JP2003057864A - One-component toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide one-component toner in which an additive is buried and whose fluidity and electrification property are not lowered, and an image forming method realizing the prevention of the deterioration of image quality caused by void or surface staining and the lowering of image density caused by the faulty replenishment of the toner. SOLUTION: In this image forming method in which the surface of a developer supply means 13 supplying the one-component toner to a developer carrier 11 has >=1 (number/mm) recessed parts per unit length, moves in a forward direction at an abutting part between the developer carrier 11 and the member 13 and also forms the thin layer of the one-component toner on the developer carrier 11; the one-component toner to be used is toner whose volume average particle size is >=5 μm and <=8 μm, and whose content of impalpable powder whose volume particle size is <=5 μm is <20 number %, and to which hydrophobic silica particles whose primary average particle size is 30 nm to 50 nm are added, and whose content of the particles whose diameter equivalent to a circle of number reference is 0.6 μm to 3 μm is <=15 number %.

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, and an image forming method using the toner. More specifically, it relates to a one-component toner for electrophotography used in a copying machine, a laser printer, a plain paper fax machine or the like using a direct or indirect electrophotographic development method, and an electrophotographic image forming method. More specifically, the present invention relates to a one-component toner for electrophotography used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax, etc. using a direct or indirect electrophotographic multi-color image developing system, and an electrophotographic image forming method.

[0002]

2. Description of the Related Art A developer used in electrophotography, electrostatic recording, electrostatic printing, etc., is temporarily transferred to an image carrier such as a photoconductor on which an electrostatic charge image is formed during the developing process. After being attached and then transferred from the photoconductor to a transfer medium such as a transfer paper in a transfer step, it is fixed on the paper surface in a fixing step. At that time, as a developer for developing the electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toner) is known. In the two-component developing method using a two-component developer, the toner particles adhere to the surface of the carrier to deteriorate the developer, and since only the toner is consumed, the toner concentration in the developer decreases, It is necessary to maintain a constant mixing ratio with the above, which causes a drawback that the developing device becomes large. On the other hand, the one-component developing method using a one-component developer does not have the above-mentioned drawbacks and has an advantage of downsizing of the apparatus, so that the developing method is becoming the mainstream. In recent years, offices have become more OA and color-oriented, and in addition to copying conventional manuscripts consisting only of characters, manuscripts created with a personal computer, including graphs, etc., are output by a printer and used as presentation materials, etc. The opportunity to make many copies is increasing. Many of the printer output images are solid images, line images, and halftone images, and the market demands for image quality are changing accordingly, and the demand for high reliability and the like is increasing.

Conventionally, an electrophotographic process using a one-component type developer has a magnetic one-component developing method using a magnetic toner,
It is classified as a non-magnetic one-component developing method using non-magnetic toner. The magnetic one-component development method uses a developer carrier having a magnetic field generator such as a magnet inside to hold the magnetic toner containing a magnetic substance such as magnetite, and develops it into a thin layer with a thin layer regulation member. In recent years, many have been put to practical use in small printers and the like. On the contrary,
In the non-magnetic one-component developing method, since the toner does not have a magnetic force, a developer supply member is pressed against the developer carrier to supply the toner onto the developer carrier and electrostatically retain it to form a thin layer. It has a restriction member to develop in a thin layer, and has the advantage of being compatible with colorization because it does not contain a colored magnetic material.Because a magnet is not used for the developer carrier, it is lighter in weight and lower in cost. In recent years, it has begun to be put into practical use in small full-color printers and the like.

However, the current situation is that the one-component developing method still has many problems to be improved. For example, in the two-component developing system, a carrier is used as a toner charging / conveying means, and the toner and the carrier are sufficiently stirred and mixed inside the developing device and then conveyed to the developer carrying member for development, so that it takes a relatively long time. It is possible to maintain stable charging and conveyance even during use, and it is also easy to support high-speed developing devices. However, in comparison with this, the one-component developing method does not have a stable charging and conveying means like a carrier, and therefore, charging and conveyance failure are likely to occur due to long-term use and speeding up. That is, in the one-component developing method, after the toner is conveyed onto the developer carrying member, the toner is thinned by the thin layer regulating member to develop, but the friction between the toner and the developer carrying member, the thin layer regulating member, etc. The contact and friction charging time with the charging member is very short, so the charging is lower than that of the two-component development method using a carrier.
The amount of reversely charged toner tends to increase.

Particularly, in the non-magnetic one-component developing method,
In general, a means for transporting toner by at least one toner transport member and developing the electrostatic latent image formed on the latent image carrier by the transported toner is adopted.
At that time, it is said that the layer thickness of the toner on the surface of the toner conveying member must be made as thin as possible. This also applies when using a two-component developer with a very small carrier diameter, and especially when using a one-component developer and using a toner with high electrical resistance as the toner. In this case, since the toner needs to be charged by the developing device, the layer thickness of the toner must be remarkably reduced. This is because if the toner layer is thick, only the vicinity of the surface of the toner layer is charged, and it becomes difficult to uniformly charge the entire toner layer. Therefore, the toner is required to maintain a faster charging speed and an appropriate amount of charge. Further, as a developing device, a thin toner layer is uniformly distributed by increasing the contact pressure of a friction regulating member such as a thin layer regulating member and a developer supplying member.
A method of maintaining the charge is being implemented. This tends to give more stress to the toner particles. The stress causes the external additive to be buried, resulting in deterioration of fluidity and chargeability. Further, although not fixed, a loose aggregate of toner particles is generated, which causes problems such as white spots, background stains, and a decrease in image density due to defective toner supply.

[0006]

More specifically, in the toner layer regulating portion on the developer carrying member, the toner is regulated to a predetermined layer thickness by using a thin layer regulating member which is in contact with the developer carrying member. ing. However, not all the toner once thinned is developed, but the toner is again rubbed by the regulating member, and at this time, the triboelectric charge amount of the toner becomes excessive and the toner strongly adheres to the developer carrier. , The charge imparting ability of the developer carrying member is lowered. In addition, the amount of charge between the toner that has been triboelectrically charged many times and the toner that has been newly replenished is likely to differ, and the toner has a distribution in particle size.
Fine powder toner, which has a large surface area per volume and a large amount of triboelectric charge per mass, is difficult to develop, and therefore adheres to the bottom layer of the developer carrier, which significantly hinders the triboelectric charge between the toner and the developer carrier. There is a problem that
As a result, sufficient triboelectrification charges are not applied to the toner, the image density is lowered, and a large amount of rubbing between the toner particles causes triboelectrification to a polarity opposite to a desired triboelectrification polarity, so-called reversal toner. Occurs, and so-called reversal fog that adheres to the background portion of the latent image on the photoconductor occurs.

The inventors of the present invention can solve this problem by installing a developer supply member which is in contact with the developer carrying member at a position upstream of the thin layer regulating member in the rotation direction of the developer carrying member. Thought. It was judged that it is possible to always keep the triboelectric charge amount of the toner uniform by scraping off the toner on the undeveloped developer carrier with this developer supply member and supplying fresh toner at the same time. According to the experiments conducted by the present inventors, when a developer supply member made of foam is used as a supply roller for supplying toner by contacting a developer carrying member, it is more than sufficient to obtain the above effects. The influential factors are
The shape of the developer supply member, the rotation conditions with respect to the developer carrier, and the toner design suitable for the developing device, and these factors must be set appropriately.

However, since these factors have not been taken into consideration in the prior art, the setting conditions and surface shapes of the developer carrying member and the developer supplying member are inappropriate, and the toner supplying property and the prevention of agglomerates are prevented. The undeveloped toner on the developer carrying member was not sufficiently peeled off. When the toner supply is insufficient, when a solid image having a high image ratio is developed, a phenomenon occurs in which the density developed in the second and subsequent rotations is lower than the density developed in the first rotation of the developer carrying member. The developing density of the part corresponding to one round of the developer carrier is the highest.
The concentration becomes lower toward the laps and beyond. This is a phenomenon that occurs because the amount of toner supplied by the elastic supply roller is smaller than the amount of toner developed and consumed in the first rotation of the developer carrier (hereinafter, this phenomenon is referred to as "solid tracking"). Called "poor sex.").

Further, when the agglomerates are generated, they are sandwiched between the developer carrying member and the thin layer regulating member to scrape off the toner formed in the thin layer, resulting in a white image. When the thin layer control member is a rotatable roller type instead of a blade for the purpose of developing the durability of the developing device, the thin layer control part is constantly changed, so toner adhesion does not easily occur, and the thin layer control is stable over a long period of time. Will be possible. However, by making the thin layer regulating member a rotatable roller type instead of a blade, the slip-through property of aggregates deteriorates,
The toner agglomerates are likely to be pinched, scraping off the thin-layered toner as described above, resulting in a white image (hereinafter, this phenomenon is referred to as "white void"). Further, when the undeveloped toner is insufficiently stripped off, the undeveloped toner is further frictionally charged by the regulating member as described above, the toner charge amount becomes excessive, and the toner is strongly charged and adhered to the developer carrier, so that the toner is not developed. It becomes difficult to cause unevenness in image density (hereinafter, such an image is referred to as “ghost”).

On the contrary, if the peeling ability is too high, the toner is damaged by the external force and deteriorates when the copying operation is continuously performed. As a result, the charging ability is lowered and the image density is lowered. Therefore, it is desirable to clearly set the shape of the developer supply member, the contact condition with the developer carrier, and the rotation condition in order to fully exert the functions of both the stripping ability and the supply ability. ing. Also, with respect to the toner, if the fluidity of the toner on the developer carrying member is poor, it cannot be scraped off by the developer supplying member and unevenness occurs in the toner layer on the developer carrying member. Is too large. When so-called charge-up occurs, unevenness similarly occurs. Therefore, the performance required for the toner is required to be extremely fluid, and the triboelectric charge amount is always constant without being influenced by the environment.

However, conventionally, in order to improve the fluidity of the toner, a fine powder of hydrophobic silica is generally added. However, since the fine powder of hydrophobic silica is strongly negatively charged, it is charged especially under low humidity. However, there is a problem that the above-mentioned requirements cannot be satisfied at the same time. Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide a one-component toner in which the external additive is not buried and the fluidity and the chargeability are not lowered. Further, it is possible to provide an image forming method which does not cause sticking but produces loose agglomerates of toner particles, which does not reduce image quality due to white spots, background stains, and image density due to poor toner supply. It is an issue.

[0012]

In order to solve the above-mentioned problems, the invention according to claim 1 is a roller type in which a one-component toner carried on a developer carrier is brought into contact with the developer carrier. The roller type thin layer regulating member has a means for regulating by a thin layer regulating member and being rotatable by contacting with the developer carrying member, and the surface of the developer supplying member has one concave portion per unit length. (Number / mm) or more, and moves in the forward direction at the contact portion with the developer carrying member, and forms a thin layer of the one-component toner on the developer carrying member. Is a one-component toner used in an image forming method in which a latent image is developed and visualized, and the primary average particle size is 30 nm to 50 nm.
The one-component toner to which the hydrophobic silica particles of 5 nm are added has a volume average particle diameter of 5 μm to 8 μm and a volume particle diameter of 5 μm.
The content of the following fine powder is less than 20% by number, and the content of particles having a number-based circle equivalent diameter of 0.6 μm to 3 μm is 1
It is a one-component toner containing 5% by number or less. The invention according to claim 2 is the one-component toner according to claim 1, wherein the content of particles having a number-based equivalent circle diameter of 0.6 μm to 3 μm is 10% by number or less. In the invention according to claim 3, in the one-component toner particles, the relationship between the number average particle diameter and the volume average particle diameter is volume average particle diameter (Dv) / number average particle diameter (Dn) ≦ 1.4. The one-component toner according to claim 1. The invention according to claim 4 is the one-component toner according to any one of claims 1 to 3, wherein one or more kinds of hydrophobic fine particles having a primary average particle diameter of 30 nm or less are added to the one-component toner. . The invention according to claim 5 is the one-component toner according to claim 4, wherein the hydrophobic fine particles are silica particles and titanium oxide. The invention according to claim 6 is the one-component toner according to any one of claims 1 to 5, wherein a fatty acid metal salt is added to the one-component toner.

According to a seventh aspect of the present invention, the one-component toner carried on the developer carrying member is regulated by a roller type thin layer regulating member which is in contact with the developer carrying member, and the roller type thin layer regulating member is regulated. The member has means capable of rotating by contacting the developer carrying member, the surface of the developer supplying member has one or more recesses per unit length (pieces / mm), and the developer carrying member. In an image forming method in which a thin layer of the one-component toner is formed on the developer carrying member while moving in a forward direction at a contact portion with a body, and the developer carrying member develops a latent image to visualize it. In the image forming method, the average primary particle size is 30 nm to 5 nm.
A one-component toner to which 0 nm hydrophobic silica particles are added, having a volume average particle size of 5 μm or more and 8 μm or less,
An image using a one-component toner in which the content of fine powder having a volume particle diameter of 5 μm or less is less than 20 number% and the content of particles having a number-based circle equivalent diameter of 0.6 μm to 3 μm is 15 number% or less. It is a forming method. The invention according to claim 8 is the image forming method, wherein the number-based circle equivalent diameter is from 0.6 μm to
The image forming method according to claim 7, wherein a one-component toner having a content of 3 μm particles of 10% by number or less is used. According to a ninth aspect of the present invention, in the image forming method, the relationship between the number average particle diameter and the volume average particle diameter is the volume average particle diameter (Dv) /
9. The image forming method according to claim 7, wherein a one-component toner having a number average particle diameter (Dn) ≦ 1.4 is used. The image forming method according to claim 10 uses a one-component toner to which one or more kinds of hydrophobic fine particles having a primary average particle diameter of 30 nm or less are added. Image forming method. The invention according to claim 11 is the image forming method, wherein the hydrophobic fine particles are
The image forming method according to claim 10, wherein a one-component toner including silica particles and titanium oxide is used. The invention according to claim 12 is characterized in that the image forming method uses a one-component toner to which a fatty acid metal salt is added.
1 is an image forming method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic diagram showing the configuration of an image forming apparatus that is an embodiment of the present invention. Figure 2
FIG. 2 is a schematic diagram showing a configuration of a developing device in FIG. 1. According to the present invention, the one-component toner carried on the developer carrying member 11 is regulated by the roller type thin layer regulating member which is in contact with the developer carrying body 11, so that the roller type thin layer forming member can be carried on the developer carrying body 11. The surface of the developer supply member 13 has a concave portion per unit length of 1 (pieces / mm) or more, and has a means capable of contacting and rotating, and at the contact portion with the developer carrying member 11. In the image forming method, the thin layer of the one-component toner is formed on the developer carrier 11 while moving in the forward direction, and the latent image is developed and visualized while being regulated by the roller-type thin-layer regulation member 12. Hydrophobic silica particles having a primary average particle diameter of 30 nm to 50 nm are added to the particles, and the volume average particle diameter (Dv) of the toner measured by a Coulter counter is 5 μ.
m to 8 μm and a fine powder content of 5 μm or less is 20
An image forming method using a one-component toner in which the content of particles having a number-based circle equivalent diameter of 0.6 μm to 3 μm measured by a flow-type particle image analyzer is 15% by number or less. Is. Further, the present invention is
A one-component toner used in the above-mentioned image forming method, which is obtained by adding hydrophobic silica particles having a primary average particle diameter of 30 nm to 50 nm and has a volume average particle diameter (Dv) of 5 μm measured by a Coulter counter. ˜8 μm, the content of fine powder of 5 μm or less is less than 20% by number, and the content of particles having a number-based circle equivalent diameter of 0.6 μm to 3 μm measured by a flow type particle image analyzer is 1
The present invention relates to a one-component toner containing 5% by number or less.

In FIG. 1, the main developing device 1 is provided with a developer carrying member 11 installed opposite to the photosensitive member 2 of the image carrying member which rotates in the direction of arrow d in the figure, and an electrostatic latent image on the photosensitive member 2 is formed. It is developed and visualized as a toner image. The developer carrier 11 is rotationally driven in the direction of arrow a with respect to the rotation direction d of the photoconductor 2. The photosensitive member 2 is not limited to the belt shape, and may have a cylindrical shape that is driven to rotate. Further, in the developing container, an elastic roller 12 is provided as a thin layer regulating member 12 below the developer carrier, and the developer is provided at a position upstream of the elastic roller 12 in the rotation direction of the developer carrier 11. A supply member 13 is provided. The developing device 1
The developer supply member 13 rotates in the direction of arrow b in the forward direction with respect to the developer carrying member 11, and the developer supply member 13 carries one-component toner (hereinafter, simply referred to as “toner”) by the rotation of the developer supply member 13. The toner on the developer supplying member 13 is rubbed against the developer carrying member 11 at the contact portion (nip portion) which is supplied near the carrying member 11 and where the developer carrying member 11 and the developer supplying member 13 come into contact with each other. As a result, it adheres onto the developer carrying member 11.

Thereafter, as the developer carrying member 11 rotates,
The toner adhered on the developer carrying member 11 enters between the thin layer regulating member 12 and the developer carrying member 11 at the abutting portion thereof, and when passing through the surface of the developer carrying member 11, It is rubbed by both of the thin layer regulating members 12 and sufficiently frictionally charged. The toner charged as described above exits the contact portion between the thin layer regulating member 12 and the developer carrying member 11 to form a thin layer of toner on the developer carrying member 11, and It is developed to 2. By applying a developing bias between the developer carrier 11 and the photoconductor 2 in the developing device 1, the toner on the developer carrier 11 is transferred corresponding to the electrostatic latent image on the photoconductor 2, The toner is attached to the electrostatic latent image and developed to be visualized as a toner image.

The toner remaining on the developer carrier 11 without being consumed for development in the developing device 1 is the developer carrier 1.
With the rotation of 1, the toner is collected from the upper portion of the developer carrier 11 into the developing container. The collected toner is the developer supply member 1
3 is peeled off from the developer carrying member 11 at the contact portion with the developer carrying member 11. At the same time, new toner is supplied onto the developer carrying member 11 by the rotation of the developer supplying member 13, and the new toner is conveyed again to the contact portion between the developer carrying member 11 and the thin layer regulating member 12. On the other hand, most of the peeled toner is conveyed and mixed into the toner in the developing container as the developer supply member 13 rotates, and the electrostatic charge of the peeled toner is dispersed.

That is, the present inventors pay attention to the contact between the developer supply member 13 and the developer carrying member 11 and change the circumferential concave portion per unit length on the surface of the developer supply member 13. As a result of repeating the copying operation many times and examining the peeling ability of the undeveloped toner on the developer carrying member and the supply ability of the new toner to the developer carrying member, the concave portions are in the range of 1 (pieces / mm) or more. We found that setting was the most effective. FIG. 3 is a schematic view showing the structure of the developer supply member used in the present invention. 3A is a perspective view of a developer supply member used in the present invention, FIG. 3B is a cross-sectional view of the developer supply member used in the present invention, and FIG. 3C is development used in the present invention. It is an enlarged view of a section of an agent supply member. The surface shape of the developer supply member 13 applicable to the present invention preferably has irregularities in the circumferential direction. With the rotation of the developer supply member 13, the convex portion rubs the developer carrying member to peel off the undeveloped toner, hold the toner in the bubble portion of the concave portion, and replenish the toner to the developer carrying member. . According to the experiments conducted by the present inventors, the rotation direction of the developer supplying member 13 is preferably such that the developer supplying member 13 moves in the forward direction at the contact portion with the developer carrying member, and the rotation direction of the developer supplying member 13 abuts. When the direction is reversed, the toner supply property and the peeling of the undeveloped toner are further improved, but the amount of loose toner aggregates is increased, which is not preferable.

As shown in FIG. 3 (c), the peripheral surface of the developer supply member 13 has one concave portion per unit length (piece / m).
m) or more, and the rotation direction of the developer supply member 13 is
When the directions are set such that they move in the forward direction at the contact portion with the developer carrying member, it is possible to most effectively strip the undeveloped toner and supply the toner, and to suppress the generation of toner aggregates. I found it. As a result, by combining with a toner described later, it is possible to obtain a stable image forming apparatus in any environment without causing solid followability, ghost, white spots and toner deterioration. As the material used for the developer supply member 13,
Any surface shape may be used as long as it has irregularities in the circumferential direction, that is, has partition walls oriented in the longitudinal direction, but those having a foam skeleton structure such as polyurethane foam and rubber sponge are particularly preferable.

The toner of the present invention has a primary average particle diameter of 30 n.
the volume average particle diameter (Dv) of the toner measured by a Coulter counter is 5 μm to 8 μm, and the content of fine powder of 5 μm or less is less than 20% by number. , The number equivalent circle equivalent diameter measured by a flow type particle image analyzer is 0.
The content of particles of 6 μm to 3 μm is set to 15% by number or less. As a result of earnest studies on the one-component toner used in the image forming apparatus having the above-described structure, the present inventors have found that the addition of hydrophobic silica particles having a primary average particle diameter of 30 nm to 50 nm as an external additive results in fluidization. It has been found that it is extremely effective in stabilizing the charging property and stabilizing the charge, preventing the generation of toner aggregates due to stress, and filming on the developer carrier, and is extremely well suited to the image forming apparatus having the above-mentioned configuration. It was. In other words, sufficiently good fluidity is obtained, the amount of charge in each environment is stable, and even in the image forming apparatus, the undeveloped toner is peeled off and the fresh toner is satisfactorily supplied by the developer supply member 13. The generation of toner aggregates is prevented, and it becomes possible to always form a uniform thin layer of toner on the developer carrying member.

The particle size of the hydrophobic silica fine particles is preferably 30 nm to 50 nm from the viewpoint of maintaining fluidity. Particle size is 50n
If it is larger than m, toner charging becomes non-uniform due to poor fluidity, resulting in toner scattering and fog.
If it is less than 30 nm, the toner is likely to be embedded on the toner surface, the toner is deteriorated quickly, and the durability is deteriorated. Also, filming is likely to occur on the developer carrying member. In addition, the toner volume average particle size is 5μ.
m to 8 μm and a fine powder content of 5 μm or less is 20
By using a toner having a particle size distribution of less than a few percent, it is possible to provide high image quality with excellent fine line reproducibility. When the toner volume average particle diameter exceeds 8 μm, the fine line reproducibility was poor. On the other hand, if it is less than 5 μm, the specific surface area of the toner becomes large, so that charge-up is likely to occur, causing a problem due to a decrease in image density. Further, when the content of fine powder of 5 μm or less was 20% by number or more, the filming on the developer carrying member was remarkably bad.

However, even with the toner having the above-mentioned particle size distribution, white spots were generated due to the agglomeration of the agglomerates between the developer carrying member and the thin layer regulating member 12 during repeated use. This is a coulter counter (TA
Since II) is measured by measuring the resistance change with an electric signal, fine particles of 2 μm or less are greatly affected by noise,
Although the measurement accuracy was lacking and measurement was impossible, the flow-type particle image analyzer measures by image analysis.
It became possible to measure fine particles of less than μm, and it was found that fine particles having an equivalent circle diameter of 3 μm or less measured by a flow-type particle image analyzer (hereinafter, these fine particles are referred to as “ultrafine powder”) affect the above problems. did. These ultrafine powders are coarse external additives. It was not crushed by the external additive treatment and could not be evenly adhered to the toner surface. These coarse external additives can be confirmed by an optical microscope. When the external additive is uniformly attached to the surface of the toner particles, it cannot be detected by the flow type particle image analyzer. If there is a floating external additive, the aggregate will be granulated with the external additive as the core. Although the mechanism by which the bulky external additive acts as a nucleus to granulate the agglomerate is unknown, there is a correlation between the bulky external additive and the amount of the agglomerate, and the amount of the agglomerate also increases when the amount of the bulky external additive is large. . 0.6μ in equivalent circle of number measured by flow type particle image analyzer
It has been found that when the number of particles of m to 3.0 μm is 15% by number or less, generation of white spots is improved. It is preferably 10% by number or less.

As the binder resin used in the present invention, a polyester resin or a polyol resin suitable as a binder resin for a full-color toner from the viewpoint of color developability and image strength is used.
In a color image, since several types of toner layers are stacked in layers, the toner layer becomes thick, and the image has cracks and defects due to insufficient strength of the toner layer, and proper gloss is lost. For this reason, polyester resin and polyol resin are used in order 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 include polyfunctional monomers having a valence of 3 or more, such as ethylene glycol, diethylene glycol, triethylene glycol,
Diols such as 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol and 1,6-hexanediol,
Bisphenol A alkylene oxide adducts such as bisphenol A, hydrogenated bisphenol A, polyoxypropyleneized bisphenol A, other dihydric alcohols, or sorbitol, 1,2,3,6-hexanetetrol, 1,4- Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2
-Methylpropanetriol, 2-methyl-1,2,4
Examples include butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, and other polyhydric alcohols having 3 or more valences.

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

Among the monomers constituting the polyester resin in the present invention, examples of the acid monomer include polyfunctional monomers having a valence of 3 or more, such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid and phthalic acid. , Isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or n-dodecenylsuccinic acid,
Alkenyl succinic acids such as n-dodecyl succinic acid or alkyl succinic acids, 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-butanetricarboxylic acid, 1,2,
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empor trimer acid, and these Examples thereof include anhydrides, alkyl esters, alkenyl esters, aryl esters and other carboxylic acids having a valence of 3 or more. The alkyl groups mentioned here,
Specific examples of the alkenyl group or aryl ester include trimethyl 1,2,4-benzenetricarboxylate,
Triethyl 1,2,4-benzenetricarboxylate, 1,
Tri-n-butyl 2,4-benzenetricarboxylate, 1,
Isobutyl 2,4-benzenetricarboxylate, 1,2,
Tri-n-octyl 4-benzenetricarboxylate, 1,
2,4-Benzenetricarboxylic acid tri-2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl, 1,2,4-benzenetricarboxylic acid tris (4-
Isopropylbenzyl) and the like.

It is known that the chargeability of a polyester resin and the acid value are almost proportional to each other, and it is known that the higher the acid value, the greater the negative chargeability of the resin. Also affects. That is, if the acid value is high, the charge amount will be high under low temperature and low humidity, and the charge amount will be low under high temperature and high humidity, and background stains, image density, and color reproducibility will be large, making it difficult to maintain high image quality. . Therefore, the acid value of the polyester resin is preferably 20 KOHmg / g or less, more preferably 5 KOHmg / g or less.

As the polyol resin used in the present invention, the end of the epoxy resin is capped from the viewpoints of environmental stability of charging, fixing stability, color reproducibility, gloss stability, curl resistance after fixing, etc. Further, those having a polyoxyalkylene portion in the main chain are preferable. For example, epoxy resin with glycidyl groups at both ends and 2 with glycidyl groups at both ends
It can be obtained by reacting an alkylene oxide adduct of a dihydric phenol with a dihalide, an isocyanate, a diamine, a diol, a polyhydric phenol, or a dicarboxylic acid. Of these, it is most preferable to react a dihydric phenol from the viewpoint of reaction stability. In addition, it is also preferable to use polyhydric phenols and polyhydric carboxylic acids in combination with dihydric phenol within the range where gelation does not occur.

Examples of the alkylene oxide adduct of dihydric phenol having glycidyl groups at both ends used in the present invention include the following. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, and reaction products of a mixture thereof with bisphenols such as bisphenol A and bisphenol F. The obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use. Particularly, glycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

[Chemical 1] (Here, R is —CH ₂ —CH ₂ —, —CH ₂ —CH
_{· CH 3 -, - CH 2} -CH 2 -CH 2 - either 1
And n and m are the number of repeating units, each being 1 or more and n + m = 2 to 7. )

As an additive used in the present invention, specific examples of silica include colloidal silica fine powder AEROS.
IL 200, 130, 50, OX50 (these are manufactured by Nippon Aerosil Co., Ltd.) and the like, specific examples of titania include MT.
150A (the above are manufactured by Teika) and the like. It is preferable that at least either silica or titania be surface-treated (hydrophobicized) with an organic silane compound. When using silica whose surface is treated with an organic silane compound, the amount of the organic silane compound treated with respect to silica is preferably 30% by weight or less with respect to silica. Also, when titania surface-treated with an organic silane compound is used, the amount of the organic silane compound treated with respect to titania is preferably 35% by weight or less with respect to titania. This is because most of silica and titania generally exist as primary particles, but in the case of silica, when the treatment amount of the organic silane compound exceeds 30% by weight, in the case of titania,
If it exceeds 35% by weight, many aggregates composed of several to several hundreds are generated. These agglomerates may remain unraveled even when the base toner and the additive are mixed, which may cause insufficient fluidity. In addition, the electrification becomes non-uniform, which may cause toner scattering, scumming and the like.

Specific examples of the organic silane compound used for the surface treatment include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane and bromomethyldimethyl. Chlorsilane, α-chloroethyltrichlorosilane, p-
Chlorethyltrichlorosilane, 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. , Octyldichlorosilane,
Dioctyldichlorosilane, didecenyldichlorosilane, dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trihexylchlorosilane, trioctylchlorosilane, trioctylchlorosilane, trioctylchlorosilane Decylchlorosilane, dioctylmethylchlorosilane, octyldimethylchlorosilane, diethylchlorosilane, isobutyltrimethoxysilane,
Methyltrimethoxysilane, octyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexamethyldisilazane, hexaethyldisilazane, diethyltetratyldisilazane, hexaphenyldisilazane, hexatolyldisilazane, etc. Is mentioned. In addition, various polysiloxanes, titanate-based coupling agents, and aluminum-based coupling agents can also be used.

The trade names of the surface-treated silica fine particles are HDK H 2000 and HDK H 2000 /
4, HDK H 2050EP, HVK21 (the above are manufactured by Hoechst), R972, R974, RX20
0, RY200, R202, R805, R812, RX
50, NAX50 (These are manufactured by Nippon Aerosil Co., Ltd.), T
There is S720 (the above is manufactured by Cabot). In addition, as specific product names of the surface-treated titania fine particles,
Anatase type or rutile type crystalline or amorphous type can be used, and T-805 (manufactured by Nippon Aerosil Co., Ltd.) or rutile type MT150AI, MT150A
There are FM (above manufactured by Teika), STT-30A (manufactured by Titanium Industry Co., Ltd.), STT-30A-FS (manufactured by Titanium Industry Co., Ltd.) and the like.

Further, the toner particles have a primary average particle size of 30.
It is preferable to add one kind or two kinds of hydrophobic fine particles having a particle size of not more than nm in addition to the hydrophobic silica fine particles having a primary particle diameter of 30 nm to 50 nm because the function can be improved.
For example, the addition of hydrophobic silica fine particles improves the chargeability and fluidity. Also, the addition of hydrophobic titanium oxide has the effect of stabilizing the thin layer forming property. If the primary average particle size is less than 30 nm, the toner fluidity will not be hindered, but if it exceeds 30 nm, the toner fluidity will be hindered.

The volume average particle size of the toner particles is 4 to 8
.mu.m and the ratio of the volume average particle diameter Dv to the number average particle diameter Dn and Dv / Dn are 1.4 or less, the difference from the initial image quality is reduced.

As the colorant, 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, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow ( G, G
R), Permanent Yellow (NCG), Balkan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Reedan, Lead Vermillion, Cadmium Red, Kad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sae Red, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRL)
L, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B ,. Bon maroon light, bon maroon medium, eosin lake, rhodamine lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, Perinone orange, oil orange,
Cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (R
S, BC), indigo, ultramarine blue, dark blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, 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 oxide, lithobon and mixtures thereof can be used. The amount used is generally 0.1 to 50 parts by weight with respect to 100 parts by weight of the binder resin.

Further, the charge control agent added if necessary includes amino compounds, quaternary ammonium compounds and organic dyes, particularly basic dyes and salts thereof, nigrosine base, salicylic acid chelate compounds and the like. A wax may be contained in the manufactured developer in order to impart a releasing property to the manufactured developer. The wax has a melting point of 40 to 120 ° C, and particularly preferably 50 to 110 ° C. When the melting point of the wax is too high, the fixability at low temperature may be insufficient, while when the melting point is too low, the offset resistance and durability may be decreased. DSC). That is, a few mg of a sample is heated at a constant heating rate, for example (10 ° C./mi
The melting peak value when heated in n) is the melting point. Examples of the wax that can be used in the present invention include solid paraffin wax, microwax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketones, fatty acid metal salt wax, fatty acid ester wax, partial wax. Examples thereof include modified fatty acid ester waxes, silicone varnishes, higher alcohols, and carnauba wax. Further, polyolefins such as low molecular weight polyethylene and polypropylene can also be used. In particular, the softening point by the ring and ball method is 70 to 1
A polyolefin of 50 ° C is preferable, and a polyolefin having a softening point of 120 to 150 ° C is more preferable.

Examples of the cleaning property improver for removing the developer after transfer remaining on the photoconductor 2 or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, for example, polymethylmethacrylate fine particles. Examples thereof include polymer particles produced by soap-free emulsion polymerization of polystyrene particles and the like. The fine polymer particles have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 μm.
Are preferred.

Now, a method for producing the one-component toner of the present invention will be described. The production method of the present invention provides a toner having at least a step of mechanically mixing a developer component containing a binder resin, a charge control agent and a pigment, a step of melt kneading, a step of pulverizing, and a step of classifying a toner. A manufacturing method can be applied. Further, in the mechanical mixing step and the melt-kneading step, a manufacturing method of returning powders other than particles to be the product obtained in the pulverizing or classifying step and reusing them is also included. After the step of melting and kneading with the powder other than the particles to be the product here (by-product), the fine particles and coarse particles other than the components to be the product of the desired particle size obtained in the crushing step and the classification step to be performed subsequently. It refers to fine particles or coarse particles other than the components that generate the product having a desired particle size. In the mixing step or the melt-kneading step of such by-products, it is preferable to mix the raw materials, preferably the other raw material 99 with respect to the by-product 1, and the other raw material 50 with respect to the by-product 50 in a weight ratio.

The mixing step of mechanically mixing the developer components including at least the binder resin, the charge control agent, the pigment, and the by-products may be carried out under ordinary conditions using an ordinary mixer having rotating blades. , There is no particular limitation. After the above mixing process is completed, the mixture is then placed in a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch type kneader using a roll mill can be used. For example, a KTK twin screw extruder manufactured by Kobe Steel, a TEM extruder manufactured by Toshiba Machine Co., a twin screw extruder manufactured by KCK, a PCM twin screw extruder manufactured by Ikegai Iron Works, and a co-kneader manufactured by Buss are suitable. Used for. It is important that this melt-kneading is performed under appropriate conditions so as not to break the molecular chains of the binder resin. 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, the cutting will be severe, and if it is too high, the dispersion will not proceed. When the above melt-kneading step is completed, the kneaded product is then pulverized. In this pulverizing step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of colliding with a collision plate in a jet stream to pulverize, colliding particles in a jet stream to pulverize, or pulverizing with a narrow gap between a rotor and a stator rotating mechanically is preferably used.

After the completion of this pulverizing step, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner having a predetermined particle size, for example, an average particle size of 5 to 8 μm. In addition, when preparing the toner, the fluidity, storability, developability of the toner,
In order to enhance the transfer property, the above-mentioned hydrophobic silica fine powder and the like are added to and mixed with the toner manufactured as described above. A general powder mixer is used for mixing the external additives, but it is preferable to equip a jacket or the like to control the internal temperature. To change the history of the load applied to the external additive, the external additive may be added midway 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, and then a relatively weak load may be applied, or vice versa. However, crushing of the external additive and adhesion to the toner surface are not good with weak stirring,
Coarse external additives are generated. Therefore, an abnormal image such as white spots occurs. It is necessary to provide a stirring force for the coarse external additive to disintegrate and adhere to the surface of the toner particles.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Loedige mixer, a Nauta mixer, and a Henschel mixer. In addition, in order to remove coarse particles and the like that are generated when external additives are mixed and strong coarse external additives, it is necessary to sieve the mixed toner. The mesh used at this time is 250 to 400 mesh. It is preferably 350 mesh or more.

[0040]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Further, in the following examples, parts and% are based on weight unless otherwise specified.

The charge control resin used in the toner of the present invention is
It synthesizes as follows. (Synthesis Example 1) 3,4-dichlorophenylmaleimide 35
8 parts of 0 part and 100 parts of 2-acrylamido-2-methylpropanesulfonic acid in dimethylformamide (DMF) under boiling point using di-t-butyl peroxide as an initiator.
Copolymerized for a time. Then add n-butyl acrylate to 500
And 50 parts of styrene were added, and graft polymerization was carried out for 4 hours using di-t-butyl peroxide as an initiator, followed by DMF.
Was distilled off with a vacuum dryer to give a volume resistance of 10.5 (Log
A charge control resin A having a weight average molecular weight of 10,000, an apparent viscosity of 10 ⁴ P (10 ⁴ P = 10 ⁴ g / cm · s) and a temperature of 96 ° C. was obtained.

(Synthesis Example 2) 600 parts of m-nitrophenylmaleimide and 100 parts of perfluorooctanesulfonic acid
Parts in dimethylformamide (DMF) under boiling point under di-t
-Copolymerized with butyl peroxide as an initiator for 8 hours. Then 250 parts of 2-ethylhexyl acrylate,
After 30 parts of styrene was added and graft polymerization was carried out for 4 hours using di-t-butyl peroxide as an initiator, DMF was distilled off by a vacuum dryer to give a volume resistance of 9.5 (Log Ω · c).
m), the weight average molecular weight is 5500, and the apparent viscosity is 10 ⁴ P.
The temperature at which (10 ⁴ P = 10 ⁴ g / cm · s) is 85 ° C.
A charge control resin B of No. 1 was obtained.

(Synthesis Example 3) 500 parts of 3,4-dichlorophenylmaleimide and 150 parts of 2-acrylamido-2-methylpropanesulfonic acid were heated in dimethylformamide (DMF) at a boiling point and di-t-butyl peroxide was used as an initiator. Copolymerized for 8 hours. Then acrylic acid n-
After adding 350 parts of butyl and 250 parts of α-methylstyrene and graft-polymerizing for 4 hours using di-t-butyl peroxide as an initiator, DMF was distilled off by a vacuum dryer to obtain a volume resistance of 11.5 (LogΩ · cm), the weight average molecular weight is 96000, and the apparent viscosity is 10 ⁴ P (10 ⁴ P = 1).
A charge control resin C having a temperature of 0 ⁴ g / cm · s) of 110 ° C. was obtained.

A synthetic example of the polyester resin used in the toner of the present invention is shown below. (Synthesis Example 1) A stirring device, a thermometer, a nitrogen inlet, a flow-down condenser, a four-neck separable flask with a cooling tube,
Polyoxypropylene (2,2) -2,2-bis (4-
Hydroxyphenyl) propane 740 g, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 300 g, dimethyl terephthalate 466
g, isododecenyl succinic anhydride 80 g, 1,2,4-
114 g of tri-n-butyl benzene tricarboxylate were added together with the esterification catalyst. First half 210 under nitrogen atmosphere
The temperature was raised to normal temperature up to 0 ° C, and the latter half was reacted at 210 ° C under reduced pressure with stirring. Acid value 2.3 KOHmg / g, hydroxyl value 28.
A polyester resin having 0 KOHmg / 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) -2,2-bis (4-hydroxyphenyl) propane 225 g, polyoxyethylene (2,2) -2,2-
165 g of bis (4-hydroxyphenyl) propane, 500 g of terephthalic acid, 13 of isododecenyl succinic anhydride
0 g, 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 formulation as in Synthesis Example 1 to give an acid value of 0.5 KOHmg / g and a hydroxyl value of 25.
A polyester resin having 0 KOHmg / 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) -2,2-bis (4-hydroxyphenyl) propane 650 g, 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 equipment and the same formulation as in Synthesis Example 1 to give 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) -2,2-bis (4-hydroxyphenyl) propane 714 g, polyoxyethylene (2,2) -2,2-
Bis (4-hydroxyphenyl) propane 663 g, isophthalic acid 648 g, isooctenyl succinic acid 150
g, 100 g of 1,2,4-benzenetricarboxylic acid were added to the flask along with the esterification catalyst. These were reacted with the same equipment and the same formulation as in Synthesis Example 1 to give an acid value of 2
1.0 KOHmg / g, hydroxyl value 24.0 KOHmg /
g, a softening point of 128 ° C. and a Tg of 65 ° C. were obtained (hereinafter referred to as polyester resin D).

The synthesis examples of the polyol resin used in the toner of the present invention are shown below. (Synthesis Example 1) 378.4 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360) was placed in a separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube.
High molecular weight bisphenol A type epoxy resin (number average molecular weight: about 2700) 86.0 g, glycidylated bisphenol A type propylene oxide adduct (n + m in general formula (1): about 2.1) 191.0 g, bisphenol F274. 5g, p-cumylphenol 7
0.1 g and xylene 200 g were added. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., and lithium chloride is 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 0.0KOHmg / g, hydroxyl value 70.0KOHm
A polyol resin having 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, a low molecular weight bisphenol A type epoxy resin (number average molecular weight:
About 360) 205.3 g, high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 3000) 54.0 g,
Glycidylated product of bisphenol A-type propylene oxide adduct (n + m in the general formula (1): about 2.2)
432.0 g, bisphenol F282.7 g, p-cumylphenol 26.0 g, and xylene 200 g were added.
In a nitrogen atmosphere, the temperature was raised to 70 to 100 ° C, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C for 6 to 8 hours. , Acid value 0.0 KOHmg / g, hydroxyl value 58.
A polyol resin having 0 KOHmg / g, a softening point of 105 ° C. and a Tg of 58 ° C. was obtained (hereinafter referred to as polyol resin B).

Specific production examples of the color one-component toner of the present invention will be described below. (Production Example 1 of toner (black toner)) Water: 1200
Part, phthalocyanine green hydrous cake (solid content 30
%): 200 parts and carbon black (Printex 35: manufactured by Dexa Co.): 540 parts with a flasher. To this, 1200 parts of polyester resin A was added and kneaded at 150 ° C. for 30 minutes, and then 1000 parts of xylene was added and kneaded for an additional 1 hour. After removing water and xylene, the mixture was cooled by rolling and pulverized with a pulperizer to obtain a masterbatch pigment.
Next, 100 parts of the polyester resin A, 5 parts of the masterbatch, and 5 parts of the charge control resin A were mixed by a mixer, melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher (I
-2 type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and wind classification by swirling flow (DS classifier: manufactured by Nippon Pneumatic Mfg. Co., Ltd.), number average diameter 5.2 μm, volume average diameter 6.5.
Black colored particles of μm (Dv / Dn = 1.3) were obtained.
The crushing amount per unit time at that time is 2.3 Kg / H
Met.

[Production Example 2 of Toner (Yellow Toner)]
Water: 600 parts, Pigment Yellow 17 water-containing cake (solid content 50%): 1200 parts are thoroughly stirred and mixed with a flasher. Add 1200 parts of polyester resin A here, knead at 150 ° C. for 30 minutes, add 1000 parts of xylene and knead for an additional 1 hour, remove water and xylene, cool by rolling, pulverize with a palpelizer, and further pass with 3 rolls twice. Then, a masterbatch pigment was obtained. Next, 100 parts of the polyester resin A, 5 parts of the masterbatch, and 5 parts of the charge control resin A were mixed by a mixer, 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 Black toner production example 1, and the number average diameter was 5.4 μm and the volume average diameter was 6.6 μm (Dv / Dn = 1.
2) Yellow colored particles were obtained. The amount of pulverization processing per unit time at that time was 2.3 Kg / H.

(Production Example 3 of Toner (Magenta Toner))
Water: 600 parts, Pigment Red 57 water-containing cake (solid content 50%): 1200 parts are thoroughly stirred and mixed with a flasher. Add 1200 parts of polyester resin A here, knead at 150 ° C. for 30 minutes, add 1000 parts of xylene and knead for an additional hour, remove water and xylene, cool by rolling, pulverize with a palpelizer, and pass twice with a three-roll mill. A masterbatch pigment was obtained. Next, 100 parts of the polyester resin A, 5 parts of the masterbatch, and 5 parts of the charge control resin A were mixed by a mixer, 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 Black toner production example 1, and the number average diameter was 5.2 μm and the volume average diameter was 6.8 μm (Dv / Dn = 1.
3) Magenta colored particles were obtained. The amount of pulverization processing per unit time at that time was 2.3 Kg / H.

(Production Example 4 of Toner (Cyan Toner))
Water: 600 parts, 1200 parts of Pigment Blue 15: 3 water-containing cake (solid content 50%) are thoroughly stirred and mixed with a flasher. Add 1200 parts of polyester resin A here, knead at 150 ° C. for 30 minutes, add 1000 parts of xylene and knead for an additional hour, remove water and xylene, cool by rolling, pulverize with a palpelizer, and pass twice with a three-roll mill. A masterbatch pigment was obtained. Next, 100 parts of polyester resin A, 3 parts of the above masterbatch, and 5 parts of charge control resin A were mixed by a mixer, 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 Black toner production example 1, and the number average diameter was 5.9 μm and the volume average diameter was 6.9 μm (Dv / Dn =
Cyan colored particles of 1.2) were obtained. The amount of pulverization processing per unit time at that time was 2.3 Kg / H. From the above, it was possible to manufacture a toner by using the synthesized polyester resin A, charge control resin A and colorant by a dry method of melting and kneading.

(Toner External Additive Treatment: Toner 1) Here, 100 parts by weight (2 kg) of particles of the black toner obtained in Production Example 1 of the above toner and a primary particle diameter of 30 nm to 50 nm as an external additive. As the hydrophobic silica and the hydrophobic fine particles having a primary average particle diameter of 30 nm or less, silica particles and an additive of titanium oxide are mixed by a Henschel mixer 20L, and coarse particles and aggregates are obtained by passing through a mesh having an opening of 300 μm. By removing, an evaluation toner is obtained. This evaluation toner is referred to as Example 1.

(Toners 2 to 11) Here, toner particles were manufactured using the synthesized binder resin and charge control resin shown in Table 1 below, and further treated with an external additive to obtain a toner for evaluation. , And Examples 1 to 8 and Comparative Examples 1 to 4, respectively. Table 1 shows the combination of the binder resin and charge control resin synthesized in the obtained toner and the powder characteristics. Among the powder characteristics, the particle size of the toner was measured with a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle size, the number average particle size, and the content of fine powder having a particle size of 5 μm or less were determined by a measuring instrument.

[Table 1] <Table 1: Toner composition and physical properties list>

Further, Table 2 shows the content of the external additive and the fine particles of 0.6 μm to 3 μm in the toners of Examples 1 to 7 and Comparative Examples 1 to 4 by combining the toners 1 to 11 and the external additive. Indicates. Further, the content of the fine particles of 0.6 μm to 3 μm can be measured by using a flow type particle image analyzer FPIA-1000 manufactured by SYSMEX CORPORATION. The measurement is performed using 1% NaCl using primary sodium chloride.
After adjusting to an aqueous solution, a surfactant, preferably alkylbenzene sulfonate, as a dispersant is added to 50 to 100 mL of a solution that has passed through a 0.45 μm filter in an amount of 0.1 to 5 mL.
In addition, add 1-10 mg of sample. This is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser (output 35 W, frequency 50 kHz), and the particle concentration is 5000 to 15000 particles / μL.
The measurement was performed using the dispersion liquid adjusted to. The number of particles is measured by measuring the area of a two-dimensional image captured by a CCD camera,
Calculation is performed with the diameter of a circle having the same area as the equivalent circle diameter. Due to the accuracy of CCD pixels, the equivalent circle diameter is 0.6 μm
The above was validated and the number of particles was obtained.

<Table 2> Table 2: Toner external additive treated external additive and 0.6
Content of fine particles of μm to 3 μm>

Images were actually formed by using the toners of Examples 1 to 7 and Comparative Examples 1 to 4, and image evaluation was performed.
However, here, the black toner shown in Table 2 above is used as the toner evaluation machine in the image forming apparatus shown in FIG. 1 to uniformly regulate the layer thickness of the developer carrier and the developer supplied onto the developer carrier. By the developing device 1 including the thin layer regulating member 12, the photoconductor 2 by the conductive brush charger and the exposing device.
This is a method in which the electrostatic latent image formed on the surface is developed and sequentially transferred onto the transfer medium in a superimposed manner. In this case, the development is performed by a reversal development method in which the polarity of the electrostatic latent image on the photoconductor 2 is the same as the polarity of the non-magnetic one-component developer. Further, the developing device 1 is the developing device (1) shown below.
A non-magnetic one-component developing unit consisting of (3) to (3) is installed. (Developing device) Developing device (1): having the configuration of FIG.
3 is a metal core having an outer diameter of 4 mm, and a urethane foam foam having a thickness of 6 mm and having a roller-like outer diameter of 16 mm. The surface has irregularities in the circumferential direction, and the number of concave portions in the circumferential direction per unit length is 2 (pieces / mm). Developing device (2): the developing device (1) has the same configuration as that of the developing device (1) except that the circumferential recesses per unit length of the developer supply member 13 are 0.2 (pieces / mm). Developing device (3): has the same configuration as the developing device (1) except that the rotation direction of the developer supply member 13 is reverse to that of the developer carrying member.

(Evaluation Items) Examples 1 to 7 and Comparative Examples 1 to 1
4 shows the image evaluation result of No. 4. In each item, the image chart having an image area of 5% was continuously run at the initial stage and up to 100,000 sheets, and then the following evaluations were performed. Table 3 shows the initial results, and Table 4 shows the results after 100,000 sheets.

<Table 3><Table 3: Evaluation results of initial Examples 1 to 7 / Comparative Examples 1 to 4>

[0059]

<Table 4><Table 4: Examples 1 to 7 after 100,000 sheets / Comparative example 1
~ 4 evaluation results>

Each evaluation item was evaluated as follows. 1) Image density After outputting a solid image, the image density is changed to X-Rite (X-Rit
(manufactured by Company e). This was measured at 5 points and the average was obtained. 2) The background stain white paper image is stopped during development, the developer on the photoconductor 2 after development is tape-transferred, and the difference from the image density of the untransferred tape is 938 spectrodensitometer (manufactured by X-Rite). ) Was measured. 3) Filming The presence or absence of toner filming on the developer bearing member or the photoconductor 2 was observed. “O” has no filming, “Δ” has filming on the streak, and “x” has filming as a whole. If it is “Δ” or more, there is practically no problem. 4) It was observed whether or not there is a thin toner layer on the white blank developer bearing member and the state of white blank generation on the image. "○" has no white spots, "△" has several white spots, and "x" has many white spots. If it is “Δ” or more, there is practically no problem. 5) Solid followability 10 continuous solid images are output continuously, and 1
The image density of the trailing edge of the 0th sheet is X-Rite (X-Rite
(Made by the company). The density difference of this solid image is 0.1
Less than "O", less than 0.2 "Δ", 0.2 or more "X". If it is “Δ” or more, there is practically no problem. 6) Charge amount The toner was conveyed onto the developer carrying member and measured by the suction tribo measurement method under each environment. 7) 100 g of toner in the developing device 1 at the initial amount of aggregate or after 100,000 sheets
Is sieved through 400 mesh and the amount of aggregate on the mesh is measured.

As is clear from Tables 3 and 4, Examples 1 to 8 all have means for allowing the roller type thin layer regulating member 12 to come into contact with the developer carrying member 11 and rotate. The surface of the developer supply member 13 has one concave portion per unit length.
In the developing device (1) having a number of (units / mm) or more and moving in the forward direction at the contact portion with the developer carrying member 11, a thin layer of one-component toner is formed on the developer carrying member 11. An image forming method in which a latent image is developed and visualized while being regulated by a roller-type thin layer regulating member 12, wherein hydrophobic silica particles having a primary average particle diameter of 30 nm to 50 nm are added to one-component toner particles. The volume average particle diameter (Dv) of the toner measured by a counter is 5 μm to 8 μm, the fine powder content of 5 μm or less is less than 20% by number, and a number-based circle measured by a flow-type particle image analyzer. Since the one-component toner in which the content of particles having an equivalent diameter of 0.6 μm to 3 μm is 15% by number or less is used,
Even in the initial image, the toner charge amount (q / m) is 20 to 37.
An image having a high μC / g and a high image density is obtained. Further, a high-quality image free of background stains, white spots, solid followability, filming, ghost, etc. can be obtained. Even after 100,000 sheets, the toner charge amount is almost the same as that at the initial stage, the toner charge amount is stable, and an image with high image density is obtained. Also, dirt on the background, white spots, solid followability,
A high-quality image without filming, ghost, etc. is obtained, and the amount of aggregates is not increased.

In Comparative Example 1, the developing device 1 in the image forming method is used, in which the developing device (2) having 0.2 (pieces / mm) circumferential recesses per unit length of the developer supply member 13 is used. There is. Therefore, the supply of the developer from the developer supply member 13 to the developer carrying member 11 is not sufficient, and even in the initial state, the background stain is 0.02 in density, and the solid followability is “Δ”.
And the ghost is "x". After 100,000 sheets, the toner charge amount has decreased. This is because toner having a high toner charge amount is generated, and contact with other magnetic carriers is hindered, so that the toner is not sufficiently charged. In addition, the white gap is “Δ” although it is within the allowable range, the solid followability is “×”, and the ghost is also “×”, which means that a high-quality image cannot be obtained. Furthermore, the amount of aggregate is 0.0
As high as 152 g, it can be seen that toner aggregates are formed.

In Comparative Example 2, the developing device 1 in the image forming method uses the developing device (3) in which the rotation direction of the developer supply member 13 is reverse to that of the developer carrying member 11. For this reason, the initial image density is a little low, and the white gap is “Δ” although it is within the allowable range. After 100000 sheets, the toner charge amount becomes high and the image density becomes 1.25.
Became low. Also, it can be seen that the white spots are “x” and the amount of aggregates is increased to 0.1562 g.

In Comparative Example 3, as shown in Table 2, the content of particles having an equivalent circle diameter of 0.6 μm to 3 μm is 15% by number or more, which is 19% by number. Comparative Example 4, as shown in Table 2,
The content of particles having an equivalent circle diameter of 0.6 μm to 3 μm is 19% by number of 15% or more, and as shown in Table 1, the content of fine powder of 5 μm or less is 20% by number or more.
Number%. Because of this, although the amount of aggregates in the initial image was large, white spots were “△”, which was not a problem for practical use, but as the image was formed with time, the density decreased and It was not possible to form an image up to 100,000 sheets because the blanking becomes severe and the solid followability and the like also deteriorate.

[0065]

As described above, according to the present invention, an abnormal image such as solid followability, ghost, and white spots does not occur, and a thin layer regulating member for a photoconductor and a developer after continuous printing for a longer period than before. And there is no filming on the developer carrier,
A one-component toner and an image forming method capable of stabilizing the charging and conveyance of toner and maintaining an image density equivalent to that of an initial image and a high-quality output image are obtained. Furthermore, since the decrease in the amount of charge during continuous use is small, it is possible to obtain a high-quality image without problems such as fluctuations in image density, low developability, background stain, and toner scattering in the developing device. As a result, since it has long-term durability, it is possible to extend the life of the developing unit, photoconductor unit, etc.
The amount of waste is less than before, and the user's time and effort for exchanging those image forming units can be reduced.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a configuration of an image forming apparatus according to an embodiment of the present invention.

FIG. 2 is a schematic diagram showing a configuration of a developing device in FIG.

FIG. 3 is a schematic view showing a configuration of a developer supply member used in the present invention. 3A is a perspective view of a developer supply member used in the present invention, FIG. 3B is a cross-sectional view of the developer supply member used in the present invention, and FIG. 3C is development used in the present invention. It is an enlarged view of a section of an agent supply member.

[Explanation of symbols]

1 Development device 2 photoconductor 3 Intermediate transfer belt 4 Charging device (charging roller or charger) 5 Cleaning device 6 fixing device 7 Transfer cleaning device 11 Developer carrier 12 Thin layer control member 13 Developer supply member 14 Leak prevention seal 15 Stirrer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/08 504 G03G 15/08 504D 507 507L (72) Inventor Osamu Uchinokura Nakamagome 1 Ota-ku, Tokyo Ricoh Co., Ltd. 3-6 (72) Inventor Mitsuteru Kato 1-3-6 Nakamagome, Ota-ku, Tokyo F-term (R) RICOH Co., Ltd. 2H005 AA06 AA08 CB07 CB13 DA01 DA05 EA05 FA07 2H077 AC04 AD02 AD06 AD14 AD17 EA14 FA01 FA22

Claims (12)

[Claims] 1. A one-component toner carried on a developer carrying body is regulated by a roller type thin layer regulating member which is in contact with the developer carrying body, and the roller type thin layer regulating member is provided on the developer carrying body. A surface of the developer supply member having a number of recesses per unit length of 1 (pieces / mm) or more, and at a contact portion with the developer carrying member. In a one-component toner used in an image forming method of moving a forward direction and forming a thin layer of the one-component toner on the developer carrying member, the developer carrying member developing and visualizing a latent image, The one-component toner to which the hydrophobic silica particles having a primary average particle size of 30 nm to 50 nm are added has a volume average particle size of 5 μm to 8 μm, and the content of fine powder having a volume particle size of 5 μm or less is less than 20% by number. The number equivalent circle equivalent diameter is 0.6 μm to 3 μm One-component toner content of the child is equal to or less than 15% by number. 2. The one-component toner according to claim 1, wherein the hydrophobic silica particles have a content ratio of particles having a number-based circle equivalent diameter of 0.6 μm to 3 μm of 10 number% or less. 3. The one-component toner particles are characterized in that the relationship between the number average particle diameter and the volume average particle diameter is volume average particle diameter (Dv) / number average particle diameter (Dn) ≦ 1.4. The one-component toner according to claim 1 or 2. 4. The one-component toner according to claim 1, further comprising one or more kinds of hydrophobic fine particles having a primary average particle diameter of 30 nm or less. toner. 5. The one-component toner according to claim 4, wherein the hydrophobic fine particles are silica particles and titanium oxide. 6. The one-component toner according to claim 1, wherein a fatty acid metal salt is added to the one-component toner. 7. A one-component toner carried on a developer carrying body is regulated by a roller type thin layer regulating member which is in contact with the developer carrying body, and the roller type thin layer regulating member is the developer carrying body. A surface of the developer supply member having a number of recesses per unit length of 1 (pieces / mm) or more, and at a contact portion with the developer carrying member. In an image forming method in which a thin layer of the one-component toner is formed on the developer carrying body while moving in the forward direction, and the developer carrying body develops and visualizes a latent image, the image forming method is a primary A one-component toner to which hydrophobic silica particles having an average particle diameter of 30 nm to 50 nm are added, wherein the volume average particle diameter is 5 μm to 8 μm and the content of fine powder having a volume particle diameter of 5 μm or less is less than 20% by number. , The equivalent circle diameter based on the number is 0.6μ
An image forming method, wherein the content of particles of m to 3 μm is 15% or less. 8. The image forming method according to claim 7, wherein hydrophobic silica having a content of particles having a number-based equivalent circle diameter of 0.6 μm to 3 μm of 10 number% or less is used. Image forming method. 9. The image forming method uses a one-component toner in which the relationship between the number average particle diameter and the volume average particle diameter is volume average particle diameter (Dv) / number average particle diameter (Dn) ≦ 1.4. The image forming method according to claim 7, wherein the image forming method comprises: 10. The image forming method according to claim 7, wherein a one-component toner containing one or more kinds of hydrophobic fine particles having a primary average particle diameter of 30 nm or less is used. The image forming method described. 11. The image forming method according to claim 10, wherein the hydrophobic fine particles use a one-component toner in which silica particles and titanium oxide are used. 12. The image forming method according to claim 7, wherein the image forming method uses a one-component toner to which a fatty acid metal salt is added.