JP2921471B2 - Full-color toner for developing electrostatic images, method for producing the same, and method for forming full-color image - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a full-color toner for developing an electrostatic image used in a heat roller fixing method such as an electrophotographic method and an electrostatic printing method, a method for producing the same, a full-color toner composition and a full-color image forming method. This full color toner is suitable for a digital copying machine.

[0002]

2. Description of the Related Art The development process of an electrostatic image is a process in which charged fine particles are attracted by electrostatic attraction and adhered to the surface of an electrostatic image support to be visualized. A toner containing an agent is used. In some cases, the visualized image is directly transferred to a support and fixed. However, usually, the image is transferred to another support such as transfer paper and then fixed. As the fixing method, there are a non-contact heating fixing method such as oven fixing and a contact heating method such as heat roller fixing. In general, a contact fixing heating method having high thermal efficiency and capable of high-speed fixing is excellent. In the case of using the heat roller in the contact fixing heating method, since a relatively low-temperature heat source can be used, the power consumption can be suppressed low, and the copier can be reduced in size and energy can be saved. Further, there is no danger of fire even when a paper jam occurs in the fixing device.

The heat roller fixing method has various advantages as described above, but has a serious disadvantage that offset is likely to occur. The offset is a phenomenon in which a part of the toner forming the image is transferred to the surface of the heat roller at the time of fixing, and is transferred to the next transfer paper to contaminate the image. As a method for preventing this, a method of fixing while applying a release oil such as silicone oil to the surface of the heat roller, or adding an anti-offset property by adding a wax represented by a polyolefin to the toner itself. A way to do that has been proposed.

The latter method does not require a silicone oil application mechanism or the like, so the structure of the fixing device is simplified, and maintenance such as replenishment of silicone oil is not required. However, the waxes added to the toner have insufficient compatibility with the binder resin, thereby deteriorating the transparency of the image after fixing. The decrease in transparency is not a direct problem in monochrome copying, but it is a problem in forming a full-color image in which light transmission is important.Therefore, the above waxes should be avoided as much as possible. Must. Therefore, development of a full-color toner used for the former method, that is, an oil supply type heat roller fixing method, is required.

In recent years, printers, facsimile machines, and copiers have been increasingly demanded for color copies having a large amount of information instead of monochrome copies, and the image quality has been improved year by year. As a method of forming a color copy, a method of forming at least three electrostatic latent images based on a three-color synthesizing method such as a subtractive coloring method and then developing with three or more different colors of toner and synthesizing on copy paper ( U.S. Pat. No. 2,962,374) is common. The color toner used in this method requires not only mechanical, environmental, and electrical stability against external factors such as impact, humidity, and temperature, but also appropriate color development and maintenance. For that purpose, optimization of the design of the binder resin of the toner, the type and amount of the colorant, the method of dispersing the colorant, and the like are required.

As colorants for color toners, light fastness,
Organic pigment-based colorants are superior to dye-based colorants from the viewpoints of migration resistance and safety. However,
Commercially available organic pigments in a dry powder state have a problem that it is difficult to disperse them in a binder resin. If the primary particles of the pigment remain as aggregates in the toner, light transmittance, which is the most important characteristic in a full-color image, will be greatly impaired, and color reproducibility will be greatly reduced. Therefore,
It becomes difficult to apply the film to an overhead projector (OHP) film.

As a method for solving the above-mentioned drawbacks of organic pigments, a commercially available organic pigment is produced by heating and melting and mixing with a binder resin of a toner at a concentration higher than the pigment concentration used for a normal toner to produce a processed pigment. After that, a method has been proposed in which the processed pigment is diluted with a binder resin and melt-mixed so that the dispersion unit of the organic pigment in the toner is reduced so that the optimum pigment concentration as a toner is obtained. (JP 6
JP-A-2-280755, JP-A-2-293867, JP-A-3-107869, JP-A-3-107
870, JP-A-3-115568, JP-A-3-185549, JP-A-3-269542, and JP-A-3-269543. However, commercially available organic pigments cannot be finely dispersed in the drying step in the pigment production, because the aggregation of the primary particles of the organic pigment cannot be avoided and does not affect the light transmittance of the toner. .

Therefore, as another method for reducing the dispersion unit of the organic pigment in the toner, an organic pigment such as phthalocyanine precipitated in the solution in the pigmentation step is washed with water and concentrated.
The resin composition is heated and mixed with an organic solvent in which the resin is dissolved, water and the organic solvent are removed to prepare a resin composition in which the organic pigment is finely dispersed at a relatively high concentration (hereinafter referred to as "flushing pigment"). Melt and knead with binder resin
A method for obtaining a toner by pulverization has been proposed (Japanese Patent Laid-Open No.
See 2-127847). The toner obtained by this method has considerably better light transmittance and color reproducibility than the above-mentioned processed pigment.

However, when phthalocyanine is pigmented by this method, for example, a phthalocyanine produced by an acid paste method or an acid slurry method is used, so that an α-type phthalocyanine crystal is formed, and a β-type phthalocyanine crystal having excellent color reproducibility is obtained. Cannot be obtained, and the above method cannot be applied to an azo lake-based magenta pigment or a yellow pigment synthesized by an azo coupling method. Since the organic solvent is used to replace the water in the water-containing paste, it is necessary to recover the organic solvent. In addition, since concentrated sulfuric acid is used in the acid paste method or the acid slurry method, sulfuric acid may remain in the pigment even after washing with water, and when polyester is used as a binder resin, ester bonds of the polyester are hydrolyzed. Therefore, there is a problem that the characteristics of the toner are changed.

In order to solve these problems, the present inventors have previously proposed a full-color toner in which light transmission and color reproducibility are greatly improved by controlling a dispersion unit of a pigment (Japanese Patent Application Laid-Open No. HEI 4 (1994) -104686). 242,752). In this method for producing a color toner, a water-containing paste of an organic pigment is heated together with a binder resin, and is heated and mixed at a temperature of 100 ° C. or more in a pressure kneader to replace water with a molten resin and to remove the organic pigment. After preparing a resin dispersed at a high concentration (hereinafter, referred to as “melt flushing pigment”), the toner is prepared through a process of melt-kneading with a binder resin and pulverizing. In addition, the water-containing paste of the phthalocyanine pigment includes water, salts,
The pigment can be produced by a salt milling method in which a pigment is pulverized by a high-shear pulverizer to make pigment particles fine. Also,
Aqueous pastes of azo lake-based magenta pigments produced by raked azo dyes can be produced by preparing a pigment dispersion while coexisting with a rosin derivative and concentrating to prevent aggregation of the pigments during rake formation. it can.

By employing the above-described method for producing a melt flushing pigment, the unit of dispersion of the pigment in the toner can be controlled, and the color reproducibility and light transmittance can be improved. By the way, in the case of a full-color toner, a polymer having a relatively low molecular weight and a narrow molecular weight distribution, for example, a number average molecular weight of 3,
200, weight average molecular weight 9,800, glass transition point 66
℃ polyester resin is used, as a result,
When the melt flushing pigment is used, when the temperature exceeds a certain temperature, the toner is suddenly excessively melted and adheres to the fixing roll, or causes a problem of causing a permeation into paper to lower the image quality.

In order to solve the above problem, it is conceivable to use a binder resin having a high molecular weight within a range not deteriorating high gloss, high color development and low-temperature fixability of a full-color toner. Since the organic pigment having a high concentration is shear-mixed with the resin, there is a problem that the molecular weight of the binder resin greatly changes, the physical properties of the obtained toner fluctuate, and the production stability is impaired. Therefore, it is required to develop a binder resin suitable for producing a melt flushing pigment.

By the way, as a binder resin for a toner, a vinyl polymer has been widely used, and the use of a high molecular weight polymer to obtain non-offset properties has been proposed. Since the vinyl-based polymer has a high softening point, it is necessary to set the temperature of the heat roller to be high in order to obtain a fixed image having excellent glossiness, which goes against energy saving. Further, the toner using the vinyl polymer is easily eroded by the plasticizer of the plasticized vinyl chloride resin, and the toner itself is plasticized by contacting with the plasticizer, and as a result, the toner becomes tacky. There is a problem of contaminating the plasticized vinyl chloride resin product, that is, a problem with the resistance to vinyl chloride.

On the other hand, polyester resins are excellent in vinyl chloride resistance and can be produced relatively easily with a low molecular weight. Further, polyester resins include toners containing a vinyl polymer as a binder resin. In comparison with the vinyl polymer having a substantially equal softening point, there is an advantage that the toner can be sufficiently fixed at a lower temperature as compared with a vinyl polymer having substantially the same softening point. Therefore, polyester resins have been used as binder resins for toner.

Also in the above-mentioned Japanese Patent Application Laid-Open No. 4-227552, the production stability in shear mixing in the melt flushing step may be ensured, and terephthalic acid / bisphenol A ethylene oxide adduct /
Polyester obtained from cyclohexanedimethanol, for example, a number average molecular weight of 3,000 to 3,600, a weight average molecular weight of 8,700 to 9,500, and a softening point of 100 to 125.
C. and a glass transition point of 55-68C. The polyester resin containing the bisphenol A ethylene oxide adduct alone is excellent in the above-mentioned production stability and fixing strength because of its high strength, but the pulverizability in producing the toner is extremely poor. In producing toner, there is a problem that the production efficiency is low, the toner cost is high, and the toner cannot be put to practical use.

In general, the production cost of a toner produced through each of the steps of melt-kneading, pulverizing, and classifying is mostly due to the pulverizing and classifying steps. Therefore, the pulverizability of the binder resin is very important in the production of toner. Element. Digital copiers, for which demand is expected in the future, have a strong tendency to reduce the particle size of toner, and it is still necessary to pulverize the toner to 7 μm or less. Therefore, the pulverizability of the binder resin is an important factor.

The pulverization of the toner using the above polyester as a binder resin can be performed by a jet pulverizer or the like.
Requires a lot of energy. Moreover, the obtained pulverized product has strong cohesiveness and poor fluidity as a powder,
The classifying yield of the toner deteriorates. It is difficult to uniformly mix the toner having strong cohesion with the external additive as described above, and the external additive cannot be uniformly attached to the toner surface. Further, adhesion and fusing to pipes of the pulverizer, the inner wall of the pulverization chamber, the collision plate, and the like are severe, which causes a decrease in toner productivity. Therefore, among binder resins containing polyester, it is required to develop a resin suitable for producing a melt flushing pigment and having excellent toner productivity.

On the other hand, a full-color toner generally uses a black toner in addition to the cyan, magenta, and yellow toners in order to clearly show black in a color image. Conventionally, carbon black is generally used as a color material used for a monochrome toner. As an example of using carbon black in monochrome toner,
For example, Japanese Patent Application Laid-Open No. Sho 59-218463 discloses a method of providing a high-density black color and improving the environmental charging stability, transferability and development life by 15% by weight based on the total weight of the toner.
Although it is described that carbon black is contained at the above ratio, this toner cannot faithfully reproduce light gray to pure black from a low density range to a high density range.

Japanese Patent Application Laid-Open No. 60-129756 discloses that the content of carbon black is set to 0.1 to 2 parts by weight with respect to 100 parts by weight of a binder resin in order to provide a color toner having good triboelectricity. 0.0 parts by weight. Toner with this content requires a large amount of toner development in order to reproduce high-density black. As a result, there are problems such as fogging to non-image areas and toner scattering around the developing machine. there were. At a content in this range, the copy becomes reddish brown overall.

On the other hand, Japanese Patent Application Laid-Open No. 2-293858 proposes to improve the reproducibility of black by incorporating carbon black having a particle size of 12 to 30 nm into a toner. However, as described above, carbon black having a small particle diameter has a reddish color tone. Therefore, there is a need to develop a black toner for forming a full-color image having excellent black color tone reproducibility and productivity.

On the other hand, with the spread of digital full-color copying machines, stability of copy image quality and higher image quality and higher reproducibility have been demanded. Japanese Patent Application Laid-Open No. 4-33 aims to achieve high image quality and high reproducibility of color copy.
JP-A-7738 and JP-A-6-75430 propose to use a small-diameter color toner. However, it is described that the smaller the diameter of the toner, the worse the development, transfer and cleaning characteristics, and the poorer the stability and maintainability of the copy image quality. Further, it is described that the smaller the diameter of the toner, the worse the fluidity of the powder, and the worse the frictional charging characteristics with the carrier and the environmental charging characteristics.

As an improvement measure, an external additive to be externally added to the toner has been devised. The present inventors have previously proposed a method of externally adding inorganic or organic spherical fine particles having a particle size of 20 to 80 nm in JP-A-4-333738. In addition, Japanese Patent Application Laid-Open No. 6-75430 has proposed a method of externally adding 0.01 to 0.2 μm of titanium oxide. However, even with these methods, stable development, transfer, cleaning characteristics, and environmental charging characteristics have not yet been obtained, and long-term stability of image quality is required.
Therefore, there is a demand for providing a full-color toner image having a stable image quality even with environmental changes and long-term use.

[0023]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned various problems of the prior art. An object of the present invention is to provide a full-color toner for developing an electrostatic image satisfying the requirements and a method for producing the same.

(1) In the heat roller fixing method, excellent color developability and melt mixing property, and excellent color reproducibility after melt mixing. (2) Even when fixing is performed on a film sheet for an overhead projector, light transmittance of a fixed image is excellent. (3) An image having a sufficient fixing strength to a transfer material can be formed. In particular, an image having an excellent fixing strength to an overhead projector sheet or the like can be formed. (4) In the production of the toner, excellent pulverizability, high classification efficiency, and low production cost. In particular, it must be effective in the production of small particle size toners that can be applied to digital copiers and the like. (5) To be able to provide a toner having excellent powder fluidity and non-aggregation properties, and good replenishment and storage stability. (6) To have stable triboelectric charging characteristics under various humidity conditions. (7) To exhibit excellent durability when used continuously and repeatedly, and to be able to stably provide high-quality images. (8) In a two-component developer, carrier contamination due to adhesion and fusion to a carrier can be prevented. (9) To provide a toner having a sufficient image density, a bright and clear image, and excellent development characteristics capable of obtaining a high-quality image with no resolving power such as background fog.

(10) It is possible to provide a toner which does not cause blocking or the like during storage of the toner and storage in the apparatus and which does not adhere to or contaminate a toner holding member or an electrostatic image. (11) To provide a black toner which is excellent in color reproducibility from white to gray and black even in a full-color image, and is excellent in reproducibility of density gradation from low density to high density. (12) A color image having excellent transparency, color reproducibility, and color clarity can be formed when a color image is formed using each of cyan, magenta, yellow, and black toners. (13) An image having excellent fixing strength can be formed on a transfer material such as an OHP sheet and paper, and a sufficient fixing tolerance is provided.

[0026]

Means for Solving the Problems The present inventors have prepared a full-color toner using a melt flushing pigment and a binder resin containing carbon black having a specific particle size and a specific polyester resin. It has been found that the above object can be achieved by obtaining a toner composition in which a specific titanium oxide having a specific particle size is externally added to this full-color toner, and the present invention has been completed.

That is, the present invention is as follows. The full-color toner of the present invention comprises a color toner for developing an electrostatic image and a black toner. The color toner for developing an electrostatic image, a binder resin, containing a colorant, the binder resin, ethoxylated bisphenol type diol and propoxylated bisphenol type diol,
An aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component, and at least one selected from an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or an acid anhydride or an ester thereof; And 7 to 25 mol% of the total monomer amount, and the color coloring agent is a melt flushing pigment prepared from a water-containing paste of an organic pigment and the polyester resin.

In the above-described color toner for developing an electrostatic image, the color colorant is contained in the binder resin in an equivalent circular diameter of 0.3 μm.
It is preferable that pigment particles having a particle size of m or more are dispersed at a content of 0.1% or less. Further, the color coloring agent is preferably a melt flushing pigment prepared using a water-containing paste of an organic pigment and the polyester resin.

Further, the black toner for developing an electrostatic image contains a binder resin and a black colorant, wherein the binder resin comprises an ethoxylated bisphenol type diol and a propoxylated bisphenol type diol, An aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component, and at least one selected from an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or an acid anhydride or an ester thereof; And carbon black having a primary particle size of 30 nm or more and less than 50 nm as a black colorant.

The color toner and the black toner for developing an electrostatic image of the present invention may contain an external additive.
The external external additive is preferably fine particles of titanium oxide produced by a wet method, and the amount of the water-soluble component is preferably 0.2% by weight or less. The average particle diameter of the titanium oxide fine particles is preferably in the range of 5 to 100 nm. The external additive is preferably surface-treated with a coupling agent or silicone oil.

The method for producing a color toner for developing an electrostatic image according to the present invention is characterized in that an organic pigment, an ethoxylated bisphenol type diol and a propoxylated bisphenol type diol, and an aromatic dicarboxylic acid or an acid anhydride or an ester thereof are used. As a main monomer component, the composition further comprises 7 to 25 mol% of at least one selected from alkyl succinic acid or an acid anhydride or an ester thereof and alkenyl succinic acid or an acid anhydride or an ester thereof based on the total amount of monomers. A step of preparing a melt flushing pigment by heating, melting, and kneading a polyester resin in a heating / pressing kneader, a step of melting and kneading the melt flushing pigment and the polyester resin, and a melt-kneaded product to be formed Have a process to grind and classify And it features. In this case, the treatment in the heating / pressing type kneader is preferably performed at a temperature of 100 to 150 ° C.

One of the full-color image forming methods of the present invention is to develop an electrostatic charge image using a color toner and transfer the toner image to form at least a cyan color toner image, a magenta color toner image and a yellow color toner image. It is formed in a superimposed manner, and the above-mentioned color toner for developing an electrostatic image is used as a color toner. Another one of the full-color image forming methods of the present invention is to develop an electrostatic charge image using a color toner and a black toner, transfer the toner image, and obtain a cyan color toner image.
A magenta color toner image, a yellow color toner image, and a black toner image are formed in a superimposed manner. The color toner for developing an electrostatic image described above is used as a color toner, and the color toner for developing an electrostatic image is used as a black toner. It is characterized by using a black toner.

[0033]

Embodiments of the present invention will be described below in detail. The polyester resin constituting the binder resin used in the color toner and the black toner for developing an electrostatic image of the present invention is an ethoxylated bisphenol type diol and a propoxylated bisphenol type diol,
An aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component, and at least one selected from an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or an acid anhydride or an ester thereof; Containing 7 to 25 mol% of the total amount of monomers, the monomers being mainly composed of ethoxylated bisphenol type diol and propoxylated bisphenol type diol, and aromatic dicarboxylic acid, anhydride or ester thereof. , Alkyl succinic acid, anhydride or ester thereof, and alkenyl succinic acid, anhydride or ester thereof as a minor component. The ethoxylated bisphenol type diol and the propoxylated bisphenol type diol are obtained by propoxylating and ethoxylating bisphenol,
These include those having 2-3 moles of oxypropylene or oxyethylene per mole of bisphenol, and are represented by the following general formula.

[0034]

Embedded image (Wherein, R is an ethylene group or a propylene group, x and y are integers of 1 or more, and the average value of x + y is 2 to 7)
It is. As specific examples, polyoxyethylene (2.2) -2,
2-bis (4-hydroxyphenyl) propane, polyoxyethylene (1.5) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.
2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-
Hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxy-2,6-
Dichlorophenyl) propane and the like.
These etherified bisphenol-type diols can be produced by directly adding ethylene oxide or propylene oxide to diphenol, or by reacting olefin halohydrin with diphenol. The ratio between the ethoxylated bisphenol type diol and the propoxylated bisphenol type diol is 1:10 to 10: 1,
In particular, the ratio is preferably in the range of 1: 4 to 4: 1.

In the polyester resin of the present invention, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5
- pentanediol, aliphatic such as 1,6-ol, 1,4-cyclohexanediol, 1,
Alicyclic bivalent alcohols such as 4-cyclohexanedimethanol can be used.

On the other hand, examples of the aromatic dicarboxylic acid include aromatic carboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid. Examples of the anhydrides include phthalic anhydride. Examples of the esters include low molecular alcohol esters of the above dicarboxylic acids, for example, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, and the like.

Examples of the alkyl succinic acid and alkenyl succinic acid, their anhydrides and esters include, for example, n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n -Octenyl succinic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, anhydrides thereof, lower alkyl esters and the like.

It is particularly important in the present invention that the polyester resin contains a propoxylated bisphenol and an ethoxylated bisphenol component, and further comprises an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or an acid anhydride thereof. Alternatively, at least one selected from esters thereof is contained in an amount of 7 to 25 mol% of the total monomer amount. That is, the propoxylated bisphenol component is crushable, powdery, and,
The ethoxylated bisphenol component is effective for improving the fixing strength, and the alkyl succinic acid, alkenyl succinic acid and their anhydrides are effective in improving the storage stability, low-temperature fixing properties, powder properties, and impact resistance. It effectively works to improve the properties and releasability.

If the content of the alkyl succinic acid component, alkenyl succinic acid component and their anhydride and ester components exceeds 25 mol%, the T
g (glass transition point) becomes too low, the storage property is deteriorated, and it is not practical. If the amount is less than 7 mol%, no effect is exerted on low-temperature fixability, powder properties, impact resistance, and mold release properties. Particularly preferably, 8 mol% to 15 mol%
By adjusting to this range, it is possible to provide a toner having the above characteristics.

Further, by using an alkyl succinic acid or alkenyl succinic acid-containing resin, since the alkyl group or alkenyl group is lipophilic, the affinity with the colorant is high and the dispersibility is good. In addition, since the toner has good dispersibility, it is considered that the toner surface is less likely to be brittle, the embedding of the external additive can be prevented, and poor charging is eliminated.

The polyester resin used in the present invention is:
Glass transition point of 50 to 80 ° C, preferably 55 to 70
C, more preferably in the range of 60 to 65C, and the softening point is in the range of 80 to 150C, preferably 90 to 140C, more preferably 95 to 135C.
When the glass transition point exceeds 80 ° C., excessive heat energy is required at the time of heat fixing, which hinders high-speed heat fixing. When the softening point is lower than 80 ° C., the offset resistance at the time of fixing decreases. When the glass transition point is less than 50 ° C.,
Storage is not enough. On the other hand, if the softening point exceeds 150 ° C., the optimum temperature for fixing becomes high, the glossiness of the image tends to decrease, and the power consumption in the fixing step increases. The polyester resin used in the present invention has a weight average molecular weight of 5,000 to 40,000.
A range of 0, preferably 6,500-35,000, more preferably 7,500-33,000 is suitable. When the weight average molecular weight is less than 5,000, there is a disadvantage that the fixed image strength is reduced. When it is more than 40,000, there is a disadvantage that the productivity in pulverization is reduced.

The glass transition point (Tg) in the present invention is J
DSC method of IS K7122 (heating rate, 10 ° C per minute)
And Tg described in this specification.
Indicates the midpoint glass transition temperature (Tmg).

The weight average molecular weight of the binder resin in the toner of the present invention is a value measured according to the general rules of JIS K124-1983, and the apparatus is JASCO manufactured by JASCO Corporation.
TRI ROTAR-V1 HPLC system
And the column is TosoTSK gel-2,000.
GPC (Gel Perm) using 0, -3,000, -4,000, -5,000, and THF as a solvent.
It is a value measured by the Chromatography.

In the binder resin of the toner of the present invention, other known binder resins can be mixed as long as the performance is not impaired. For example, polyester resins other than the above-mentioned polyester resins in the present invention, silicone resins, epoxy resins, styrene resins and the like can be mentioned. When the above resins are mixed and used, at least 30% by weight of the polyester resin in the present invention is contained in the binder resin.
More preferably, the content is 60% by weight or more.

In the present invention, when an organic pigment is used as a colorant in a full-color toner, it is necessary to uniformly disperse the organic pigment particles as fine particles in a binder resin. The organic pigment used in the present invention includes C.I.
I. Pigment Red 48: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 57: 1, C.I.
I. Pigment Red 238, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 17, C.I. I.
Pigment Yellow 185, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 3, C.I. I. Pigment Blue 15: 3 and the like can be exemplified as typical ones.

The dispersion state of the organic pigment may be such that the binder resin contains 0.1% or less of pigment particles having a circular equivalent diameter of 0.3 μm or more, and preferably a circular equivalent diameter of 0.2 μm.
The pigment particles having a diameter of m or more may be contained in an amount of 0.1% or less, and more preferably 0.1% or less of the pigment particles having an equivalent circular diameter of 0.1 μm or more. If the number ratio of the pigment particles having an equivalent circular diameter of 0.3 μm or more is larger than 0.1%, the absorbance at the same pigment concentration decreases, and the brightness and the sharpness of the projected image decrease. In the present invention, the circular equivalent diameter of the pigment is measured as follows. That is, a color toner in which a pigment is dispersed in a binder resin is cut with a microtome to form a section, an optical microscope photograph at a magnification of 600 times is taken, and measured using an image analyzer.

The full-color toner for developing an electrostatic image of the present invention uses a flushing pigment, and a melt flushing pigment is particularly preferable. As a manufacturing method, first, a melt-flashing pigment excellent in pigment dispersibility is manufactured by melting and kneading a water-containing paste of an organic pigment and the binder resin in a heating and pressure kneader, and producing the melt-flushing pigment. Can be produced by melting and kneading with the binder resin and pulverizing, whereby the organic pigment particles can be uniformly dispersed as fine particles in the binder resin. The melt flushing pigment is prepared by heating a water-containing paste of an organic pigment and the binder resin in a heating / pressure kneader in a range of 0.5 to 5 k.
gf / cm ² , 100-150 ° C., rotor peripheral speed 3-2
It can be manufactured by heating, melting and kneading under conditions of 5 cm / sec.

The content of the organic pigment is in the range of 2 to 30 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the toner.
20 parts by weight. If the amount is less than 2 parts by weight, the coloring power will be weak, and if it exceeds 30 parts by weight, the transparency will be reduced and the condition for full-color toner will not be satisfied. In particular, the range of 3 to 20 parts by weight is preferable because the image quality granularity of the halftone portion of the color toner can be remarkably improved.

In the present invention, when a black toner is prepared as a full-color toner, carbon black is used as a colorant. The carbon black used in the present invention has an average primary particle diameter as determined by electron microscope observation. It is necessary to be 30 to 50 nm, preferably 40 to 50 nm, more preferably 40 to 48 nm. If the primary particle size is less than 30 nm, the color rendering properties will be poor, that is, the color tone will change when the light source is changed, making it difficult to obtain an image with good gradation. On the other hand, if it exceeds 50 nm, it is necessary to increase the amount of internal addition to the toner in order to increase the black density of the image quality. As a result, the saturation charge amount of the toner is reduced and the image quality is deteriorated.

In the present invention, carbon black may be blended in the toner particles in an amount of 2 to 10% by weight, preferably 3 to 9% by weight. If the compounding amount is less than 2% by weight, a desired image density cannot be obtained.
If the content is more than 10% by weight, the conductivity becomes too large to obtain a desired charge amount. The black toner of the present invention is obtained by heating, melting, kneading the carbon black with the binder resin, a Banbury mixer, a kneader, a continuous mixer, a roll mill, an extruder, and the like together with an additive added as necessary. After cooling, it can be produced by coarsely pulverizing, finely pulverizing with a jet mill or the like, and further classifying with a classifier.

The particle size range of the full-color toner for developing electrostatic images of the present invention is such that the 50% diameter of the toner particles is 3 to 8 μm.
m, preferably in the range of 4 to 7 μm. If the volume 50% diameter is less than 3 μm, crushing becomes difficult with a jet crusher, and the cloud in the copying machine is so severe that it cannot withstand practical use in an office environment. On the other hand, if the thickness exceeds 8 μm, the sharpness of the image quality becomes poor, and it becomes difficult to reproduce fine image quality. The measurement of the particle size in the present invention is a value measured by Coulter Multisizer II.

In the particle size distribution of the full-color toner for developing an electrostatic image of the present invention, the diameter of 16% by volume is changed to 84% by volume.
Is preferably in the range of 1.4 to 1.8, more preferably in the range of 1.5 to 1.75. When the above value is less than 1.4, the classification yield in the classification step in the toner production step is 20%.
% Or less, and the cost of the toner becomes extremely high. When the ratio exceeds 1.8, the particle size distribution of the toner is too wide, so that the rise of charging is slow and the charging distribution is wide. In addition, the particle size in the developing machine varies greatly with time, and it is difficult to obtain a stable image quality.

Further, the color toner and the black toner for developing an electrostatic image of the present invention are provided in a range not impairing the performance thereof.
Other known additives can be added. Specifically, a colorless or light-colored charge control agent such as a salicylic acid metal salt, a boron compound and a quaternary ammonium salt, a fixing aid, and the like may be added to the binder resin.

An external additive may be added to the color toner and the black toner for developing an electrostatic image of the present invention.
As the external additive, any known ones such as silica and alumina can be used. In particular, it is preferable to externally add the following titanium oxide. As a result, under high temperature and high humidity, while maintaining the charge amount of the toner necessary for development, uniformity of charge on the toner particle surface, charge exchange property between toner particles is accelerated, charge speed is improved, and charge is improved. Can be sharpened. As a result, it is possible to significantly improve the environmental dependence of the charge amount of the toner composition. In particular, when the polyester resin is used as the binder resin as in the present invention, the above-mentioned disadvantages of the polyester resin relating to the environment dependency of charging are eliminated, which is preferable.

In the present invention, as the external additive externally added to the toner particles, those prepared by a wet method and having a surface treatment of titanium oxide having a water-soluble component content of 0.2% by weight or less are preferably used. Is done. Here, the wet method is a method of producing a compound through a chemical reaction in a solvent, and a main production method includes a sulfuric acid method and a hydrochloric acid method. In the sulfuric acid method, the following reaction proceeds in the liquid phase to form insoluble titanium oxide hydroxide. FeTiO ₃ + 2H ₂ SO ₄ → FeSO ₄ + TiS
O ₄ + 2H ₂ O TiOSO ₄ + 2H ₂ O → TiO (OH) ₂ + H ₂
SO _{4 In} the hydrochloric acid method, titanium tetrachloride is first dissolved in water. At this time, the aqueous solution becomes an aqueous hydrochloric acid solution. Next, a strong base such as caustic soda is charged, and titanium hydroxide Ti (OH)
₄ is produced and titanium hydroxide is precipitated. Both the hydrous titanium oxide and the titanium hydroxide undergo a firing step to become titanium oxide fine particles.

The amount of the water-soluble component of titanium oxide is preferably 0.2% by weight or less. 0.2 of water soluble component
When the content is higher than the weight%, the charge amount is low similarly to the conventional titanium oxide, and the charge amount does not become sufficiently high even if the surface treatment is performed. However, the amount of the water-soluble component is 0.2% by weight.
In the case where the following titanium oxide is used, the charge amount increases, and when the surface treatment is performed, a higher charge amount is maintained. The reasons may be as follows. Essentially, titanium oxide is completely insoluble in water and has no water-soluble components. However, it is inevitable that trace amounts of water-soluble components remain in the titanium oxide produced by the wet method from the production process. From the viewpoint of chargeability, it is presumed that this water-soluble component lowers the chargeability of titanium oxide. It has been conventionally considered that the charging property is affected by the environment of contact charging and the electric resistance of the material itself. In consideration of this point, it is presumed that the water-soluble component remaining in the titanium oxide powder becomes water-absorbing, easily attracts water, lowers its own resistance, and lowers the charge amount. . In other words, it is inferred that if the water-soluble component is removed or reduced, the resistance of the toner composition increases and a high charge amount is maintained.

The water-soluble components include K ⁺ , Na ⁺ , Li ⁺ , Mg contained in the conditions used in the production process and the flocculant.
²⁺ , PO ₄ ²⁻ , SO ₄ ²⁻ , Cl ^{− and the} like. The measurement of the water-soluble component is carried out by boiling 5 g of titanium dioxide with 250 ml of water, cooling and filtering, evaporating 100 ml of the filtrate obtained to dryness, and weighing the remaining amount. The details are described in JIS K5116-1973 titanium dioxide (pigment), and the amount of the water-soluble component of the present invention is in accordance with this JIS, and the above-mentioned remaining amount is represented by weight% based on the original titanium dioxide. It is.

As the treating agent used for the surface treatment of the titanium oxide fine particles, those which react with hydroxyl groups are used.
For example, a coupling agent such as a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconium coupling agent, or a silicone oil can be used. Among them, a silane coupling agent or a silicone oil represented by the following chemical formula is preferable. R _4-x Si (NCO) _x R _4-x Si (OR ₁ ) _x R _4-x SiCl _x (where x is an integer of 1 to 3, and R is 1 to 16 carbon atoms)
And OR ₁ represents an alkoxy group such as a methoxy group or an ethoxy group. Specifically, (CH ₃ ) ₂ Si (NCO) ₂ , CH ₃ S
i (NCO) ₃ , CH ₃ Si (OCH ₃ ) ₃ , C ₁₀ H ₂₁
Si (OCH ₃ ) ₃ , CF ₃ Si (OCH ₃ ) ₃ , CH
₃ Si (OC ₂ H ₅ ) _{3 and the} like, and those having x of 3 are preferable in terms of increasing the charge amount. For similar reasons,
R is preferably an alkyl group having 7 to 16 carbon atoms or a perfluoroalkyl group. In addition, as the silicone oil, dimethyl silicone, methyl phenyl silicone,
In addition to monomethyl silicone and the like, modified silicone oil can also be used.

When externally added to the full-color toner for developing an electrostatic image of the present invention, the titanium oxide fine particles having a water-soluble component content of 0.2% by weight or less are used in an amount of 0.5 to 0.5% based on the toner particles.
8% by weight, more preferably 0.5 to 5% by weight. Further, titanium oxide fine particles having an average particle diameter in the range of 5 to 100 nm are used. Other additives such as silica and alumina may be used together with titanium oxide.

The external additive can be attached to the surface of the toner particles by, for example, a high-speed mixer. Specifically, the toner particles and the external additive may be mixed using a Henschel mixer or a V-type blender. The full-color toner for developing an electrostatic image of the present invention may be used as a non-magnetic one-component developer using no carrier, or as a two-component developer using a carrier. However, in order to maximize the effects of the present invention, it is preferable to use it as a two-component developer.

When a carrier is used, the carrier is not particularly limited as long as it is a known carrier, and an iron powder carrier or the like can be used. However, in order to maximize the effects of the present invention, a surface-coated ferrite carrier, a magnetic powder-dispersed carrier, or the like is preferable. Further, the average particle size of the carrier is desirably in the range of 20 to 80 μm, and more preferably in the range of 30 to 60 μm.

As the resin that can be used for the surface coat, any known resin can be used.
Styrene / acrylic resin, polyester resin, polyurethane resin, epoxy resin, silicone resin,
Known resins such as polyamide resins can be used.

Next, the full-color image forming method of the present invention will be described with reference to the drawings. FIG. 1 is an image forming apparatus used in the full-color image forming method of the present invention,
The reflected light emitted from the illumination 1 to the color image of the original 2 is read by the color CCD 3 and is read by the image processing device 4.
Color separation into three colors of yellow, magenta and cyan,
As a signal to which image processing has been applied, a light signal is output from the semiconductor laser 5 in order for each color, and is exposed through the optical system 6 to the photoconductor 8 previously charged by the charger 7 so that the image portion has a low potential. An electrostatic latent image is formed. The developer of the color toner obtained by the above method is charged into a yellow developing device 9, a magenta developing device 10, and a cyan developing device 11, and a developing bias is applied.
The color toner is developed on the photoconductor 8 by electrostatic force. The developed toner is transferred one by one to the transfer body 13 electrostatically attracted to the transfer drum 15 by the electric field provided by the transfer corotron 14. This is repeated three times in the order of a yellow developing device, a magenta developing device, and a cyan developing device to obtain a color toner image in which three colors are superimposed on a transfer body. This is heated and fixed by the heating roll fixing device 16,
Obtain a full color image. When the black toner is used together with the color toner, the black toner is charged into the black developing device 12 and the operation is performed in the same manner as described above.

[0064]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to a production example of a binder resin, a production example of a surface-treated titanium oxide, a production example of a melt flushing pigment, and examples and comparative examples of the present invention. The invention is not limited to these examples. 1) Production Example of Binder Resin [Resin Production Example 1] Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 2.0 mol-n-dodecenyl succinic acid: 0.35 mol (7.5 mol%) The above-mentioned raw material compound is put into a glass 2 liter four-necked flask. , A stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer were set, and the mantle heater was set. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and a normal pressure reaction was performed at about 150 ° C. in the first half and a reduced pressure at 220 ° C. in the second half under a nitrogen stream while heating with a mantle heater. I let it. The degree of polymerization is ASTME
Tracking was performed from a softening point according to 28-51T, and when the softening point reached 115 ° C, the reaction was terminated. After the completion of the reaction, the resultant was gradually cooled to room temperature. Glass transition temperature Tg of the obtained resin
Was 64 ° C. (Hereinafter, referred to as “resin-1”)

[Resin Production Example 2] Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol Terephthalic acid: 2.0 mol n-Dodecenyl succinic acid: 0.46 mol (10 mol%) The above-mentioned starting compounds were reacted under the same conditions as in Resin Production Example 1; The reaction was terminated when the softening point reached 110 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 60 ° C.
Met. (Hereinafter, referred to as “resin-2”)

[Resin Production Example 3] Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 1.3 mol-n-dodecenyl succinic acid: 1.1 mol (23 mol%) The above-mentioned starting compounds were reacted under the same conditions as in Resin Production Example 1; The reaction was terminated when the softening point reached 105 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 57 ° C.
Met. (Hereinafter, referred to as “resin-3”)

[Resin Production Example 4] Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 1.8 mol-Isooctenyl succinic acid: 0.5 mol (10 mol%) The above-mentioned starting compounds are reacted under the same conditions as in Resin Production Example 1 to soften. The reaction was terminated when the point reached 115 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 62 ° C.
Met. (Hereinafter, referred to as “resin-4”)

[Resin Production Example 5] Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 1.8 mol-n-dodecylsuccinic acid: 0.5 mol (10 mol%) The above-mentioned starting compounds are reacted under the same conditions as in Resin Production Example 1. The reaction was terminated when the softening point reached 113 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 60 ° C.
Met. (Hereinafter, referred to as “resin-5”)

Comparative Example 1 Resin Production Example Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 2.0 mol-n-dodecenylsuccinic acid: 0.3 mol (6.5 mol%) The above-mentioned raw material compound is reacted under the same conditions as in Resin Production Example 1. The reaction was terminated when the softening point reached 115 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 65 ° C.
Met. (Hereinafter, referred to as “Comparative Resin-1”)

Comparative Example 2 Resin Production Example Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 1.1 mol-n-dodecenylsuccinic acid: 1.25 mol (26 mol%) The above-mentioned starting compounds were reacted under the same conditions as in Resin Production Example 1; The reaction was terminated when the softening point reached 100 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 53 ° C.
Met. (Hereinafter, referred to as “Comparative Resin-2”)

Comparative Example Resin Production Example 3 Polyoxyethylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane: 1.3 mol polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 1.0 mol-Terephthalic acid: 2.3 mol The above-mentioned starting compounds were reacted under the same conditions as in Resin Production Example 1, and the reaction was terminated when the softening point reached 120 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. Tg of the obtained resin is 63 ° C.
Met. (Hereinafter, referred to as “Comparative Resin-3”)

Comparative Example Resin Production Example 4 Polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 2.3 mol-Terephthalic acid: 1.7 mol-n-dodecenylsuccinic acid: 0.6 mol (13 mol%) The above-mentioned starting compounds are reacted under the same conditions as in Resin Production Example-1. The reaction was terminated when the softening point reached 110 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. The Tg of the obtained resin is 57
° C. (Hereinafter, referred to as “Comparative Resin-4”)

2) External additive Production example of surface-treated titanium oxide In the production of the following additives a to f, an average particle diameter of 15 nm produced by a sulfuric acid method except for additives d and e as wet titanium oxide. Rutile-type titanium oxide (MT-150A,
Teica Co., Ltd.). In addition, this titanium oxide is 0.1.
It contained 30% by weight of a water-soluble component.

[Additive a] Titanium oxide fine powder obtained by washing with a mixed solvent of methanol-water (95: 5) in which 1.0 g of methyltrimethoxysilane was dissolved to reduce the amount of water-soluble components to 0.11% by weight. 10 g of powder was added and ultrasonically dispersed. Then, after evaporating methanol and the like in the dispersion with an evaporator and drying, heat treatment was performed with a dryer set at 120 ° C., and crushed in a mortar to obtain titanium oxide surface-treated with methyltrimethoxysilane. .

[Additive b] Titanium oxide fine powder which was washed with water in a mixed solvent of methanol-water (95: 5) in which 2.0 g of decyltrimethoxysilane was dissolved to reduce the water-soluble component content to 0.08% by weight. 10 g was added and ultrasonically dispersed.
Thereafter, the same treatment as in the production of the additive a was performed to obtain a titanium oxide surface-treated with decyltrimethoxysilane.

[Additive c] Silicone oil (KF9
9, 10 g of fine powder of titanium oxide having a water-soluble component content of 0.13% by weight was added to toluene in which 2.0 g of 2.0 g was dissolved, followed by ultrasonic dispersion. Then, the toluene in the dispersion was evaporated by an evaporator and dried, and then heat-treated with a drier set at 140 ° C. and pulverized with a mortar to obtain titanium oxide surface-treated with silicone oil.

[Additive d] In a mixed solvent of methanol-water (95: 5) in which 1.5 g of decyltrimethoxysilane is dissolved, a wet method obtained by a hydrochloric acid method having a water-soluble component amount of 0.05% by weight or less is used. 10 g of fine powder of titanium oxide (TTO-55, manufactured by Ishihara Sangyo Co., Ltd.) was added, followed by ultrasonic dispersion. Thereafter, the same treatment as in the case of the additive a was performed to obtain titanium oxide surface-treated with decyltrimethoxysilane.

[Additive e] Rutile-type titanium oxide (MT-500B, manufactured by Teica) having an average particle size of 40 nm produced by a sulfuric acid method was used. The titanium oxide contained 0.30% by weight of a water-soluble component. Using this titanium oxide, without washing with water, the same treatment as in the case of the additive b was performed to obtain a titanium oxide surface-treated with decyltrimethoxysilane.

[Additive f] Titanium oxide fine powder (water-soluble component amount: 0.30% by weight) is not washed with water, but is treated under the same conditions as in the preparation of additive b, and surface-treated with decyltrimethoxysilane. Thus, titanium oxide was obtained.

[Additive g] Surface treatment of titanium oxide having an average particle diameter of 30 nm produced by a dry method in which titanium tetrachloride is vaporized and reacted with water with octyltrimethoxysilane (T805, manufactured by Nippon Aerosil Co., Ltd.) Was defined as additive g.

3) Production Example of Pigment Pigment Production Example 1 (Production of Cyan Melt Flushing Pigment) Cyan pigment (CI Pigment Blue 15: 3) having a water content of 30% by weight based on 100 parts of Resin-2 ) And melted and kneaded in a 3 liter pressure kneader to evaporate the water to obtain a cyan melt flushing pigment-a having a pigment content of 30% by weight. That is, 50 parts of Resin-2 was placed in a pressure kneader previously heated to 110 ° C., and 3 kg
Rotating the rotor at a peripheral speed of 20 rpm while applying pressure at a pressure of f / cm ²
m to melt the resin, then add 30 parts of the cyan pigment water-containing paste and knead for about 15 minutes, further add 30 parts of resin-2 and knead for about 15 minutes, and then add 20 parts of the cyan pigment water-containing paste. In addition, knead for 15 minutes.
2 was added and kneaded for about 15 minutes, and 12 parts of a water-containing paste for cyan pigment was added and kneaded for about 30 minutes to obtain cyan melt flushing pigment-a.

[Pigment Production Example 2] (Production of Cyan Melt Flushing Pigment) To 100 parts of Resin-2, 60 parts of a cyan pigment (CI Pigment Blue 15: 3) having a water content of 30% by weight was added. 3kgf / with a pressure kneader heated to about 100 ° C
20 min peripheral speed of the rotor under a pressure of cm ² 20
Rotate at cm / sec, melt and knead to obtain a pigment content of 30
% Of cyan melt flushing pigment-b.

Pigment Production Example 3 (Production of Magenta Melt Flushing Pigment) 62 parts of a magenta pigment (CI Pigment Red 57: 1) having a water content of 30% by weight was added to 100 parts of Resin-2. The magenta melt flushing pigment having a pigment content of 30% by weight was obtained in the same manner as in the processing procedure of Pigment Production Example 1, and melted and kneaded with a pressure kneader to evaporate water.

[Pigment Production Example 4] (Production of Yellow Melt Flushing Pigment) To 100 parts of Resin-2, 62 parts of a yellow pigment (CI Pigment Yellow 17) having a water content of 30% by weight was added, and pigment production was performed. In the same manner as in the treatment procedure of Example 1, the mixture was melted and kneaded with a pressure kneader to evaporate water, thereby obtaining a yellow melt flushing pigment having a pigment content of 30% by weight.

[Pigment Production Example 5] (Production of Comparative Cyan Pigment) Resin-2 was melted in a pressure kneader in which 70 parts of a resin were heated, and then a blue pigment (CI Pigment Blue 15: 3,
30 parts of DIC KET BLUE)
After the entire amount was added, the mixture was melt-kneaded while applying pressure, cooled, and then subjected to a coarse pulverization process to obtain a comparative cyan pigment.

Example 1 Resin-1 96 parts Carbon black (primary particle diameter: 48 nm) 4 parts The above components were melt-kneaded by a Banbury mixer, cooled, pulverized by a jet type pulverizer, and further classified by a classifier. The distribution was aligned. The particle size of the obtained toner is as follows: volume average diameter d50 = 7.2 μm, and volume particle size distribution d16 / d84 = 1.7.
(Measured with a Coulter counter).
The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Example 2 The procedure of Example 1 was repeated except that resin-2 was used in place of resin-1 of example 1.
A toner was prepared according to the method described in (1). The particle size of the obtained toner was such that the volume average particle diameter d50 was 7.4 μm and the volume particle size distribution was d16 / d84 = 1.7. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Example 3 The procedure of Example 1 was repeated except that resin-3 was used in place of resin-1 of example 1.
A toner was prepared according to the method described in (1). The particle size of the obtained toner was such that the volume average diameter d50 = 7.2 μm and the volume particle size distribution d16 / d84 = 1.6. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Example 4 Example 1 was repeated except that resin-4 was used in place of resin-1 of example 1.
A toner was prepared according to the method described in (1). The particle size of the obtained toner was such that the volume average diameter d50 = 7.3 μm and the volume particle size distribution d16 / d84 = 1.7. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Example 5 The procedure of Example 1 was repeated except that resin-5 was used in place of resin-1 of example 1.
A toner was prepared according to the method described in (1). The particle size of the obtained toner was such that the volume average particle diameter d50 was 6.8 μm and the volume particle size distribution was d16 / d84 = 1.7. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Comparative Example 1 A toner was produced in the same manner as in Example 1 except that Comparative Resin-1 was used in place of Resin-1 of Example 1. The particle size of the obtained toner was such that the volume average diameter d50 = 7.3 μm and the volume particle size distribution d16 / d84 = 1.6. The ratio of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner is 0%.
Met.

Comparative Example 2 A toner was produced in accordance with the method shown in Example 1, except that Comparative Resin-2 was used in place of Resin-1 of Example 1. The particle size of the obtained toner was such that the volume average diameter d50 = 7.3 μm and the volume particle size distribution d16 / d84 = 1.7. The ratio of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner is 0%.
Met.

Comparative Example 3 A toner was produced in the same manner as in Example 1 except that Comparative Resin-3 was used in place of Resin-1 of Example 1. The particle size of the obtained toner was such that the volume average diameter d50 = 7.0 μm and the volume particle size distribution d16 / d84 = 1.7. The ratio of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner is 0%.
Met.

Comparative Example 4 A toner was produced in the same manner as in Example 1 except that Comparative Resin-4 was used instead of Resin-1 of Example 1. The resulting toner particles had a volume average diameter d50 = 7.0 μm and a volume particle size distribution d16 / d84 = 1.7. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

(Evaluation of crease fixing strength) Silica fine powder (R812, manufactured by Nippon Aerosil Co., Ltd.) as an external additive was added to the above toner at 0.6 part with respect to 100 parts of the toner.
Additive a was added in an amount of 0.8 part based on 100 parts of the toner and mixed with a Henschel mixer. 8 parts of the obtained externally added toner is mixed with a ferrite carrier coated with a styrene-methyl methacrylate polymer to prepare a developer, and an unfixed solid sample is prepared using a digital full-color remodeling machine (Acolor, manufactured by Fuji Xerox Co., Ltd.). did. In that case, the weight per unit area of the toner in the solid sample was adjusted to be 1.1 to 1.2 mg / cm ² . The paper used was Acolor paper.

The fixing method is as follows. The fixing device for Acolor is removed, and an off-line fixing device modified so that the temperature of the heating roll can be adjusted is used, and the gloss after fixing is about 40% (75%).
The temperature of the heating roll was adjusted to −75 ° measurement / 3GM-260TYPE, manufactured by Murakami Color Research Laboratory, and a fixed image was obtained. After gently bending the obtained fixed sample in half, 5
The sample was rolled over a bent portion of the sample at a constant speed with a roll (outer diameter: 60 mm) having a load of about 00 g, and the fold of the fixed image was rubbed lightly with a rag to observe the image missing state. The evaluation was performed according to the following criteria. ：: The fold is formed, but the image is not missing or small. Δ: Small white folds are intermittently observed. ×: White band-like fold is clearly recognized.

(Evaluation of Powder Characteristics) 2 g of the toner was placed on a test sieve having an opening of 75 μm, and the state of the powder was observed while vibrating the suction sieve from the lower part of the test sieve. The evaluation was performed according to the following criteria. ：: Good fluidity, light vibration, and all of the toner is sucked. Δ: There is cohesion, but no lumps are generated, and all of the toner is sucked by vibration. ×: Strong cohesiveness, lumps occur when vibrating, and all toner is not sucked unless vibrating.

(Evaluation of Toner Manufacturability) Pulverizability (fixed pulverizing pressure): Amount of pulverization per unit time Ratio based on pulverizability of toner of Comparative Example 2 × Classification yield ○: 1.3 times Δ: 1.1 times or more and less than 1.3 times ×: less than 1.1 times

(Evaluation of Toner Storage Property) 10 g of an unexternally added toner was weighed and placed in a 50 cc beaker.
It was left for 20 hours in a constant temperature / humidity constant temperature chamber of 90 ° C./90% RH. Thereafter, the mixture was left at room temperature for 5 hours, gradually cooled, and the state of aggregation was observed using a spatula. The evaluation was performed according to the following criteria. ：: No blocking was observed, and the powder was almost untreated. Δ: Slight blocking occurs, but can be easily broken by pressing with a spatula. No fusion between the powders is observed. X: Strong blocking occurred, and it was not crushed into a powder even when pressed with a spatula. Fusion between powders is observed.

(Evaluation results)

[Table 1]

Example 6 In this example, the effect of adding an external additive to a developer using a toner composition to which an external additive was added was evaluated. [Toner Composition 1] 2.0 parts of Additive a was added to 100 parts of the toner of Example 2, and mixed with a Henschel mixer.
A toner composition 1 was obtained. [Toner Composition 2] 2.0 parts of Additive b was added to 100 parts of the toner of Example 2, and mixed with a Henschel mixer.
Thus, a toner composition 2 was obtained. [Toner Composition 3] 2.0 parts of Additive c was added to 100 parts of the toner of Example 2, and mixed with a Henschel mixer.
Thus, a toner composition 3 was obtained. [Toner Composition 4] 4.0 parts of Additive d was added to 100 parts of the toner of Example 2, and mixed with a Henschel mixer.
Thus, a toner composition 4 was obtained. [Toner Composition 5] To 100 parts of the toner of Example 2, 2.0 parts of additive e was added, and mixed with a Henschel mixer.
Thus, a toner composition 5 was obtained. [Toner Composition 6] To 100 parts of the toner of Example 2, 2.0 parts of Additive f was added, and mixed with a Henschel mixer.
Thus, a toner composition 6 was obtained. [Toner Composition 7] 2.0 parts of additive g was added to 100 parts of the toner of Example 2, and mixed with a Henschel mixer,
Thus, a toner composition 7 was obtained. [Toner Composition 8] Hydrophobic silica part powder (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the toner of Example 2.
0 parts were added and mixed with a Henschel mixer to obtain a toner composition 8.

[Production of developer] As a carrier, a ferrite carrier coated with a styrene-methyl methacrylate copolymer and having a particle diameter of about 50 μm was used.
8 parts of each of the above toner compositions 1 to 8 were added to 00 parts. Then, mix with a tumbler mixer for 1 minute,
The obtained developers 1 to 8 were subjected to a copy test described below.
Regarding these developers 1 to 8, electrophotographic copying machines (A-
color 630 (manufactured by Fuji Xerox Co., Ltd.), and the charge amount, charge distribution and reverse polarity toner amount under the environment of high temperature and high humidity (30 ° C., 85% RH) and low temperature and low humidity (10 ° C., 15% RH). It was measured. Further, 1.7 parts of toner particles were mixed with 100 parts of each developer, and the above values after 5 seconds were measured to evaluate the admix property of the toner. The charge amount is CSG (charge
This is a value obtained by image analysis using a spectrograph method, and the charge distribution is the 20% charge amount Q (20) of the cumulative integration of the charge distribution.
And the difference between the 80% charge amount Q (80) and the 50% charge amount Q (5
0). That is, charge distribution = {Q (80) −Q (20)} / Q (50)

Tables 2 and 3 show the measurement results after mixing each of the toner compositions and the carrier for 1 minute and the evaluation results of the toner admixability.

[Table 2]

[0104]

[Table 3]

In the present invention, when the toner compositions 1 to 5 are used, the toner compositions can be used under low temperature, low humidity and high temperature, high humidity.
The charge amount hardly changed, and the distribution of the charge amount was very sharp. A copy test of 10,000 sheets was performed using these toner compositions. As a result, slight in-machine contamination was observed in the toner composition 3, but there was no change in image density or background contamination due to environmental fluctuations. And a stable image was obtained. On the other hand, the toner composition 6 which had been subjected to a surface treatment and to which titanium oxide having a water-soluble component amount of 0.30% by weight was externally added had a low charge amount, and some background staining was observed. Further, in the toner composition 8 to which hydrophobic silica was externally added, the amount of charge varied greatly due to environmental changes, the charge amount distribution was wide, and it took a long time to charge the toner when adding toner.

In the toner composition 7 obtained by externally adding a titanium oxide produced by a dry method and subjected to a surface treatment, the change in the environment of the charge amount is small, but the copy test is about 3,000 sheets.
Some soil and cloud were seen depending on the environment.

Example 7 After 16.7 parts of cyan melt flushing pigment-a and 83.7 parts of Resin-2 were preliminarily mixed, they were melt-kneaded with a Banbury mixer, cooled, and then pulverized with a jet mill. , Classified and a volume average particle diameter d of 4% by weight pigment content
A cyan toner having a particle size distribution d16 / d84 = 1.6 was obtained. The ratio of particles having an average dispersed pigment equivalent diameter of 0.3 μm or more in the toner was 0%. Additive b as an external additive to 100 parts of the cyan toner
Was added and 3.0 parts of additive e were added and mixed with a Henschel mixer to obtain an externally added cyan toner. 10 parts of this externally added cyan toner was mixed with 100 parts of a ferrite carrier coated with a styrene methyl methacrylate polymer to prepare a cyan developer.

Comparative Example 5 16.7 parts of the comparative cyan pigment and 83.3 parts of Resin-2 were preliminarily mixed and then treated under the same conditions as in Example 7.
A volume average particle diameter d50 of 5.7 μm with a pigment content of 4% by weight,
A cyan toner having a volume particle size distribution d16 / d84 = 1.6 was obtained. An external additive was added to this cyan toner in the same manner as in Example 7 to obtain an externally added cyan toner, and further mixed with a carrier in the same manner as in Example 7 to prepare a cyan developer. The ratio of particles having an equivalent circular diameter of 0.3 μm or more in the average dispersed pigment in the toner was 3%.

Comparative Example 6 Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (molecular weight 300) 1.3 mol Polyoxypropylene (2.2) -2,2 -Bis (4-hydroxyphenyl) propane (molecular weight 326) 0.9 mol-Terephthalic acid (molecular weight 166) 1.1 mol-Fumaric acid (molecular weight 116) 1.1 mol Was reacted. The obtained polyester resin had a midpoint glass transition temperature Tmg of 58 ° C., a softening point of 100 ° C., and a weight average molecular weight of 8,500.

100 parts of this polyester resin, 5 parts of a cyan pigment (CI Pigment Blue 15: 3), and 5 parts of a graft-modified polyolefin polymerized in a ratio of 8 parts of styrene / 2 parts of acrylic acid / 100 parts of polyethylene, After pre-mixing, the mixture is melt-kneaded with a Banbury mixer, then cooled and pulverized by a jet mill, classified and classified to have a pigment-containing 4% by weight volume average diameter d50 = 5.3 μm and a volume particle size distribution d16 / d84 = 1. Thus, a cyan toner of No. 6 was obtained. The ratio of particles having an equivalent circular diameter of 0.3 μm or more in the average dispersed pigment in the toner was 7%. This cyan toner 100
Parts by weight of additive b as an external additive and additive e
Was added and mixed with a Henschel mixer to obtain an externally added cyan toner. 10 parts of this externally added cyan toner
A cyan developer was prepared by mixing with 100 parts of a 50 μm particle size ferrite carrier coated with a styrene methyl methacrylate polymer.

(OHP Copy Sample Test) Embodiment 7
A solid digital original was copied from a cyan developer of Comparative Examples 5 and 6 using an Acolor digital full-color remodeling machine manufactured by Fuji Xerox Co., Ltd. to create an OHP copy sample. Then, they were projected with an OHP, and the transparency and vividness of both were compared. As a result, the cyan developer of Example 7 had high transparency and high color clarity. on the other hand,
The cyan developers of Comparative Examples 5 and 6 had cloudy colors,
The definition was also inferior to the cyan developer of Example 7.

Example 8 14 parts of magenta melt flushing pigment (Preparation Example 3) and 86 parts of Resin-2 were premixed and then treated under the same conditions as in Example 7 to obtain a pigment content of 4% by weight. And the volume average particle size d50 = 5.3 μm and the volume particle size distribution d16 / d84 = 1.
Thus, magenta toner No. 6 was obtained. An external additive was added to this magenta toner in the same manner as in Example 7 to obtain an externally added magenta toner, and further mixed with a carrier in the same manner as in Example 7 to prepare a magenta developer. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Example 9 Yellow melt flushing pigment (Production Example 4)
After premixing 7 parts and 83.3 parts of resin-2, the mixture was treated under the same conditions as in Example 7 to obtain a pigment content of 4% by weight.
Volume average particle size d50 = 5.4 μm, volume particle size distribution d16 / d
84 = 1.6 yellow toner was obtained. An external additive was added to this yellow toner in the same manner as in Example 7 to obtain an externally added yellow toner, and further mixed with a carrier in the same manner as in Example 7 to prepare a yellow developer. The proportion of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%.

Example 10 Carbon black (primary particle diameter 48 nm, manufactured by Mitsubishi Kasei
25) 4 parts and 96 parts of Resin-2 were melt-kneaded with a Banbury mixer, cooled, pulverized with a jet-type fine pulverizer, and the particle size distribution was further adjusted with a classifier to obtain a volume average particle diameter d50.
= 7.2 μm and a black toner having a volume particle size distribution d16 / d84 = 1.7. To 100 parts of this black toner, 1.4 parts of additive b and 2 parts of additive e were added,
The mixture was mixed with a Henschel mixer to obtain an externally added black toner. 10 parts of this externally added black toner was coated with a styrene methyl methacrylate polymer and ferrite carrier 1
The resulting mixture was mixed with 00 parts to prepare a black developer. Example 11 Example 10 (Primary particle diameter of carbon black: 48 nm)
Is placed in a Fuji Xerox Acolor digital full-color machine, and in a monochrome black mode, a halftone dot of 10% to 8%
Copy samples were made using gray solid manuscripts up to 0%.

Comparative Example 7 Four parts of carbon black (primary particle diameter 25 nm, manufactured by Cabot Corp., Mogar L) and 96 parts of Resin-1 were melt-kneaded with a Banbury mixer, cooled, and ground with a jet mill. The particle size distribution is further adjusted by a classifier, and the volume average particle size d50 = 7.3 μm and the volume particle size distribution d16 / d84 = 1.
6 was obtained. An external additive was added to this black toner in the same manner as in Example 10 to obtain an externally added black toner, and further mixed with a carrier in the same manner as in Example 10 to prepare a black developer. This black developer was placed in an Acolor digital full-color machine manufactured by Fuji Xerox Co., Ltd., and a copy sample was prepared in a monochromatic black mode using a gray solid original having a dot value of 10% to 80%.

(Evaluation of Color Tone and Gray Balance) The copy sample of Comparative Example 7 had a strong reddish-brown color tone under A light source and a poor gray balance as compared with Example 11, but the copy sample of Example 11 No color shift was observed under the A light source and the C light source, and a color with a well-balanced gray balance was obtained, which was very refreshing.

(Comparative evaluation with color toner kit developer)
For full-color development, the color toner developers of Examples 7, 8, 9, and 10 were used. These combinations were used as the developer for the color toner kit of the example. The above color toner kit developer was placed in Acolor (manufactured by Fuji Xerox Co., Ltd.), and a cyan color toner image, a magenta color toner image, a yellow color toner image and a black toner image were superimposed to form a full color image, and the image quality stability was evaluated. . A chart with pictures / characters was used as the chart. Table 4 shows the results.

A color toner kit developer for comparison was prepared as follows, and the image quality stability was evaluated in the same manner as described above. Table 4 shows the results. [Comparative Cyan Toner] A cyan melt flushing pigment was obtained under the same conditions except that Resin-2 of Pigment Production Example 1 was replaced with Comparative Resin-3. Using the obtained pigment and the comparative resin-3, in the same manner as in Example 7, the volume average particle diameter d50 of the pigment content of 4% by weight = 5.3 µm, and the volume particle size distribution d16 / d84 =
1.6 cyan toner was obtained. The ratio of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner is 0%.
Met. [Comparative Magenta Toner] A magenta melt flushing pigment was obtained under the same conditions except that Resin-2 of Pigment Production Example 3 was replaced with Comparative Resin-3. Using the obtained pigment and comparative resin-3, in the same manner as in Example 8, the pigment content was 4% by weight, the volume average particle size d50 = 5.2 μm, and the volume particle size distribution d16 / d84 =
A magenta toner of 1.6 was obtained. The ratio of particles having a circular equivalent diameter of 0.3 μm or more of the average dispersed pigment in the toner is 0%.
%Met.

[Comparative Yellow Toner] A yellow melt flushing pigment was obtained under the same conditions except that Resin-2 of Pigment Production Example 4 was replaced with Comparative Resin-3. The pigment content of 4 was obtained in the same manner as in Example 9 using the obtained pigment and Comparative Resin-3.
By weight, a yellow toner having a volume average particle size d50 = 5.3 µm and a volume particle size distribution d16 / d84 = 1.6 was obtained. The ratio of particles having a circular equivalent diameter of 0.3 μm or more in the average dispersed pigment in the toner was 0%. [Comparative Black Toner] The toner of Comparative Example 3 was used.

To 100 parts of each of the cyan, magenta and yellow toners, 2 parts of additive b and 3.0 parts of additive e were added as external additives, and mixed with a Henschel mixer. , Magenta and yellow externally added toners were obtained. Further, 1.4 parts of additive b and 2 parts of additive e were added to 100 parts of the black toner, and mixed with a Henschel mixer to obtain an externally added black toner. 10 parts of each of these four color externally added toners was mixed with 100 parts of a 50 μm ferrite carrier coated with a styrene-methyl methacrylate copolymer to prepare a comparative color toner kit developer.

[0121]

[Table 4] ：: No fog on the background. Image quality is stable. Δ: Fog is slightly observed in the background, but there is no practical problem. ×: The fog in the background part is severe. The image quality is partially blurred.

[0122]

According to the present invention, the color toner and the black toner for developing an electrostatic image of the present invention are excellent in transparency, color reproducibility, sharpness, reproducibility of black gradation and color tone balance by adopting the above constitution. Thus, a full-color copy image having a high fixing strength can be formed. Further, the developer using the color toner and the black toner for developing an electrostatic image of the present invention has excellent environmental stability, is suitable for use in a heat roller fixing method, and stabilizes a full-color image having good image quality. Can be formed. In addition, the color toner for developing an electrostatic image of the present invention is excellent in pulverizability and classifying property, and has good powder fluidity, so that the productivity of the toner can be greatly improved. Further, by externally adding the above-mentioned specific titanium oxide, the environmental charging stability of the toner is improved, and a stable full-color copy image can be provided for a long period of time.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an image forming apparatus used in a full-color image forming method of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Illumination, 2 ... Original, 3 ... CCD, 4 ... Image processing device,
5 semiconductor laser, 6 optical system, 7 charger, 8 photoconductor, 9 yellow developing device, 10 magenta developing device, 1
1: cyan developing device, 12: black developing device, 13: transfer body,
14: transfer corotron, 15: transfer drum, 16: heating roll fixing device.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Torikoshi 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd. (56) References JP-A-6-250444 (JP, A) JP-A-63-68853 ( JP, A) JP-A-2-190866 (JP, A) JP-A-2-208241 (JP, A) JP-A-6-148935 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , (DB name) G03G 9/09 G03G 9/087 G03G 9/08 G03G 15/01

Claims (12)

(57) [Claims] 1. A color toner for developing an electrostatic image, comprising a binder resin and a colorant, wherein the binder resin comprises:
An ethoxylated bisphenol type diol and a propoxylated bisphenol type diol, and an aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component, and further an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or a A polyester resin containing at least one selected from acid anhydrides or esters thereof in an amount of 7 to 25 mol% of the total monomer amount, wherein a colorant is prepared from a water-containing paste of an organic pigment and the polyester resin. A color toner for developing an electrostatic image, characterized in that the toner is a flushing pigment. 2. The color toner for developing electrostatic images according to claim 1, wherein the binder resin contains 0.1% or less of pigment particles having an equivalent circular diameter of 0.3 μm or more. 3. The color toner for developing an electrostatic image according to claim 1, further comprising an external additive. 4. The color toner for developing an electrostatic image according to claim 3, wherein the external additive is titanium oxide particles produced by a wet method. 5. The static external additive according to claim 4, wherein the external additive is titanium oxide particles produced by a wet method, and the amount of the water-soluble component is 0.2% by weight or less. Color toner for developing charge images. 6. The color toner for developing an electrostatic image according to claim 4, wherein the external additive is surface-treated with a surface treating agent. 7. The color toner for developing an electrostatic image according to claim 6, wherein a coupling agent or silicone oil is used as the surface treatment agent. 8. An organic pigment, an ethoxylated bisphenol-type diol and a propoxylated bisphenol-type diol, an aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component, and an alkyl succinic acid or an acid anhydride thereof. Or a polyester resin containing 7 to 25 mol% of at least one selected from an ester thereof and an alkenyl succinic acid or an acid anhydride thereof or an ester thereof in a heating and pressure type kneader. An electrostatic charge image, comprising: a step of preparing a flushing pigment by kneading, a step of melting and kneading the flushing pigment and the polyester resin, and a step of pulverizing and classifying the formed melt-kneaded product. A method for producing a color toner for development. 9. The treatment in a heating / pressing kneader is performed by
9. The method for producing a color toner for developing an electrostatic image according to claim 8, wherein the method is performed at a temperature of 00 to 150 [deg.] C. 10. A color toner for developing an electrostatic image, comprising a binder resin and a black colorant, wherein the binder resin comprises an ethoxylated bisphenol type diol and a propoxylated bisphenol type diol, and an aromatic dicarboxylic acid or a dicarboxylic acid thereof. An acid anhydride or an ester thereof as a main monomer component; and at least one selected from an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or an acid anhydride or an ester thereof in a total monomer amount of 7%. A black toner for developing an electrostatic image, wherein the black colorant is a carbon black having a primary particle diameter of 30 nm or more and 50 nm or less. 11. A full-color image forming method for developing an electrostatic charge image using a color toner to form at least a cyan color toner image, a magenta color toner image, and a yellow color toner image in a superimposed manner. Ethoxylated bisphenol type diol and propoxylated bisphenol type diol,
An aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component, and at least one selected from an alkyl succinic acid or an acid anhydride or an ester thereof and an alkenyl succinic acid or an acid anhydride or an ester thereof; Contains a polyester resin containing 7 to 25 mol% of the total monomer amount, and contains, as a colorant, a water-containing paste of an organic pigment and a flushing pigment prepared from the polyester resin. A full-color image forming method. 12. A full-color image forming method for developing an electrostatic image using a color toner and a black toner to form a cyan color toner image, a magenta color toner image, a yellow color toner image, and a black toner image in a superimposed manner. The color toner, as a binder resin, an ethoxylated bisphenol type diol and a propoxylated bisphenol type diol, and an aromatic dicarboxylic acid or an acid anhydride or an ester thereof as a main monomer component,
And a polyester resin containing at least one selected from alkyl succinic acid or acid anhydride or ester thereof and alkenyl succinic acid or acid anhydride or ester thereof in an amount of 7 to 25 mol% of the total monomer amount. And a flushing pigment prepared from a water-containing paste of an organic pigment and the polyester resin as a colorant, and the black toner contains, as a binder resin, an ethoxylated bisphenol-type diol and a propoxylated bisphenol. Type diol and an aromatic dicarboxylic acid as a main monomer component,
And a black colorant containing a polyester resin containing at least one selected from alkyl succinic acid or an acid anhydride thereof and alkenyl succinic acid or an acid anhydride thereof in an amount of 7 to 25 mol% of the total monomer amount. A carbon black having a primary particle diameter of 30 nm or more and 50 nm or less.