JP2003021934A - Dry electrophotographic toner, developer, image forming method and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dry electrophotographic toner ensuring a stable quantity of electric charges on the toner and a stable quantity of the toner conveyed even when used over a long period of time and giving high image density and high image quality with little surface stain and to provide a developer and an image forming method. SOLUTION: In the dry electrophotographic toner comprising a binder resin, a colorant, an electrostatic charge controlling agent and an additive, the binder resin contains at least one polyester not containing a THF-insoluble component, having <=4 wt.% content of a component whose molecular weight is <=500 and having one peak in the molecular weight range of 3,000-9,000 in its molecular weight distribution by gel permeation chromatography(GPC) and the electrostatic charge controlling agent is a resinous electrostatic charge controlling agent having at least a sulfonate-containing monomer, an aromatic monomer having an electron withdrawing group and an acrylic ester and/or methacrylic ester monomer as constitutional units.

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 charge image in electrophotography, electrostatic recording, electrostatic printing and the like, and an electrophotographic developing device using the toner. . More specifically, the present invention relates to a copying machine using a direct or indirect electrophotographic development system, a laser printer, and an electrophotographic toner, an electrophotographic developer and an electrophotographic developing device used for plain paper fax machines and the like.
Further, the present invention relates to a full-color copying machine using a direct or indirect electrophotographic multi-color image developing method, a full-color laser printer, and an electrophotographic toner, an electrophotographic developer and an electrophotographic developing apparatus used in a full-color plain paper fax machine or the like.

[0002]

2. Description of the Related Art A developer used in electrophotography, electrostatic recording, electrostatic printing or the like is once attached to an image carrier such as a photoconductor on which an electrostatic charge image is formed in the developing process. Next, after being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the 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.

Here, in the two-component developing system, 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, so It is necessary to maintain the mixing ratio of (1) at a constant ratio, which causes a disadvantage that the developing device becomes large. On the other hand, the one-component developing system is becoming the mainstream of the developing system because it does not have the above-mentioned drawbacks and has the advantage of downsizing of the apparatus.

In recent years, offices have become more OA and color-coded, and not only the conventional copying of originals consisting only of characters but also originals including graphs and the like created by a personal computer are output by a printer, presentation materials, etc. As a result, the chances of making many copies are 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 is further increasing.

Conventionally, the electrophotographic process using a one-component developer is classified into a magnetic one-component developing system using a magnetic toner and a non-magnetic one-component developing system using a non-magnetic toner. The magnetic one-component developing method is a method of holding a magnetic toner containing a magnetic substance such as magnetite by using a developer carrying member provided with a magnetic field generating means such as a magnet inside, and developing a thin layer by a layer thickness regulating member. Recently, many have been put to practical use in small printers. On the other hand, in the non-magnetic one-component developing method, since the toner does not have a magnetic force, a toner replenishing roller or the like is pressed against the developer carrier to supply the toner onto the developer carrier and electrostatically retain it. A layer is formed by a layer thickness regulating member to develop the layer. Since it does not contain a colored magnetic material, it has the advantage of being compatible with colorization, and because it does not use a magnet for the developer bearing member, it can be made lighter in weight and lower in cost. There is.

However, the current situation is that the one-component developing system still has many problems to be improved. In the two-component developing method, a carrier is used as a toner charging and 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 the toner and carrier are used for a relatively long time. It is possible to maintain stable charging and conveyance, and it is also easy to support high-speed developing devices.

On the other hand, in the one-component developing system, since there is no stable charging and conveying means like a carrier, charging and conveying defects are likely to occur due to long-term use and high speed. That is, in the one-component developing method, after the toner is conveyed onto the developer carrier,
Although the toner is made thin by the layer thickness regulating member to develop, the carrier was used because the contact / friction charging time between the toner and the friction carrying member such as the developer carrying member and the layer thickness regulating member is very short. Compared to the two-component development method, the amount of low-charged and reverse-charged toner tends to increase.

Particularly in the non-magnetic one-component developing method, toner (developer) is usually conveyed by at least one toner conveying member, and the electrostatic latent image formed on the latent image carrier is developed by the conveyed toner. However, it is said that at this time, the layer thickness of the toner on the surface of the toner conveying member must be made as thin as possible.

This also applies to the case where a two-component developer having a very small carrier diameter is used, and in particular, a one-component developer is used and a toner having a high electric resistance is used. When used, it is necessary to charge this toner by the developing device, so the layer thickness of the toner must be remarkably thin. 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. For this reason, the toner is required to maintain a faster charging speed and an appropriate amount of charge.

Conventionally, it has been practiced to add a charge control agent in order to stabilize the charge of the toner. The charge control agent controls the triboelectric charge amount of the toner and maintains the triboelectric charge amount. Typical negative charge control agents include monoazo dyes, salicylic acid, naphthoic acid, metal salts / complex salts of dicarboxylic acids, diazo compounds, complex compounds with boron, and typical positive charge agents. Examples of the charge control agent include quaternary ammonium salt compounds, imidazole compounds, nigrosine and azine dyes.

However, some of these charge control agents have a color, and many cannot be used for color toners. In addition, since these charge control agents have poor compatibility with the binder resin, those existing on the toner surface, which are greatly involved in charging, are likely to be detached, resulting in uneven charging of the toner, development sleeve, and photosensitivity. It has a drawback that it is easily polluted such as body filming. Therefore, in the past, a good image was obtained in the initial stage, but the image quality gradually changed, and there was a phenomenon that scumming and blurring occurred.
Especially when it is applied to color copying and continuously used while replenishing toner, the charge amount of the toner decreases and the color tone of the copied image remarkably differs from that of the initial copy image. However, it has a drawback that the image forming unit called process cartridge must be replaced at an early stage. Therefore, the load on the environment is large and the user's time and effort are required. Further, since many of these contain heavy metals such as chromium, they are becoming a problem in terms of safety in recent years.

In order to solve the above problems, Japanese Patent Laid-Open Nos. 63-88564, 63-184762 and 3-56974, 6-230609 disclose compatibility with a binder resin and transparency of a toner-fixed image. A resin charge control agent having improved properties 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 of being inferior in charge amount and charge rate as compared with toners using a metal salt / metal complex salt of a monoazo dye, salicylic acid, naphthoic acid, or dicarboxylic acid. Further, although the chargeability is improved by increasing the addition amount of the resin charge control agent, it adversely affects the toner fixability (low temperature fixability, offset resistance). Furthermore, these compounds have large environmental stability of the charge amount (humidity resistance). Therefore, there is also a problem that scumming (fog) is likely to occur.

Therefore, again, Japanese Patent Laid-Open Nos. 8-30017, 9
-171271, 9-21189, 11-21896
Japanese Patent Publication No. 5 proposes a copolymer of a monomer containing an organic acid salt such as a sulfonate group and an aromatic monomer having an electron-withdrawing group. However, due to hygroscopicity and adhesiveness that are thought to be due to monomers containing organic acid salts such as sulfonate groups, a sufficient amount of charge is secured, but the dispersion in the binder resin is not sufficient, and the toner is charged for a long time. The effect of suppressing the variation of the above and preventing the developing sleeve and the photoconductor filming are not sufficient. Further, in order to further improve the compatibility with the binder resin such as styrene resin or polyester resin, a monomer containing an organic acid salt such as a sulfonate group, an aromatic monomer having an electron-withdrawing group, a styrene monomer or a polyester, respectively. Copolymers with system monomers have also been proposed, but maintaining the charge amount for a long time,
The effect of preventing the filming of the developing sleeve and the photoconductor is not sufficient. Especially as a binder resin for full color toner,
It is insufficient for polyester resins and polyol resins suitable in terms of color developability and image strength.

In recent years, the demand for printers has expanded, and the downsizing, speeding up, and cost reduction of devices have advanced, and higher reliability and longer service life have begun to be demanded for the devices, and toner has various characteristics for a long period of time. Although it is required that these resin charge control agents cannot maintain their charge control effect, they contaminate the developing sleeve and the developer layer thickness control member (blade and roller), and the charging performance of the toner decreases, There was a problem of filming the photoconductor. Further, due to downsizing and speeding up, a process for developing in a short time with a small amount of developer is required, and a developer having a better charge rising property is required.

[0015]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not impair the advantages of the resin charge control agent that are excellent in compatibility with a binder resin, transparency of a toner-fixed image, and safety, and the problem thereof is solved. It was made for the purpose of solving the problems. That is, an object of the present invention is to provide a toner for electrophotography, a developer, and an image forming method which can obtain a high image quality with a high image density and a small amount of background stain, in which the charge amount and the transport amount of the toner are stable even when used for a long period of time. Is to provide. In particular, a two-component developing method in which a two-component developer consisting of a carrier and toner is formed on a developer carrying member (developing sleeve) by a developer layer thickness regulating member to perform development,
Also, in the one-component developing method in which a thin layer of the developer is formed on the developer carrying member (developing roller) by the developer layer thickness regulating member and the development is performed, there is no change in the charging property of the toner after continuous printing,
It is an object of the present invention to provide an electrophotographic toner, a developer, and an image forming method capable of obtaining tens of thousands or more of image quality equivalent to an initial image.

Another object of the present invention is to prevent the contamination of the developer carrying member and the developer layer thickness regulating member (blade and roller) and the filming of the photoconductor for tens of thousands or more of electrophotography during long-term use. A toner, a developer, and an image forming method are provided. Another object of the present invention is to provide an electrophotographic toner, a developer, and an image forming method which cause less toner scattering in the developing machine even after long-term use. Another object of the present invention is to provide an electrophotographic toner, a developer, and an image forming method that reduce the burden on the environment and reduce the user's replacement time by using the developing unit and the photoconductor unit for a long period of time. It is provided. Another object of the present invention is to provide an electrophotographic toner having good color reproducibility by using a colorless or light colored resin charge control agent. Another object of the present invention is a method obtained from a production process of kneading, pulverizing and classifying toner, which is free from sticking in the pulverizing process.
It is an object of the present invention to provide an electrophotographic toner which is not over-pulverized and has a high productivity such as a large amount of pulverization processing per unit time. Further, another object of the present invention is to provide a developer having excellent charge rising property.

[0017]

In order to solve the above-mentioned problems, the inventors of the present invention have made diligent studies by paying attention to the constitutional components and constitutional ratios of the resin charge control agent, and as a result, as a binder resin for full-color toners, color developability and image strength are obtained. From the point of view, when a resin charge control agent having a specific constituent component and a constituent ratio to a suitable polyester resin is used, a high charge amount and a sharp charge amount distribution can be obtained, and the charge rises well to prevent stains. Excellent, moreover tens of thousands of sheets can prevent contamination of developer carrier (developing roller, sleeve) and developer layer thickness control member (blade and roller) and filming of photoconductor for a long time, and good pulverizability and productivity. The inventors have found the finding that a high-quality electrophotographic toner, developer, and image forming method can be obtained, and were able to reach the present invention.

That is, the first aspect of the present invention is a dry electrophotographic toner containing at least a binder resin, a coloring material, a charge control agent, and an additive, wherein the binder resin does not contain at least a THF-insoluble component, and gel permeation is performed. In the molecular weight distribution in cation chromatography (GPC), the content ratio of components having a molecular weight of 500 or less is 4% by weight or less, and at least one polyester having one peak in the molecular weight range of 3000 to 9000 is contained, and The charge control agent is a resin charge control agent containing at least a sulfonate group-containing monomer as a monomer, an aromatic monomer having an electron-withdrawing group, and an acrylic ester and / or methacrylic acid ester monomer as a constituent unit. And dry electrophotographic toner.

A second aspect of the present invention is that the binder resin D
The first electrophotographic toner has an endothermic peak in SC in the range of 60 to 70 ° C.

A third aspect of the present invention is that the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin is 2
≦ Mw / Mn ≦ 10, wherein the first
Alternatively, it is in the toner for electrophotography described in 2.

A fourth aspect of the present invention is characterized in that the binder resin has an acid value of 20 KOHmg / g or less.
In the first to third electrophotographic toners.

A fifth aspect of the present invention is characterized in that the temperature at which the apparent viscosity of the binder resin by a flow tester is 10 ⁴ Pa · s is 95 to 120 ° C., and the temperature is 95 to 120 ° C. Toner.

In a sixth aspect of the present invention, the resin charge control agent is
At least a sulfonate group-containing monomer as a monomer,
An aromatic monomer having an electron-withdrawing group and an acrylic acid ester and / or a methacrylic acid ester monomer as constitutional units, and the repeating unit of the sulfonic acid group-containing monomer is 1 with respect to the weight of the resin charge control agent. ˜30% by weight, the repeating unit of the aromatic monomer having the electron withdrawing group is 1 to the weight of the resin charge control agent.
80% by weight, the repeating unit of the acrylic acid ester and / or methacrylic acid ester monomer is contained in a proportion of 10 to 80% by weight with respect to the weight of the resin charge control agent. For toner.

A seventh aspect of the present invention is characterized in that the aromatic monomer having an electron-withdrawing group is a phenylmaleimide-substituted product or a phenylitaconimide-substituted product substituted with a chlorine atom or a nitro group. .About.6 electrophotographic toner.

An eighth aspect of the present invention is characterized in that the temperature at which the apparent viscosity of the resin charge control agent by the flow tester becomes 10 ⁴ Pa · s is 85 to 110 ° C. In photographic toner.

A ninth aspect of the present invention is the electrophotographic toner according to any one of the first to eighth aspects, wherein the resin charge control agent has a number average molecular weight of 1,000 to 10,000.

In the tenth aspect of the present invention, the temperature at which the apparent viscosity of the binder resin by the flow tester becomes 10 ⁴ Pa · s is T ₁ , and the apparent viscosity of the resin charge control agent by the flow tester is 10 ⁴ Pa · s. temperature when was the T ₂ comprising, in the first to ninth toner for electrophotography, wherein T _1, T ₂ is _{0.9 <T 1 / T 2 <} 1.4.

The eleventh aspect of the present invention is the electrophotographic toner according to any one of the first to tenth aspects, wherein the resin charge control agent is contained in the toner particles in an amount of 0.1 to 20% by weight.

The twelfth aspect of the present invention is a two-component developer using the electrophotographic toners of the first to eleventh aspects and a carrier.

The thirteenth aspect of the present invention is a one-component developer comprising the electrophotographic toners of the first to eleventh aspects.

The fourteenth aspect of the present invention is the twelfth or thirteenth aspect.
Located in a container containing developer.

The fifteenth aspect of the present invention is a latent image forming step of forming a latent image on a latent image holding member, a developing step of developing the latent image with a developer on a developer carrying member, and a developed toner. An image forming method comprising a transfer step of transferring an image onto a transfer body and a fixing step of heating and fixing a toner image on the transfer body, wherein the twelfth or thirteenth developer is used as a developer. It is in the forming method.

The sixteenth aspect of the present invention is the fifteenth aspect, wherein the developing step forms a thin layer of the developer on the developer carrying member and develops it with or without contact with the latent image holding member. Image forming method.

In the seventeenth aspect of the present invention, the electrostatic latent image formed on the latent image carrier is divided into a plurality of electrostatic charges corresponding to the respective colors by the developers corresponding to the respective colors. In the electrophotographic developing method, the image is developed on the image carrier, the transfer means is brought into contact with the surface of the latent image carrier through a transfer material, and the toner images are sequentially electrostatically transferred to the transfer material.
The image forming method is characterized in that the developer is used.

The eighteenth aspect of the present invention is the twelfth or thirteenth aspect.
It is equipped with a container containing the developer of
A latent image forming step of forming a latent image on a latent image carrier, a developing step of developing the latent image with a developer on a developer carrying body, and a transfer step of transferring the developed toner image onto a transfer body. And an image forming apparatus used in an image forming method having at least a fixing step of heating and fixing a toner image on a transfer body.

The nineteenth aspect of the present invention is the twelfth or thirteenth aspect.
It is equipped with a container containing the developer of
A latent image is formed by developing a multicolored electrostatic latent image formed on the latent image holding member on a plurality of electrostatic image bearing members corresponding to the respective colors by using developers corresponding to the respective colors. An image forming apparatus for use in an image forming method in which a transfer unit is brought into contact with the surface of a holding body through a transfer material to electrostatically transfer the toner images sequentially to the transfer material.

A twentieth aspect of the present invention is provided with at least a developer carrying member, a developer conveying member, a developer layer thickness regulating member, and a developer replenishing auxiliary member, and the developer carrying member is provided with the developer layer thickness regulating member. The developer carrying member is in contact with the developer carrying member, the developer carrying member is rotatably movable, the developer layer thickness regulating member is rotatably movable, fixed or intermittently rotatable, and the developer carrying member is rotatably movable. The member is located on the upstream side of the developer layer thickness regulating member in the rotation direction of the developer carrier, and the developer carrying member is 160 mm / sec or more and 280 mm / sec.
The image forming apparatus according to the eighteenth or nineteenth aspect is characterized in that it is rotatable below.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present invention, the binder resin is polyester, and the charge control agent has at least a sulfonate group-containing monomer as a monomer, an aromatic monomer having an electron-withdrawing group and an acrylic ester and / or a methacrylic acid ester monomer as a structural unit. An electrophotographic toner containing a resin charge control agent.

As the binder resin used in the present invention, a polyester resin suitable as a binder resin for a full-color toner in terms of color developability and image strength is used. In a color image, several types of toner layers are layered in layers, so that the toner layer becomes thick and cracks or defects occur in the image 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 of 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, 1,2-propylene glycol, 1,3- Propylene glycol, 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol and other diols, bisphenol A, hydrogenated bisphenol A, polyoxypropylene Bisphenol A alkylene oxide adduct such as bisphenol A, other dihydric alcohol, or sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol Le, tripentaerythritol, 1,2,4-butane triol, 1,2,5
Pentanetriol, glycerol, diglycerol,
2-methylpropanetriol, 2-methyl-1,2,
Examples thereof include 4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, and other polyhydric alcohols having 3 or more valences.

Among these monomers, those using 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-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-octanetetra Carboxylic acid, empol trimer acid, and their anhydrides,
Examples thereof include alkyl ester, alkenyl ester, aryl ester, and other trivalent or higher carboxylic acids.

Specific examples of the alkyl group, alkenyl group or aryl ester described herein include 1,2,
4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid trimethyl, 1,2,4-benzenetricarboxylic acid triethyl, 1,2,4-benzenetricarboxylic acid tri-n-butyl, 1,2,4-benzenetricarboxylic acid Acid isobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl, 1,2,4-benzenetricarboxylic acid Acid tris (4-isopropylbenzyl) and the like.

The production method for obtaining the polyester of the present invention is not particularly limited, and the esterification reaction can be carried out by a known method. The transesterification reaction can be carried out by a known method, and at this time, a known transesterification catalyst can be used. For example, magnesium acetate, zinc acetate, manganese acetate, calcium acetate, tin acetate, lead acetate, titanium tetrabutoxide and the like can be mentioned. The polycondensation reaction can be carried out by a known method, in which case a known polymerization catalyst can be used. Specific examples include antimony trioxide, germanium dioxide and the like.

The binder resin of the present invention is particularly free of THF insoluble matter, and has a molecular weight of 500 in gel permeation chromatography (GPC) distribution.
The content ratio of the following components is 4% by weight or less, and the molecular weight is 3
It is characterized by having one peak in the region of 000 to 9000. When the THF-insoluble matter is contained, the gloss is lowered and the transparency is lowered, so that a high-quality image cannot be obtained when an OHP sheet is used. If the component having a molecular weight of 500 or less is 4% by weight or more, the blade or sleeve is contaminated by long-term use, and filming easily occurs.

The molecular weight distribution of the present invention is determined by GPC as follows.
Is measured as. In a heat chamber at 40 ° C
Stabilize the ram and load the column with solvent at this temperature.
And flow THF at a flow rate of 1 ml / min to determine the sample concentration.
Toner base THF adjusted to 0.05 to 0.6% by weight
Inject 200 μl of the sample solution for measurement. THF sample dissolution
The liquid is 0.45μm filter for liquid chromatography before injection, and T
HF insoluble components are removed. For measuring the molecular weight of toner samples
For this purpose, the molecular weight distribution of the sample should be calculated using several types of monodisperse
The logarithmic value of the calibration curve created by the styrene standard sample and
It was calculated from the relationship with the count number. Standard for creating a calibration curve
As a polystyrene sample, for example, Pressure
  Chemical Co. Or Toyo Soda Industry
The molecular weight manufactured by the company is 6 × 10², 2.1 x 10³4x1
0³1.75 x 10^Four5.1 × 10^Four, 1.1 x 1
0^Five3.9 x 10^Five, 8.6 × 10^Five2 x 10⁶4.
48 x 10 ⁶Using at least 10 points
Suitably a quasi-polystyrene sample is used. Also detected
An RI (refractive index) detector is used as the container. Note that the binder
-The presence or absence of THF insoluble matter in the resin is determined by THF
Judged when preparing the sample solution. That is, 0.45 μm
Attach the filter unit of to the tip of the syringe to remove the liquid.
When pushing out from inside the syringe, make sure that the filter is not clogged.
If so, it is judged that there is no THF insoluble matter.

The binder resin of the present invention is characterized in that the endothermic peak in DSC is in the range of 60 to 70 ° C. If the temperature is lower than 60 ° C., there is a problem in toner storage stability. On the other hand, if the temperature exceeds 70 ° C., the toner productivity will decrease. The endothermic peak in the DSC of the present invention is Rigaku THRMOFLEX TG8110 manufactured by Rigaku Denki Co., Ltd.
The measurement is performed under the condition that the temperature rising rate is 10 ° C./min, and the main maximum peak of the endothermic curve is read.

The binder resin of the present invention has a ratio Mw of its weight average molecular weight (Mw) and number average molecular weight (Mn).
/ Mn is preferably 2 to 10. When Mw / Mn exceeds 10, gloss is not obtained when the toner is fixed as a toner, and a glossy high-quality image cannot be obtained. Further, when Mw / Mn is less than 2, the productivity is lowered in the pulverizing step at the time of toner production, the blade or sleeve is contaminated by long-term use, and filming easily occurs.

The binder resin of the present invention has an acid value of 2
It is characterized in that it is 0 KOHmg / g or less. It is known that the chargeability of a polyester resin is substantially proportional to the acid value, and that the higher the acid value, the greater the negative chargeability of the resin. That is, when the acid value is high, the charge amount is high under low temperature and low humidity, and the charge amount is low under high temperature and high humidity, and the background stain, image density, and color reproducibility are large, and it is difficult to maintain high image quality. If the acid value exceeds 20 KOHmg / g, the charge amount will increase and environmental fluctuations will worsen. In the polyester resin of the present invention, the acid value is preferably 20 KOHmg / g or less, more preferably 5 KOHmg / g or less.

Further, the binder resin of the present invention is characterized in that the temperature at which the apparent viscosity by the flow tester becomes 10 ⁴ Pa · s is 95 to 120 ° C. Below 95 ° C, there is no room for hot offset during fixing. 12
At 0 ° C or higher, sufficient gloss cannot be obtained. The temperature at which the apparent viscosity is 10 ⁴ Pa · s was measured using a Shimadzu CFT-500 type as a flow tester and a load of 10
Viscosity was measured at kg / cm ² , orifice 1 mm × length 1 mm, temperature rising rate 5 ° C./min, and apparent viscosity was 10 ⁴ Pa.
The temperature at which the temperature reaches s is read.

Examples of the sulfonate group-containing monomer constituting the resin charge control agent of the present invention include aromatic sulfonate group-containing monomers and aliphatic sulfonate group-containing monomers. Aromatic sulfonate group-containing monomers include vinyl sulfonic acid, allyl vinyl sulfonic acid, 2
-Acrylamido-2 methylpropanesulfonic acid, methacryloyloxyethylsulfonic acid, and other alkali metal salts, alkaline earth metal salts, amine salts, quaternary ammonium salts, and the like. Examples of the aliphatic sulfonate group-containing monomers include alkali metal salts such as styrene sulfonic acid, sulfophenylacrylamide, sulfophenylmaleimide, and sulfophenylitaconimide, alkaline earth metal salts, amine salts, and quaternary ammonium salts. . Salts of heavy metals (nickel, copper, zinc, mercury, chromium, etc.) are not preferable in terms of safety.

As the aromatic monomer having an electron-withdrawing group, styrene substitution products such as chlorostyrene, dichlorostyrene, bromostyrene, fluorostyrene, nitrostyrene and cyanstyrene, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, Phenyl (meth) acrylate substitution products such as nitrophenyl (meth) acrylate and chlorophenyloxyethyl (meth) acrylate, phenyl (meth) acrylamides such as chlorophenyl (meth) acrylamide, bromophenyl (meth) acrylamide and nitrophenyl (meth) acrylamide Substitute, chlorophenylmaleimide, dichlorophenylmaleimide, nitrophenylmaleimide,
Examples include phenylmaleimide substitution products such as nitrochlorophenylmaleimide, chlorophenylitaconimide, dichlorophenylitaconimide, nitrophenylitaconimide, phenylitaconimide substitution products such as nitrochlorophenylitaconimide, and phenylvinyl ether substitution products such as chlorophenyl vinyl ether and nitrophenyl vinyl ether. . Particularly, a phenylmaleimide-substituted product and a phenylitaconimide-substituted product substituted with a chlorine atom or a nitro group are preferable in terms of charging property and filming resistance.

Examples of acrylic acid ester and / or methacrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. Acid isobutyl, stearyl (meth) acrylate,
Dodecyl (meth) acrylate, (meth) acrylic acid 2-
Examples include ethylhexyl 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 negative charge to the resin charge control agent is improved, but the environmental stability of the toner due to its hygroscopicity is improved. (Temperature and humidity stability)
It is generally known to be used as a copolymer with an aromatic monomer having an electron-withdrawing group, etc.
Thousands of sheets may be used, but if used for a long time of tens of thousands or more, toner on the developing sleeve and layer thickness control members (blades and rollers) may be contaminated and toner filming may occur, resulting in stable toner charging. Properties and high image quality are not sufficiently maintained, and there is a problem that productivity is reduced.

In order to make up for such drawbacks, polyester resins and polyol resins suitable as binder resins for full-color toners from the viewpoints of color developability and image strength are compared with sulfonate group-containing monomers, aromatic monomers having electron-withdrawing groups, and acryl. By using a copolymer containing three types of monomers of acid ester and / or methacrylic acid ester as a resin charge control agent, the developing sleeve and the developer layer thickness regulating member are excellent in charging and environmental stability for a long period of time. Thus, a thin layer is formed without contamination of (blades and rollers), photoconductor filming is prevented, high image quality is maintained, and highly productive electrophotographic toner is obtained.

It is presumed that these effects are due to the following reasons. That is, by using a sulfonate group-containing monomer and an aromatic monomer having an electron-withdrawing group in combination, the negative charge imparting effect is enhanced, and by using an acrylic acid ester and / or a methacrylic acid ester monomer, the environmental stability of charging is further improved. In addition to increasing the resin hardness and improving the pulverizability, there is no contamination of the developing sleeve or the layer thickness regulating member (blade or roller), the effect of preventing photoconductor filming is improved, and the binder resin for full-color toner is improved. By combining with a polyester resin suitable from the viewpoints of color developability and image strength, an appropriate dispersibility can be obtained, and an electrophotographic toner having a sharp charge amount distribution can be obtained.

The constituent ratio of the monomer in the oil charge control agent of the present invention is 1 to 30% by weight, more preferably 2 to 20% by weight, of the sulfonic acid group-containing monomer. 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 insufficient, and the image is likely to be affected. On the other hand, if it exceeds 30% by weight, the environmental stability of charging is deteriorated, the charging amount at high temperature and high humidity is low, and the charging amount at low temperature and low humidity is high, so that the charging stability of the toner and the maintenance of high image quality are not sufficient. Further, there is a problem that the developing sleeve and the layer thickness regulating member (blade and roller) are apt to be contaminated and the filming of the photoconductor is caused, and the productivity at the time of toner production by the kneading / pulverizing method is also lowered.

The aromatic monomer having an electron-withdrawing group is 1 to
It is 80% by weight, more preferably 20 to 70% by weight. If the amount of the aromatic monomer having an electron-withdrawing group is less than 1% by weight, the amount of charge is insufficient and scumming and toner scattering easily occur. On the other hand, if it exceeds 80% by weight, the dispersion in the toner is poor, the charge amount distribution of the toner is widened, and scumming and toner scattering easily occur, and the maintenance of high image quality is not sufficient.

The amount of acrylic acid ester and / or methacrylic acid ester monomer is 10 to 80% by weight, more preferably 20 to 70% by weight. If the acrylic acid ester and / or methacrylic acid ester monomer is less than 10% by weight, sufficient environmental stability of charging cannot be obtained, and the pulverizability at the time of toner production by the kneading / pulverization method is not sufficient, so that the developing sleeve It is not possible to sufficiently prevent the contamination of the developer layer thickness regulating member (blade or roller) and the filming of the photoconductor. If it exceeds 80% by weight, the rise of electrification and the electrification amount are not sufficient and the image is likely to be affected.

The resin charge control agent of these combinations can be used as a binder resin for a full-color toner in combination with a polyester resin or a polyol resin suitable in terms of color developability and image strength to obtain appropriate dispersibility and charge amount. An electrophotographic toner having a sharp distribution can be obtained, and long-term charge stability and high image quality can be obtained.

The resin charge control agent of the present invention is a flow tester.
Apparent viscosity is 10^FourThe temperature at which Pa · s becomes 85
It is preferably ˜110 ° C. Below 85 ° C
The proper dispersibility in the toner cannot be obtained and the charging is reduced.
Not only that, but also the storage stability becomes poor and it tends to aggregate and solidify.
In addition, in the method obtained from the production process of kneading, crushing and classifying
Therefore, sticking is likely to occur in the crushing process, reducing productivity.
It Also, when the temperature exceeds 110 ° C, the dispersibility in the toner decreases.
However, the distribution of the amount of charge becomes wider, causing background stains and toner scattering inside the machine.
Is likely to occur. In addition, toner fixability, especially color
The color developability when the color of the toner is overlapped becomes poor. Apparent viscosity is 1
0^FourA flow tester was used to measure the temperature at which Pa · s was reached.
Shimadzu CFT-500 type, load 10k
g / cm ², Orifice 1mm x Length 1mm, heating rate
Viscosity is measured at 5 ° C / min and apparent viscosity is 10^FourPa · s
It reads the temperature that becomes.

The number average molecular weight of the resin charge control agent of the present invention is preferably 1,000 to 10,000. 1
If it is less than 000, proper dispersibility in the toner cannot be obtained, and not only the charge is lowered but also in the method obtained from the kneading, crushing and classifying production process, sticking easily occurs in the crushing process and productivity is improved. Lower. On the other hand, if it exceeds 10,000, the dispersibility in the toner is deteriorated, the charge amount distribution is widened, and background stains and toner scattering easily occur in the machine, resulting in poor toner fixability and color developability.

Further, the flow of the binder resin of the present invention is
-The apparent viscosity by the tester is 10 ^FourTemperature that becomes Pa · s
Degree T₁The float of the resin charge control agent according to the present invention
Apparent viscosity by star is 10^FourThe temperature that becomes Pa · s
T₂And then T₁, T₂Is 0.9 <T₁/ T₂<1.4
It is preferable to satisfy the requirement of.

The dispersion of the charge control agent in the binder resin is
It is a major factor that determines the charging performance of the toner. In the present invention, a toner having good chargeability and excellent charge rising property can be obtained by combining a specific binder resin and a specific resin charge control agent. However, it is apparent that the dispersibility of the binder resin and the resin charge control agent affects the charging performance as described above.

The present inventors have solved the problems by paying attention to the apparent viscosities of the binder resin and the resin charge control agent by the individual flow testers and defining the dispersity thereof. When the T ₁ / T ₂ ratio is less than 0.9, the apparent viscosities of the binder resin and the resin charge control agent are close to each other, and the binder resin and the resin charge control agent become compatible with each other, resulting in insufficient saturated charge amount, poor charging start-up, etc. Occurs. Also, the T ₁ / T ₂ ratio is 1.
When it exceeds 4, the apparent viscosities of the binder resin and the resin charge control agent are too far apart from each other, the resin charge control agent becomes poorly dispersed, and initial scumming and a decrease in charge over time occur.

The addition amount of the resin charge control agent of the present invention is preferably 0.1 to 20% by weight, and more preferably 0.5 to 10% by weight, based on the toner particles. If it is less than 0.1% by weight, the rise of electrification and the electrification amount are not sufficient, and the image is likely to be affected by scumming and scatter. If it exceeds 20% by weight, the dispersion is poor and the distribution of the amount of charge is widened, and scumming and toner scattering in the machine are likely to occur.

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,
Loess, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Balkan fast yellow (5G) , R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, red iron oxide, red lead, lead vermilion, cadmium red, cadmium mercury red, antimon verm, permanent red 4R, para red, Faise Red, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4R)
H), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resor Rubin G
X, 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, Rhodamin Lake B, Rhodamine Lake. Y, Alizarin Rake,
Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC),
Indigo, Ultramarine, Navy 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 white, lithobon and mixtures thereof can be used. Generally, the amount of binder resin is 10
It is 0.1 to 50 parts by weight with respect to 0 parts by weight.

In the present invention, a known charge control agent may be used together with the resin charge control agent. Nigrosine dyes,
Triphenylmethane dye, chromium-containing metal complex dye,
Examples thereof include molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts, fluorine-modified quaternary ammonium salts, alkyl amides, phosphorus simple substances or compounds, tungsten simple substances or compounds, and salicylic acid derivative metal salt compounds.

In order to impart releasability to the developer, it is preferable to add wax to the produced developer.
As the wax, one having a melting point of 40 to 120 ° C. is preferable, and one having a melting point of 50 to 110 ° C. is particularly preferable. 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, the melting peak value when a few mg of sample is aged at a constant temperature rising rate, for example (10 ° C./min), is taken as 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. , Partially saponified fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Further, 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. according to the 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 improver for removing the post-transfer developer remaining on the photoconductor or the primary transfer medium include zinc stearate, calcium stearate, stearic acid and other fatty acid metal salts such as polymethylmethacrylate fine particles, Examples thereof include polymer particles produced by soap-free emulsion polymerization such as polystyrene particles. It is preferable that the fine polymer particles have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 μm.

The toner of the present invention contains other additives such as colloidal silica, hydrophobic silica, Teflon (registered trademark), fluoropolymer, low molecular weight polyolefin,
Fatty acid metal salts (zinc stearate, aluminum stearate, calcium stearate, etc.), metal oxides (titanium oxide, aluminum oxide, tin oxide, antimony oxide, etc.), conductivity imparting agents (carbon black, tin oxide, etc.), magnetic materials In addition, a material obtained by surface-treating these additives may be contained. These additives may be used alone or in combination of two or more, and the content thereof is generally 0.1 to 10 parts by weight with respect to 100 parts by weight of the toner.

The toner of the present invention may be a magnetic toner containing a magnetic material. Examples of magnetic materials include iron oxide (magnetite, ferrite, hematite, etc.), metal (iron, cobalt, nickel, etc.), the metal and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, cadmium,
Examples include alloys or mixtures of manganese, selenium, titanium, tungsten, vanadium and the like. These magnetic materials preferably have a volume average particle diameter of about 0.1 to 2 μm, and the amount contained in the toner is 5 to 150 parts with respect to 100 parts by weight of the binder resin content.

The toner of the present invention may be used as a two-component developer using a carrier. The carrier used here may be any conventional system such as iron powder, ferrite, magnetite, or glass beads. Further, these carriers may be resin-coated. The resin used in this case is a known one such as polyfluorocarbon, polyvinyl chloride, polyvinylidene chloride, phenol resin, polyvinyl acetal, acrylic resin, and silicone resin, but the silicon-coated carrier is excellent from the viewpoint of developer life. There is.
If necessary, conductive powder or the like may be contained in the coating resin. As the conductive powder, metal powder, carbon black,
Titanium oxide, tin oxide, zinc oxide and the like can be used. It is preferable that these conductive powders have an average particle diameter of 1 μm or less.
When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance. The mixing ratio of the toner and the carrier of the two-component developer is generally 0.5 to 20.0 parts by weight of the toner with respect to 100 parts by weight of the carrier.

The method for producing the toner of the present invention may be any conventionally known method, including a step of mechanically mixing at least a developer component containing a binder resin, a charge control agent and a pigment, a step of melt-kneading, and a pulverization. A method of manufacturing a toner having a step of performing and a step of classifying 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), fine particles or coarse particles other than the components to be the product of the desired particle size obtained in the crushing step, and subsequent processing are carried out. It means fine particles or coarse particles other than the components that become the product having a desired particle size generated in the classification step.

It is preferable to mix 1 to 20 parts by weight of the by-product with the raw material, preferably the main raw material 100, in the step of mixing or melt-kneading such by-product. The mixing step of mechanically mixing the developer components including at least the binder resin, the charge control agent and the pigment, and the by-product may be performed under normal conditions using an ordinary mixer having a rotating blade, and there is no particular limitation. Absent.

Upon completion of the above mixing steps, 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, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by KCK, PCM twin screw extruder manufactured by Ikegai Iron Works, Buss manufactured by Bus Co. A co-kneader or the like is preferably used.

It is important that this melt-kneading is carried out under appropriate conditions so that the molecular chain of the binder resin is not broken. Specifically, the melt-kneading temperature should be performed with reference to the softening point of the binder resin, and if the temperature is lower than the softening point, the cutting is severe, and if it is too high, the dispersion does not proceed.

After the above melt-kneading process 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 material is classified in an air stream by centrifugal force or the like to produce a developer having a predetermined particle diameter, for example, an average particle diameter of 5 to 20 μm.

When preparing a developer, in order to improve the fluidity, storability, developability and transferability of the developer, the above-prepared hydrophobic agent is added to the above-prepared developer. Fine inorganic particles such as fine silica powder may be added and mixed.
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.

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

[0083]

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. In the following examples, parts and% are based on weight unless otherwise specified.

(Synthesis Example of Polyester Resin) Synthesis Example 1 Stirrer, thermometer, nitrogen inlet, flow-down condenser,
In a 4-neck separable flask equipped with a cooling tube, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2
2) -2,2-bis (4-hydroxyphenyl) propane 300 g, dimethyl terephthalate 466 g, isododecenyl succinic anhydride 80 g, and tri-n-butyl 1,2,4-benzenetricarboxylate 114 g were added together with the esterification catalyst. In a nitrogen atmosphere, the atmospheric pressure was raised to 210 ° C. in the first half, and the reaction was performed while stirring at 210 ° C. in the latter half under reduced pressure. As a result, the content of the compound having a molecular weight of 500 or less is 3.5%, the molecular weight peak is 7500, the Tg is 62 ° C., the Mw / Mn ratio is 5.1, the acid value is 2.3 KOHmg / g, the apparent viscosity by the flow tester is 10 ⁴ Pa · s, the temperature is 112 ° C. To obtain a polyester resin (hereinafter referred to as polyester resin A).

Synthesis Example 2 Polyoxypropylene (2,2) -2,2-bis (4-)
Hydroxyphenyl) propane 71225 g, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 165 g, terephthalic acid 500 g,
130 g of isododecenyl succinic anhydride and 170 g of triisopropyl 1,2,4-benzenetricarboxylate were added to the flask together with an esterification catalyst. These were reacted with the same equipment and the same formulation as in Synthesis Example 1 to give a molecular weight of 50.
Content of 0 or less 3.0%, molecular weight peak 8000, Tg
62 ° C., Mw / Mn ratio 4.7, acid value 0.5 KOHmg /
g, a polyester resin (hereinafter polyester resin B) having an apparent viscosity of 10 ⁴ Pa · s temperature of 116 ° C. by a flow tester was obtained.

Synthesis Example 3 Polyoxypropylene (2,2) -2,2-bis (4-)
Ester of 650 g of hydroxyphenyl) propane, 650 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 515 g of isophthalic acid, 70 g of isooctenylsuccinic acid and 80 g of 1,2,4-benzenetricarboxylic acid It was added to the flask together with the oxidization catalyst. These were reacted with the same apparatus and the same formulation as in Synthesis Example 1, and the content was 2.1% with a molecular weight of 500 or less, peak molecular weight 8200, Tg 61 ° C., Mw / Mn ratio 4.6,
A polyester resin (hereinafter polyester resin C) having an acid value of 10.0 KOHmg / g and an apparent viscosity of 10 ⁴ Pa · s by a flow tester of 117 ° C. was obtained.

Synthesis Example 4 Polyoxypropylene (2,2) -2,2-bis (4-)
Ester of 714 g of hydroxyphenyl) propane, 663 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 648 g of isophthalic acid, 150 g of isooctenylsuccinic acid and 120 g of 1,2,4-benzenetricarboxylic acid It was added to the flask together with the oxidization catalyst. These were reacted with the same apparatus and the same formulation as in Synthesis Example 1, and the content of the polymer having a molecular weight of 500 or less was 4.8%,
Molecular weight peak 9500, Tg 67 ° C., Mw / Mn ratio 8.
5, a polyester resin (hereinafter referred to as polyester resin D) having an acid value of 23.2 KOHmg / g and an apparent viscosity of 10 ⁴ Pa · s by a flow tester of 126 ° C. was obtained.

(Synthesis Example of Resin Charge Control Agent) Synthesis Example 1 Di-t-butyl peroxide was started under the boiling point of 600 parts of 3,4-dichlorophenylmaleimide and 100 parts of perfluorooctanesulfonic acid in dimethylformaldehyde (DMF). As an agent, it was copolymerized for 8 hours. Then, 300 parts of n-butyl acrylate was added, and graft polymerization was carried out for 4 hours using di-t-butyl peroxide as an initiator.
DMF was removed by vacuum drying to obtain a number average molecular weight of 1000.
A resin charge control agent A having a temperature of 95 ° C. and an apparent viscosity of 10 ⁴ Pa · s was obtained.

Synthesis Example 2 600 parts of m-nitrophenylmaleimide and 100 parts of 2-acrylamido-2-methylpropanesulfonic acid were added as D.
Copolymerization was carried out for 8 hours using di-t-butyl peroxide as an initiator in MF under boiling point. Then, 250 parts of 2-ethylhexyl acrylate was added, and after graft polymerization for 4 hours using di-t-butyl peroxide as an initiator, DMF was removed by vacuum drying to give a number average molecular weight of 1500 and an apparent viscosity of 10 ⁴ Pa. A resin charge control agent B having a temperature of s of 85 ° C. was obtained.

Synthesis Example 3 500 parts of 3,4-dichlorophenylmaleimide and 2-
Acrylamide-2-methylpropanesulfonic acid 150
Part was copolymerized in DMF at a boiling point for 8 hours using di-t-butyl peroxide as an initiator. Then acrylic acid n-
After 350 parts of butyl was added and dissolved, graft polymerization was carried out for 4 hours using di-t-butyl peroxide as an initiator,
DMF was removed by vacuum drying to give a number average molecular weight of 9850.
0, the temperature at which the apparent viscosity is 10 ⁴ Pa · s is 110 ° C.
A resin charge control agent C was obtained.

Synthesis Example 4 3,4-Dichlorophenylmaleimide (500 parts) and perfluorooctanesulfonic acid (200 parts) were copolymerized in DMF at a boiling point for 8 hours using di-t-butyl peroxide as an initiator. Next, 300 parts of n-butyl acrylate was added, and di-t-butyl peroxide was used as an initiator to prepare 4 parts.
After graft polymerization for a period of time, DMF was removed by vacuum drying to obtain a number average molecular weight of 12,000 and an apparent viscosity of 10 ⁴ Pa.
A resin charge control agent D having a temperature of s of 102 ° C. was obtained.

Synthesis Example 5 3,4-dichlorophenylmaleimide 400 parts and 2-
Acrylamide-2-methylpropanesulfonic acid 100
Parts were copolymerized in DMF at a boiling point for 8 hours using di-t-butyl peroxide as an initiator, and then DMF was removed by vacuum drying to give a number average molecular weight of 5000 and an apparent viscosity of 10
^A resin charge control agent E having a temperature of ⁴ Pa · s of 101 ° C. was obtained.

Synthesis Example 6 3,4-dichlorophenylmaleimide 400 parts and 2-
Acrylamide-2-methylpropanesulfonic acid 200
Part was copolymerized in DMF at a boiling point for 8 hours using di-t-butyl peroxide as an initiator. Then acrylic acid n-
After 750 parts of butyl was added and dissolved, DMF was removed by drying under reduced pressure to give a number average molecular weight of 11,500 and an apparent viscosity of 1
A resin charge control agent F having a temperature of 0 ⁴ Pa · s of 110 ° C. was obtained.

Synthesis Example 7 450 parts of 3,4-dichlorophenylmaleimide and 150 parts of perfluorooctasulfonic acid were dissolved in DMF under boiling point.
Copolymerization was carried out for 3 hours using di-t-butyl peroxide as an initiator. Then, 400 parts of methyl acrylate was added, and graft polymerization was performed for 4 hours using di-t-butyl peroxide as an initiator, and then DMF was removed by vacuum drying to obtain a number average molecular weight of 950 and an apparent viscosity of 10 ⁴ Pa · s. A resin charge control agent G having a temperature of 82 ° C. was obtained.

Example 1 A coloring material was treated according to the following formulation. Yellow colorant formulation: Polyester resin A 200 parts C.I. I. Pigment Yellow 180 100 parts Red colorant formulation: Polyester resin A 200 parts C.I. I. Pigment Red 122 100 parts Blue colorant formulation: Polyester resin A 200 parts C.I. I. Pigment Blue 15 100 parts Black colorant formulation: Polyester resin A 200 parts Carbon black 100 parts For each color, the above materials are put into a Henschel mixer and mixed, and then the mixture is put into a two-roll mill heated to 100 ° C. Melt kneading for 30 minutes. Thereafter, the kneaded product was cooled and coarsely pulverized with a hammer mill to obtain a resin A-treated pigment.

Next, a toner was prepared according to the following formulation. Yellow toner formulation: Polyester resin A 88 parts Resin A treated yellow colorant 18 parts Resin charge control agent A 3 parts Magenta toner formulation: Polyester resin A 90 parts Resin A treated red colorant 15 parts Resin charge control agent A 3 parts Cyan toner formulation: Polyester resin A 94 parts Resin A-treated blue colorant 9 parts Resin charge control agent A 3 parts Black toner formulation: Polyester resin A 86 parts Resin A-treated black colorant 18 parts Resin A-treated blue colorant 3 parts Resin charge control agent A 3 parts

The above materials for each color were put into a Henschel mixer and mixed, and the resulting mixture was put into a roll mill heated to 110 ° C., and after that, melt-kneaded for 30 minutes. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. Polyester resin A
The apparent viscosity ratio of the resin charge control agent A and that of the resin charge control agent A measured by a flow tester was 1.18. 0.8 parts of hydrophobic silica and 0.6 parts of hydrophobic titanium oxide for 100 parts of each color toner obtained
Parts were mixed with a Henschel mixer to obtain a one-component developer.

A commercially available digital full-color printer (IPSiO Colo manufactured by Ricoh Co., Ltd.) was used as the obtained one-component developer.
r 4100N) to form an image. The image obtained was clear and no abnormalities such as scumming were observed. The amount of charge on the developing roller was measured by the suction method. As a result, the yellow developer was -38 μC / g and the magenta developer was -3.
It was 5 μC / g, the cyan developer was −36 μC / g, and the black developer was −34 μC / g. An image was formed and the charge amount was measured in the same manner under high temperature and high humidity of 30 ° C. and 90% RH, and under low temperature and low humidity of 10 ° C. and 15% RH, but no significant change was observed and good images were formed in both cases. . O at room temperature
When a full color image was formed on the HP sheet and projected by an overhead projector, a clear full color image was projected.

Further, when a durability test was carried out on a full-color image up to 50,000 sheets at room temperature, no remarkable change was found in the fixed image, and the 50,000th image was a clear image without background stain. The charge amount of the developer is yellow developer-37μ.
C / g, magenta developer-33 μC / g, cyan developer-36 μC / g, and black developer-32 μC / g were stable. The developing roller, blade, and photoreceptor were visually observed after 50,000 sheets, but there was no filming. Also, 10 g of each color toner is placed in a heat-resistant glass container of 30 cc, and this is 5
A storage test was conducted by leaving the toner in a constant temperature bath at 0 ° C. for 5 days. As a result, the toner did not show aggregation and the good fluidity was maintained.

Example 2 A coloring agent was treated according to the following formulation. Yellow colorant formulation: Polyester resin B 100 parts C.I. I. Pigment Yellow 180 100 parts Red colorant formulation: Polyester resin B 100 parts C.I. I. Pigment Red 57: 1 100 parts Blue colorant formulation: Polyester resin B 100 parts C.I. I. Pigment Blue 15 100 parts For each color, the above materials were put into a Henschel mixer and mixed, and then the mixture was put into an air-cooled two-roll mill, and the mixture was kneaded for 15 minutes. Then, the kneaded product was cooled and coarsely pulverized with a hammer mill to obtain a polyester resin B-treated pigment.

Next, a toner was prepared according to the following formulation. Yellow toner formulation: Polyester resin B 94 parts Resin B-treated yellow colorant 12 parts Resin charge control agent B 2 parts Magenta toner formulation: Polyester resin B 95 parts Resin B treated red colorant 10 parts Resin charge control agent B 4 parts Cyan toner formulation: Polyester resin B 96 parts Resin B treated blue colorant 8 parts Resin charge control agent B 3 parts Black toner formulation: Polyester resin B 99 parts Resin B treated blue colorant 2 parts Carbon black 6 parts Resin charge control Agent 3 parts

The above materials for each color were placed in a Henschel mixer and mixed, and the resulting mixture was heated to 80 ° C.
It was charged into an axial continuous kneader and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow type pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. The ratio of apparent viscosities of polyester resin B and resin charge control agent B measured by a flow tester was 1.36. To 100 parts of each color toner obtained, 1.0 part of hydrophobic silica and 0.6 part of hydrophobic titanium oxide were mixed by a Henschel mixer to prepare a one-component developer.

A commercially available digital full-color printer (IPSi manufactured by Ricoh Co., Ltd.) was used as in Example 1.
O Color 4100N), and an image was formed in the same manner as in Example 1. The obtained image was clear without scumming. The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was -40 μC / g, the magenta developer was -38 μC / g, and the cyan developer was -39 μ.
The C / g and black developer were -38 μC / g. O
The projected image on the HP sheet was also vivid. No abnormal image was observed under high temperature and high humidity and low temperature and low humidity, and no significant change was observed in both image and charge in the durability test of 50,000 sheets. The developing roller, blade, and photoreceptor were visually observed after 50,000 sheets, but there was no filming. In addition, each color toner 5
A storage test was conducted by leaving the toner in a constant temperature bath of 0 ° C. for 5 hours. As a result, the toner did not show agglomeration and the like, and good fluidity was maintained.

Example 3 A coloring agent was treated according to the following formulation. Yellow colorant formulation: Polyester resin C 200 parts C.I. I. Pigment Yellow 180 100 parts Red colorant formulation: Polyester resin C 200 parts C.I. I. Pigment Red 146 100 parts Blue colorant formulation: Polyester resin C 200 parts C.I. I. Pigment Blue 15 100 parts Black colorant formulation: Polyester resin C 200 parts Carbon black 100 parts

The above materials for each color were put into a Henschel mixer and mixed, and then the mixture was put into a two-roll mill heated to 110 ° C. and kneaded for 30 minutes. Thereafter, the kneaded product was cooled and coarsely pulverized with a hammer mill to obtain a resin C-treated pigment.

Next, a toner was prepared according to the following formulation. Yellow toner formulation: Polyester resin C 88 parts Resin C-treated yellow colorant 18 parts Resin charge control agent C 1 part Magenta toner formulation: Polyester resin C 90 parts Resin C-treated red colorant 15 parts Resin charge control agent C 2 parts Cyan toner prescription: Polyester resin C 94 parts Resin C-treated blue colorant 9 parts Resin charge control agent C 2 parts Black toner prescription: Polyester resin C 96 parts Resin C-treated black colorant 18 parts Resin C-treated blue colorant 3 parts Resin charge control agent C 2 parts

The above materials for each color were placed in a Henschel mixer and mixed, and the resulting mixture was heated to 80 ° C.
It was charged into an axial continuous kneader and melt-kneaded. Then, the kneaded product was cooled, coarsely pulverized by a hammer mill and finely pulverized by a mechanical pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. The ratio of the apparent viscosities of the polyester resin C and the resin charge control agent C measured by a flow tester was 1.06. 0.8 parts of hydrophobic silica and 0.4 part of hydrophobic titanium oxide were mixed with 100 parts by weight of each color toner obtained by a Henschel mixer. Then, 8 parts of each color toner and 92 parts of silicone resin-coated magnetite carrier were mixed to prepare a two-component developer of each color. The charge amount of the obtained developer was measured by the blow-off method.
18 μC / g, -15 μC / g for magenta developer, -17 μC / g for cyan developer, -16 μ for black developer
It was C / g.

A commercially available digital full-color copying machine (ImagioColor 405 manufactured by Ricoh Co., Ltd.) was used as the obtained developer.
5) and an image was formed in the same manner as in Example 1. The obtained image was clear without scumming. The projected image on the OHP sheet was also vivid. No significant change was observed in both images and charging at high temperature and high humidity, low temperature and low humidity. 5
No abnormal image was seen in the 10,000-sheet durability test. The developing roller and the photoconductor after 50,000 sheets were visually observed, but there was no filming. Further, a storage test was conducted in which each color toner was allowed to stand in a constant temperature bath of 50 ° C. for 5 hours. As a result, no agglomeration was observed in the toner after standing and good fluidity was maintained.

Comparative Example 1 A coloring agent was treated according to the following formulation. Yellow colorant formulation: Polyester resin D 200 parts C.I. I. Pigment Yellow 180 100 parts Red colorant formulation: Polyester resin D 200 parts C.I. I. Pigment Red 122 100 parts Blue colorant formulation: Polyester resin D 200 parts C.I. I. Pigment Blue 15 100 parts Black colorant formulation: Polyester resin D 200 parts Carbon black 100 parts

The above materials for each color were placed in a Henschel mixer and mixed, and then the mixture was placed in a two-roll mill heated to 100 ° C., and the mixture was melted and kneaded for 30 minutes. Thereafter, the kneaded product was cooled and coarsely pulverized with a hammer mill to obtain a resin D-treated pigment.

Next, a toner was prepared according to the following formulation. Yellow toner formulation: Polyester resin D 88 parts Resin D-treated yellow colorant 18 parts Resin charge control agent B 3 parts Magenta toner formulation: Polyester resin D 90 parts Resin D-treated red colorant 15 parts Resin charge control agent B 3 parts Cyan toner prescription: Polyester resin D 94 parts Resin D-treated blue colorant 9 parts Resin charge control agent B 3 parts Black toner prescription: Polyester resin D 86 parts Resin D-treated black colorant 18 parts Resin D-treated blue colorant 3 parts Resin charge control agent B 3 parts

The above materials for each color were put into a Henschel mixer and mixed, and the resulting mixture was put into a roll mill heated to 110 ° C., and after that, melt-kneaded for 30 minutes. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. Polyester resin D
And the apparent viscosity ratio of the resin charge control agent B by the flow tester was 1.48. 0.8 parts of hydrophobic silica and 0.6 parts of hydrophobic titanium oxide for 100 parts of each color toner obtained
Parts were mixed with a Henschel mixer to obtain a one-component developer.

A commercially available digital full color printer (IP manufactured by Ricoh Co., Ltd.
An image was formed by setting on SiO Color 4100N). The obtained image was an abnormal image with noticeable background stains. The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was -25 μC / g, the magenta developer was -19 μC / g, and the cyan developer was -23 μC / g.
The black developer was -21 μC / g, which was relatively low. Under high temperature and high humidity of 30 ° C. and 90% RH, the ground stain became severe. When a full-color image was formed on the OHP sheet and projected by an overhead projector, a full-color image with poor transparency was obtained. In addition, a durability test of up to 50,000 full-color images was performed at room temperature.
After about 10,000 sheets, the background stain became severe, and visual observation of the developing roller, blade, and photoconductor revealed that filming had occurred. It should be noted that each color toner 5
In the storage test in which the toner was allowed to stand for a period of time, the toner did not show agglomeration or the like after standing and the fluidity was maintained.

Comparative Example 2 A coloring agent was treated according to the following formulation. Yellow colorant formulation: Polyester resin D 200 parts C.I. I. Pigment Yellow 180 100 parts Red colorant formulation: Polyester resin D 200 parts C.I. I. Pigment Red 122 100 parts Blue colorant formulation: Polyester resin D 200 parts C.I. I. Pigment Blue 15 100 parts For each color, the above materials were put into a Henschel mixer and mixed, and then the mixture was put into a two-roll mill heated to 100 ° C., and the mixture was melt-kneaded for 30 minutes. Thereafter, the kneaded product was cooled and coarsely pulverized with a hammer mill to obtain a resin D-treated pigment.

Next, a toner was prepared according to the following formulation. Yellow toner formulation: Polyester resin D 88 parts Resin D-treated yellow colorant 18 parts Resin charge control agent D 2 parts Magenta toner formulation: Polyester resin D 90 parts Resin D-treated red colorant 15 parts Resin charge control agent D 3 parts Cyan toner formulation: Polyester resin D 96 parts Resin D-treated blue colorant 8 parts Resin charge control agent D 3 parts Black toner formulation: Polyester resin D 98 parts Resin D-treated blue colorant 3 parts Carbon black 6 parts Resin charge control Agent D 3 parts

The above materials for each color were placed in a Henschel mixer and mixed, and the resulting mixture was heated to 80 ° C.
It was charged into an axial continuous kneader and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow type pulverizer. Further, fine powder was removed by an air classifier to obtain toners of the same colors as in Example 1. The ratio of apparent viscosities of the polyester resin D and the resin charge control agent B measured by a flow tester was 1.24. To 100 parts of each color toner obtained, 0.8 parts of hydrophobic silica and 0.6 part of hydrophobic titanium oxide were mixed with a Henschel mixer to prepare a one-component developer.

A commercially available digital full color printer (IP manufactured by Ricoh Co., Ltd.) was used in the same manner as in Example 1 to obtain the one-component developer.
A clear image was obtained when an image was formed by setting it on SiO Color 4100N). The OHP sheet was also projected clearly. No abnormal images were seen even at high temperature and high humidity and low temperature and low humidity. When a durability test up to 50,000 sheets was carried out with a full-color image at room temperature, scumming was noticeable on about 30,000 sheets and an abnormal image was formed on the 50,000th sheet.
When the developing roller, the blade, and the photoconductor were visually observed, filming occurred. In the storage test in which each color toner was left in a constant temperature bath at 50 ° C. for 5 hours, the toner did not show aggregation and the fluidity was maintained after the storage.

Comparative Example 3 A coloring agent was treated according to the following formulation. Yellow colorant formulation: Polyester resin A 100 parts C.I. I. Pigment Yellow 180 100 parts Red colorant formulation: Polyester resin A 100 parts C.I. I. Pigment Red 57: 1 100 parts Blue colorant formulation: Polyester resin A 100 parts C.I. I. Pigment Blue 15 100 copies

The above materials for each color were put into a Henschel mixer and mixed, and then the mixture was put into an air-cooled two-roll mill, and the mixture was kneaded for 15 minutes. Thereafter, the kneaded product was cooled and coarsely pulverized with a hammer mill to obtain a polyester resin A-treated pigment.

Next, a toner was prepared according to the following formulation. Yellow toner formulation: Polyester resin A 94 parts Resin A-treated yellow colorant 12 parts Resin charge control agent G 2 parts Magenta toner formulation: Polyester resin A 95 parts Resin A-treated red colorant 10 parts Resin charge control agent G 4 parts Cyan toner formulation: Polyester resin A 96 parts Resin A-treated blue colorant 8 parts Resin charge control agent G 3 parts Black toner formulation: Polyester resin A 99 parts Resin A-treated blue colorant 2 parts Carbon black 6 parts Resin charge control Agent G 3 parts

The above materials for each color were placed in a Henschel mixer and mixed, and the resulting mixture was heated to 80 ° C.
It was charged into an axial continuous kneader and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow type pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. The ratio of the apparent viscosities of polyester resin B and resin charge control agent B measured by a flow tester was 1.37. To 100 parts of each color toner obtained, 1.0 part of hydrophobic silica and 0.6 part of hydrophobic titanium oxide were mixed by a Henschel mixer to prepare a one-component developer.

The obtained developer was applied to a commercially available digital full color printer (IPSi manufactured by Ricoh Co., Ltd.) in the same manner as in Example 1.
O Color 4100N), and an image was formed in the same manner as in Example 1. The obtained image was clear without scumming. The projected image on the OHP sheet was also vivid. No abnormal images were seen under high temperature and high humidity and low temperature and low humidity. When a durability test was performed on 50,000 sheets, scumming began to stand out on 20,000 sheets and an abnormal image was formed on the 50,000th sheet. 5
Filming occurred when the tenth roller, blade, and photoreceptor were visually observed. In addition, each color toner 50
When a storage test was carried out by leaving it in a constant temperature bath at ℃ for 5 hours,
The toner was solidified after standing.

[0123]

According to the present invention, in both the two-component and one-component color developing systems, after the continuous printing for a longer period than the conventional one, the photoreceptor, the developer layer thickness regulating member and the developing sleeve are filled. It is possible to obtain an electrophotographic toner that does not cause mingling, stabilizes the charging and conveyance of the toner, and can maintain an image density equivalent to the initial image and a high-quality output image. Further, since there is little reduction in charging during continuous use, there are no problems such as fluctuations in image density, low developability, background stains, and toner scattering in the developing device, and an image with good color development and color reproducibility can be obtained. Due to such long-term durability, it is possible to extend the service life of the developing unit, photoconductor unit, etc., and to reduce the amount of recycled materials and waste generated after use, which is much easier for users to use. It is possible to reduce the trouble of replacing the image forming unit.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/08 504 G03G 9/08 346 331 506 325 507 361 15/08 507L (72) Inventor Osamu Uchinokura Ricoh Co., Ltd. 1-3-3 Nakamagome, Ota-ku, Tokyo (72) Inventor Shinichiro Yagi 1-3-6 Nakamagome-Chome Magome, Ota-ku, Tokyo (72) Inventor Mitsuteru Kato Ota-ku, Tokyo Nakamagome 1-chome 3-6 F-term in Ricoh Co., Ltd. (reference) 2H005 AA01 CA04 CA08 CA20 DA02 EA03 EA06 EA07 FA02 2H077 AC04 AD06 AD13 AD14 AD17 AD23 BA07 EA03 EA16 GA03 GA13

Claims (20)

[Claims] 1. A dry electrophotographic toner containing at least a binder resin, a colorant, a charge control agent, and an additive, wherein the binder resin does not contain at least a THF-insoluble component, and is used in gel permeation chromatography (GPC). In the molecular weight distribution, molecular weight 500
The content ratio of the following components is 4% by weight or less, and at least one type of polyester having one peak in the molecular weight range of 3000 to 9000 is contained, and the charge control agent is a sulfonate group as a monomer. A dry electrophotographic toner, which is a resin charge control agent containing at least a constituent monomer, an aromatic monomer having an electron-withdrawing group, and an acrylic acid ester and / or a methacrylic acid ester monomer. 2. The electrophotographic toner according to claim 1, wherein an endothermic peak in DSC of the binder resin is in a range of 60 to 70 ° C. 3. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin is 2 ≦ Mw / Mn.
3. The electrophotographic toner according to claim 1, wherein ≦ 10. 4. The acid value of the binder resin is 20 KOH
4. The toner for electrophotography according to claim 1, wherein the toner is less than or equal to mg / g. 5. The temperature at which the apparent viscosity of the binder resin by a flow tester becomes 10 ⁴ Pa · s is 95 to 1
The toner for electrophotography according to any one of claims 1 to 4, wherein the temperature is 20 ° C. 6. The resin charge control agent comprises as a monomer at least a sulfonate group-containing monomer, an aromatic monomer having an electron-withdrawing group, and an acrylic acid ester and / or a methacrylic acid ester monomer as structural units. And the repeating unit of the sulfonic acid group-containing monomer is 1 to 30% by weight based on the weight of the resin charge control agent, and the repeating unit of the aromatic monomer having an electron-withdrawing group is 1 based on the weight of the resin charge control agent. 7. 80% by weight, the repeating unit of the acrylic acid ester and / or methacrylic acid ester monomer is contained in a ratio of 10 to 80% by weight with respect to the weight of the resin charge control agent. The electrophotographic toner according to any one of the above. 7. The aromatic monomer having an electron-withdrawing group is a phenylmaleimide substituent or a phenylitaconimide substituent substituted with a chlorine atom or a nitro group. The described electrophotographic toner. 8. The temperature at which the apparent viscosity of the resin charge control agent by a flow tester becomes 10 ⁴ Pa · s is 85 to 1
The toner for electrophotography according to any one of claims 1 to 7, which has a temperature of 10 ° C. 9. The number average molecular weight of the resin charge control agent is 1
It is 000-10000, It is characterized by the above-mentioned.
8. The electrophotographic toner according to any one of items 8. 10. The temperature at which the apparent viscosity of the binder resin by a flow tester becomes 10 ⁴ Pa · s is T ₁ , and the temperature at which the apparent viscosity of the resin charge control agent by the flow tester is 10 ⁴ Pa · s is T ₂ The toner for electrophotography according to claim 1, wherein T ₁ and T ₂ are 0.9 <T ₁ / T ₂ <1.4. 11. The toner for electrophotography according to claim 1, wherein the resin charge control agent is contained in an amount of 0.1 to 20% by weight based on the toner particles. 12. A two-component developer comprising the electrophotographic toner according to claim 1 and a carrier. 13. A one-component developer comprising the electrophotographic toner according to claim 1. 14. A container containing a developer according to claim 12 or 13. 15. A latent image forming step of forming a latent image on a latent image holding body, a developing step of developing the latent image with a developer on a developer carrying body, and a developed toner image on a transfer body. An image forming method comprising: a transfer step of transferring the toner image onto a sheet; and a fixing step of heating and fixing the toner image on the transfer body, wherein the developer according to claim 12 or 13 is used as the developer. 16. The image forming method according to claim 15, wherein in the developing step, a thin layer of the developer is formed on the developer carrying member, and the thin film is developed in contact or non-contact with the latent image holding member. . 17. A multicolor electrostatic latent image formed on a latent image holding member is applied onto a plurality of electrostatic image carrying members corresponding to respective colors by a developer corresponding to each color. The developer according to claim 12 or 13, which is used in an electrophotographic developing method of developing and electrostatically transferring the toner image to the transfer material by sequentially contacting the transfer means with the transfer material on the surface of the electrostatic image carrier. An image forming method characterized by the above. 18. A latent image forming step of forming a latent image on a latent image holding member, comprising a container containing the developer according to claim 12 or 13, and carrying the latent image with a developer. Used in an image forming method having at least a developing step of developing with a developer on the body, a transfer step of transferring the developed toner image onto a transfer body, and a fixing step of heating and fixing the toner image on the transfer body. Image forming apparatus. 19. A multi-colored electrostatic latent image formed on a latent image holding member, characterized in that a container containing the developer according to claim 12 is mounted. Is developed on a plurality of electrostatic charge image bearing members corresponding to respective colors, and the transfer means is brought into contact with the surface of the latent image holding member via the transfer material to sequentially transfer the toner images to the transfer material. An image forming apparatus used in an image forming method of electrostatic transfer. 20. At least a developer carrying member, a developer carrying member, a developer layer thickness regulating member, and a developer replenishing auxiliary member, wherein the developer carrying member is provided with the developer layer thickness regulating member and the developer carrying member. Are in contact with each other, the developer transport member is rotatably movable, the developer layer thickness regulating member is rotatably movable, fixed or intermittently rotatable, and the developer transport member is the developer. It is located on the upstream side of the layer thickness regulating member in the rotation direction of the developer carrier, and the developer transport member is 16
20. The image forming apparatus according to claim 18, which is rotatable at 0 mm / sec or more and 280 mm / sec or less.