further improved, and a higher effect on the object of the present invention can be obtained.

The amount of the low-crystalline or aromatic metal complex compound, metal salt, or mixture of the metal complex compound and the metal salt is 0.005 to 1.
0 parts by mass is preferred.

When the amount is less than 0.005 parts by mass, the effect of improving the chargeability is hardly obtained, and when it exceeds 1.0 parts by mass, the effect of further improving the chargeability is hardly obtained.

Examples of the metal complex compound include a metal complex and a metal complex salt.

In the present invention, any known metal complex compounds or metal salts of aromatic compounds can be used.
Examples thereof include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acid-based metal compounds, and monoazo metal compounds.

In the present invention, in the step A, the metal complex compound of the oxycarboxylic acid compound, the metal salt, or the mixture of the metal complex compound and the metal salt is mixed and dispersed together with the toner particles and the inorganic fine particles 1. Is more preferred. At this time, the charging characteristics of the toner are further improved, and a higher effect on the object of the present invention can be obtained.

A metal complex compound of an oxycarboxylic acid compound,
The addition amount of the metal salt or the mixture of the metal complex compound and the metal salt is preferably from 0.005 to 1.0 part by mass based on the toner particles.

If the amount is less than 0.005 parts by mass, it is difficult to obtain the effect of improving the chargeability, and if it exceeds 1.0 parts by mass, it is difficult to obtain the effect of further improving the chargeability.

Further, it is particularly preferred that the central metal of the metal complex compound of the oxycarboxylic acid compound, the metal salt, or the mixture of the metal complex compound and the metal salt is aluminum or zirconium.

In the present invention, “low crystallinity or non-crystallinity” means that an X-ray diffractometer has a measurement intensity of 10,000 cps (count per se) as shown in FIG.
cond) or more and the half width at half maximum 0.3 degree
This is a state having no peak equal to or less than e, which is clearly different from the diffraction pattern of the metal complex compound of the crystalline aromatic compound (FIG. 2). In general, in X-ray diffraction measurement, a crystalline substance shows a unique diffraction peak according to the crystal plane spacing under Bragg's diffraction conditions, and the diffraction intensity depends on the crystal state and the degree of crystallinity. X-ray diffraction intensity is 1
0000 cps or more and half width at half maximum 0.3 de
Substances that do not have a peak that is less than or equal to green can be considered low crystalline or amorphous substances. In the actual measurement, when the measurement angle 2θ is less than 6 degrees, the influence of the direct beam is large, and when the measurement angle 2θ is large, the measurement intensity is small.
The measurement intensity is low in a range exceeding the egree, and in these ranges, it is not preferable to determine whether the crystal is crystalline or non-crystalline.

For the measurement of X-ray diffraction of the present invention, for example,
Using an X-ray diffractometer MXP18 manufactured by Mac Science Co., Ltd., measurement is performed using CuKα radiation under the following conditions. -X-ray tube: Cu-Tube voltage: 50 kV-Tube current: 300 mA-Scan method: 2θ / θ scan-Scan speed: 2 deg. / Min Sampling interval: 0.02 deg. -Divergence slit: 0.50 deg.・ Light receiving slit: 0.3mm

In the present invention, a charge control agent may be added to the toner as needed.

Examples of the negative charge controlling agent for controlling the toner to negative charge include the following substances.

For example, organometallic compounds such as organometallic complexes and chelate compounds are effective. Specifically, monoazo metal complexes, acetylacetone metal complexes, metal complexes of aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metals are useful. There are complexes. In addition, it is also possible to use aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol.

Further, as the positive charge control agent for controlling the positive charge, there are the following substances.

Modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments; triphenylmethane dyes and these lake pigments (as the lacking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) Lauric acid, gallic acid, ferricyanide, ferrocyanide); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin Diorganotin borates such as borate; these can be used alone or in combination of two or more.

The charge control agents described above are preferably used in the form of fine particles. In this case, the number average particle size of these charge control agents is preferably 4 μm or less, more preferably 3 μm or less. When these charge control agents are internally added to the toner, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the binder resin.

Further, in the present invention, when the toner particles are produced by a polymerization method, a charge control agent having no polymerization inhibition and having no water-soluble substance is particularly preferable. Specific compounds include negative charge control agents such as a metal compound of salicylic acid, a metal compound of naphthoic acid, a metal compound of dicarboxylic acid, a polymer compound having a sulfonic acid or carboxylic acid in a side chain, a boron compound, and a urea compound. Compounds, silicon compounds and curryx arenes can be used. As the positive charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound are preferably used. These charge control agents are preferably used in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin.

With respect to the colorant used in the toner according to the present invention, black colorants such as carbon black and magnetite may be used in addition to the following yellow colorants.
A black-colored one using a magenta / cyan colorant is used.

Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
Compounds represented by azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168 and 180 are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
22, 144, 146, 166, 169, 177, 18
4, 185, 202, 206, 220, 221, 254
Is particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66 can be suitably used.

These coloring agents can be used alone or as a mixture, or in the form of a solid solution.

In the present invention, the colorant used in the toner is
It is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner.

The content of the colorant in the toner is 100
The amount is preferably 1 to 20 parts by mass with respect to parts by mass.

When magnetite is used as a black colorant, the toner preferably contains 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin, unlike other colorants.

The method for producing the toner particles of the present invention includes the following.
Henschel mixer, ball mill,
A mixing step using a V-type mixer or another mixer; a kneading step using a hot kneader such as a hot roll kneader or an extruder; a pulverizing step using a pulverizer such as a jet mill after cooling and solidifying the kneaded material; There is a method of manufacturing through a classifying step of a pulverized material.

As another method, there is a polymerization method produced through a step of granulating / polymerizing a component containing a monomer, a colorant and the like.

The toner of the present invention has the following manufacturing steps.
It is particularly preferable that the compound is produced through a step of granulating / polymerizing a component containing at least a monomer and a colorant. As for the toner produced by this production method, a shape having a smooth surface can be obtained, and the charge control of the toner by the external additive composition of the present invention works more effectively. High effects are obtained, and the effect of preventing image defects due to contamination of the charging member is higher.

This manufacturing method will be described in detail below.

Examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile) and 2,2 ′
-Azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-
Azo or diazo polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichloro A peroxide-based polymerization initiator such as benzoyl peroxide and lauroyl peroxide is used.

The amount of the polymerization initiator to be added varies depending on the desired degree of polymerization, but is generally 0.5 to 2 parts by weight per monomer.
0 mass% is added and used. The type of the polymerization initiator varies slightly depending on the polymerization method, but may be used alone or in combination with reference to the 10-hour half-life temperature.

In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be further added and used.

Examples of the crosslinking agent include compounds having two or more polymerizable double bonds, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, A carboxylic acid ester having two double bonds such as 3-butanediol dimethacrylate; a divinyl compound such as divinylaniline, divinylether, divinylsulfide, or divinylsulfone; and a compound having three or more vinyl groups alone or Can be used as a mixture.

As the dispersant, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate are used as inorganic compounds. , Calcium sulfate,
Examples include barium sulfate, bentonite, silica, alumina, a magnetic material, and ferrite. As organic compounds,
Polyvinyl alcohol, gelatin, methylcellulose,
Methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like can be used by dispersing them in an aqueous phase.

These dispersants are preferably used in an amount of 0.2 to 2.0 parts by mass based on 100 parts by mass of the polymerizable monomer.

As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound may be formed under high-speed stirring in a dispersion medium. it can. For example, in the case of tricalcium phosphate, a dispersant suitable for suspension polymerization can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

To make these dispersants finer, 0.001
You may use together 0.1-0.1 mass part of surfactant. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used, and examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, and potassium stearate. ,
And calcium oleate.

In the present invention, the toner can be specifically manufactured by the following manufacturing method.

That is, a releasing agent comprising a low softening point substance, a colorant, a charge control agent, a polymerization initiator, and other additives are added to the polymerizable monomer, and the mixture is uniformly mixed with a homogenizer, an ultrasonic disperser or the like. The dissolved or dispersed monomer system is dispersed in an aqueous phase containing a dispersion stabilizer using a conventional stirrer, homomixer, homogenizer, or the like. Preferably, the agitation speed and time are adjusted so that the monomer droplets have the desired size of the toner particles, and granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. Polymerization temperature is 40
The polymerization is preferably carried out at a temperature of at least 50 ° C., generally from 50 to 90 ° C. The temperature may be raised in the second half of the polymerization reaction, and further, the second half of the reaction to remove unreacted polymerizable monomers, by-products, etc. which cause odor at the time of fixing the developer, or
After the completion of the reaction, a part of the aqueous medium may be distilled off. In the suspension polymerization method, water 3 is usually added to 100 parts by mass of the monomer system.
It is preferable to use 00 to 3000 parts by mass as the dispersion medium.

In the present invention, when a toner is produced by a polymerization method, a resin having a polarity such as a polyester resin (hereinafter, referred to as a polyester resin) is used together with the above-mentioned polymer monomer for providing a binder resin.
(Referred to as "polar resin").

The amount of the polar resin added is 100
It is preferable to use 1 to 25 parts by mass with respect to parts by mass,
More preferably, it is 2 to 15 parts by mass. If the amount is less than 1 part by mass, the existence state of the polar resin in the toner particles becomes non-uniform, and if it exceeds 25 parts by mass, the thin layer of the polar resin formed on the surface of the toner particles becomes thick. It is difficult to obtain a proper charging characteristic.

The composition of a typical polyester resin used as such a polar resin is as follows.

As the alcohol component monomer of the polyester resin, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Examples thereof include 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (a), and diols represented by the following formula (b).

[0156]

Embedded image

In the present invention, in addition to the polar resin as described above, another polymer can be further contained in the toner. As other polymers, for example, epoxy resin,
Polycarbonate resin, polyolefin, polyvinyl acetate, polyvinyl chloride, polyalkyl vinyl ether, polyalkyl vinyl ketone, polystyrene, poly (meth)
Acrylic ester, melamine formaldehyde resin, polyethylene terephthalate, nylon, and polyurethane are exemplified.

In the present invention, as a method of the step A for mixing and dispersing the toner particles and the inorganic fine particles 1 to obtain a toner precursor, the toner particles and the inorganic fine particles 1 are stirred using an apparatus such as a Henschel mixer or a hybridizer. -A method of mixing can be mentioned.

In the present invention, as the method of the step B of mixing and dispersing the toner precursor, the inorganic fine particles 2 and the silica fine particles, the same method as described above can be used.

The method for measuring the physical properties of the toner of the present invention is as follows.

The molecular weight of the resin is measured by GPC (gel permeation chromatography). As a specific GPC measurement method, the toner is extracted in advance with a toluene solvent using a Soxhlet extractor for 20 hours, and then toluene is distilled off using a rotary evaporator. Further, the substance having a low softening point is dissolved, but the resin is dissolved. After adding an organic solvent (eg, chloroform) that cannot be obtained and washing well, the solution dissolved in THF (tetrahydrofuran) was filtered through a solvent-resistant membrane filter having a pore diameter of 0.3 μm. Use
The column configuration is A-801, 802, 803, manufactured by Showa Denko
804, 805, 806 and 807 are connected, and the molecular weight distribution is measured using a standard polystyrene resin calibration curve.

The acid value is determined as follows. The basic operation conforms to JIS-K0070.

(1) Reagent (a) Solvent: Ethyl ether-ethyl alcohol mixed liquid (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixed liquid (1 + 1 or 2 + 1). These solutions were prepared immediately before use using phenolphthalein as an indicator. / 10
Neutralize with potassium hydroxide ethyl alcohol solution. (B) Phenolphthalein solution; 1 g of phenolphthalein in 100 m of ethyl alcohol (95 v / v%)
Dissolve in l. (C) N / 10 potassium hydroxide-ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to make 1 liter, leave for 2 to 3 days, and filter. . The orientation is JIS-
K8006 (Basic matters concerning titration during reagent content test)
Perform according to.

(2) Operation 1 to 20 g of a sample were weighed correctly, and the solvent was
Add ml and a few drops of phenolphthalein solution as indicator and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve by heating on a water bath. After cooling, this is N / 1
The solution is titrated with a potassium hydroxide ethyl alcohol solution, and the end point of the neutralization is defined as the point at which the indicator remains slightly red for 30 seconds.

(3) Calculation formula The acid value is calculated by the following formula.

[0166]

(Equation 1) A: Acid value (mgKOH / g) B: Usage amount of N / 10 potassium hydroxide ethyl alcohol solution (ml) f: Factor of N / 10 potassium hydroxide ethyl alcohol solution S: Sample (g)

A method for measuring the particle size distribution will be described.

The weight average particle size and particle size distribution of the toner can be measured by various methods such as Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter). And a PC9801 personal computer (manufactured by NEC) were connected, and the data was output as data obtained by dividing the particle size range into 16 parts.

The electrolytic solution is 1% using primary sodium chloride.
Prepare an aqueous NaCl solution. For example, ISOTON-I
I (manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic aqueous solution 100 to
In 150 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant,
Further, 2 to 20 mg of a measurement sample is added. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles having a size of 2 μm or more are measured by using the measuring device using a 100 μm aperture. Distribution was calculated. Then, the weight-based weight average particle diameter D4 obtained from the volume distribution according to the present invention is
(The central value of each channel is set as a representative value for each channel).

A method for measuring the charge amount of the fine particles will be described.

As a method for measuring the charge amount of the fine particles of the present invention, EFV200 / 300 (manufactured by Powder Deck) as a carrier is used in an environment of a temperature: 23 ° C. and a humidity: 60%.
Then, 10.0 g of the carrier and 0.2 g of the fine particles are put into a polyethylene container having a capacity of 50 ml, and shaken by hand 90 times.

Next, as shown in FIG. 3, about 1 g of the mixture is put into a metal measuring container 62 having a 500-mesh screen 63 at the bottom, and a metal lid 64 is placed.
At this time, the mass of the entire measurement container 62 is measured and defined as W1 (g). Next, in the suction device 61 (the part in contact with the measurement container 62 is an insulator), suction is performed from the suction port 67 and the air volume control valve 6
6 to adjust the pressure of the vacuum gauge 65 to 2450 Pa (250
mmAq). In this state, suction is performed for 2 minutes to remove fine particles. The potential of the electrometer 69 at this time is set to V (volt). Here, reference numeral 68 denotes a capacitor whose capacity is C (mF). The mass of the entire measurement container 62 after the suction is measured, and it is defined as W2 (g). Charge amount T of fine particles
(MC / kg) is determined by the following formula.

The charge amount T (mC / kg) = C × V / (W1−W2)

The method for measuring the charge amount of the toner of the present invention is the same as that described above except that the amount of the toner is 0.5 g.

A method for measuring SF-1 and SF-2 indicating the shape factor will be described.

In the present invention, SF-
1. SF-2 is, for example, FE-SEM manufactured by Hitachi, Ltd.
Using (S-800), 100 toner images of 2 μm or more, which were magnified 1000 times, were randomly sampled, and the image information was introduced into, for example, an image analyzer (Luzex III) manufactured by Nireco via an interface and analyzed. And the values calculated from the following equation are used as shape factors SF-1, S
Defined as F-2.

[0177]

(Equation 2) (Where MXLNG is the absolute maximum length of the particle, PERIME
Is the perimeter of the grain, and AREA is the projected area of the grain. )

The shape factor SF-1 indicates the degree of roundness of the particles, and the shape coefficient SF-2 indicates the degree of irregularities of the particles.

A method of measuring an endothermic peak in differential thermal analysis will be described.

The endothermic peak in the differential thermal analysis according to the present invention is measured by a high-precision internal heating type input compensation type differential scanning calorimeter.

For example, a DSC manufactured by PerkinElmer, Inc.
-7 can be used. The measuring method is ASTM D3418.
Perform according to -82.

The DSC curve used in the present invention is a DSC curve measured when the temperature is raised once, the pre-history is taken, and then the temperature is lowered and raised at a temperature rate of 10 ° C./min and a temperature range of 0 to 200 ° C. Use a curve.

The endothermic peak temperature is a peak temperature in the positive direction in the DSC curve, that is, a point at which the differential value of the peak curve becomes zero when the value changes from positive to negative.

A method for measuring the average primary particle size of the inorganic fine particles 1 and 2 and the silica fine particles will be described.

The measurement of the average primary particle diameter of the inorganic fine particles 1 and 2 and the silica fine particles according to the present invention was performed by using a scanning electron microscope FE-SEM (S-4700 manufactured by Hitachi, Ltd.) with a photograph magnified 100,000 times. An image is taken, and the particle size of 500 or more particles is measured using a ruler, calipers, and the like with reference to the horizontal direction on the photograph. If necessary, the photograph is further enlarged for measurement.

The average number of each of the measured particles is calculated, and the average primary particle size of the present invention is determined.

When the inorganic fine particles 1 and 2 have the same composition, a graph of the number distribution with respect to the primary particle size is made, and the particles having the minimum number frequency between the peaks of the inorganic fine particles 1 and 2 are prepared. Based on the diameter, the inorganic fine particles 1 and the inorganic fine particles 2 are distinguished, and the number average in each particle size region is calculated.

The composition of the fine particles was determined by the FE-SEM
This is performed by detecting only a specific element specified by the X-ray microanalyzer described above.

A method for measuring the molecular weight distribution of the wax will be described.

The molecular weight distribution of the wax according to the present invention was determined by measuring apparatus: Gel permeation chromatography (GPC): GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o- Dichlorobenzene (addition of 0.1% ionol) Flow rate: 1.0 ml / min Sample: Inject 0.4 ml of 0.15% sample Measure under the above conditions, and prepare the molecular weight of the sample using a monodisperse polystyrene standard sample Use the calibrated molecular weight curve. Further, it is calculated by converting to polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

Next, the image forming method of the present invention will be described.

The image forming method of the present invention comprises: (I) a step of supplying a non-magnetic toner onto a toner carrier by a supply roller; and (II) a process of applying the electrostatic latent image formed on the latent image carrier to the toner carrier. Developing with the non-magnetic toner of the toner layer formed thereon to form a developed image; (III) pressing the non-magnetic toner on the toner carrier with a toner coating blade to form the toner layer on the toner carrier. Forming and rubbing the non-magnetic toner to apply a charge to the non-magnetic toner; (IV) transferring a developed image to a transfer material; and (V) fixing the transferred developed image. The toner of the present invention described above is used as the non-magnetic toner.

In the image forming method of the present invention, the peripheral speed of rotation of the toner carrier is preferably 100 to 800 mm / sec.
c, more preferably from 200 to 700 mm / sec, the effect of controlling the charge of the toner is further increased.

The rotational peripheral speed of the toner carrier is 100 mm / s
If it is lower than ec, the relative peripheral speed difference between the toner carrier and the toner application blade cannot be sufficiently obtained, and it is difficult to obtain the toner charge control effect. If the rotational peripheral speed of the toner carrier is faster than 800 mm / sec, mechanical stress on the toner increases, and it is difficult to obtain the toner charge control effect when printing a large number of sheets.

The image forming method of the present invention will be described below with reference to the drawings.

FIG. 4 is an example of a schematic process diagram of the image forming method of the present invention. FIG. 5 is an example of a schematic view of a developing unit suitably used in the present invention.

Reference numeral 102 denotes a charging roller, which is a charging unit that is brought into contact with the latent image carrier 101 with a predetermined pressure, and a conductive rubber layer 102b is provided on a metal core 102a, and a release coating is formed on the peripheral surface thereof. A surface layer 102c is provided. The conductive rubber layer preferably has a thickness of preferably 0.5 to 10 mm, more preferably 1 to 5 mm. The surface layer 102c is a release coating, and the provision of the release coating prevents the softening agent from the conductive rubber layer 102b from seeping out into a portion in contact with the latent image carrier 101, which is a charged body. To do that. Therefore, when the softener adheres to the photoreceptor, image flow due to lowering of the resistance of the photoreceptor and reduction in charging ability due to filming of residual toner on the photoreceptor can be prevented, and reduction in charging efficiency can be suppressed.

Furthermore, by using a conductive rubber layer for the charging roller, sufficient contact between the charging roller and the photosensitive member can be maintained, and no charging failure occurs.

The thickness of the release film is preferably within 30 μm, more preferably 10 to 30 μm. The lower limit of the thickness of the releasable film is 5 if the film is not peeled or blunt.
It is considered about μm.

[0200] Nylon resin PVDF is used for the release coating.
(Polyvinylidene fluoride) and PVDC (polyvinylidene chloride) can be used. As the photosensitive layer of the latent image carrier 101, OPC, amorphous silicon, selenium, or ZnO can be used. In particular, when amorphous silicon is used for the photoconductor, the softener for the conductive rubber layer 102b is more softened than when the other is used.
Even if it adheres to the photosensitive layer of No. 01, the image flow becomes severe, so that the effect of the insulating coating on the outside of the conductive rubber layer is great.

It is also a preferable embodiment to form a high-resistance layer, for example, a hydrin rubber layer with small environmental fluctuation, between the conductive rubber layer and the surface layer of the release coating to prevent leakage to the photoreceptor. Reference numeral 115 denotes a power supply unit for applying a voltage to the charging roller 102, and supplies a predetermined voltage to the metal core 102a of the charging roller 102.

Reference numeral 103 denotes a transfer charger as transfer means. A predetermined bias is applied from the constant voltage power supply 114 to the transfer charger. The bias condition is that the current value is 0.1
And a voltage value (absolute value) of 500 to 400 μA.
It is preferably 0V.

A latent image carrier 10 is charged by a charging roller 102 as a charging unit having a power supply unit (voltage applying unit) 115.
The surface of the OPC photoconductor 1 is charged and exposed by light image exposure as the latent image forming means 105 to form an electrostatic latent image. The developing means for developing the electrostatic latent image has the following configuration. Reference numeral 104 denotes a toner carrier made of a non-magnetic sleeve made of aluminum or stainless steel. The toner carrier may be aluminum, a stainless steel coarse tube may be used as it is, but preferably the surface is uniformly roughened by spraying glass beads or the like, the mirror-treated one,
Alternatively, a material coated with a resin is preferable. The toner 110 is stored in the hopper 116 of the developing unit 109 and is supplied onto the toner carrier 104 by the supply roller 113. The supply roller 113 is made of polyurethane rubber. The supply roller 113 is pressed against the toner carrier 104 and rotates in a forward or reverse direction at a relative speed other than 0 to supply the toner.
Stripping of 0 (undeveloped toner) is also performed. The toner 110 supplied onto the toner carrier 104 is uniformly and thinly applied by a toner application blade 111, and is triboelectrically charged and charged. Next, the toner 11
0 is very close to the latent image carrier 101 (50 to 500 μm).
m) to develop the latent image formed on the latent image carrier 101.

The base on the upper side of the toner application blade 111 is fixedly held in the toner container, and the lower side is the toner carrier 104 against the elasticity of the toner application blade 111.
And the outer surface side of the blade is brought into contact with an appropriate elastic pressure.

The toner application blade 111 is preferably made of a material of a triboelectric series suitable for charging the toner to a desired polarity. When the toner is negatively chargeable, urethane rubber, urethane resin, polyamide or nylon is preferred, and among them, those which are easily charged to positive polarity are particularly preferred. If the toner is positively charged,
Urethane rubber, urethane resin, silicone rubber, silicone resin, polyester resin, fluorine resin (for example, Teflon (registered trademark) resin) or polyimide resin is preferable, and among them, those which are easily charged to negative polarity are particularly preferable. Further, conductive rubber or conductive resin may be used. When the portion contacting the toner carrier 104 is a molded body such as a resin or rubber, metal oxides such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide are included therein to adjust the chargeability of the toner. , Carbon black, and a charge control agent generally used for toner.

When durability is required for the blade,
It is preferable that a resin and a rubber are stuck on the metal elastic body so as to abut on a portion in contact with the toner carrier 104.

In the image forming method of the present invention, when a negatively chargeable toner is used, the toner coating blade may be a toner coating blade having a polyamide-containing rubber layer on the surface of the toner carrier, so that the toner can be used. The charge control effect increases.

Further, in the image forming method of the present invention,
Shore D hardness of the polyamide-containing rubber layer is from 25 to 6
By setting the angle to 5 degrees, the effect of controlling the charge of the toner is further increased.

In the image forming method of the present invention, the Shore D hardness of the polyamide-containing rubber layer is less than 25 degrees,
In all cases, the toner is not sufficiently charged by the toner application blade, the amount of insufficiently charged toner increases, and fogging tends to occur.

The latent image carrier 101 is developed by using the developing means.
In the developing unit that develops the electrostatic latent image, an AC bias or a pulse bias may be applied between the toner carrier 104 and the surface of the latent image carrier 101 from a bias power source 112 as a bias unit. As the bias condition, Vpp = 1000 to 3000 as an AC bias
V, f = 1000-4500 (Hz), DC bias is | DC | = 200-500 V, and the absolute value | Vd | of the primary charging potential of the photoconductor and | D of the DC bias
Difference from C | | Difference from DC | | Vback | = 150-3
It is preferably 00V. When the toner 110 is transferred in the developing section formed at and near the toner carrier 104 and the latent image carrier 101 at the closest portion, the electrostatic force of the electrostatic image carrying surface of the latent image carrier 101, and The toner 110 transfers to the latent image carrier 101 while reciprocating between the toner carrier 104 and the latent image carrier 101 by the action of an AC bias or a pulse bias.

When the transfer paper P is conveyed and reaches the transfer section, the latent image is charged by the voltage applying means 114 from the back surface (opposite to the latent image carrier side) of the transfer paper P by the transfer charger 103. The developed image (toner image) on the surface of the carrier 101 is electrostatically transferred onto the transfer paper P. Latent image carrier 1
The transfer sheet P separated from the transfer sheet P is subjected to a fixing process for fixing a toner image on the transfer sheet P by a heating / pressing roller fixing device 107 as a fixing unit.

The toner 110 remaining on the latent image carrier 101 after the transfer step is removed by a cleaning device 108 having a cleaning blade. After the cleaning process, the latent image carrier 101 is neutralized by the erase exposure 106,
The process starting from the charging process by the charger 102 is repeated again.

As the photosensitive layer of the latent image carrier 101, OPC
Insulating drum for electrostatic recording, α-Se,
A photosensitive drum having a photoconductive insulating material layer such as CdS, ZnO ₂ and α-Si can be appropriately selected and used according to the development conditions.

FIG. 6 and FIG. 7 are examples of schematic process diagrams when the present invention is applied to a full-color image forming method.

The latent image carrier 101 is primarily charged by a charging roller 102 which rotates in contact with and rotates against the latent image carrier 101.
An electrostatic latent image is formed by the exposure unit 105 by giving a surface potential thereon. The electrostatic latent images are developed by developing units 44, 45, 46 and 4
7 to form a toner image. The toner image is multiplex-transferred onto the intermediate transfer body 11 for each color, and a multiplex toner image is formed. From the latent image carrier 101 to the intermediate transfer member 5
To transfer the toner image to 0, a transfer current is obtained by applying a bias to the core metal of the intermediate transfer body 50 from the power supply 49 to transfer the toner image. Corona discharge or roller charging from the back of the holding member or belt may be used. The multiple toner images on the intermediate transfer member 50 are collectively transferred onto the transfer material P by the transfer charging member 51 to which a bias has been applied by the transfer bias application power supply 52. As the transfer charging member, a contact electrostatic transfer unit using a corona charger, a transfer roller, or a transfer belt is used. As the transfer charging member 51, a roller member as shown in FIG. 6 or a belt member as shown in FIG. 7 is used.

The image forming apparatus according to the first embodiment of the present invention comprises: (I) a latent image carrier for carrying an electrostatic latent image; (II) a charging device for primary charging the latent image carrier; (III) exposure means for forming an electrostatic latent image on the primary charged latent image carrier; (IV) a plurality of developing means for developing the electrostatic latent image with a non-magnetic toner to form a toner image (V) an intermediate transfer member for sequentially transferring the toner images formed by the respective developing devices; and (VI) a multi-toner image transferred on the intermediate transfer member is collectively transferred to a transfer material. A non-magnetic toner using the above-described toner of the present invention.

Hereinafter, an image forming apparatus of a first embodiment using an intermediate transfer member will be described.

FIG. 8 is a schematic diagram of an image forming apparatus of the present invention which collectively transfers multiple toner images to a recording material using an intermediate transfer drum as an intermediate transfer member.

A rotatable charging roller 2 to which a charging bias voltage is applied as a charging member is brought into contact with the surface of a photosensitive drum 1 as a latent image carrier while rotating,
The surface of the photoconductor drum is uniformly primary charged, and a first electrostatic latent image is formed on the photoconductor drum 1 by a laser beam E emitted from a light source device L as an exposure unit. The formed first electrostatic latent image is used as a first developing device provided in a rotatable rotary unit 4 as a black developing device 4B.
The black toner image is developed with the black toner in k and a black toner image is formed. The black toner image formed on the photosensitive drum 1 is primarily transferred onto the intermediate transfer drum 5 electrostatically by the action of a transfer bias voltage applied to the conductive support of the intermediate transfer drum. Next, a second electrostatic latent image is formed on the surface of the photoreceptor drum 1 in the same manner as described above, and the rotary unit 4 is rotated to use the yellow toner in the yellow developing device 4Y as the second developing device. The yellow toner image is formed by development, and the yellow toner image is electrostatically primary-transferred onto the intermediate transfer drum 5 on which the black toner image is primarily transferred. Similarly, by rotating the rotary unit 4, the third electrostatic latent image and the fourth electrostatic latent image are
The magenta toner in the magenta developing device 4M as the developing device and the cyan toner in the cyan developing device 4C as the fourth developing device sequentially perform development and primary transfer to form a toner image of each color on the intermediate transfer drum 5. Each is primarily transferred. The multiple toner image primarily transferred onto the intermediate transfer drum 5 is electrostatically transferred onto the recording material P by the action of a transfer bias voltage from the second transfer device 8 located on the opposite side via the recording material P. The secondary transfer is performed at once. The multiple toner image secondary-transferred onto the recording material P is heat-fixed to the recording material P by a fixing device 3 having a heating roller and a pressure roller.
The transfer residual toner remaining on the surface of the photosensitive drum 1 after the transfer is collected by a cleaner having a cleaning blade in contact with the surface of the photosensitive drum 1, and
Is cleaned.

The primary transfer from the photosensitive drum 1 to the intermediate transfer drum 5 is performed by the intermediate transfer drum 5 as a first transfer device.
A transfer current is obtained by applying a bias from a power supply (not shown) to the conductive support of (1), and the transfer of the toner image is performed.

The intermediate transfer drum 5 comprises a conductive support 5a which is a rigid body, and an elastic layer 5b which covers the surface.

As the conductive support 5a, metals and alloys such as aluminum, iron, copper and stainless steel, and conductive resins in which carbon and metal particles are dispersed can be used. And those in which a shaft passes through the center of the cylinder, and those in which the inside of the cylinder is reinforced.

The elastic layer 5b is not particularly limited, but includes styrene-butadiene rubber, high styrene rubber, butadiene rubber, isoprene rubber, ethylene-propylene copolymer, nitrile butadiene rubber (NB
R), elastomer rubbers such as chloroprene rubber, butyl rubber, silicone rubber, fluorine rubber, nitrile rubber, urethane rubber, acrylic rubber, epichlorohydrin rubber and norbornene rubber are preferably used. Resins such as polyolefin-based resins, silicone resins, fluorine-based resins, and polycarbonates, and copolymers and mixtures thereof may be used.

Further, a surface layer in which a lubricant powder having high lubricity and water repellency is dispersed in an arbitrary binder may be provided on the surface of the elastic layer.

Although there is no particular limitation on the lubricant, various types of fluororubber, fluoroelastomer, carbon fluoride having graphite or graphite bonded to fluorine, polytetrafluoroethylene (PTFE), polyvinyldene fluoride (PVDF), ethylene-tetrafluoroethylene Copolymer (ETFE)
And fluorine compounds such as tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA),
Silicone compounds such as silicone resin particles, silicone rubber, silicone elastomer, polyethylene (P
E), polypropylene (PP), polystyrene (P
S), an acrylic resin, a polyamide resin, a phenol resin, an epoxy resin and the like are preferably used.

A conductive agent may be added to the binder of the surface layer as needed to control the resistance. As the conductive agent,
Examples include various conductive inorganic particles and carbon black, an ionic conductive agent, a conductive resin, and a conductive particle-dispersed resin.

The multi-toner image on the intermediate transfer drum 5 is secondarily transferred onto the recording material P by the second transfer device 8 collectively. The transfer device 8 is a non-contact electrostatic transfer device using a corona charger. Alternatively, a contact electrostatic transfer unit using a transfer roller and a transfer belt can be used.

As the fixing device 3, instead of a heat roller fixing device having a heating roller 3a and a pressure roller 3b, the toner image on the recording material P is heated by heating a film in contact with the toner image on the recording material P. Is heated and the recording material P
Alternatively, a film heat fixing device that heats and fixes a multiple toner image can be used.

Instead of the intermediate transfer drum as an intermediate transfer member used in the image forming apparatus shown in FIG. 8, it is also possible to collectively transfer multiple toner images onto a recording material using an intermediate transfer belt.

Next, an image forming apparatus having a transfer device for sequentially transferring a plurality of toner images onto a transfer material will be described as an image forming apparatus according to a second embodiment of the present invention.

The second image forming apparatus of the present invention comprises: (I) a latent image carrier for carrying an electrostatic latent image; (II) a charging device for primary charging the latent image carrier; (III) ) Exposure means for forming an electrostatic latent image on the primary charged latent image carrier; (IV) a plurality of developing devices for developing the electrostatic latent image with non-magnetic toner to form a toner image; And (V) a transfer device for sequentially transferring the toner images formed by each of the developing devices to a transfer material, wherein the toner of the present invention described above is used as the non-magnetic toner.

FIG. 9 shows a second embodiment of the present invention in which a toner image is sequentially transferred to a recording material on a transfer drum to form a multiple toner image.
1 is a schematic view of an image forming apparatus according to the first embodiment.

The electrostatic latent image formed on the photosensitive drum 31 as a latent image carrier by the exposure unit 33 as a latent image forming unit is developed by a developing unit attached to a rotary developing unit 32 which rotates in the direction of the arrow. Is visualized by a one-component developer having the first non-magnetic color toner in the developing device 32-1. The color toner image on the photosensitive drum 31 is
The image is transferred by a transfer charger 38 to a recording material P as a transfer material held on a transfer drum 36 by a gripper 37.

As the transfer charger 38, a corona charger or a contact charger is used. When a corona charger is used as the transfer charger 38, a voltage of -10 kV to +10 kV is applied, and the transfer current is-. 500 μA to +500 μA. A holding member is stretched on the outer peripheral surface of the transfer drum 36,
The holding member is formed of a film-like dielectric sheet such as a polyvinylidene fluoride resin film or polyethylene terephthalate. For example, a thickness of 100 μm to 20 μm
A sheet having a thickness of 0 μm and a volume resistance of 10 ¹² to 10 ¹⁴ Ω · cm is used.

Next, the rotary developing unit rotates as the second color, and the developing device 32-2 faces the photosensitive drum 31. Then, it is developed with a one-component developer having the second non-magnetic color toner in the developing device 32-2, and this color toner image is also transferred onto the recording material P as the same transfer material as above.

Further, the third color and the fourth color are performed in the same manner.
In this way, the transfer drum 36 rotates a predetermined number of times while holding the transfer material (recording material), and the toner image of a predetermined number of colors is multiplex-transferred. The transfer current for electrostatic transfer is the first color <
It is preferable to increase the order of the second color <the third color <the fourth color in order to reduce transfer residual toner remaining on the photosensitive drum 31.

If the transfer current is too high, the transferred image is disturbed, which is not preferable.

[0238] The transfer material P subjected to the multiple transfer is supplied to the separation charger 3
The toner image is separated from the transfer drum 36 by a fixing unit 9 and is fixed by a heating and pressurizing roller fixing unit 40 having a web impregnated with silicone oil.

In the case of an apparatus for replenishing toner to the developing device, the replenishing toner supplied to the developing devices 32-1 to 32-4 is supplied from a replenishing hopper provided for each color to a fixed amount based on a replenishing signal. The toner is transported to the toner supply cylinder at the center of the rotary developing unit 2 via the transport cable, and is sent to each developing device.

An image forming apparatus according to a third embodiment of the present invention comprises: (I) a latent image carrier for carrying an electrostatic latent image, a charging device for primary charging the latent image carrier, A plurality of image forming units each including exposure means for forming an electrostatic latent image on the latent image carrier, and a developing device for developing the electrostatic latent image with a non-magnetic toner to form a toner image;
And (II) a transfer device for sequentially transferring the toner images formed by the development units to a transfer material, wherein the toner of the present invention described above is used as the non-magnetic toner.

FIG. 10 also shows an image forming apparatus capable of implementing an image forming method in which a toner image of each color is formed by a plurality of image forming units, and the toner images are sequentially superimposed and transferred onto the same transfer material. This will be explained.

Here, the first, second, third and fourth image forming units 28 _a , 28 _b , 28 _c , 28 _d are arranged side by side, and each image forming unit has a dedicated latent image carrier. body, and provided with a so-called photosensitive drum 19 _a, 19 _b, 19 _c and 19 _d.

The photosensitive drum 19_aTo 19_dIs on the outer side
Exposure means 23 as latent image forming means _a, 23_b, 23_cYou
And 23_d, Developing device 17_a, 17_b, 17_cAnd 1
7_d, Transfer discharger 24_a, 24_b, 24_cAnd 24
d and the cleaning device 18_a, 18_b, 18_cYou
And 18_dIs arranged.

[0244] In this structure, first, a latent image forming means on the photosensitive drum 19 _a of the first image forming unit 28 _a 23
_{By a} , an electrostatic latent image of, for example, a yellow component color in _a document image is formed. This electrostatic latent image is developed by developing means _17a.
Is a visible image in a one-component developer having non-magnetic yellow toner, at the transfer device 24 _a, is transferred onto the recording material P as a transfer material.

While the yellow toner image is being transferred to the recording material P as described above, the second image forming unit 28 _b
In a magenta component color latent image is formed on the photosensitive drum 19 _b, followed are visible image in a one-component developer having non-magnetic magenta toner in the developing device 17 _b with. This visible image (magenta toner image), when the transfer material P transferred in the first image forming unit 28 _a of the is finished is carried to the transfer device 24 _b, a transfer material the yellow toner image is transferred The image is superimposed and transferred to a predetermined position of P.

Hereinafter, the third and fourth steps are performed in the same manner as described above.
The cyan and black images are formed by the image forming units 28 _c and 28 _d of the same recording material P.
Then, the cyan toner image and the black toner image are sequentially superimposed and transferred. When such an image forming process is completed, the recording material P is conveyed to the fixing unit 22, and the image on the recording material P is fixed. Thus, a multi-color image (multi-color image or full-color image) is obtained on the recording material P. Each photosensitive drum 1 whose transfer has been completed
9 _a , 19 _b , 19 _c and 19 _d correspond to the cleaning device 18.
_a, 18 _b, by 18 _c and 18 _d are removed residual toner, is subjected to subsequent next latent image formation is performed.

In the image forming apparatus, the transport belt 25 is used to transport the recording material P as a transfer material. In FIG. 10, the recording material P is transported from right to left, and the transport is performed. In the process, each image forming unit 2
Each transfer device in 8 _a, 28 _b, 28 _c and 28 _d 24
_a, it passes through the 24 _b, 24 _c and 24 _d, subjected to transfer.

In this image forming method, a transport belt using a mesh of Tetron (registered trademark) fiber as a transport means for transporting the recording material and a polyethylene terephthalate resin, a polyimide resin, A transport belt using a thin dielectric sheet such as a urethane resin is used.

[0249] When the recording material P passes through the fourth image forming unit 28 _d, AC voltage is applied to the static eliminator 20, the recording material P is discharged, it is separated from the belt 25 and then placed into a fixing device 22, the image The toner is fixed and discharged from the discharge port 26.

In the present invention, it is preferable that the image forming units are arranged in rows as shown in FIG. 10, and the image forming units may be arranged vertically or horizontally as long as they are arranged in rows.

In the present invention, in the configuration shown in FIG. 10, it is more preferable that the transfer material is a recording material and the toner image is directly transferred and fixed from the latent image carrier to the recording material. This is because the configuration of the image forming apparatus of the present invention can maintain high image quality regardless of the state of the transfer material (recording material) and toner.

Further, in the configuration of the image forming apparatus of the present invention, since toner charging is stable, toner scattering is prevented,
Since high image quality can be maintained without being mixed into other image units, it is suitable for a multicolor image forming method.

[0253]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, which do not limit the present invention in any way.

Example 1 450 parts by mass of a 0.1 M Na ₃ PO ₄ aqueous solution were charged into 700 parts by mass of ion-exchanged water, heated to 50 ° C., and then mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). ) And stirred at 10,000 rpm. To this, 70 parts by mass of a 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate salt. (Monomer) 170 parts by mass of styrene 30 parts by mass of n-butyl acrylate (colorant) I. Pigment Blue 15: 3 14 parts by mass (Charge control agent) Aluminum salicylate compound 2 parts by mass (Polar resin) Saturated polyester 20 parts by mass (Acid value 10 mgKOH / g, peak molecular weight; 15,000) (Release agent) Behenylbehe Nate (melting point: 73 ° C.) (wax A) 30 parts by mass (crosslinking agent) divinylbenzene 0.5 part by mass The above formulation was heated to 50 ° C. and 9000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) Dissolve uniformly in
Dispersed. Into this, 5 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 8000 rpm with a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer composition. did.

Thereafter, the temperature was raised to 70 ° C. in 2 hours while stirring with a paddle stirring blade, and after 4 hours, the temperature was raised at a rate of 40 ° C./H.
r. At 80 ° C. for 5 hours. After the completion of the polymerization reaction, the remaining monomers were distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve the calcium phosphate, followed by filtration, washing with water, drying and classification to obtain cyan toner particles (1).

Silica fine particles (silica-A) surface-treated with hexamethyldisilazane having an average primary particle size of 8 nm: 1 part by mass and an average primary particle size of 45 nm with respect to 100 parts by mass of cyan toner particles (1). Rutile type titanium oxide fine particles surface-treated with isobutylsilane
A): 0.15 parts by mass, untreated rutile-type titanium oxide fine particles having an average primary particle diameter of 200 nm and a charge amount of -2.1 mC / kg (inorganic fine particles 1-A): 0.8 part by mass of a Henschel mixer And the toner No. of the present invention. 1 was obtained.

Toner No. 1 has a weight average particle size of 7.3 μm
m, particles of 4 μm or less were 8.3 number%. Toner No. The endothermic peak in the differential thermal analysis of No. 1 was at 73 ° C.,
The half width of the endothermic peak was 3.2 ° C. Toner N
o. The peak molecular weight in GPC measurement of No. 1 was 22000, the acid value was 4.1 mgKOH / g, and the charge amount was -58 mC / kg.
Met. Toner No. The shape factor SF-1 of 1 is 11
2, SF-2 was 104. Toner No. SE of 1
From the result of measuring the number-based particle size distribution of the silica fine particles and the titanium fine particles from the M photograph, the silica fine particles have a single-peak particle size distribution with an average primary particle size of 8 nm, and the titanium oxide fine particles have an average primary particle size of 200 nm and 45 nm. It was confirmed that the particles had a particle size distribution having peaks respectively.

The toner No. As in the image forming apparatus shown in FIG. 8, a first color developing unit provided in a rotary unit of a commercially available full-color printer LBP-2160 (manufactured by Canon) as an image forming apparatus using an intermediate transfer member is used. Applied and evaluated. In addition, LBP-2
Reference numeral 160 denotes a rotary unit provided with three color developing devices, a yellow developing device having a yellow toner, a magenta developing device having a magenta toner, and a cyan developing device having a cyan toner. This is a full-color image forming apparatus provided around the photoconductor separately from the rotary unit.

In the case of toner fusing to a latent image holding member and image defects due to roughness of a halftone image, fog, and contamination of a charging member, which occur in a low humidity environment, a temperature of 15 ° C./5% R
In a low-temperature and low-humidity environment of H, evaluation was performed after 5,000 continuous printing of line images at a printing rate of 4%.

For the fusion of the toner to the latent image holding member,
The evaluation was made based on the number of dot-shaped white spot defects accompanying toner fusion appearing on three-size solid images.

As for the roughness of the halftone image,
With a dot size of 600 dpi, evaluation is performed with a halftone image in which one dot is hit for an area equivalent to 4 dots,
A, AB, B and C are shown in four stages.

The evaluation criteria for roughness of a halftone image are shown below. A: There is no roughness on the image. AB: There is slight roughness at the end of the image. B: There is roughness at the end of the image. C: There is roughness on the entire surface of the image.

As for fog, the fog on the latent image holding member was transferred with a tape, the tape was stuck on a blank sheet, and the difference from the reflectance of the reference tape was measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.). did.

Evaluation of image defects due to contamination of the charging member is as follows.
The evaluation was made based on the number of vertical streaks appearing in the halftone image.

For retransfer development, 32.5 ° C./95
20% line image with 4% printing rate in high temperature and high humidity environment
Evaluation was performed after printing 00 sheets continuously. Put the developing cartridge in the color station which is the first in the developing order,
From the difference between the reflection density of the halftone image printed out in the four-color superimposition (four times transfer step) mode and the reflection density of the halftone image printed out in the one-color mode (one transfer step) evaluated.

Regarding the toner dropping phenomenon when the toner is left in a high temperature environment, the toner is left in an environment of 50 ° C. for one week and a halftone image is printed in an environment of 15 ° C./5% RH. And the number of dots that appeared on the A3 size image.

The evaluation results are shown in Table 4.

Comparative Example 1 Comparative toner No. 1 was prepared in the same manner as in Example 1 except that the inorganic fine particles 1-A used in Example 1 were not used. 1 was obtained and evaluated in the same manner as in Example 1. Table 4 shows the results.

Comparative Example 2 Comparative toner No. 1 was prepared in the same manner as in Example 1 except that the inorganic fine particles 2-A used in Example 1 were not used. 2 was obtained and evaluated in the same manner as in Example 1. Table 4 shows the results.

<Comparative Example 3> Silica-A used in Example 1
Comparative toner N in the same manner as in Example 1 except that no toner was used and the amount of the inorganic fine particles 2-A was changed to 1.0 part by mass.
o. 3 was obtained and evaluated in the same manner as in Example 1. Table 4 shows the results.

<Examples 2 to 7, Comparative Examples 4 to 8>
In the same manner as in Example 1 except that the inorganic fine particles shown in Table 1 were used instead of the inorganic fine particles 1-A used in Example 1, Nos. 2 to 7 and Comparative Toner Nos. Get 4-8,
The same evaluation as in Example 1 was performed. Table 4 shows the results.

<Examples 8 to 13 and Comparative Examples 9 to 10> In the same manner as in Example 1 except that the inorganic fine particles shown in Table 2 were used instead of the inorganic fine particles 2-A used in Example 1, respectively. Toner No. Nos. 8 to 13 and Comparative Toner Nos. 9-1
0 was obtained, and the same evaluation as in Example 1 was performed. Table 5 shows the results.
Shown in

<Examples 14 to 15, Comparative Example 11> Toner N was prepared in the same manner as in Example 1 except that the inorganic fine particles shown in Table 3 were used instead of silica A used in the examples.
o. 14 and 15 and Comparative Toner Nos. 11 was obtained and evaluated in the same manner as in Example 1. Table 5 shows the results.

[0275]

[Table 1]

[0276]

[Table 2]

[0277]

[Table 3]

[0278]

[Table 4]

[0279]

[Table 5]

<Examples 16 to 19> Except for using the toner particles (2) to (5) shown in Table 6 produced in the same manner as in Example 1 except that the classification conditions in the classification step of toner production were changed,
In the same manner as in Example 1, toner Nos. 1
6 to 19 were obtained and evaluated in the same manner as in Example 1. Table 9 shows the physical properties of the toner, and Table 10 shows the evaluation results.

Examples 20 to 23 Toner particles (6) to (6) shown in Table 6 obtained in the same manner as in Example 1 except that waxes B to E shown in Table 8 were used as wax components to be contained in the toner. 9), except that toner No. 9 was used in the same manner as in Example 1. 20 to 23 were obtained and evaluated in the same manner as in Example 1. Table 9 shows the physical properties of the toner, and Table 10 shows the evaluation results.

<Examples 24 to 27> The toner particles (10) shown in Table 6 obtained in the same manner as in Example 1 except that the peak molecular weight in GPC measurement was adjusted by adjusting the amount of the polymerization initiator and the reaction temperature. ) To (13), except that toner Nos. 24 to 27 were obtained and evaluated in the same manner as in Example 1. Table 9 shows the physical properties of the toner, and Table 10 shows the evaluation results.

Examples 28 to 30 The toner particles (14) shown in Table 6 obtained in the same manner as in Example 1 except that monobutyl maleate was used in combination as a monomer component.
To (16), except that toner N
o. 28 to 30 were obtained and evaluated in the same manner as in Example 1. Table 11 shows the physical properties of the toner, and Table 12 shows the evaluation results.

<Example 31> A toner was prepared in the same manner as in Example 1 except that the toner particles (17) shown in Table 7 obtained in the same manner as in Example 1 except that an aluminum salicylate compound as a charge control agent was not added were used. No. Example 1
Was evaluated in the same way as Table 11 shows the physical properties of the toner, and Table 12 shows the evaluation results.

Example 32 Table 7 obtained in the same manner as in Example 1 except that the addition amount of the aluminum salicylate compound as the charge control agent was changed to 4 parts by mass, and the classification step and the classification conditions were changed. Except for using the toner particles (18), the toner No. 32 were obtained and evaluated in the same manner as in Example 1. Table 11 shows the physical properties of the toner, and Table 12 shows the evaluation results.

<Examples 33 to 35> • 100 parts by mass of styrene-butyl acrylate copolymer • C.I. I. Pigment Blue 15:37 parts by mass Behenyl behenate (melting point: 73 ° C) (wax A) 10 parts by mass Aluminum salicylate compound 2 parts by mass After premixing the above materials, biaxial kneading and extrusion set at 130 ° C. Melt kneading was performed by a machine. After cooling the kneaded material, it was roughly pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier. Furthermore, using a hybridization system type 1 (manufactured by Nara Machinery Co., Ltd.), surface treatment is performed by mechanical impact force,
Toner particles (19) shown in Table 7 with adjusted surface shape factors
To (21), except that toner N was used in the same manner as in Example 1.
o. 33 to 35 were obtained and evaluated in the same manner as in Example 1. Table 11 shows the physical properties of the toner, and Table 12 shows the evaluation results.

<Example 36> A table obtained in the same manner as in Example 33 except that a polyester resin (a condensation polymer of propoxylated bisphenol and fumaric acid) was used instead of styrene-butyl acrylate as the binder resin. 7, except that the toner particles (22) shown in FIG. 36 was obtained and evaluated in the same manner as in Example 1. Table 11 shows the physical properties of the toner, and Table 12 shows the evaluation results.

<Example 37> Inorganic fine particles 1 of Example 1
A: Instead of 0.8 parts by mass, inorganic fine particles 1-A: 0.1.
In the same manner as in Example 1, except that 4 parts by mass and 0.4 parts by mass of the inorganic fine particles 1-C were used together, 37 was obtained and evaluated in the same manner as in Example 1. Table 11 shows the physical properties of the toner, and Table 12 shows the evaluation results.

<Example 38> Inorganic fine particles 2 of Example 1
A: Instead of 0.15 parts by mass, inorganic fine particles 2-A:
In the same manner as in Example 1, except that 0.1 parts by mass of the inorganic fine particles 2-C and 0.1 part by mass of the inorganic fine particles 2-C were used together, 38 were obtained and evaluated in the same manner as in Example 1. Table 11 shows the physical properties of the toner.
And the evaluation results are shown in Table 12.

[0290]

[Table 6]

[0291]

[Table 7]

[0292]

[Table 8]

[0293]

[Table 9]

[0294]

[Table 10]

[0295]

[Table 11]

[0296]

[Table 12]

(Production Example 23 of Toner Particles) In 700 parts by mass of ion-exchanged water in a two-liter four-necked flask, 0.1 part was added.
450 parts by mass of a 1M-Na ₃ PO ₄ aqueous solution is charged, and
Then, the mixture was stirred at 10,000 rpm using a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 75 parts by mass of a 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous dispersion medium containing a minute water-insoluble dispersion stabilizer.

On the other hand, as a dispersoid, (monomer) styrene 170 parts by mass n-butyl acrylate 30 parts by mass (colorant) C.I. I. Pigment Blue 15: 3 14 parts by mass (charge control agent) Al compound of salicylic acid 2 parts by mass (release agent) behenyl behenate (melting point: 73 ° C.) (wax A) 30 parts by mass (polar resin) saturated polyester resin 20 Parts by mass (acid value; 10 mg KOH / g, peak molecular weight: 15,000) (Crosslinking agent) 0.5 parts by mass of divinylbenzene was prepared, the above formulation was heated to 50 ° C., and a TK homomixer (specialized (Manufactured by Kogyo Co., Ltd.) at 9000 rpm. To this, 5 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a polymerizable monomer composition.

The above monomer composition was charged into the aqueous dispersion medium prepared in the 2-liter flask of the homomixer. Using a TK homomixer in a nitrogen atmosphere at 60 ° C., the mixture was stirred at 8000 rpm to granulate the monomer composition. Then, while stirring with a paddle stirring blade, the temperature was raised to 70 ° C. at a heating rate of 40 ° C./hr after 1 hour, and further increased to 80 ° C. at a heating rate of 40 ° C./hr after 4 hours. Polymerization was carried out at 80 ° C. for 5 hours.

After the completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure, the reaction product was cooled, hydrochloric acid was added to dissolve the calcium phosphate salt, and the mixture was filtered, washed with water, dried and classified to obtain cyan toner particles ( 23) was obtained.

<Example 39> Cyan toner particles (2
3); the average primary particle size is 200 n with respect to 100 parts by mass.
m (charge amount: -2.1 mC / kg) rutile-type titanium oxide fine particles (inorganic fine particles 1A); 0.5 parts by mass of 4000 parts by Henschel mixer 10B (Mitsui Miike Kakoki Co., Ltd.)
After mixing and dispersing at 3 rpm for 3 minutes to obtain a toner precursor, silica particles (silica A) surface-treated with hexamethyldisilazane having an average primary particle size of 8 nm in the Henschel mixer; 1 part by mass, and , Average primary particle size is 45n
titanium oxide fine particles (inorganic fine particles 2A) surface-treated with m-isobutylsilane; 0.15 parts by mass;
The mixture was mixed and dispersed at 000 rpm for 5 minutes. 39
I got

Toner No. 39 has a weight average particle size of 7.0.
The number of particles having a particle diameter of 4 μm or less was 8.3% by number. The endothermic peak of the toner 1 in the differential thermal analysis was at 73 ° C., and the half width of the endothermic peak was 3.2 ° C. Toner No.
The peak molecular weight in GPC measurement of 39 was 21,000. Toner No. The acid value of 39 was 4.2 mgKOH / g. Toner No. 39 has a charge of -58 mC / kg
Met. Toner No. The shape factor SF-1 of 39 is 10
9, SF-2 was 104.

<Examples 40 to 45 and Comparative Examples 12 to 16>
> Instead of the inorganic fine particles 1A used in Example 39, Table 1
Is used in the same manner as in Example 39 except that the inorganic fine particles shown in Table 15 are used as shown in Table 15. 40 to 45 and Comparative Toner No. 12-16 were obtained. Obtained toner N
o. 40 to 45 and Comparative Toner No. Table 15 shows the physical properties of 12 to 16.

<Comparative Example 17> Comparative toner No. 1 was prepared in the same manner as in Example 39 except that the inorganic fine particles 1A used in Example 39 were not used. 17 was obtained. The obtained comparative toner No.
Table 15 shows the physical properties of No. 17.

<Comparative Example 18> Comparative toner No. 1 was prepared in the same manner as in Example 39 except that the inorganic fine particles 2A used in Example 39 were not used. 18 was obtained. The obtained comparative toner No.
Table 15 shows the physical properties of Sample No. 18.

Comparative Example 19 Comparative toner N was prepared in the same manner as in Example 39, except that silica A used in Example 39 was not used, and the addition amount of inorganic fine particles 2A was changed to 1.0 part by mass.
o. 19 was obtained. The obtained comparative toner No. Table 15 shows the physical properties of No. 19.

<Examples 46 to 51 and Comparative Examples 20 to 21>
> Instead of the inorganic fine particles 2A used in Example 39, Table 2
Is used in the same manner as in Example 39 except that the inorganic fine particles shown in Table 15 are used as shown in Table 15. Nos. 46 to 51 and Comparative Toner Nos. 20-21 were obtained. Obtained toner N
o. Nos. 46 to 51 and Comparative Toner Nos. Table 15 shows the physical properties of Nos. 20 to 21.

<Examples 52 to 53 and Comparative Example 22> In the same manner as in Example 39 except that the silica fine particles shown in Table 3 were used as shown in Table 15 instead of the silica fine particles A used in Example 39, Toner No. 52 to 53 and Comparative Toner Nos. 22 was obtained. The obtained toner No. 52-5
3 and Comparative Toner No. Table 15 shows the physical properties of Sample No. 22.

(Production Examples 24 to 27 of Toner Particles) The toner particles shown in Table 13 were prepared in the same manner as in Production Example 23 of the toner particles, except that the classification conditions in the classification step of toner production were changed. 24-27 were obtained.

<Examples 54 to 57> The same procedure as in Example 39 was carried out except that toner particles 24 to 27 were used instead of toner particles 23 used in Example 39. 54-57
I got The obtained toner No. Table 1 shows the physical properties of 54 to 57.
FIG.

(Production Examples 28 to 31 of Toner Particles) The same procedures as in Production Example 23 of toner particles were carried out except that waxes BE shown in Table 8 were used instead of wax A used in Production Example 23 of toner particles. , Toner particles 28 to 31 shown in Table 13
I got

<Examples 58 to 61> Toner Production Example 23
28 to 31 in place of the toner particles 23 used in
Except that toner No. was used in the same manner as in Example 23. 5
8-61 were obtained. The obtained toner No. Table 17 shows the physical properties of 58 to 61.

(Production Examples 32 to 35 of Toner Particles) Production Example 23 of toner particles except that the peak molecular weight in GPC measurement was adjusted by adjusting the polymerization initiator and the reaction temperature in Production Example 23 of toner particles. In the same manner as in the above, toner particles 32-35 shown in Table 13 were obtained.

<Examples 62 to 65> The same procedure as in Example 39 was carried out except that toner particles 32 to 35 were used instead of toner particles 23 used in Example 39. 62-65
I got The obtained toner No. Table 1 shows the physical properties of 62 to 65.
FIG.

(Production Examples 36 to 38 of Toner Particles) The same procedures as in Production Example 23 of toner particles were carried out except that n-butyl acrylate and butyl maleate were used in place of n-butyl acrylate. Similarly, toner particles 36 to 38 shown in Table 13 were obtained.

<Examples 66 to 68> Toner Nos. Nos. 66 to 68 were used in the same manner as in Example 39, except that toner particles 66 to 68 were used instead of toner particles 23 used in Example 39. 66-68
I got The obtained toner No. Table 1 shows the physical properties of 66 to 68.
FIG.

(Production Examples 39 to 41 of Toner Particles) (Binder resin) 100 parts by mass of styrene-butyl acrylate copolymer (colorant) I. Pigment Blue 15:37 parts by mass (release agent) behenyl behenate (melting point: 73 ° C.) (wax A) 10 parts by mass (charge control agent) Al compound of salicylic acid 2 parts by mass After premixing the above materials, After cooling the kneaded material that had been melt-kneaded by a twin-screw kneading extruder set at 130 ° C., the mixture was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier. Further, using a hybridization system type 1 (manufactured by Nara Machinery Co., Ltd.), toner particles 32 shown in Table 17 were obtained by performing surface treatment by mechanical impact force and adjusting the surface shape factor. The surface treatment conditions according to the hybridization system type were changed and the toner particles 33 and 34 shown in Table 17 were changed.
I got

<Examples 69 to 71> The same procedure as in Example 39 was carried out except that toner particles 32 to 34 were used instead of toner particles 23 used in Example 39. 69-71
I got The obtained toner No. Table 1 shows the physical properties of 69 to 71.
FIG.

(Production Example 42 of Toner Particles) The same procedures as in Production Example 39 of toner particles except that a polyester resin (a condensation polymer of propoxylated bisphenol and fumaric acid) was used instead of styrene-butyl acrylate as the binder resin. In the same manner as in Production Example 39 of toner particles, toner particles 42 shown in Table 18 were obtained.

<Example 72> [0320] The same procedure as in Example 39 was repeated except that toner particles 42 were used instead of toner particles 23 used in Example 39. 72 was obtained. The obtained toner No. Table 18 shows the physical properties of 72.

<Example 73> In Example 39, the inorganic fine particles 1A were replaced by 0.5 parts by mass.
A; 0.3 parts by mass of inorganic fine particles 1C; 73
I got The obtained toner No. Table 18 shows the physical properties of 73.

<Example 74> In Example 39, the inorganic fine particles 2A were replaced by 0.15 parts by mass.
A: 0.1 part by mass and inorganic fine particles 2C; 0.1 part by mass in the same manner as in Example 39 except that 0.1 part by mass was used. 74
I got The obtained toner No. Table 18 shows the physical properties of 74.

<Example 75> The procedure of Example 39 was repeated, except that the inorganic fine particles 1A and 2A and the silica fine particles A were simultaneously mixed and dispersed with the toner particles 23 at 3000 rpm for 5 minutes. 75 was obtained. The obtained toner No. Table 19 shows the formulation of 75, and Table 20 shows the physical properties.
Shown in

Example 76 Toner No. 39 was prepared in the same manner as in Example 39, except that 0.25 parts by mass of an amorphous aluminum dialkylsalicylic acid complex compound was mixed and dispersed simultaneously with the inorganic fine particles 1A. 76 was obtained.
This amorphous aluminum complex compound of dialkylsalicylic acid has a measurement angle 2θ of 6 to 4 in X-ray diffraction measurement.
It was confirmed that there was no peak in a range of 0 degree where the measured intensity was 10000 cps or more and the half width at half maximum was 0.3 degree or less. Obtained toner N
o. Table 19 shows the formulation of 76, and Table 20 shows physical properties.

<Examples 77 to 84> In Example 76, the amount of the aromatic compound shown in Table 14 was replaced with the amount of the aromatic compound shown in Table 19 in place of 0.25 parts by mass of the amorphous aluminum dialkylsalicylic acid complex. Example 76 except that
In the same manner as in 77-84 were obtained. here,
“Amorphous dialkylsalicylic acid zirconium complex compound 4B”, “Amorphous dialkylsalicylic acid chromium complex compound 4C”, and “Amorphous monoazo-based Fe complex compound 4”
D "indicates that the measurement angle 2θ is 6 to 4 in the X-ray diffraction measurement.
It was confirmed that there was no peak in a range of 0 degree where the measured intensity was 10000 cps or more and the half width at half maximum was 0.3 degree or less. The “crystalline azo Fe complex compound 4E” has a maximum intensity of 2θ = 13.6 degr in X-ray diffraction measurement.
The measured intensity is 15000 cps in ee, and the half width at half maximum =
It had a peak at 0.13 and was confirmed to be a crystalline material. The obtained toner No. Table 19 shows the formulations of 77 to 84, and Table 20 shows the physical properties.

[0326]

[Table 13]

[0327]

[Table 14]

[0328]

[Table 15]

[0329]

[Table 16]

[0330]

[Table 17]

[0331]

[Table 18]

[0332]

[Table 19]

[0333]

[Table 20]

(Evaluation Method) As with the image forming apparatus shown in FIG. 8, a commercially available full-color printer LBP-2160 (manufactured by Canon) is used as an image forming apparatus using an intermediate transfer member.
Examples 39 to 84 and Comparative Examples 12 to 22, toner N
o. 39 to 84 and Comparative Toner Nos. 12 to 22 were applied and evaluated.

Regarding the fusion of the toner to the latent image holding member which occurs in a low humidity environment, a solid image having a printing rate of 25% is continuously printed in a low temperature and low humidity environment of 15 ° C./10% RH (5).
(000 sheets).

Regarding the fusion of the toner to the latent holding member, A3
The evaluation was made based on the number of white spot defects on the dots due to the fusion of the toner which appeared on the solid image of the size.

In addition, the number of white spot defects on the dots due to the fusion of the toner is 0 to 2 is excellent, 3 to 6 is good, 7 to 9 is acceptable, and 10 or more is an unacceptable level. .

Regarding the fogging phenomenon that occurs in a low humidity environment, fog on the latent image holding member is measured after continuously printing a line image with a 1% printing rate (5000 sheets) in an environment of 23 ° C./5% RH. did.

As for fog, the fog on the latent image holding member was transferred with a tape, the tape was stuck on white paper, and the difference from the reflectance of a reference tape was measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.). .

The level of fog on the latent image holding member is less than 10%, the level is excellent when 10% or more and less than 18% is acceptable, and the fog is 18% or more.

The evaluation results of Examples and Comparative Examples are shown in Tables 21 to 21.
25.

[0342]

[Table 21]

[0343]

[Table 22]

[0344]

[Table 23]

[0345]

[Table 24]

[0346]

[Table 25]

<Examples 85 to 122, Comparative Examples 23 to 33>
As in the image forming apparatus shown in FIG. 8, a commercially available full-color printer L is used as an image forming apparatus using an intermediate transfer member.
BP-2160 (manufactured by Canon Inc.) was modified so that the rotation peripheral speed of the toner carrier was 400 mm / sec, and the toner application blade was an elastic blade having a polyamide-containing rubber layer having a Shore D hardness of 50 degrees. AC bias: Vpp = 1700 (V), f = 3400 (H
z), DC bias: | DC | = 300 to 450, | V
back│ = 220 ± 20 V, the distance between the developing sleeve and the photosensitive drum = 270 μm, and the toner layer thickness on the developing sleeve = 20 ± 10 μm. Nos. 1 to 38 and Comparative Toner Nos. 1 to 11 were applied and evaluated.

The fusing of the toner to the latent image carrier and the roughness and fog of the halftone image generated in a low humidity environment were reduced by 4% in a low temperature and low humidity environment of 15 ° C./5% RH.
The printing rate was evaluated after continuous printing (5000 sheets) of line images.

As for the fusion of the toner to the latent image holding member,
The evaluation was made based on the number of dot-shaped white spot defects accompanying toner fusion appearing on three-size solid images.

As for the roughness of the halftone image,
The evaluation was made on a halftone image of 600 lines with a reflection density of 0.6, and was indicated in four stages of A, AB, B and C. The evaluation criterion for the roughness of the halftone image is the same as that of the first embodiment.

For fog, the fog on the latent image holding member was transferred with a tape, the tape was stuck on a blank sheet, and the difference from the reflectance of the reference tape was measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.). did.

Regarding the toner dropping phenomenon at the time of printing a large number of sheets, in a 23 ° C./50% RH environment, after printing 20,000 continuous line images at a 1% printing rate, a halftone image was printed. Evaluation was made based on the number of dots that appeared on the image.

Regarding the fog phenomenon when printing a large number of sheets,
After continuously printing 10,000 line images at a printing rate of 1% in an environment of 3 ° C./50% RH, fog on the latent image holding member was measured.

For retransfer development, 32.5 ° C./95
The evaluation was performed after continuously printing a line image having a printing rate of 4% in a high-temperature and high-humidity environment of% RH. The reflection density of a halftone image when a developing cartridge is placed in the first yellow station in the order of development and printed out in a four-color superimposition (four times transfer step) mode and a one-color mode (one time transfer) The evaluation was made based on the difference from the reflection density of the halftone image printed out in the step).

With respect to the phenomenon of dropping of the toner when the toner is left in a high temperature environment, the toner is left in an environment of 50 ° C. for one week and a halftone image is printed in an environment of 15 ° C./5% RH. And the number of dots appeared on the image.

The evaluation results are shown in Tables 26 to 29.

[0357]

[Table 26]

[0358]

[Table 27]

[0359]

[Table 28]

[0360]

[Table 29]

<Examples 123 to 127> As the image forming apparatus shown in FIG. 8, a commercially available full-color printer LBP-
2160 (manufactured by Canon), the rotational peripheral speed of the toner carrier,
And the toner application blade were modified as shown in Table 30. 1 was applied and evaluated.

The evaluation results are shown in Table 31.

[0363]

[Table 30]

[0364]

[Table 31]

<Examples 128-165 and Comparative Examples 34-
44> As the image forming apparatus shown in FIG. 10, a commercially available developing device of CLC-1000 (manufactured by Canon Inc.) is shown in FIG.
The developing device was changed to the one-component developing system shown in FIG. Nos. 1 to 38 and Comparative Toner Nos. 1 to 11 were applied and evaluated. A4 size transfer paper (basis weight 80 g / cm ² ) was used as the evaluation paper.

The fusing of the toner to the latent image carrier and the roughness and fog of the halftone image generated in a low humidity environment were reduced by 4% in a low temperature and low humidity environment of 15 ° C./5% RH.
The printing rate was evaluated after continuous printing (5000 sheets) of line images.

With respect to the fusion of toner to the latent image holding member,
The evaluation was made based on the number of dot-shaped white spot defects accompanying toner fusion appearing on three-size solid images.

As for the roughness of the halftone image,
With a dot size of 600 dpi, 1 for an area equivalent to 4 dots
A, A
B, B and C are shown in four stages. The evaluation criterion for the roughness of the halftone image is the same as that of the first embodiment.

For fog, the fog on the latent image holding member was transferred with a tape, the tape was stuck on a blank sheet, and the difference from the reflectance of the reference tape was measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.). did.

For retransfer development, 32.5 ° C./95
The evaluation was performed after continuous printing (5000 sheets) of a line image with a printing rate of 4% in a high temperature and high humidity environment of% RH. 1 in development order
Insert the yellow station development unit,
Evaluation was made based on the difference in reflection density between the four-color superimposition mode and the single-color mode.

Regarding the toner dropping phenomenon when the toner is left in a high-temperature environment, the toner is left in an environment of 50 ° C. for one week and a halftone image is printed in an environment of 15 ° C./5% RH. And the number of dots that appeared on the A3 size image.

The evaluation results are shown in Tables 32 to 35.

[0373]

[Table 32]

[0374]

[Table 33]

[0375]

[Table 34]

[0376]

[Table 35]

<Example 166> The recording paper used in Example 128 was replaced with a recording paper having a basis weight of 80 g / m ² instead of a basis weight of 64 g / m ^2.
Evaluation was performed in the same manner as in Example 128 except that the recording paper of m ² was used. The results are shown in Table 36.

<Example 167> The evaluation apparatus used in Example 128 was used as an image forming apparatus shown in FIG.
The developing device (manufactured by Canon) was changed to the one-component developing system developing device shown in FIG. 5, and the developing conditions were the same as in Example 128 except that the developing conditions were changed to the same as in Example 85. evaluated. The results are shown in Table 36.

<Example 168> The recording paper used in Example 167 was replaced with a recording paper having a basis weight of 80 g / m ² instead of a basis weight of 64 g.
The evaluation was performed in the same manner as in Example 128 except that the recording paper of / m ² was used. The results are shown in Table 36.

<Comparative Example 45> The comparative toner no. Evaluation was performed in the same manner as in Example 167 except that No. 1 was used. The results are shown in Table 36.

<Comparative Example 46> The comparative toner no. Evaluation was performed in the same manner as in Example 168 except that No. 1 was used. The results are shown in Table 36.

Table 36 also shows the evaluation results of Example 128.

[0383]

[Table 36]

<Example 169> Cyan toner particles (1)
Silica fine particles surface-treated with hexamethyldisilazane having an average primary particle size of 8 nm (silica-A): 100 parts by mass, untreated aluminum oxide fine particles having an average primary particle size of 25 nm (inorganic) Fine particles 2-C): 0.
15 parts by mass, average primary particle size is 200 nm, charge amount is-
Untreated rutile-type titanium oxide fine particles of 2.1 mC / kg (inorganic fine particles 1-A): 0.8 parts by mass were mixed with a Henschel mixer, and toner No. 1 of the present invention was mixed. 85 was obtained.

Toner No. 85 has a weight average particle size of 7.3.
The number of particles having a particle diameter of 4 μm or less was 8.3% by number. Toner No. The endothermic peak in the differential thermal analysis of No. 85 was at 73 ° C., and the half width of the endothermic peak was 3.2 ° C. Toner No. The peak molecular weight in GPC measurement of 85 was 2200.
0, acid value is 4.1mgKOH / g, charge amount is -56mC
/ Kg. Toner No. 85 shape factor SF-1
Was 112 and SF-2 was 104.

[0386] This toner No. 85 is a commercially available full-color printer LBP-2160 as an image forming apparatus using an intermediate transfer member, similarly to the image forming apparatus shown in FIG.
(Manufactured by Canon Inc.), and evaluation was performed in the same manner as in Example 1.

Table 37 shows the results of the evaluation.

Example 170 In place of the untreated aluminum oxide fine particles (inorganic fine particles 2-C) used in Example 169, aluminum oxide fine particles (inorganic fine particles) having been subjected to a surface treatment with isobutyl having an average primary particle diameter of 25 nm. 2-J)
Was used in the same manner as in Example 169 except that 0.15 parts by mass of the toner No. of the present invention was used. 86 was obtained.

Toner No. 86 has a weight average particle size of 7.3.
The number of particles having a particle diameter of 4 μm or less was 8.3% by number. Toner No. The endothermic peak in differential thermal analysis of No. 86 was at 73 ° C., and the half width of the endothermic peak was 3.2 ° C. Toner No. The peak molecular weight in GPC measurement of 86 was 2200.
0, acid value is 4.1mgKOH / g, charge amount is -63mC
/ Kg. Toner No. 86 shape factor SF-1
Was 112 and SF-2 was 104.

The toner No. Example 16 using 86
Evaluation was performed in the same manner as in Example 9. Table 37 shows the evaluation results.

[0391]

[Table 37]

[0392]

According to the toner of the present invention, by the improvement of the external additive of the toner described above, the phenomenon of fusing of the toner on the latent image holding member in a low humidity environment does not occur, and a halftone image can be formed. There is no occurrence of “roughness”, and further, there is no occurrence of toner dropping under a high temperature environment.

Further, according to the toner of the present invention, a high-quality image free from fogging and retransfer phenomenon can be obtained.

Further, according to the toner of the present invention, there is no occurrence of image defects due to contamination of the charging member.

According to the method for producing a toner of the present invention, an extremely effective synergistic effect can be exhibited by defining not only the type and particle size of the fine particles but also the order of addition. In other words, when printing a large number of images having a low color printing ratio in a low humidity environment, there is no fogging phenomenon, and even when printing an image having a high color printing ratio in a low humidity environment, the image on the latent image holding member is printed. It is possible to obtain a toner that does not cause the toner fusion phenomenon.

According to the image forming method of the present invention, the phenomenon of fusion of the toner on the latent image holding member in a low humidity environment does not occur due to the improvement of the external additive of the toner used. There is no "crack" in the image. Furthermore, there is no occurrence of toner dropping during printing of a large number of sheets or in a high temperature environment.

Further, according to the image forming method of the present invention,
A high-quality image free from fog and retransfer phenomenon can be obtained.

According to the image forming apparatus of the present invention, due to the improvement of the external additive of the toner to be used, the phenomenon of fusion of the toner on the latent image holding member in a low humidity environment does not occur, and the halftone image can be formed. There is no occurrence of “roughness”, and further, there is no occurrence of toner dropping under a high temperature environment.

Further, according to the image forming apparatus of the present invention,
A high-quality multi-color or full-color image without fog or retransfer phenomenon can be obtained.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction chart of a metal complex compound of an amorphous aromatic compound.

FIG. 2 is an X-ray diffraction chart of a metal complex compound of a crystalline aromatic compound.

FIG. 3 is an explanatory view of an apparatus used for measuring a charge amount of inorganic fine particles or toner.

FIG. 4 is an explanatory diagram of an image forming method of the present invention.

FIG. 5 is an explanatory diagram of a developing unit of the image forming apparatus.

FIG. 6 is an explanatory diagram of a full-color image forming method.

FIG. 7 is an explanatory diagram of a full-color image forming method.

FIG. 8 is an explanatory diagram illustrating an example of the image forming apparatus according to the first embodiment of the present invention.

FIG. 9 is an explanatory diagram illustrating an example of another image forming apparatus according to the first embodiment of the present invention.

FIG. 10 is an explanatory diagram illustrating an example of an image forming apparatus according to a second embodiment of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photoconductor drum (latent image carrier) 2 charging roller 3 fixing device 4 (4Y, 4M, 4C, 4Bk) developing device 5 intermediate transfer member 6 cleaning mechanism 7 tray 8 transfer means L light source device E laser beam P transfer material 101 Latent image carrier (photoconductor) 102 Charging roller 104 Toner carrier 109 Developing means 110 Toner 111 Toner application blade 113 Supply roller

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 501 G03G 15/08 504B 504 9/08 325 507 384 15/08 507L (31) Claim of priority No. Japanese Patent Application No. 2000-52719 (P2000-52719) (32) Date of priority February 29, 2000 (Feb. 29, 2000) (33) Countries claiming priority Japan (JP) (72) Inventor Kiyowa Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tomoaki Igarashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Atsushi Kubo Ota-ku, Tokyo Shimomaruko 3-30-2 Canon Inc. F-term (reference) 2H005 AA06 AA08 AA15 AB06 AB09 AB10 CA03 CA04 CA14 CA25 CA26 CB07 CB13 DA10 EA01 EA03 EA05 EA07 FA07 2H077 AD02 AD06 AD13 AD17 AD23 AD36 EA14 FA13 FA22 GA13

Claims (90)

[Claims] 1. A toner particle containing at least a binder resin and a colorant, and an average primary particle size mixed with the toner particle is 80 to 800 nm, and is selected from the group consisting of titanium, aluminum, zinc and zirconium. A toner comprising: a metal oxide inorganic fine particle (1), an inorganic fine particle other than silica having an average primary particle size of less than 80 nm (2), and a silica fine particle having an average primary particle size of less than 30 nm. 2. The inorganic fine particles (1) are 100 to 500
2. An average primary particle size of 1 nm.
The toner according to 1. 3. The inorganic fine particles (1) have an absolute value of 10 m.
3. The toner according to claim 1, having a charge amount of C / kg or less. 4. The method according to claim 1, wherein the inorganic fine particles (1) include inorganic oxide fine particles selected from the group consisting of titanium oxide fine particles, aluminum oxide fine particles, and a mixture thereof. The toner according to any one of the above. 5. The toner according to claim 1, wherein the inorganic fine particles (2) have an average primary particle size of 70 nm or less. 6. The inorganic fine particles (2) have a thickness of 25 to 70 nm.
The toner according to claim 1, having an average primary particle size of 7. The method according to claim 1, wherein the inorganic fine particles (2) include inorganic oxide fine particles selected from the group consisting of titanium oxide fine particles, aluminum oxide fine particles, and a mixture thereof. The toner according to any one of the above. 8. The toner according to claim 1, wherein the inorganic fine particles (1) include untreated inorganic fine particles, and the inorganic fine particles (2) include hydrophobic fine inorganic particles. . 9. The method according to claim 1, wherein the inorganic fine particles (1) include untreated titanium oxide fine particles, and the inorganic fine particles (2) include hydrophobicized titanium oxide fine particles. Toner. 10. The inorganic fine particles (1) include untreated inorganic fine particles, and the inorganic fine particles (2) include hydrophobic-treated inorganic fine particles and untreated inorganic fine particles. Item 7. The toner according to Item 1. 11. The inorganic fine particles (1) contain untreated titanium oxide fine particles, and the inorganic fine particles (2) contain hydrophobicized titanium oxide fine particles and untreated aluminum oxide fine particles. The toner according to claim 1, wherein 12. The inorganic fine particles (1) have a particle size of 100 to 50.
Having an average primary particle size of 0 nm, and the inorganic fine particles (2)
The toner according to any one of claims 1 to 11, wherein the toner has an average primary particle size of 70 nm or less. 13. The inorganic fine particles (1) have a particle size of 100 to 50.
Having an average primary particle size of 0 nm, and the inorganic fine particles (2)
The toner according to any one of claims 1 to 11, wherein the toner has an average primary particle size of 25 to 70 nm. 14. The toner contains 0.05 to 5% by mass of the inorganic fine particles (1), 0.01 to 1.0% by mass of the inorganic fine particles (2), and silica fine particles based on the mass of the toner particles. The toner according to any one of claims 1 to 13, wherein the toner content is 0.2 to 5.0% by mass. 15. The mass ratio of the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles in the toner is as follows:
The following condition is satisfied: the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles = 1: (0.01 to 1) :( 0.1 to 6). Toner. 16. The mass ratio of the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles in the toner is as follows:
The following conditions: The inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles = 1: (0.02 to 0.9): (0.2 to 5.6). Item 15. The toner according to Item 14, 17. The toner according to claim 1, wherein the fine silica particles are treated with a silane coupling agent and / or silicone oil. 18. The toner according to claim 1, wherein the toner has a weight average particle diameter of 4 to 8 μm and 3 to 20% by number of toner particles of 4 μm or less. The toner according to any one of the above. 19. The method according to claim 1, wherein at least one endothermic peak exists in a temperature range of 60 to 90 ° C. in an endothermic curve at the time of temperature rise in the differential thermal analysis of the toner. The toner described in the above. 20. The toner according to claim 19, wherein a half width of the endothermic peak is 10 ° C. or less. 21. The toner according to claim 19, wherein a half width of the endothermic peak is 6 ° C. or less. 22. The toner according to claim 1, wherein the toner contains a wax having at least one endothermic peak in a temperature range of 60 to 90 ° C. in an endothermic curve at the time of temperature rise in differential thermal analysis. 22. The toner according to any one of claims 21 to 21. 23. The toner according to claim 13, wherein a wax having at least one endothermic peak in a temperature range of 60 to 90 ° C. in an endothermic curve at the time of temperature increase in differential thermal analysis is 0.3 to 3%.
3. The composition according to claim 1, which contains 0% by mass.
2. The toner according to any one of 1. 24. The toner according to claim 1, wherein the toner contains a styrene-based polymer as a binder resin.
4. The toner according to any one of 3. 25. The toner according to claim 1, wherein in the molecular weight distribution of the toner measured by gel permeation chromatography (GPC), a peak molecular weight is present in a molecular weight range of 15,000 to 30,000. Toner. 26. The toner according to claim 1, wherein the toner has an acid value of 10 mg KOH / g or less. 27. The toner according to claim 1, wherein the toner has an absolute value of a charge amount of 40 to 80 mC / kg. 28. The toner according to claim 1, wherein the toner has a shape factor SF-1 of 100 to 170 and a shape factor SF-2 of 100 to 140. toner. 29. The toner according to claim 1, wherein the toner has a shape factor SF-1 of 100 to 120 and a shape factor SF-2 of 100 to 115. toner. 30. The toner particles are produced through a step of granulating and polymerizing a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in an aqueous medium. The toner according to any one of claims 1 to 29. 31. The toner according to claim 1, wherein the toner is a non-magnetic toner having non-magnetic toner particles containing a dye and / or a pigment as the colorant. 32. A first mixing and dispersing step of mixing and dispersing toner particles containing at least a binder resin and a colorant and inorganic fine particles (1) to obtain a toner precursor; In a method for producing a toner having a second mixing and dispersing step of mixing and dispersing inorganic fine particles (2) and silica fine particles to obtain a toner, the inorganic fine particles (1) have an average primary particle size of 80 to 800 n
m, an oxide of a metal selected from the group consisting of titanium, aluminum, zinc and zirconium. The inorganic fine particles (2) are inorganic fine particles other than silica having an average primary particle size of less than 80 nm. A method for producing a toner, wherein the silica fine particles have an average primary particle size of less than 30 nm. 33. The inorganic fine particles (1) are 100 to 50.
33. The method according to claim 32, wherein the toner has an average primary particle size of 0 nm. 34. The inorganic fine particles (1) have an absolute value of 10
34. The method according to claim 32, wherein the toner has a charge amount of mC / kg or less. 35. The method according to claim 32, wherein the inorganic fine particles (1) include inorganic oxide fine particles selected from the group consisting of titanium oxide fine particles, aluminum oxide fine particles, and a mixture thereof. Or a method for producing a toner. 36. The method according to claim 32, wherein the inorganic fine particles (2) have an average primary particle size of 70 nm or less. 37. The inorganic fine particles (2) have a particle size of 25 to 70 n.
33. The composition of claim 32 having an average primary particle size of m.
3. The method for producing a toner according to item 1. 38. The method according to claim 32, wherein the inorganic fine particles (2) include inorganic oxide fine particles selected from the group consisting of titanium oxide fine particles, aluminum oxide fine particles, and a mixture thereof. A method for producing the toner according to any one of the above. 39. The toner according to claim 32, wherein the inorganic fine particles (1) include untreated inorganic fine particles, and the inorganic fine particles (2) include hydrophobic fine inorganic particles. Manufacturing method. 40. The method according to claim 32, wherein the inorganic fine particles (1) include untreated titanium oxide fine particles, and the inorganic fine particles (2) include hydrophobic titanium oxide fine particles. Production method of toner. 41. The inorganic fine particles (1) include untreated inorganic fine particles, and the inorganic fine particles (2) include hydrophobic treated inorganic fine particles and untreated inorganic fine particles. Item 34. The method for producing a toner according to Item 32. 42. The inorganic fine particles (1) include untreated titanium oxide fine particles, and the inorganic fine particles (2) include hydrophobic treated titanium oxide fine particles and untreated aluminum oxide fine particles. The method for producing a toner according to claim 32, wherein 43. The inorganic fine particles (1) have a particle size of 100 to 50.
Having an average primary particle size of 0 nm, and the inorganic fine particles (2)
43. The method for producing a toner according to claim 32, wherein the toner has an average primary particle size of 70 nm or less. 44. The inorganic fine particles (1) have a particle size of 100 to 50.
Having an average primary particle size of 0 nm, and the inorganic fine particles (2)
The method for producing a toner according to any one of claims 32 to 43, wherein the toner has an average primary particle diameter of 25 to 70 nm. 45. The mixing ratio of the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles is 0.05 to 5% by mass based on the mass of the toner particles. 45. The method according to claim 32, wherein the amount of the inorganic fine particles (2) is 0.01 to 1.0% by mass and the amount of the silica fine particles is 0.2 to 5.0% by mass. Method. 46. The mixing mass ratio of the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles to the toner particles is determined under the following conditions: the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles = The toner production method according to claim 45, wherein the ratio satisfies 1: (0.01 to 1) :( 0.1 to 6). 47. The mixing mass ratio of the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles to the toner particles is determined under the following conditions: the inorganic fine particles (1), the inorganic fine particles (2) and the silica fine particles = 47. The method according to claim 45, wherein the ratio satisfies 1: (0.02 to 0.9) :( 0.2 to 5.6). 48. The method according to claim 32, wherein the silica fine particles are treated with a silane coupling agent and / or a silicone oil. 49. The obtained toner has a weight average particle diameter of 4 to 8 μm and a toner particle of 4 μm or less of 3 to
49. The method for producing a toner according to claim 32, wherein the amount is 20% by number. 50. An endothermic curve at the time of temperature rise in a differential thermal analysis of the obtained toner, wherein at least one endothermic peak exists in a temperature region of 60 to 90 ° C. Or a method for producing a toner. 51. The method according to claim 50, wherein a half width of the endothermic peak is 10 ° C. or less. 52. The method according to claim 50, wherein a half width of the endothermic peak is 6 ° C. or less. 53. The obtained toner contains a wax having at least one endothermic peak in a temperature range of 60 to 90 ° C. in an endothermic curve at the time of temperature rise in differential thermal analysis. Item 53. The method for producing a toner according to any one of Items 32 to 52. 54. The obtained toner has a wax having at least one endothermic peak in a temperature range of 60 to 90 ° C. in an endothermic curve at the time of temperature rise in differential thermal analysis.
4. The composition according to claim 3, wherein the content is 3 to 30% by mass.
53. The method for producing a toner according to any one of 2 to 52. 55. The obtained toner contains a styrene-based polymer as a binder resin.
55. The method for producing a toner according to any one of 2 to 54. 56. In the molecular weight distribution of the obtained toner measured by gel permeation chromatography (GPC), the peak molecular weight has a molecular weight of 15,000 to 30,000.
55. The image processing apparatus according to claim 32, wherein
The method for producing a toner according to any one of the above. 57. The obtained toner has a concentration of 10 mg KOH /
The method for producing a toner according to any one of claims 32 to 56, having an acid value of not more than g. 58. The obtained toner is 40 to 80 mC /
57. The method according to claim 32, wherein the toner has an absolute value of a charge amount of kg. 59. The obtained toner has a shape factor SF-1 of 100 to 170 and a shape factor SF of 100 to 140.
60. The method of claim 32, wherein
The method for producing a toner according to any one of the above. 60. The obtained toner has a shape factor SF-1 of 100 to 120 and a shape factor SF of 100 to 115.
60. The method of claim 32, wherein
The method for producing a toner according to any one of the above. 61. The toner particles are produced through a step of granulating and polymerizing a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in an aqueous medium. A method for producing the toner according to any one of claims 32 to 60. 62. The obtained toner is a non-magnetic toner having non-magnetic toner particles containing a dye and / or a pigment as the colorant.
2. The method for producing a toner according to any one of 1. 63. In the first mixing and dispersing step, the toner particles, the inorganic fine particles (1) and X-ray diffraction have a measurement angle 2θ within a range of 6 to 40 degrees.
A metal complex compound, a metal salt, or a metal complex compound and a metal salt of a low-crystalline or amorphous aromatic compound having a peak having a measured intensity of 10,000 cps or more and a half-width at half maximum of 0.3 degree or less. 4. A toner precursor is obtained by mixing and dispersing a mixture of
63. The method for producing a toner according to any one of items 2 to 62. 64. In the first mixing and dispersing step, the toner particles, the inorganic fine particles (1), and a metal complex compound, a metal salt of the oxycarboxylic acid compound, or a mixture of the metal complex compound and the metal salt are mixed. 63. The method for producing a toner according to claim 32, wherein the toner precursor is obtained by mixing and dispersing. 65. The method according to claim 64, wherein the central metal of the metal complex compound, the metal salt, or the mixture of the metal complex compound and the metal salt of the oxycarboxylic acid compound is aluminum or zirconium. Manufacturing method of toner. 66. (I) a step of supplying non-magnetic toner onto a toner carrier by a supply roller; and (II) a toner formed on the toner carrier by transferring an electrostatic latent image formed on the latent image carrier. (III) pressing the non-magnetic toner on the toner carrier with a toner coating blade to form a toner layer on the toner carrier and developing the non-magnetic toner on the toner carrier. (Iv) transferring the developed image to a transfer material; and (v) fixing the transferred developed image. The toner has non-magnetic toner particles containing at least a binder resin and a colorant, and has an average primary particle size of 80 to 800 nm mixed with the non-magnetic toner particles. Oxide fine particles of a metal selected from the group consisting of, zinc and zirconium (1), inorganic fine particles other than silica having an average primary particle size of less than 80 nm (2), and silica fine particles having an average primary particle size of less than 30 nm An image forming method comprising: 67. A rotating peripheral speed of the toner carrier is 100
7. The pressure is from 800 mm / sec.
7. The image forming method according to item 6. 68. The rotational peripheral speed of the toner carrier is 200
7. The method according to claim 6, wherein the speed is about 700 mm / sec.
7. The image forming method according to item 6. 69. The image forming method according to claim 66, wherein said toner coating blade has a polyamide-containing rubber layer on the surface of the toner carrier. 70. The image according to claim 66, wherein the toner coating blade has a polyamide-containing rubber layer having a Shore D hardness of 25 to 65 degrees on the toner carrier side surface. Forming method. 71. An image forming apparatus according to claim 66, wherein said latent image carrier has a photosensitive layer made of an organic photoconductor, amorphous silicon, selenium or zinc oxide. Method. 72. The image forming method according to claim 66, wherein in the developing step, the developing is performed by applying a developing bias to the toner carrier. 73. The image forming method according to claim 66, wherein in the developing step, the developing is performed by applying a developing bias having an AC bias or a pulse bias to the toner carrier. 74. The image forming method according to claim 66, wherein the non-magnetic toner is the toner according to any one of claims 2 to 31. 75. (I) a latent image carrier for carrying an electrostatic latent image, a charging device for primary charging the latent image carrier,
A plurality of images including an exposure unit for forming an electrostatic latent image on a primary charged latent image carrier, and a developing device for developing the electrostatic latent image with a non-magnetic toner to form a toner image And (II) an image forming apparatus having a transfer device for sequentially transferring the toner images formed by the image forming units to a transfer material, wherein the non-magnetic toner contains at least a binder resin and a colorant. Non-magnetic toner particles, and metal oxide inorganic fine particles selected from the group consisting of titanium, aluminum, zinc and zirconium having an average primary particle size of 80 to 800 nm mixed with the non-magnetic toner particles (1) And inorganic fine particles (2) other than silica having an average primary particle size of less than 80 nm, and silica fine particles having an average primary particle size of less than 30 nm. An image forming apparatus. 76. The image forming apparatus according to claim 75, wherein the plurality of image forming units are arranged in a line. 77. A method according to claim 77, wherein said plurality of image forming units are arranged in a line, and said image forming apparatus further comprises a conveying means for sequentially conveying said transfer material between each image forming unit. The image forming apparatus according to claim 75, wherein: 78. The image forming apparatus according to claim 77, wherein said carrying means is a carrying belt. 79. The image forming apparatus according to claim 77, further comprising fixing means for fixing the multi-toner image sequentially transferred on the transfer material to the transfer material.
An image forming apparatus according to claim 1. 80. The image forming apparatus according to claim 75, wherein the non-magnetic toner is the toner according to any one of claims 2 to 31. 81. (I) a latent image carrier for carrying an electrostatic latent image; (II) a charging device for primary charging the latent image carrier; and (III) a primary charged latent image carrier. (IV) a plurality of developing devices for developing the electrostatic latent image with a non-magnetic toner to form a toner image; and (V) forming each of the developing devices. (VI) an image forming apparatus having a transfer device for sequentially transferring the multiple toner images transferred on the intermediate transfer member to a transfer material; Each of the non-magnetic toners has non-magnetic toner particles containing at least a binder resin and a colorant, and has an average primary particle size of 80 to 800 nm mixed with the non-magnetic toner particles, and includes titanium, aluminum, zinc and zirconium. Consists of A metal oxide selected from the group consisting of inorganic fine particles (1), inorganic fine particles other than silica having an average primary particle size of less than 80 nm (2), and silica fine particles having an average primary particle size of less than 30 nm. Image forming apparatus. 82. The image forming apparatus according to claim 81, wherein said intermediate transfer member is a drum-shaped intermediate transfer drum. 83. The image forming apparatus according to claim 81, wherein said intermediate transfer member is a belt-shaped intermediate transfer drum. 84. The image forming apparatus according to claim 81, wherein said plurality of developing devices are provided in a rotatable rotary unit. 85. The image forming apparatus according to claim 81, wherein said intermediate transfer member is arranged in contact with a surface of said latent image carrier. 86. The image forming apparatus further includes a bias applying unit for applying a transfer current to the intermediate transfer body in order to primarily transfer the toner image formed on the latent image carrier onto the intermediate transfer body. 85. The device according to claim 85, wherein
An image forming apparatus according to claim 1. 87. The image forming apparatus according to claim 8, further comprising fixing means for fixing the multi-toner image collectively transferred onto the transfer material to the transfer material.
The image forming apparatus according to any one of Items 1 to 86. 88. An image forming apparatus according to claim 81, wherein said non-magnetic toner is the toner according to any one of claims 2 to 31. 89. (I) a latent image carrier for carrying an electrostatic latent image; (II) a charging device for primary charging the latent image carrier; and (III) a latently charged latent image carrier. (IV) a plurality of developing devices for developing the electrostatic latent image with a non-magnetic toner to form a toner image; and (V) a developing device. An image forming apparatus having a transfer device for sequentially transferring a formed toner image to a transfer material, wherein each of the non-magnetic toners includes a non-magnetic toner particle containing at least a binder resin and a colorant, and the non-magnetic toner particle And an inorganic fine particle (1) of a metal selected from the group consisting of titanium, aluminum, zinc and zirconium having an average primary particle size of 80 to 800 nm, and a silicon oxide having an average primary particle size of less than 80 nm. Other inorganic fine particles (2), and an image forming apparatus, wherein an average primary particle size has fine silica particles of less than 30 nm. 90. An image forming apparatus according to claim 89, wherein said non-magnetic toner is the toner according to any one of claims 2 to 31.