JP2002351133A - Electrostatic charge image developing toner, image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide developer or toner for electrophotography not causing an abnormal image such as a void even in a single component developing system, free from filming on a photoreceptor, a developer layer thickness regulating member or a developing roller after long-term consecutive printing more prolonged than conventional printing, and maintaining a high-quality outputted image having image density equal to that of an initial image by stabilizing the electrification and the feeding of the toner, and to provide an image forming method and an image forming device. SOLUTION: The single-component type electrostatic charge developing toner satisfies following required conditions (1) to (4) and contains at least binding resin and a colorant. (1) Hydrophobic silica particles whose primary average particle size is 30 to 50 nm is added to toner particles. (2) The volume average particle size (Dv) of the toner measured by a Coulter counter is 5 to 8 μm. (3) The content of powder whose particle size is <=5 μm is <20 number %. (4) The content of the particles whose number-based equivalent circle diameter measured by a flow type particle image analyzing device is >=0.6 μ and <3 μm is <=15%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, an image forming method using the toner, And an electrophotographic developing device. More specifically,
The present invention relates to an external additive for an electrophotographic toner, an electrophotographic toner, an electrophotographic developer, and an electrophotographic developing device used for a copier, a laser printer, a plain paper fax, and the like using a direct or indirect electrophotographic developing method. Further, the present invention relates to an electrophotographic toner, an electrophotographic developer, and an electrophotographic developing device used for a full-color copying machine, a full-color laser printer, a full-color plain paper facsimile, etc. using a direct or indirect electrophotographic multicolor image developing system.

[0002]

2. Description of the Related Art A developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is, for example, once applied to an image carrier such as a photosensitive member on which an electrostatic image is formed in a developing process. After being adhered and then transferred from the photoreceptor to a transfer medium such as transfer paper in a transfer step, it is fixed on the paper surface in a fixing step. At this time, as a developer for developing an electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer (a magnetic toner, Non-magnetic toner) is known.

[0003] In the two-component developing method, the developer deteriorates when toner particles adhere to the carrier surface, and the toner concentration in the developer decreases because only the toner is consumed. Must be maintained at a constant ratio, which results in a disadvantage that the size of the developing device is increased. On the other hand, the one-component developing method does not have the above-mentioned disadvantages,
Since the apparatus has advantages such as miniaturization, it is becoming the mainstream of the developing system.

[0004] In recent years, office automation and colorization in offices have been further advanced. In addition to conventional copying of originals consisting only of characters, originals including graphs and the like created by a personal computer are output by a printer and used for presentation materials. For example, the opportunity to copy many sheets is increasing. Many of printer output images are solid images, line images, and halftone images, and accordingly, the market demand for image quality is changing, and demands for high reliability and the like are further increasing.

Heretofore, an electrophotographic process using a one-component developer has a magnetic one-component developing method using a magnetic toner,
It is classified into a non-magnetic one-component developing method using a non-magnetic toner. The magnetic one-component developing method uses a developer carrier provided with a magnetic field generating means such as a magnet inside, holds a magnetic toner containing a magnetic substance such as magnetite, and develops a thin layer by a layer thickness regulating member. In recent years, a large number of printers have been put to practical use. On the contrary,
In the non-magnetic one-component developing method, since the toner does not have a magnetic force, a toner supply roller or the like is pressed against the developer carrier to supply the toner onto the developer carrier and electrostatically hold the toner.
The layer thickness regulating member is used to develop a thin layer, which has the advantage that it does not contain a colored magnetic material and can respond to colorization.In addition, since a magnet is not used for the developer carrier, the weight and weight can be reduced. Cost reduction has become possible, and in recent years it has begun to be put to practical use in small full-color printers and the like.

However, in the present situation, there are still many problems to be improved in the one-component developing system. In the two-component developing method, a carrier is used as a means for charging and conveying toner,
After the toner and the carrier are sufficiently stirred and mixed in the developing device, the toner and the carrier are conveyed to the developer carrier and developed, so that even when used for a relatively long time, stable charging and conveyance can be maintained, and It is easy to cope with high-speed developing devices.

On the other hand, in the one-component developing system, since there is no stable charging and conveying means such as a carrier, charging and conveying defects due to long-time use and high speed are likely to occur. That is, in the one-component developing method, after the toner is conveyed onto the developer carrying member, the toner is thinned and developed by the layer thickness regulating member, but the toner and the developer carrying member, the layer thickness regulating member and the like are charged by friction. Since the contact and frictional charging time with the member is very short, the amount of low-charge and reverse-charge toner tends to increase more than in the two-component developing method using a carrier. In particular, in a non-magnetic one-component developing method, a means for conveying toner (developer) by at least one toner conveying member and developing an electrostatic latent image formed on a latent image carrier by the conveyed toner is usually used. However, at that time, the thickness of the toner layer on the surface of the toner conveying member must be reduced as much as possible.

This applies to the case where a two-component developer having a very small carrier diameter is used. In particular, a one-component developer having a high electric resistance as a toner is used. When the toner is used, it is necessary to charge the toner by the developing device, so that the layer thickness of the toner must be extremely thin. This is because if the toner layer is thick, only the vicinity of the surface of the toner layer is charged, and it is difficult to uniformly charge the entire toner layer. For this reason,
Toner is required to maintain a faster charging speed and an appropriate charging amount.

Further, as a developing device, a method of maintaining uniform and charged toner thin layer by a method of increasing a contact pressure of a friction regulating member such as a thin layer regulating member is performed. This tends to give more stress to the toner particles. The external additive adhering to the surface of the toner particles is buried in the toner particles due to the stress, and the fluidity and the chargeability are reduced. As a result, problems such as background contamination and a decrease in image density due to insufficient toner supply occur.

To improve the above problem, Japanese Patent Laid-Open No.
JP-A-288369 discloses an example in which the embedding of an external additive in toner particles is improved. By adding and mixing silica fine particles having a large particle diameter to these, the silica fine particles are prevented from being buried in the toner surface, and stable chargeability and fluidity are obtained. However, when used in a one-component developing device based on this technology, the silica fine particles are prevented from being buried in the toner surface, and stable chargeability and fluidity can be obtained. There is also a problem that the aggregates are caught in the gaps between them and an abnormal white spot image is generated. In addition, with only silica fine particles having a large particle diameter, background contamination may occur due to insufficient charge amount.

In a one-component developing process requiring high charge, a charge control agent is conventionally added to stabilize charge as a toner base. The charge control agent functions to control the frictional charge amount of the toner and maintain the frictional charge amount. Representative charge control agents with negative charge include monoazo dyes, salicylic acid, naphthoic acid,
Metal salts of dicarboxylic acids and metal complexes, diazo compounds, complex compounds with boron, and the like.Examples of typical charge control agents having positive charge include quaternary ammonium salt compounds, imidazole compounds, nigrosine, azine dyes, and the like. No.

However, since these charge control agents are colored, there is a problem that the hue changes when used in a color toner. In addition, since such a charge controlling agent has poor compatibility with the binder resin, those present on the surface of the toner, which are greatly involved in the charging, are likely to be detached, causing variations in the charging of the toner, the development sleeve, and the photosensitive drum. There are drawbacks such as body filming that easily contaminates.

For this reason, in the prior art, a good image can be obtained in the initial stage, but the image quality gradually changes, causing a phenomenon that the background becomes dirty and the image is blurred. While using continuously,
As the charge amount of the toner decreases, the color tone of the copied image becomes significantly different from the initial color image, and it cannot withstand long-term use. It had disadvantages that should not be encountered. As a result, the burden on the environment was large, and the user was also troublesome. Furthermore, since many of them contain heavy metals such as chromium, they have recently become a problem in terms of safety.

To solve the above problems, Japanese Patent Application Laid-Open Nos. 63-88564 and 63-184762 and Japanese Patent Laid-Open Publication No. 3-56974 / 6-230609 disclose compatibility with a binder resin and an image of a toner fixed image. A resin charge control agent having improved transparency and safety is disclosed. Since these resin charge control agents have good compatibility with the binder resin, they are excellent in stable chargeability and transparency. However, these resin charge control agents have the drawback that the charge amount and the charge speed are inferior to toners using a monoazo dye, a metal salt or a metal complex salt of salicylic acid, naphthoic acid, or dicarboxylic acid. Although the chargeability is improved by increasing the amount of the resin charge control agent added, the toner fixability (low-temperature fixability, anti-offset property) is adversely affected. Further, these compounds have high environmental stability (humidity resistance) of the charge amount. For this reason, there is also a problem that background soiling (fogging) easily occurs.

Therefore, Japanese Patent Laid-Open Publication No. Hei 8-30017, 9
171271, 9-21896, 11-21896
In JP-A No. 5 (1999) -1994, a copolymer of a monomer containing an organic acid salt such as a sulfonate group and an aromatic monomer having an electron-withdrawing group is proposed. However, due to the hygroscopicity and adhesiveness, which are considered to be caused by the monomer containing an organic acid salt such as a sulfonic acid salt group, a sufficient amount of charge is secured, but the dispersion in the binder resin is not sufficient, and the toner is not used for a long time. The effect of suppressing the variation in the charging of the toner and preventing the filming of the developing sleeve and the photoconductor is not sufficient.

The volatile components of the binder resin for toner obtained by a known polymerization method such as solution polymerization or bulk polymerization are usually as follows:
Although the content is 0.5 to 2.0 wt% due to the devolatilization step, the resin negative charge control agent of the present invention contains more water and a polymerization solvent which are considered to be caused by a monomer containing an organic acid salt such as a sulfonate group. Minutes increase. For this reason, there are problems in storage stability of the resin negative charge control agent itself, and problems in handling such as agglomeration of the material before kneading before standing and agglomeration to prevent powder transport. Further, the dispersion in the binder resin is not sufficient, and the effect of suppressing the variation in the charging of the toner over a long period of time and the effect of preventing the developing sleeve, the photoconductor filming, and the like are not sufficient.

Further, regarding the productivity in the toner pulverization method,
Productivity is lower than when monoazo dyes, salicylic acid, naphthoic acid, metal salts of dicarboxylic acids and metal complex salts are used as charge control agents, as they are fixed to each part in the crusher and the crushing amount per unit time is small. The negative effect was also seen.

Further, in order to further improve the compatibility with a styrene resin or a polyester resin as a binder resin, a monomer containing an organic acid salt such as a sulfonate group and an aromatic monomer having an electron-withdrawing group are used. When the bonding resin is a styrene resin, a copolymer with a styrene monomer has been proposed, and when the binding resin is a polyester resin, a copolymer with a polyester monomer has been proposed.
The effect of preventing the developing sleeve and the photoconductor filming is not sufficient. In particular, as a binder resin for a full-color toner, a polyester resin or a polyol resin, which is suitable in terms of color development and image strength, is insufficient.

In recent years, the demand for printers has increased, and the size, speed, and cost of devices have been reduced, and higher reliability and longer life have been required of the devices. However, these resin charge control agents cannot maintain the charge control effect, and the developing sleeve and layer thickness regulating members (blades and rollers)
And the toner has poor charging performance and filming of the photoreceptor.

[0020]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a latent image forming step of forming a latent image on a latent image holding member, and using the latent image with a developer on a developer carrier. A developing process of transferring the developed toner image onto a transfer member, and a fixing process of heating and fixing the toner image on the transfer member. An object of the present invention is to provide an electrophotographic toner, an image forming method, and an image forming apparatus, which have a stable amount, have a high image density, and have high image quality with little background contamination. In particular, in a one-component developing system in which a thin layer of toner is formed on a toner conveying member (developing roller) by a layer thickness regulating member and development is performed, there is no abnormal image such as white spots, and there is no change in toner chargeability after continuous printing. It is an object of the present invention to provide an electrophotographic toner, an image forming method, and an image forming apparatus capable of obtaining tens of thousands or more of images having the same image quality as an initial image.

Another object of the present invention is to provide an image forming method for preventing contamination of a developing roller or a layer thickness regulating member (blade or roller) or photo filming of tens of thousands of sheets or more in long-term use. To provide a toner for use. Further, another object of the present invention is to provide an electrophotographic toner or a developer having a small amount of toner scattering in a developing machine even during long-term use, an image forming method using the electrophotographic toner or a developer, or an image forming apparatus. To provide. Still another object of the present invention is to provide a toner for electrophotography, an image forming method, or an image forming method, which can reduce the burden on the environment and reduce the user's labor for replacement because the developing unit and the photoreceptor unit can be used for a long period of time. A forming apparatus is provided.

[0022]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such problems, and as a result, the following (1) to (4)
The technical problem was solved by providing a one-component electrostatic image developing toner characterized by containing at least a binder resin and a colorant satisfying the above requirements. (1) A hydrophobic silica particle having a primary average particle diameter of 30 to 50 nm is added to the toner particles. (2) A volume average particle diameter (Dv) of the toner measured by a Coulter counter is 5 μm to 8 μm. Yes, (3) the content of fine powder having a particle size of 5 μm or less is less than 20% by number, and (4) the content of particles having a number-based equivalent circle diameter of 0.6 μm or more and less than 3 μm measured by a flow type particle image analyzer. Rate is 15%
It is as follows.

The volume average particle size is 5 μm to 8 μm and 5 μm
By using a toner having a particle size distribution in which the content of fine powder of m or less is less than 20% by number, it is possible to provide high image quality with excellent fine line reproducibility. When the toner volume average particle diameter is 8
When the particle size is more than μm, fine line reproducibility is poor. On the other hand, when the particle size is less than 5 μm, the specific surface area of the toner is large, so that the toner is liable to be charged up, resulting in a problem due to a decrease in image density.
When the content of fine powder of 5 μm or less was 20% by number or more, filming on the developing roller was extremely poor.

Further, by using hydrophobic silica particles having a primary average particle diameter of 30 to 50 nm, the silica fine particles are prevented from being buried in the toner surface, filming to the developing roller is prevented, and stable chargeability and fluidity are obtained. Has been obtained. When the primary average particle size is less than 30 nm, the silica fine particles are buried in the toner surface, the charge amount and the fluidity are significantly reduced, and the image density is reduced, the background is stained, and filming to the developing roller occurs. Conversely, if the primary average particle size is larger than 50 nm, the initial toner fluidity and charge amount will be insufficient, resulting in insufficient image density and background stain.

However, even with the toner having the above-mentioned particle size distribution, white spots occur due to pinching of the aggregates between the developing roller and the thin layer regulating member during repeated use. This is because the Coulter Counter (TAII) measures by measuring the change in resistance with an electrical signal.
Particles of m or less are greatly affected by noise, and measurement accuracy was lacking and measurement could not be performed. On the other hand, the flow type particle image analyzer performs measurement by image analysis, so that particles of 2 μm or less can be measured. It has been found that fine particles having a diameter of 3 μm or less (hereinafter referred to as “ultrafine powder”) equivalent to a circle measured by a particle image analyzer have an effect on the above problem.

These ultrafine powders are coarse external additives. It was not disintegrated by the external additive treatment, and did not adhere uniformly to the toner surface. These coarse external additives can also be confirmed with an optical microscope. When the external additive is uniformly attached to the surface of the toner particles, it is not detected by the flow type particle image analyzer. If there is a floating coarse external additive, an aggregate is formed with the coarse external additive as a core.

Although the mechanism by which the coarse external additives serve as nuclei to granulate the aggregates is unknown, there is a correlation between the coarse external additives and the amount of aggregates. Also increase. If the number of particles having a diameter of 0.6 μm or more and less than 3.0 μm in a number-equivalent circle measured by a flow type particle image analyzer is 15% by number or less, preferably 10% by number or less, the generation of white streaks is improved. I found it.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The toner for developing an electrostatic image of the present invention is as described above. Here, the sulfonic acid group-containing monomer constituting the resin charge control agent of the present invention includes an aromatic sulfonic acid group-containing monomer and an aliphatic sulfonic acid group. Contained monomers and the like.

Examples of the aromatic sulfonic acid group-containing monomer include vinyl sulfonic acid, allyl vinyl sulfonic acid,
Alkali metal salts such as acrylamido-2-methylpropanesulfonic acid and methacryloyloxyethylsulfonic acid;
Examples thereof include alkaline earth metal salts, amine salts, and quaternary ammonium salts.

Examples of the aliphatic sulfonic acid group-containing monomer include alkali metal salts such as styrenesulfonic acid, sulfophenylacrylamide, sulfophenylmaleimide and sulfophenylitaconimide, alkaline earth metal salts, amine salts and quaternary ammonium salts. Is mentioned.
Salts of heavy metals (nickel, copper, zinc, mercury, chromium, etc.) are not preferred in terms of safety.

Examples of the phenylmaleimide-substituted or phenylitaconimide-substituted monomer substituted with a chlorine atom and / or a nitro group constituting the resin charge control agent of the present invention include chlorophenylmaleimide, dichlorophenylmaleimide, nitrophenylmaleimide, and nitrochlorophenyl. Substituted phenylmaleimides such as maleimide, and substituted phenylitaconimides such as chlorophenylitaconimide, dichlorophenylitaconimide, nitrophenylitaconimide, and nitrochlorophenylitaconimide are preferable from the viewpoint of chargeability and filming resistance.

The acrylate and / or methacrylate monomers constituting the resin charge control agent of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylate.
N-butyl acrylate, isobutyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Examples of the aromatic vinyl monomer constituting the resin charge control agent of the present invention include styrene, vinyl toluene, α-methylstyrene and the like.

By adding a sulfonic acid group-containing monomer as a monomer constituting the resin charge control agent of the present invention, the effect of imparting a negative charge to the resin charge control agent is improved. (Temperature and humidity stability)
Since it is generally known to use an aromatic monomer having an electron-withdrawing group as a copolymer,
Although it is sufficient to use several thousand sheets, long-term use of tens of thousands of sheets may cause contamination of the developing roller and the layer thickness regulating members (blades and rollers) and filming of the photoreceptor. There is a problem that stability and high image quality are not sufficiently maintained, and productivity is reduced.

In order to compensate for such a drawback, a polyester resin or a polyol resin which is suitable as a binder resin for a full-color toner from the viewpoint of color developability and image strength is compared with a sulfonic acid group-containing monomer and a chlorine atom and / or a nitro group. By using a copolymer containing a substituted phenylmaleimide-substituted and / or phenylitaconimide-substituted monomer and an acrylic acid ester and / or methacrylic acid ester monomer as a resin charge control agent, a long-term use is obtained. Excellent charging and environmental stability, developing roller and layer thickness regulating member (blade and roller)
Thus, a thin layer can be formed without contamination, the filming of the photoreceptor can be prevented, high image quality can be maintained, and a high productivity electrophotographic toner can be obtained.

These effects are presumed to be due to the following reasons. That is, by using a sulfonic acid group-containing monomer in combination with a phenylmaleimide-substituted and / or substituted monomer substituted by a chlorine atom and / or a nitro group, the effect of imparting a negative charge is enhanced, and the acrylate ester and / or The use of an acrylate monomer further enhances the environmental stability of charging, increases the resin hardness, improves the pulverizability, and eliminates contamination of the developing roller and the layer thickness regulating members (blades and rollers). The effect of preventing body filming is improved, and by combining it with a polyester resin or polyol resin suitable for color development and image strength as a binder resin for full-color toner, appropriate dispersibility is obtained and the charge distribution is sharp. An electrophotographic toner is obtained.

The resin negative charge control agent of the present invention may be a catalyst, a polymerization inhibitor or a solvent for synthesizing a phenylmaleimide-substituted and / or phenylitaconimide-substituted monomer substituted with a chlorine atom and / or a nitro group. Volume resistance, which is thought to be caused by residues such as
This affects the desired amount of toner charge. For this reason, problems such as rising of the charge of the toner containing the resin negative charge control agent and charge-up of the saturated charge amount may occur.

The volume resistance of the resin negative charge control agent is 9.5 (L
ogΩ · cm), the toner on the developing roller cannot obtain a desired amount of charge at the initial stage, causing background smear and toner scattering. Volume resistance of resin negative charge control agent is 1
If it exceeds 1.5 (Log Ω · cm), the toner on the developing roller will initially have a desired charge amount, but will charge up over time, and the toner thin layer on the developing roller will not be uniform, Color streaks and unevenness occur on the image. The volume resistance of the resin negative charge control agent is 10.0 to 11.0 (Lo)
gΩ · cm) is preferred.

The composition ratio of the monomer in the resin charge control agent of the present invention is such that the sulfonic acid group-containing monomer is 1 to 30% by weight, more preferably 2 to 20% by weight. When the amount of the sulfonic acid group-containing monomer is less than 1% by weight, the rise of charge and the amount of charge are not sufficient, and the image is likely to be affected.
If the content exceeds 30% by weight, the environmental stability of charging deteriorates.
The charge amount at high temperature and high humidity is low, and the charge amount at low temperature and low humidity is high, and the charge stability and high image quality of the toner are not sufficiently maintained. Furthermore, there is a problem that contamination of the developing roller and the layer thickness regulating member (blade and roller) and filming of the photoreceptor are apt to occur, and the productivity at the time of toner production by the kneading / pulverizing method is reduced.

The content of the phenylmaleimide-substituted or phenylitaconimide-substituted monomer substituted with a chlorine atom and / or a nitro group is 1 to 80% by weight, more preferably 20 to 70% by weight. When the amount of the phenylmaleimide-substituted and / or phenylitaconimide-substituted monomer substituted with a chlorine atom and / or a nitro group is less than 1% by weight, the charge amount is not sufficient, and background fouling and toner scattering are likely to occur. On the other hand, if it exceeds 80% by weight, the dispersion in the toner is poor, the charge distribution of the toner is widened, the background smear and the toner are easily scattered, and the maintenance of high image quality is not sufficient.

The content of the acrylate and / or methacrylate monomer is 10 to 80% by weight, more preferably 20 to 70% by weight. 1 acrylate and / or methacrylate monomer
If the amount is less than 0% by weight, sufficient environmental stability of charging cannot be obtained, the pulverizability at the time of toner production by the kneading / pulverization method is not sufficient, and the developing roller and the layer thickness regulating member (blade or roller) ) And filming of the photoreceptor cannot be sufficiently prevented. If it exceeds 80% by weight, the rise of the charge and the amount of charge are not sufficient, and the image is likely to be affected.

0 to 30% by weight of an aromatic vinyl monomer,
More preferably, it is 3 to 20% by weight. When the amount of the aromatic vinyl monomer exceeds 30% by weight, the resin becomes hard, the dispersibility in the toner is reduced, the charge distribution is widened, and the background smear and the toner scattering in the machine tend to occur. Further, the fixability of the toner, particularly the color developability at the time of color mixing of the color toner, becomes poor.

The resin charge control agent of the above-mentioned combination can be combined with a polyester resin or a polyol resin which is suitable in terms of color development and image strength as a binder resin for a full-color toner, so that an appropriate dispersibility can be obtained and the charge distribution can be improved. Is obtained, and a long-term charge stability and high image quality are obtained.

The apparent viscosity of the resin charge controlling agent of the present invention measured by a flow tester is 10 ⁴ P (10 ⁴ P = 10 ⁴ g / cm).
It is preferable that the temperature at which s) is reached is 85 to 110 ° C. When the temperature is lower than 85 ° C., an appropriate dispersibility in the toner cannot be obtained, and not only the charge is reduced, but also the storage stability becomes poor and solidification (aggregation) is liable to occur. In the method obtained from the production process of kneading, pulverizing and classifying, sticking in the pulverizing process is likely to occur, and the productivity is deteriorated. On the other hand, when the temperature exceeds 110 ° C., the dispersibility in the toner is reduced, the charge distribution is widened, and the background is easily scattered and the toner is scattered in the machine. Further, the fixability of the toner, particularly the color developability at the time of color mixing of the color toner, becomes poor. The apparent viscosity is 10 ⁴ P (10 ⁴ P = 10
⁴ g / cm · s) using a flow tester at a load of 10 kg / cm ² , an orifice of 1 mm × 1 mm,
The viscosity was measured at a heating rate of 5 ° C./min and the apparent viscosity was 10 ⁴ P
(10 ⁴ P = 10 ⁴ g / cm · s). Shimadzu CFT as a flow tester
-500 type can be used.

The number average molecular weight of the resin charge control agent of the present invention is preferably 5,000 to 100,000. If it is less than 5,000, appropriate dispersibility in the toner cannot be obtained, and not only does the charge decrease, but also kneading, pulverization,
In the method obtained from the production step of classifying, sticking in the pulverization step is likely to occur, thereby deteriorating productivity. Also, 10
If it exceeds 0000, the dispersibility in the toner is reduced, the charge distribution is widened, the toner is liable to be scummed or the toner is scattered in the machine, and the fixing property and the coloring property of the toner are poor.

The particle diameter of the dispersion of these resin negative charge control agents in the toner was 0.05 to 1.50 μm in major axis and 0.02 to 1.00 μm in minor axis when observed with a transmission electron microscope.
Is preferred. The major axis is 1.50 μm and the minor axis is 1.00 μm
When the ratio exceeds, the charge distribution of the toner is widened, and the background stain and the toner scattering in the machine are easily generated. The major axis is 0.05μ
When m and the minor axis are 0.02 μm or less, the rise of charge and the amount of charge are not sufficient, and the image is likely to be affected. The weight average diameter of the toner at this time is 6.0 to 8.0 μm.
m.

The addition amount of the resin charge control agent of the present invention is preferably 0.1 to 20% by weight based on the toner particles.
5 to 10% by weight is more preferred. If the amount is less than 0.1% by weight, the rising of the charge and the amount of charge are not sufficient, and the image is likely to be affected. If it exceeds 20% by weight, the dispersion will be poor, the charge distribution will be wide, and the background will be soiled and the toner will scatter in the machine. In addition, at least one selected from the group consisting of a chromium complex or salt of salicylic acid and a chromium complex or salt of alkyl salicylic acid may be used in combination as the charge control agent.

As the binder resin used in the present invention, a polyester resin or a polyol resin which is suitable as a binder resin for a full-color toner in terms of color development and image strength is used.
In a color image, several types of toner layers are superimposed one upon another, so that the toner layer becomes thicker, and the image may be cracked or defective due to insufficient strength of the toner layer, or an appropriate gloss may be lost. For this reason, a polyester resin or a polyol resin is used to maintain appropriate gloss and excellent strength.

The polyester resin can be generally obtained by an esterification reaction between a polyhydric alcohol and a polycarboxylic acid. Among the monomers constituting the polyester resin in the present invention, examples of the alcohol monomer including tri- or higher-valent polyfunctional monomers include ethylene glycol, diethylene glycol triethylene glycol, 1,2-propylene glycol, and 1,3-propylene. Glycols such as glycol, 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxypropylene Bisphenol A alkylene oxide adducts such as bisphenol A, other dihydric alcohols, or sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol Le, tripentaerythritol, 1,2,4-butanetriol, 1, 2, 5
-Pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,
Examples thereof include 2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, and other trihydric or higher polyhydric alcohols.

Among these monomers, those using a bisphenol A alkylene oxide adduct as a main component monomer are particularly preferably used. Bisphenol A
When an alkylene oxide adduct is used as a constituent monomer, a polyester having a relatively high glass transition point can be obtained due to the nature of the bisphenol A skeleton, and the copy blocking resistance and the heat storage stability are improved. In addition, the presence of the alkyl groups on both sides of the bisphenol A skeleton functions as a soft segment in the polymer, and improves color developability and image strength during toner fixing. In particular, among the bisphenol A alkylene oxide adducts, those having an ethylene group or a propylene group are preferably used.

Among the monomers constituting the polyester resin in the present invention, examples of the acid monomer include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and phthalic acid, including trifunctional or higher polyfunctional monomers. , Isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or n-dodecenylsuccinic acid,
Alkenyl succinic acids or alkyl succinic acids such as n-dodecyl succinic acid, anhydrides of these acids, alkyl esters, other divalent carboxylic acids, and 1,
2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid,
2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetra Carboxylic acids, empole trimer acids and their anhydrides,
Examples thereof include alkyl esters, alkenyl esters, aryl esters, and other trivalent or higher carboxylic acids.

Specific examples of the above-mentioned alkyl group, alkenyl group or aryl ester include 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid trimethyl and 1,2,4-benzenetricarboxylic acid triethyl. , 1,2,4-benzenetricarboxylic acid tri-n
-Butyl, isobutyl 1,2,4-benzenetricarboxylate, tri-n-octyl 1,2,4-benzenetricarboxylate, tri2-1,2,4-benzenetricarboxylate
Examples include ethylhexyl, tribenzyl 1,2,4-benzenetricarboxylate, and tris (4-isopropylbenzyl) 1,2,4-benzenetricarboxylate.

It is known that the relationship between the chargeability of a polyester resin and the acid value is almost proportional to each other. It is known that the higher the acid value, the greater the negative chargeability of the resin. Also affect. That is, when the acid value is high, the charge amount becomes high under low temperature and low humidity, and the charge amount becomes low under high temperature and high humidity, the background stain, the image density, the change in color reproducibility become large, and it is difficult to maintain high image quality. . Therefore, the acid value of the polyester resin is preferably 20 KOH mg / g or less,
Further, 5 KOH mg / g or less is preferable.

The polyol resin used in the present invention may be obtained by capping the end of the epoxy resin from the viewpoints of environmental stability of charging, fixing stability, color reproducibility, gloss stability, curling prevention after fixing, and the like. Further, those having a polyoxyalkylene moiety in the main chain are preferred. For example, the epoxy resin of both terminal glycidyl groups and the two
It can be obtained by reacting an alkylene oxide adduct of a divalent phenol with a dihalide, isocyanate, diamine, diol, polyhydric phenol, or dicarboxylic acid. Of these, the reaction with a dihydric phenol is most preferable in terms of reaction stability. It is also preferable to use a polyhydric phenol or a polycarboxylic acid together with a dihydric phenol within a range not causing gelation.

Examples of the alkylene oxide adduct of a dihydric phenol having a glycidyl group at both terminals used in the present invention include the following. Examples include ethylene oxide, propylene oxide, butylene oxide, and reaction products of these mixtures with bisphenols such as bisphenol A and bisphenol F. The obtained adduct may be used after glycidylation with epichlorohydrin or β-methylepichlorohydrin. In particular, a glycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

[0055]

Embedded image In the above formula, n and m are the number of repeating units, each being 1 or more, and n + m = 2 to 6. R represents at least one group represented by the following chemical formula 2.

[0056]

Embedded image

Specific examples of silica used as an additive in the present invention include colloidal silica fine powder AEROS.
Specific examples of titania such as IL200, 130, 50 and OX50 (manufactured by Nippon Aerosil Co., Ltd.) include MT150A
(Manufactured by Teica). Preferably, at least either silica or titania has been subjected to a surface treatment (hydrophobic treatment) with an organic silane compound.

When using a silica surface-treated with an organic silane compound, the amount of the organic silane compound to be treated with respect to the silica is preferably 30% by weight or less based on the silica. Also, when using titania surface-treated with an organic silane compound, the amount of the organic silane compound treated with respect to titania is preferably 35% by weight or less with respect to titania.

Generally, most of silica and titania are present as primary particles. In the case of silica, when the treatment amount of the organic silane compound exceeds 30% by weight, in the case of titania, 35% %, Many aggregates consisting of several to several hundreds are generated. These aggregates remain unraveled even when the base toner and the additive are mixed, which may cause insufficient fluidity to be obtained. In addition, the charging becomes non-uniform, which may cause toner scattering and background contamination.

Specific examples of the organic silane compound used for the surface treatment include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, and bromomethyldimethyl. Chlorosilane, α-chloroethyltrichlorosilane, p-
Chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyltris (β -Methoxyethoxy) silane, γ
-Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, (4-t-propylphenyl) trichlorosilane,
(4-t-butylphenyl) trichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dinonyldichlorosilane, didecyldichlorosilane, didodecyldichlorosilane, dihexadecyldichlorosilane , (4-t-butylphenyl) octyldichlorosilane, dioctyldichlorosilane, didecenyldichlorosilane, dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-
3,3-dimethylpentyldichlorosilane, trihexylchlorosilane, trioctylchlorosilane, tridecylchlorosilane, dioctylmethylchlorosilane, octyldimethylchlorosilane, (4-t-propylphenyl) diethylchlorosilane, isobutyltrimethoxy Silane, methyltrimethoxysilane, octyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexamethyldisilazane, hexaethyldisilazane, diethyltetratyldisilazane, hexaphenyldisilazane, hexatolyldi Silazane and the like. In addition, various polysiloxanes, titanate coupling agents, and aluminum coupling agents can also be used.

The trade names of the surface-treated silica fine particles include HDK H2000, HDK H2000 /
4, HDK H 2050EP, HVK21,
Hoechst), R972, R974, RX200, R
Y200, R202, R805, R812, RX50,
NAX50 (all manufactured by Nippon Aerosil Co., Ltd.), TS720
(Made by Cabot). Further, as specific trade names of the surface-treated titania fine particles, anatase-type or rutile-type crystalline or non-crystalline one can be used, and T-805 (manufactured by Nippon Aerosil Co., Ltd.) or the like can be used. MT150AI, MT150AFM (manufactured by Teika), STT-30A (manufactured by Titanium Industry), ST
T-30A-FS (manufactured by Titanium Industry Co., Ltd.) and the like.

By adding one or more kinds of hydrophobic fine particles having a primary average particle diameter of 30 nm or less to the toner particles, for example, one or two kinds are added separately from the hydrophobic silica fine particles having a primary average particle diameter of 30 to 50 nm. It is preferable because it can be improved. For example, by adding hydrophobic silica fine particles, chargeability and fluidity are improved. Further, by adding a hydrophobic acid value titanium, effects such as stabilization of thin layer forming property can be obtained. When the primary average particle size is 30 nm or less, the fluidity of the toner is not impaired.
If it is more than 0 nm, the fluidity of the toner is impaired.

The volume average particle diameter of the toner particles is 4 to 8
μm, the ratio of the volume average diameter Dv to the number average diameter Dn, D
When v / Dn is 1.4 or less, the difference from the initial image quality is reduced.

As the coloring agent, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (1
0G, 5G, G), cadmium yellow, yellow iron oxide, ocher, graphite, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow ( G, G
R), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Tan, Lead Zhu, Cadmium Red, Cad Muum Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phisaed Red, Parachlor Ortho Nitroaniline Red, Risor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine Min BS, Permanent Red (F2R, F4R, FRL, FRL)
L, F4RH), Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Lisor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F
2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Museum, Eosin Lake,
Rhodamine lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue , Alkaline blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (R
S, BC), indigo, ultramarine, navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc White, Lithobon and mixtures thereof can be used. The amount used is generally 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.

A wax may be contained in the produced developer so that the produced developer has releasability. The wax has a melting point of 40 to 120 ° C., preferably 50 to 110 ° C. When the melting point of the wax is too high, the fixability at low temperatures may be insufficient, while when the melting point is too low, the offset resistance and durability may decrease. The melting point of the wax is determined by a differential scanning calorimetry ( DSC). That is, the melting peak value when a few mg of the sample is ripened at a constant heating rate, for example (10 ° C./min), is defined as the melting point.

Examples of the wax usable in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketones, fatty acid metal salt wax, and fatty acid ester wax. And partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols, and carnauba wax. Polyolefins such as low molecular weight polyethylene and polypropylene can also be used. In particular, a polyolefin having a softening point of 70 to 150 ° C by a ring and ball method is preferable,
Further, a polyolefin having a softening point of 120 to 150 ° C is preferable.

Examples of the cleaning property improving agent for removing the developer after transfer remaining on the photoreceptor and the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, for example, fine particles of polymethyl methacrylate, Examples include polymer fine particles produced by soap-free emulsion polymerization of polystyrene fine particles and the like. Polymer fine particles have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
Are preferred.

(Manufacturing Method of Toner) The manufacturing method of the toner for developing an electrostatic image of the present invention comprises a step of mechanically mixing a developer component containing at least a binder resin, a main charge controlling agent and a pigment; A toner manufacturing method including a kneading step, a pulverizing step, and a classifying step can be applied. Also, in the step of mechanical mixing and the step of melt-kneading,
It also includes a production method in which powder other than the particles serving as a product obtained in the pulverizing or classifying step is returned and reused.

The powder (by-product) other than the product particles referred to here is subjected to the melt-kneading step, and then to the fine particles and coarse particles other than the components which become the product having the desired particle size obtained in the pulverization step, and subsequently. It means fine particles and coarse particles other than the components that are generated in the classification step and have a desired particle size. In the mixing step or the melt-kneading step of such a by-product, it is preferable to mix the raw materials and preferably the by-product 1 at a weight ratio of the other raw materials 50 to the by-product 50 from the other raw materials 99. At least a binder resin, a main charge control agent and a pigment,
The mixing step of mechanically mixing the developer components including by-products may be performed under ordinary conditions using an ordinary mixer or the like using a rotating blade, and is not particularly limited.

After the above mixing step is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., a twin screw extruder manufactured by KCK, a PCM type 2 manufactured by Ikegai Iron Works, Ltd.
A screw extruder, a bus kneader and the like are preferably used.
It is important that the melt-kneading be performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be cut. Specifically, the melt-kneading temperature should be determined with reference to the softening point of the binder resin. If the temperature is lower than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.

After the completion of the above-described melt-kneading step, the kneaded material is then pulverized. In this pulverization step, it is preferable to first perform coarse pulverization and then finely pulverize. At this time, a method of crushing by colliding with a collision plate in a jet stream, crushing by colliding particles in a jet stream, or crushing with a narrow gap between a mechanically rotating rotor and a stator is preferably used. . After the completion of the pulverizing step, the pulverized product is classified in a gas stream by centrifugal force or the like, thereby producing a toner having a predetermined particle size, for example, an average particle size of 5 to 8 μm.

In preparing the toner, the hydrophobic silica fine particles mentioned above are further added to the toner produced as described above in order to enhance the fluidity, storage property, developability and transferability of the toner. Add powder and mix. A general powder mixer is used for mixing the external additive, but it is preferable that the internal temperature can be adjusted by equipping with a jacket or the like. To change the history of the load applied to the external additive, the external additive may be added during or gradually. Of course, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load may be applied first, followed by a relatively weak load, or vice versa. However, if the stirring is weak, the external additive is not sufficiently disintegrated and adhered to the toner surface, and a coarse external additive is generated. Therefore, an abnormal image such as a white spot occurs.
The coarse external additive must be provided with a stirring force for crushing and adhering to the toner particle surface.

Examples of mixing equipment that can be used include a V-type mixer, a rocking mixer, a Loedige mixer, a Nauter mixer, a Henschel mixer and the like.
Further, in order to remove coarse particles and the like which are generated at the time of mixing the external additives and strong coarse external additives and the like, it is necessary to sieve the toner after mixing. The mesh used at this time is 250-4
00 mesh is used. Preferably it is 350 mesh or more.

(Full Color Image Developing Method) Further, in the non-magnetic one-component developing method using a conductive brush according to the present invention, development is sequentially performed a number of times using a full-color toner having a specific degree of circularity on a transfer medium. In a non-magnetic one-component full-color process in which image data is sequentially transferred and superimposed, the effect can be effectively used particularly for uniform reproducibility of halftone. A full-color non-magnetic one-component image forming method according to the present invention comprises a conductive brush, a multi-color developing device including a developing roller and a developing blade that uniformly regulates a layer thickness of a developer supplied on the developing roller. The electrostatic latent images divided into the respective colors formed on the photoreceptor by the charger and the exposure device are sequentially developed by the developers corresponding to the respective colors,
This is a method of transferring to a transfer medium.

The method for forming a full-color non-magnetic one-component image of the present invention comprises the steps of: developing a plurality of multi-color images having a developing roller and a developing blade for uniformly regulating the layer thickness of a developer supplied onto the developing roller; The apparatus forms, on a plurality of photoconductors corresponding to each color, an electrostatic latent image divided into each color by a conductive brush charger and an exposure device, and sequentially develops with a developer of a corresponding color to transfer the image. This is a method of transferring to a medium. In this case, it is preferable that the developing is performed by a reversal developing method in which the polarity of the electrostatic latent image on the photoconductor and the polarity of the non-magnetic one-component developer are the same. Further, it is preferable that the developing is performed by rotating the developing roller at a higher speed than the photoconductor by directly contacting the electrostatic latent image on the photoconductor with the developing roller.

[0076]

EXAMPLES The present invention will be specifically described below with reference to examples, reference examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and percentages are by weight unless otherwise specified.

Reference Example (Synthesis Example of Charge Control Resin) Synthesis Example 1: 3,4-dichlorophenylmaleimide 350
And 100 parts of 2-acrylamido-2-methylpropanesulfonic acid were copolymerized in dimethylformaldehyde (DMF) at a boiling point for 8 hours using di-tert-butyl peroxide as an initiator. Next, 500 parts of n-butyl acrylate and 50 parts of styrene were added, and graft polymerization was carried out for 4 hours using ditertiary butyl peroxide as an initiator.
0.5 (Log Ω · cm), weight average molecular weight 1000
0, apparent viscosity is 10 ⁴ P (10 ⁴ P = 10 ⁴ g / cm ·
Thus, a charge control resin A having a temperature of 96 ° C. was obtained.

Synthesis Example 2 600 parts of m-nitrophenylmaleimide and 100 parts of perfluorooctanesulfonic acid were copolymerized in dimethylformaldehyde (DMF) at a boiling point of 8 hours using ditertiary butyl peroxide as an initiator. Then, 2-ethylhexyl acrylate was added to 2
After 50 parts of styrene and 30 parts of styrene were added and graft polymerization was carried out for 4 hours using ditertiary butyl peroxide as an initiator, DMF was removed by a reduced-pressure drier and the volume resistance was 9.5.
(Log Ω · cm), a weight average molecular weight of 5,500, and a charge control resin B having an apparent viscosity of 10 ⁴ P (10 ⁴ P = 10 ⁴ g / cm · s) at a temperature of 85 ° C. were obtained.

Synthesis Example 3: 500 parts of 3,4-dichlorophenylmaleimide and 150 parts of 2-acrylamido-2-methylpropanesulfonic acid were mixed in dimethylformaldehyde (DMF) under boiling point for 8 hours using ditertiary butyl peroxide as an initiator. Polymerized. Next, 350 parts of n-butyl acrylate and 250 parts of α-methylstyrene were added.
After adding 4 parts, graft polymerization was performed for 4 hours using ditertiary butyl peroxide as an initiator, DMF was removed by a reduced pressure drier, and the volume resistance was 11.5 (LogΩ · cm).
Weight average molecular weight 96,000, apparent viscosity 10 ⁴ P (1
^{0 4 P = 10 4 g /} cm · s) to become the temperature to obtain a 110 ° C. charge control resin C.

Synthesis Example 4: 400 parts of 3,4-dichlorophenylmaleimide and perfluorooctanesulfonic acid 2
00 parts were copolymerized in dimethylformaldehyde (DMF) at a boiling point for 8 hours using ditertiary butyl peroxide as an initiator. Then, n-butyl acrylate was added to 3
After adding graft copolymer for 4 hours using ditertiary butyl peroxide as an initiator, DMF was removed by a reduced-pressure drier to obtain a volume resistance of 10.4 (LogΩ · c).
m), weight average molecular weight of 15,000, apparent viscosity of 10 ⁴
The temperature at which P (10 ⁴ P = 10 ⁴ g / cm · s) is 105
C. A charge control resin D was obtained.

Synthesis Example 5 400 parts of 3,4-dichlorophenylmaleimide and 100 parts of 2-acrylamido-2-methylpropanesulfonic acid were mixed in dimethylformaldehyde (DMF) at a boiling point of 8 hours using ditertiary butyl peroxide as an initiator. Polymerized. Next, 500 parts of n-butyl acrylate and 100 parts of styrene were added, and after 4 hours of graft polymerization using ditertiary butyl peroxide as an initiator, DMF was removed by a reduced-pressure dryer, and DMF was removed by a reduced-pressure dryer. Volume resistance 9.3
(Log Ω · cm), a weight average molecular weight of 30,000, and an apparent viscosity of 10 ⁴ P (10 ⁴ P = 10 ⁴ g / cm · s).

Synthesis Example 6: 400 parts of 3,4-dichlorophenylmaleimide and 200 parts of 2-acrylamido-2-methylpropanesulfonic acid were mixed in dimethylformaldehyde (DMF) under boiling point for 8 hours using ditertiary butyl peroxide as an initiator. Polymerized. Next, 200 parts of n-butyl acrylate and 400 parts of styrene were added and dissolved, and then DMF was removed by a reduced pressure drier to obtain a volume resistance of 11.6 (Log Ω · cm) and a weight average molecular weight of 1160.
00, apparent viscosity is 10 ⁴ P (10 ⁴ P = 10 ⁴ g / cm
A charge control resin F having a temperature of 110 ° C. was obtained.

Synthesis Example 7: 450 parts of 3,4-dichlorophenylmaleimide and perfluorooctanesulfonic acid 1
Fifty parts were copolymerized in dimethylformaldehyde (DMF) at a boiling point for 3 hours using ditertiary butyl peroxide as an initiator. Then, methyl acrylate was added to 500
After graft polymerization for 4 hours using di-tert-butyl peroxide as an initiator, DMF was removed by a reduced-pressure drier, and the volume resistance was 9.2 (Log Ω · cm), the weight average molecular weight was 3000, and the apparent viscosity was 10 ⁴ P. (10 ⁴ P
= 10 ⁴ g / cm · s) to obtain a charge control resin G having a temperature of 80 ° C.

Reference Example (Synthesis Example of Polyester Resin) Synthesis Example 1: Polyoxypropylene (2,2)-was placed in a four-neck separable flask equipped with a stirrer, thermometer, nitrogen inlet, falling condenser, and cooling tube. 740 g of 2,2-bis (4-hydroxyphenyl) propane, 300 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, dimethyl terephthalate 466
g, isododecenyl succinic anhydride 80 g, 1,2,4-
114 g of tri-n-butyl benzenetricarboxylate were added along with the esterification catalyst. First half 210 under nitrogen atmosphere
The temperature was raised to normal pressure and the reaction was carried out while stirring at 210 ° C. under reduced pressure in the latter half. Acid value 2.3 KOHmg / g, hydroxyl value 28.
A polyester resin having 0 KOH mg / g, a softening point of 106 ° C. and a Tg of 62 ° C. was obtained (hereinafter referred to as polyester resin A).

Synthesis Example 2: Polyoxypropylene (2,
2) 725 g of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-
165 g of bis (4-hydroxyphenyl) propane, 500 g of terephthalic acid, isododecenyl succinic anhydride 13
0 g and 170 g of triisopropyl 1,2,4-benzenetricarboxylate were added to the flask along with the esterification catalyst. These were reacted with the same apparatus and the same prescription as in Synthesis Example 1 to obtain an acid value of 0.5 KOHmg / g and a hydroxyl value of 25.25 mg / g.
A polyester resin having 0 KOH mg / g, a softening point of 109 ° C. and a Tg of 63 ° C. was obtained (hereinafter referred to as polyester resin B).

Synthesis Example 3: Polyoxypropylene (2,
2) 650 g of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-
650 g of bis (4-hydroxyphenyl) propane, 515 g of isophthalic acid, 70 g of isooctenylsuccinic acid,
80 g of 1,2,4-benzenetricarboxylic acid was added to the flask along with the esterification catalyst. These were reacted with the same apparatus and the same recipe as in Synthesis Example 1 to obtain an acid value of 19.5K.
A polyester resin having an OH mg / g, a hydroxyl value of 35.0 KOH mg / g, a softening point of 110 ° C. and a Tg of 60 ° C. was obtained (hereinafter referred to as polyester resin C).

Synthesis Example 4: Polyoxypropylene (2,
2) 714 g of -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-
663 g of bis (4-hydroxyphenyl) propane, 648 g of isophthalic acid and 150 of isooctenylsuccinic acid
g, 100 g of 1,2,4-benzenetricarboxylic acid was added to the flask together with the esterification catalyst. These were reacted with the same apparatus and the same formulation as in Synthesis Example 1 to obtain an acid value of 2
1.0 KOHmg / g, hydroxyl value 24.0 KOHmg / g
g, a polyester resin having a softening point of 128 ° C. and a Tg of 65 ° C. (hereinafter referred to as polyester resin D).

Reference Example (Synthesis Example of Polyol Resin) Synthesis Example 1: A low-molecular bisphenol A type epoxy resin (number average molecular weight: about 360) 378 was placed in a separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a condenser. .4 g, high molecular bisphenol A type epoxy resin (number average molecular weight:
86.0 g of bisphenol A type propylene oxide adduct (n + m in the general formula (1): about 2.1) 191.0 g, bisphenol F 274.5 g, p-cumylphenol 7
0.1 g and xylene 200 g were added. The temperature was raised to 70 to 100 ° C. in a nitrogen atmosphere, and lithium chloride was added to 0.183.
9 g was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerization was carried out at a reaction temperature of 180 ° C. for 7 to 9 hours.
Acid value 0.0 KOHmg / g, hydroxyl value 70.0 KOHm
Thus, a polyol resin having a g / g, a softening point of 110 ° C. and a Tg of 62 ° C. was obtained (hereinafter referred to as polyol resin A).

Synthesis Example 2: Using the apparatus of Synthesis Example 1, 205.3 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360) and a high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 3000) 54.0 g, a glycidylated product of a bisphenol A-type propylene oxide adduct (n + m in the general formula (1): about 2.
2) 432.0 g, bisphenol F 282.7 g, p
-26.0 g of cumylphenol and 200 g of xylene were added. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
After polymerization for 8 hours, acid value 0.0 KOH mg / g, hydroxyl value 58.0 KOH mg / g, softening point 105 ° C., Tg 58
A polyol resin at a temperature of ° C was obtained (hereinafter referred to as polyol resin B).

Example 1 (Toner Production Example 1) (Production of Black Colored Particles) Water 1200 parts Phthalocyanine green water-containing cake (solid content 30%) 200 parts Carbon black (Printex 35, manufactured by Dexa Corporation) 540 parts (DBP oil absorption) = 42 ml / 100 mg, pH = 9.5) The above is stirred well with a flasher. Here, 1200 parts of polyester resin A was added, kneaded at 150 ° C. for 30 minutes, 1000 parts of xylene was added, kneading was further performed for 1 hour, water and xylene were removed, roll-cooled, and pulverized with a pulperizer.
A masterbatch pigment was obtained. Subsequently, 100 parts of polyester resin A 5 parts of master batch pigment 5 parts of charge control resin A 5 parts The above materials were mixed by a mixer, then melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a jet plate mill (I-2 type mill; manufactured by Nippon Pneumatic Industries Co., Ltd.) using a jet mill and a wind classifier (DS classifier;
Nippon Pneumatic Industry Co., Ltd.), and a number average particle size of 5.2 μm and a volume average particle size of 6.5 μm (Dv / Dn =
1.3) Black colored particles were obtained. At that time, the pulverization amount per unit time was 2.3 kg / H.

(Production of Yellow Colored Particles) 600 parts of water 1200 parts of Pigment Yellow 17 water-containing cake (50% of solid content) is thoroughly stirred with a flasher. To this, 1200 parts of polyester resin A was added, kneaded at 150 ° C. for 30 minutes, 1000 parts of xylene was added, kneading was continued for 1 hour, water and xylene were removed, rolled and cooled, pulverized with a pulperizer, and further passed twice with three rolls. Thus, a master batch pigment was obtained.
Subsequently, 100 parts of polyester resin A 5 parts of master batch pigment 5 parts of charge control resin A 5 parts The above materials were mixed by a mixer, then melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were carried out in the same manner as in the production example of black colored particles, and the number average particle size was 5.4 μm and the volume average particle size was 6.6 μm (Dv / Dn =
1.2) Yellow colored particles were obtained. At that time, the pulverization amount per unit time was 2.3 kg / H.

(Production of magenta colored particles) Water 600 parts Pigment Red 57 water-containing cake (solid content 50%) 1200 parts The above is thoroughly stirred with a flasher. Here, 1200 parts of the polyester resin A is added, kneaded at 150 ° C. for 30 minutes, 1000 parts of xylene is added, and kneading is further performed for 1 hour. Pass to obtain a masterbatch pigment. Subsequently, 100 parts of polyester resin A 5 parts of master batch pigment 5 parts of charge control resin A 5 parts The above materials were mixed by a mixer, then melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the production example of black colored particles, and the number average particle size was 5.
2 μm, volume average particle size 6.8 μm (Dv / Dn = 1.
3) Magenta colored particles were obtained. At that time, the pulverization amount per unit time was 2.3 kg / H.

(Production of Cyan Colored Particles) 600 parts of water 1200 parts of Pigment Blue 15: 3 water-containing cake (50% of solid content) are thoroughly stirred with a flasher. To this, 1200 parts of polyester resin A was added, kneaded at 150 ° C. for 30 minutes, 1000 parts of xylene was added, kneading was further performed for 1 hour, water and xylene were removed, roll-cooled, pulverized with a pulperizer, and further passed twice with a three-roll mill. Then, a master batch pigment was obtained. Subsequently, 100 parts of polyester resin A 3 parts of master batch pigment 3 parts of charge control resin A 5 parts The above materials were mixed by a mixer, then melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the production example of the black colored particles, and the number average particle diameter was 5.9 μm and the volume average particle diameter was 6.9 μm (Dv / Dn =
1.2) Cyan colored particles T1 were obtained. At that time, the pulverization amount per unit time was 2.3 kg / H.

(Toner Obtained by Mixing the Colored Particles and External Additive, and Evaluation of the Toner) 100 parts (2 kg) of the obtained four colored particles and an external additive having a primary average particle diameter of 30 〜50 nm of hydrophobic silica and other additives were mixed with a 20 L Henschel mixer, and the opening
An electrophotographic toner TS1 was obtained by removing coarse particles and aggregates by passing through a mesh of μm. Table 3 shows the image evaluation results of the combinations and the obtained toners.

(Toner Evaluation Machine) The obtained toner is developed by a four-color developing unit in which a non-magnetic one-component developer is sequentially developed for each color on one belt photoreceptor, and is sequentially transferred to an intermediate transfer body. The evaluation was performed using a remodeling machine of a full-color laser printer (Epsio 4100, manufactured by Ricoh Company) that transfers colors all at once. The developing unit has a non-magnetic one-component developing unit including a developing roller made of an elastic body and a roller for regulating the layer thickness. In addition, all of the four types of evaluation machines are of the reversal development type in which the polarity of the electrostatic latent image on the photoconductor and the polarity of the non-magnetic one-component developer are the same.

(Evaluation Items) For each item, the following evaluation was performed after continuously running an image chart having a 5% image area up to 100,000 sheets.

1) Image Density After outputting a solid image, the image density is changed to X-Rite (X-Rit).
e). This was measured at five points for each color alone, and the average was determined for each color.

2) Background Stain The white paper image was stopped during development, the developer on the photoreceptor after development was transferred to a tape, and the difference between the image density of the untransferred tape and the image density was measured using a 938 spectrodensitometer (X-Rite). Measured by the company).

3) Filming The occurrence of toner filming on the developing roller or the photosensitive member was observed.が indicates no filming, Δ indicates filming on streaks, and × indicates filming as a whole.

4) Streaks The occurrence of color streaks on the developing roller and the thin toner layer on the image was observed. ○ has few color streaks, Δ has several lines, and X has color streaks as a whole.

5) Measurement of Physical Properties 5-1) [Particle Size] The particle size of the toner was measured with a particle size analyzer “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle size and the number average particle size were determined by the above particle size analyzer.

5-2) [Powder Particle Size] The circle equivalent diameter and the number distribution can be measured using a flow particle image analyzer FPIA-1000 manufactured by SYSMEX CORPORATION. The outline of the device and measurement is described in
No. 136439. The measurement was performed by adjusting the solution to 1% NaCl aqueous solution using first-grade sodium chloride and then passing the solution through a 0.45 μm filter through 50 to 100 m.
1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, as a dispersant,
Add 10 mg. This is connected to an ultrasonic disperser (output 35W,
The dispersion treatment was performed for 1 minute at a frequency of 50 kHz), and the measurement was performed using a dispersion liquid in which the particle concentration was adjusted to 5000 to 15000 particles / μl. The number of particles is measured by calculating the diameter of a circle having the same area as a two-dimensional image area picked up by a CCD camera as a circle equivalent diameter. Based on the accuracy of the CCD pixel, the number of particles was obtained by making the equivalent circle diameter 0.6 μm or more effective.

5-3) [Charge Amount] The toner was conveyed onto a developing roller (sleeve) and measured by a suction tribo measurement method under each environment.

5-4) Volume resistance of resin negative charge control agent For example, 3 g of resin powder sized using a
A pellet having a size of 12.5 cm ² and a thickness of about 1.8 to 2.2 mm was formed by applying a pressure of 00 kgf / cm ² and a commercially available dielectric loss measuring device (TR-1 manufactured by Ando Electric Co., Ltd.)
(0C type), measurement is performed in a state where a frequency of 1 KHz is applied, and a volume resistance is calculated from the measurement.

Other examples of toner production are shown in Tables 1 and 2 below. A toner of each color was prepared in the same manner as in Example 1 except for the toner particle size, the charge control resin and its addition amount, and the binder resin.

Table 1 below shows the constitution and physical properties of the toner.

[Table 1]

The results of the toner external additive treatment are shown in Table 2 below.

[Table 2]

Table 3 below shows the evaluation results.

[Table 3]

[0109]

According to the present invention, even in the one-component developing system, an abnormal image such as white spots does not occur, and after continuous printing for a longer period of time than before, the photosensitive member, the developer layer thickness regulating member and the developing roller are developed. A developer or an electrophotographic toner, an image forming method, and an image forming apparatus capable of stabilizing the charging and conveyance of the toner, maintaining the same image density as the initial image, and maintaining a high-quality output image without filming . Further, since the charge of the developer or the toner for electrophotography of the present invention during continuous use is small, there is no problem such as fluctuation of image density, low developability, background fouling, toner scattering in a developing device, and the like.
An image with good coloring and color reproducibility can be obtained. Because of this long-term durability, the life of the developing unit, photoreceptor unit, etc. can be extended, and the amount of recycle and waste generated after use is smaller than conventional ones. It is possible to reduce the trouble of replacement.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a full-color laser printer of the present invention.

FIG. 2 is a diagram illustrating a developing unit and a toner container of the image forming apparatus of the present invention.

DESCRIPTION OF SYMBOLS 1 Developing unit 2 Photoconductor 3 Intermediate transfer belt 4 Charging roller and charger 5 Cleaning 6 Fixing 7 Transfer cleaning 8 Toner cartridge stirring and conveying agitator 9 Developing roller 10 Thin layer regulating member 11 Supply roller 12 Toner stirring and conveying agitator 13 toner cartridge stirring / conveying gear 14 toner supply port

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Toshiki Minatani 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Osamu Uchinokura 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Mitsuteru Kato 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H005 AA01 AA08 AA21 CA04 CA08 CB13 DA02 EA03 EA05 EA06 EA07 EA10 FA05

Claims (16)

[Claims] 1. Satisfies the following requirements (1) to (4),
A one-component type electrostatic image developing toner comprising at least a binder resin and a colorant. (1) A hydrophobic silica particle having a primary average particle diameter of 30 to 50 nm is added to the toner particles. (2) A volume average particle diameter (Dv) of the toner measured by a Coulter counter is 5 μm to 8 μm. Yes, (3) the content of fine powder having a particle size of 5 μm or less is less than 20% by number, and (4) the content of particles having a number-based equivalent circle diameter of 0.6 μm or more and less than 3 μm measured by a flow type particle image analyzer. Rate is 15%
It is as follows. 2. A phenylmaleimide-substituted and / or phenylitaconimide-substituted resin wherein the binder resin of the toner is a polyester and / or a polyol, and is substituted with a sulfonic acid group-containing monomer and a chlorine atom and / or a nitro group. The volume resistance of a monomer, an acrylate monomer and / or a methacrylate monomer and / or an aromatic vinyl monomer as constituent units is 9.5 to 11.5 (Log Ω · cm).
2. The toner for developing a one-component electrostatic image according to claim 1, further comprising a resin negative charge control agent. 3. A phenylmaleimide-substituted product wherein the repeating unit of the sulfonic acid group-containing monomer is substituted with 1 to 30% by weight based on the weight of the resin negative charge control agent and the chlorine atom and / or nitro group and / or The repeating unit of the phenylitaconimide substituted monomer is 1 to 80% by weight based on the weight of the resin negative charge control agent, and the repeating unit of the acrylate monomer and / or the methacrylate ester monomer is based on the weight of the resin negative charge control agent. 3. A one-component electrostatic image according to claim 2, wherein the repeating unit of the aromatic vinyl monomer is contained in an amount of 0 to 30% by weight based on the weight of the resin negative charge controlling agent. Development toner. 4. A flow tester for a resin negative charge control agent.
10 apparent viscosity ^FourP (10^FourP = 10^Fourg / cm
s) is a temperature of 85 to 110 ° C.
4. A toner for developing a one-component electrostatic image according to claim 2 or 3.
- 5. The resin negative charge control agent having a weight average molecular weight of 5
3. The method according to claim 2, wherein the number is from 000 to 100,000.
5. The toner for developing a one-component electrostatic image according to any one of items 1 to 4. 6. The one-component electrostatic image developing method according to claim 2, wherein the resin negative charge control agent is contained in an amount of 0.1 to 20% by weight based on the toner particles. toner. 7. The one-component electrostatic image developing toner according to claim 1, wherein the binder resin has an acid value of 20 KOH mg / g or less. 8. The relationship between the number average particle diameter and the volume average particle diameter of the toner particles is expressed as volume average particle diameter (Dv) / number average particle diameter (D
The electrostatic image developing toner according to claim 1, wherein n) ≦ 1.4. 9. The one-component system according to claim 1, wherein one or more kinds of hydrophobic fine particles having a primary average particle diameter of 30 nm or less are further added to the toner particles. Charge image developing toner. 10. The one component according to claim 9, wherein the hydrophobic fine particles having a primary average particle size of 30 nm or less are at least one selected from the group consisting of silica particles, titanium oxide and an aliphatic metal salt. System electrostatic image developing toner. 11. A container containing the toner for developing a one-component electrostatic image according to claim 1. Description: 12. An image forming apparatus comprising the container according to claim 11. 13. A latent image forming step of forming a latent image on a latent image holding member, a developing step of developing the latent image using a developer on a developer carrying member, and transferring the developed toner image. The one-component electrostatic image development according to claim 1, further comprising at least a transfer step of transferring the toner image on the body and a fixing step of heating and fixing the toner image on the transfer body, and as a developer. An image forming method characterized by using a toner for printing. 14. The image forming method according to claim 13, wherein in the developing step, a thin layer of the developer is formed on the developer carrier, and the development is performed in contact with or in non-contact with the latent image holding member. . 15. An image forming method in which an electrostatic latent image divided into respective colors is formed on a photoreceptor by a latent image forming means, and the electrostatic latent is sequentially developed with a developer corresponding to each color. A full-color image forming method using the toner for developing a one-component electrostatic image according to any one of claims 1 to 10 as a developer. 16. A photoreceptor, a latent image forming means for forming an electrostatic latent image on the photoreceptor divided into respective colors, and an electrostatic latent image formed on the photoreceptor by being divided into respective colors by the latent image forming means. 2. An image forming apparatus comprising at least a multi-color developing means for sequentially developing with a developer corresponding to the color of the above, and a transfer means for transferring a multi-color image formed by the multi-color developing means to a transfer medium. A full-color image forming apparatus comprising the toner for developing a one-component electrostatic charge image according to any one of claims 10 to 10.