JP2000010350A - Electrophotographic carrier, electrophotographic developer and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method capable of forming a fog-free high-quality image by providing a CMB developing carrier capable of eliminating an image defect by a brush mark and carrier-over being a weak point of the CMB developing carrier, having stable charging imparting performance to a toner and capable of restraining environmental dependency. SOLUTION: In a conductive magnetic brush developing electrophotographic carrier having a resin-covered layer on a core material, the electrophotographic carrier is constituted in such a way that the resin-covered layer has resin containing a monomer having an amino group in a range of 0.5 to 2 mole % and conductive powder having specific resistance of 100 to 106 Ωcm and the carrier falls within a range where of dynamic electric resistance under an electric field of 104 V/cm is 100 to 108 Ωcm in a magnetic brush state, an electrophotographic developer is composed of a toner using a polyester resin as a binding resin and the carrier, and an image forming method uses the developer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic carrier and a developing method for developing an electrostatic latent image formed by an electrophotographic method, an electrostatic recording method or the like by a conductive magnetic brush (CMB) developing method. And an image forming method using the developer.

[0002]

2. Description of the Related Art Methods of visualizing image information via an electrostatic image such as electrophotography are currently used in various fields.
In the electrophotographic method, an electrostatic latent image is formed on a photoreceptor in a charging and exposing step, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing step. The developer used here includes a two-component developer composed of a toner and a carrier, and a one-component developer used alone such as a magnetic toner. In a two-component developer, the carrier is used for stirring and transporting the developer. ,
It is widely used at present because it shares functions such as charging and separates functions as a developer, so that it has good controllability.

Further, as a developing method, a
A magnetic brush method using a magnetic roll as a developer carrying carrier has been mainly used at present.
In the two-component magnetic brush development, a conductive magnetic brush (CMB) developing method using a conductive carrier and an insulating magnetic brush (IMB) developing method using an insulating carrier are known. Among these, in CMB development, charge is injected from a development roll due to low carrier resistance, and the carrier near the photoreceptor acts as a development electrode to increase the effective development electric field, so that toner transfer is ensured. Performed and has excellent reproducibility of solid images. On the other hand, there is a problem in that image defects such as a white line called a brush mark and a carrier called a carrier over which are transferred to a photosensitive member, which are caused by charge injection from a developing roll, are likely to occur.

[0004] In recent years, colorization has rapidly progressed, and the required level of image quality has been increasing more and more. The solid image is particularly important in this color image quality, and in that respect, the CMB developing method is more suitable than the IMB developing method. Therefore, it is strongly desired to further improve the performance of the CMB developing carrier having the stability and durability of the image output.

In order to enhance the durability of the CMB developing carrier, a method of using a resin-dispersed carrier having a small specific gravity of a magnetic carrier in order to reduce the stress between the carrier and toner, In order to prevent contamination, a resin-coated carrier using a low surface energy material or the like has been proposed.

[0006] On the other hand, there are various characteristics required for a resin-coated carrier.
It is necessary to maintain the chargeability for a long time. It is particularly important that the characteristics required for this purpose include impact resistance, abrasion resistance, and that the chargeability of the toner does not change even when the environment such as humidity and temperature changes. Has been proposed.

It is known to use a resin containing an amino group as a coating resin in order to impart a negative charge to the toner. Specifically, a method of using a copolymer of a nitrogen-containing alkyl (meth) acrylate and a vinyl monomer or a copolymer of a fluorinated alkyl (meth) acrylate and a vinyl monomer has been proposed. (Japanese Patent Laid-Open No. 64-35)
562, JP-A-2-24670). However, when a large amount of an amino group is contained, as in the above-mentioned amino group-containing resin, the difference in charging characteristics under low-temperature and low-humidity conditions and under high-temperature and high-humidity conditions increases, and the environmental dependence of developing characteristics increases, thereby stabilizing the stability. It is difficult to obtain image quality.

Incidentally, the carrier for CMB development is designed in a place where the electric resistance of the coating resin layer is low. It is generally known that, in a coat carrier, the electric resistance is adjusted by dispersing a conductive powder in a coating resin layer. As the conductive powder, carbon black, metal powder, metal oxide powder and the like are used. Among them, carbon black is inexpensive and widely used because the electric resistance can be adjusted with a small amount of addition.However, when the dispersion in the coating resin layer fluctuates, the electric resistance is easily changed and the production stability is reduced. Chip.

Further, if the carbon black resin coating layer of the carrier is mixed in a developing machine and peeled off by impact, it is developed not only in the image area but also in the non-image area together with the toner at the time of development, and the image quality deteriorates. It becomes a factor. In particular, this is an important problem when outputting a color image. Further, since the carbon black-containing resin coating layer has a low electric resistance, particularly in the case of the CMB developing method, the bias re-coating is performed.
This tends to cause image defects such as brush marks.

On the other hand, in order to reduce the resistance of the resin coating layer of the carrier by using metal oxide powder, it is necessary to mix a large amount of metal oxide powder unlike carbon black.
However, the charge-imparting ability of the metal oxide powder is strong, and it is difficult to adjust the charge of the toner.

As the binder resin for color toners, styrene acrylic resin, polyester resin, hybrid resin of styrene acrylic and polyester resin, epoxy resin and the like have been mainly used. Environmental load, negative charging characteristics, performance with heat fixing method,
At present, polyester resins are mainly used from the viewpoint of controlling the molecular weight.

As a colorant for the color toner, an organic pigment is used from the viewpoints of light fastness, color transfer (transfer fastness), chargeability, heat stability and the like. However, commercially available organic pigments in the form of dry powder are difficult to finely disperse in a binder resin and tend to form aggregates. If there is a large amount of pigment aggregates in the toner, the image will have a reduced saturation, narrow the color reproduction space by mixing with other colors, and it will be difficult to reproduce a color image with vivid transparency. Become.

In order to improve the dispersion of these pigments, a commercially available organic pigment is heated and melt-mixed with a toner binder resin at a concentration higher than the pigment concentration usually used for toner, and then a processed pigment is produced. A method has been proposed in which the processed pigment is diluted with a binder resin so as to have an optimum pigment concentration in the toner and melt-mixed to reduce the dispersion unit of the organic pigment in the toner. JP-A-62-280755,
JP-A-3-269543)

As another method for reducing the dispersion unit of the organic pigment in the toner, the organic pigment precipitated in the solution in the pigmentation step is washed with water, concentrated, and then mixed with an organic solvent in which the resin is dissolved by heating. And, removing the water and the organic solvent, to produce a resin composition in which the organic pigment is finely dispersed at a relatively high concentration,
A method for obtaining a toner by heating, melting, kneading, and pulverizing the resin with a binder resin has been proposed (Japanese Patent Application Laid-Open No. 62-127847). The toner obtained by this method has considerably better dispersibility in light transmittance and color reproducibility than the above-mentioned processed pigment. However, when an organic solvent is used, if the solvent remains in the binder resin, an unpleasant odor is generated when the toner is fixed by toner, and the load on the environment is undesirably increased.

In the conventional method for producing an electrophotographic toner by melt-kneading, pulverizing and classifying, fine powder and coarse powder discharged in the classification step are reused. As one of them, it has been proposed to incorporate them into a melt-kneading process.

On the other hand, with the recent improvement in the quality of color images, the average particle size of color toners is also decreasing.
However, as the diameter of the toner decreases, the cohesive force of the toner powder increases and the fluidity deteriorates, which makes it difficult to automate the production of the toner and improve the productivity. In particular. Toner
This is a problem when a polyester resin having a high cohesive energy is used as the binder resin.

On the other hand, with the spread of digital full-color copying machines and printers, there has been a growing demand for stable copy image quality, high image quality, and low cost per copy. For the purpose of high quality and high reproducibility of color copy,
3738 and JP-A-6-75430 propose to use a small-diameter color toner. However, as the diameter of the toner becomes smaller, the development, transfer, and cleaning characteristics deteriorate, the stability and maintainability of the copy image deteriorate, and the frictional charging characteristics with the carrier and the environmental charging characteristics may deteriorate. There is.

As an improvement measure, an external additive externally added to the toner has been devised. The present inventors have disclosed in JP-A-4-333738 that the particle size is from 20 to
A method of externally adding 80 nm inorganic or organic spherical fine particles was proposed. Also, in Japanese Patent Application Laid-Open No. 6-75430, 0.1 is used.
A method of externally adding titanium oxide of 01 to 0.2 μm was proposed. However, even if these external addition methods are employed alone, they have not yet sufficiently responded to long-term high image quality and stable image quality.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned various problems in a carrier for CMB development. An object of the present invention is to provide a photographic carrier and a developer, and an image forming method.

(I) Eliminating image defects due to brush marks and carrier over, which are disadvantages of the CMB developing method, to provide high quality images. (ii) To provide a carrier having a stable charge-imparting property to a toner and suppressing environmental dependency. (iii) It exhibits excellent durability when used continuously and repeatedly, and can stably provide high-quality images. (iv) Toner having excellent development characteristics capable of obtaining high quality image with sufficient image density, bright and clear, and high resolution without fogging on the ground.

(V) Toner which is excellent in powder fluidity and non-agglomeration, and has good replenishment and storage stability can be provided. (vi) In particular, it must be effective for manufacturing small-diameter toners that can be applied to digital copiers, printers, and the like. (vii) In the heat fixing method, the color developability of the toner image and the color reproducibility are excellent. (viii) When forming a color image using each toner of cyan, magenta, yellow and black, transparency,
A color image having excellent color reproducibility and color clarity can be formed.

[0022]

The present invention has succeeded in solving the above-mentioned problems by adopting the following constitution. (1) An electrophotographic carrier for developing a conductive magnetic brush having a resin coating layer on a core material, wherein the resin coating layer contains a monomer having an amino group in a range of 0.5 to 2 mol%. And a conductive powder having a specific resistance of 10 ⁰ to 10 ⁶ Ωcm, and the carrier has a dynamic electric resistance of 10 ⁰ to 10 ⁴ V / cm in an electric field of 10 ⁴ V / cm in the state of a magnetic brush. An electrophotographic carrier characterized by being in the range of 10 ⁸ Ωcm.

(2) The carrier for electrophotography according to (1), wherein a metal oxide powder is blended in the resin coating layer as the conductive powder in a range of 30 to 85% by weight. (3) The carrier for electrophotography according to (1) or (2), wherein the thickness of the resin coating layer is in the range of 0.3 to 5.0 μm.

(4) The average particle diameter of the carrier is 10 to 8
The carrier for electrophotography according to any one of the above (1) to (3), which is in a range of 0 μm. (5) the dynamic resistance value of the core material is characterized in that it is a ferrite in the range of ^{10 -5 ~10 2 Ωcm (1)} ~ (4)
The electrophotographic carrier according to any one of the above items.

(6) For electrophotography for developing a conductive magnetic brush, comprising the electrophotographic carrier according to any one of the above (1) to (5), and a toner containing a binder resin and a colorant. An electrophotographic developer, wherein the developer contains a polyester resin as the toner binder resin. (7) The polyester resin is a polyoxyalkylene bisphenol type diol, particularly preferably a polyoxyethylene bisphenol type diol and / or a polyoxypropylene bisphenol type diol, and an aromatic dicarboxylic acid, an acid anhydride thereof, or an ester thereof. One or more selected from the group consisting of an alkyl succinic acid, an acid anhydride thereof, an ester thereof, and an alkenyl succinic acid, an acid anhydride thereof, an ester thereof;
The electrophotographic developer according to the above (6), comprising at least one kind of succinic acid derivative as a monomer.

(8) The developer for electrophotography according to (7), wherein the polyester resin contains the succinic acid derivative in a range of 2 to 25 mol%. (9) The polyester resin further comprises one or more monomers selected from tri- or higher-valent polycarboxylic acids, acid anhydrides, esters thereof, and tri- or higher-valent polyhydric alcohols. The developer for electrophotography according to the above (7) or (8), which is contained in an amount of at most mol%.

(10) The toner according to (6) to (9), wherein the toner is a color toner, and the polyester resin has an acid value of 20 mgKOH / g or less and a hydroxyl value of 30 mgKOH / g or less. The electrophotographic developer according to any one of the above. (11) The glass transition temperature of the polyester resin is 60 ° C. or more, and the melt viscosity of the polyester resin is 10
The developer for electrophotography according to any one of (6) to (10), wherein the temperature at which the pressure becomes 00 Pas is in the range of 115 to 150 ° C.

(12) The color toner is composed of cyan, magenta, yellow and black, and the coloring material contained in the toner is Pigmentable 15: 3 as a cyan coloring material and pigment as a magenta coloring material. Red 122, Pigment Red 57-1, Yellow-Pigment Yellow 180 as coloring material
185, 17, and a color material selected from carbon black as the black color material.
(6) The electrophotographic developer according to any one of (1) to (11). (13) The carbon black has a primary particle size of 30 to 50 n.
m, wherein the developer is in the range of m. (14) The electrophotographic developer according to any one of the above (11) to (13), wherein the color toner has a volume average diameter in a range of 3 to 9 μm.

(15) The toner as described in any one of (6) to (14) above, wherein the toner contains, as an external additive, silicon oxide fine particles or titanium compound fine particles subjected to hydrophobic treatment. Electrophotographic developer. (16) The developer for electrophotography according to any one of (6) to (15), wherein the toner is blended in a range of 3 to 8% by weight.

(17) a step of forming an electrostatic latent image on the latent image carrier, a step of developing the electrostatic latent image by a conductive magnetic brush developing method using a developer, and transferring the developed toner image A fixing step of heating and fixing a toner image on a transfer member, wherein the developer is a toner according to any one of the above (6) to (16). An image forming method using a latent image developer.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a conductive magnetic brush (CM
B) In the developing method, by containing a resin containing a specific amount of a monomer having an amino group in the resin coating layer of the carrier, and a conductive powder, and adjusting the dynamic resistance of the carrier to a specific region, By using a toner that binds a polyester resin containing a specific amount of a succinic acid derivative together with the above-described carrier, image defects such as brush marks, carrier over, fog, etc. are prevented, and the toner is charged with the carrier. Properties can be stably maintained over a long period of time, and as a result, a good solid image can be provided.

More specifically, the carrier for CMB development of the present invention uses a metal oxide powder as a conductive powder instead of carbon black, which has various problems, and uses the charge-imparting ability of the metal oxide powder to coat the carrier coating resin. By using a resin containing a specific amount of amino groups as
Furthermore, the toner is balanced by using a polyester resin containing a specific amount of a succinic acid derivative monomer as a binder resin of the toner, and as a result, an appropriate charge imparting property to the toner, environmental resistance, and their properties are obtained. Has enabled the provision of careers with the ability to maintain a long term.

In the present invention, by using the above-mentioned carrier and toner, image defects due to brush marks and carrier over, which are disadvantages of the CMB developing system, are eliminated, and a sufficient image density, a bright and clear image, and a high resolution are obtained. It has made it possible to stably provide high-quality images without certain ground fog.

The core material of the carrier used in the present invention is:
Any conventionally known core material can be used, but a core of a low-resistance ferrite or magnetic powder-dispersed resin carrier is particularly preferably selected. As another carrier core,
For example, iron powder and magnetite are known, but iron powder has a large specific gravity, so that toner and external additives are apt to adhere to it, and therefore, its stability is inferior to ferrite. In the case of magnetite, there is a problem that resistance control is difficult and the latitude of electric resistance is narrow. However, ferrite is particularly preferable because various electric resistances can be obtained after firing by controlling the reduction time and the like in a specific temperature range in a hydrogen stream, for example.

The volume average particle diameter of the carrier core material composed of magnetic particles such as ferrite is suitably in the range of 10 to 100 μm, preferably 20 to 80 μm. If the volume average particle diameter is smaller than 10 μm, the developer is liable to be scattered from the developing device, and is developed together with toner during development, which adversely affects an image. On the other hand, if it is larger than 100 μm, toner cannot be supplied faithfully with respect to the development potential on the photoreceptor, and good image quality cannot be obtained.

The core of the magnetic powder-dispersed resin carrier is obtained by dispersing magnetic material powder such as ferrite, iron powder, and magnetite in a thermoplastic resin or a thermosetting resin.
Specific examples of such thermoplastic resins and thermosetting resins include polyolefin resins, polyester resins, polyurethane resins, polycarbonate resins, melamine resins, and phenol resins.

The particle diameter of the magnetic powder used in the magnetic powder-dispersed resin carrier is 0.01 to 10 μm, preferably 0.05 to 10 μm.
A range of ５5 μm is suitable. The volume average particle diameter of the core of the magnetic powder-dispersed carrier in which these are dispersed in a resin is as follows:
The same as the above magnetic particles, 10 to 100 μm, preferably 2 to 100 μm.
A range from 0 to 80 μm is suitable.

The above-mentioned carrier core has a resin coating layer formed on its surface. However, an intermediate layer made of a silane coupling agent, a titanate coupling agent or the like may be provided between the carrier core and the resin coating layer. Good. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (β-methoxyethoxy) vinylsilane, vinyl and riacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β-mercaptoethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, isopropyltristearoyl titanate, isopropylmethacrylisostearoyl titanate Publicly known compounds such as-

As the monomer having an amino group to be incorporated in the resin coating layer of the carrier of the present invention, a monomer represented by the following general formula can be exemplified.

[0040]

Embedded image

In the general formula (1), R ₁ represents a hydrogen atom or a methyl group, A represents — (CH ₂ ) _n1 —NR ₂ R ₃ ,
R ₂ and R ₃ are each independently alkyl or ants - represents Le group, n ₁ represents an integer in the range of 0. Specific examples of the monomer represented by the general formula (1) are as follows.

[0042]

[Table 1]

[0043]

Embedded image

In the general formula (2), R ₄ represents a hydrogen atom or a methyl group, B represents — (CH ₂ ) _n2 —NR ₅ R ₆ ,
R ₅ and R ₆ each independently represents an alkyl group or ants - represents Le group, n ₂ represents an integer in the range of 0. Specific examples of the monomer represented by the general formula (2) are as follows.

[0045]

[Table 2]

The amino group-containing resin composed of these monomers is a random copolymer which is a copolymer containing the monomer represented by the general formula (1) and / or (2) as an essential component,
Block copolymers or graft copolymers can be mentioned.

The content of the amino group-containing monomer in the carrier coating resin of the present invention is suitably in the range of 0.5 to 2 mol%. When the amount is less than 0.5 mol%, the charge amount of the toner is low when combined with the toner, and a predetermined charge amount cannot be obtained particularly under high temperature and high humidity. On the other hand, if it exceeds 2 mol%, the charge amount of the toner becomes too high under low temperature and low humidity, so that it is difficult to obtain an appropriate toner development amount.

In the present invention, the amino group-containing resin may be used in combination with another resin. Resin that can be used in combination can be used within a range that does not adversely affect the chargeability of the toner, and is preferably an acrylic resin, a vinyl resin such as styrene / acrylic resin, or a polyester resin.

In the carrier of the present invention, the above-mentioned copolymer may be coated on the surface of the carrier core particles by, for example, a dipping method in which the core particles are dipped in a coating layer forming solution, or a coating layer forming solution. Spray method of spraying on the surface of core particles, fluidized bed method of spraying a coating layer forming solution in a state where the core particles are suspended by flowing air,
It can be carried out by any known method such as a kneader coater method in which the solvent is removed while mixing the core particles and the coating layer forming solution in a kneader coater.

The solvent used for the coating solution for forming the coating layer can be used irrespective of the type as long as it can dissolve the coating resin. For example, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran and dioxane can be used. Further, a mixed form of these solvents may be used.

In the coating resin solution, conductive powder is dispersed as a resistance adjuster, and metal oxide powder is used as the conductive powder. These conductive powder particles have an electrical resistance of 10 ⁶ Ωcm
The following is preferred. Particle shape of conductive powder is spherical, fiber (needle)
Shapes and scales can be used. Although the size of the particles depends on the size of the carrier core to be used, considering the maximum length of the particle diameter shape, it is preferable to use 3 μm or less, preferably 1 μm or less.
μm or less is good.

The material of the conductive powder may be a simple substance such as zinc oxide, tin oxide, titanium oxide, iron oxide, or titanium black, or a fine particle surface such as titanium oxide, zinc oxide, aluminum borate or potassium titanate, or barium sulfate. Can be used in the form of a composite material coated with a conductive metal oxide.

Examples of the conductive metal oxide include metal oxides doped with antimony (for example, antimony-doped tin oxide) and oxygen-deficient metal oxides (for example, oxygen-deficient tin oxide). In the oxygen-deficient type, it is preferable to use an antimony pump type since water is relatively easily adsorbed to the oxygen-deficient portion.

[0054] specific resistance of the conductive powder of the present invention, 10 ^0-1
0 range of ^{6 Ωcm} is appropriate. If a conductive powder exceeding 10 ⁶ Ωcm is used, it must be added in a large amount to obtain a desired carrier resistance. As a result, the resin coating layer of the carrier becomes brittle, and the charge retention of the developer is secured. Becomes difficult.

An appropriate amount of the conductive powder is in the range of 30 to 85% by weight. When the content exceeds 85% by weight, the resin coating layer of the carrier becomes brittle, and when the content is less than 30% by weight, a desired carrier resistance cannot be obtained.

As a method for dispersing the conductive powder in the resin solution, a known method can be used, but a method using a medium mill is preferable. The resin solid content concentration in the coating resin solution is preferably 20% by weight or less. If it exceeds 20% by weight, it is difficult to secure the dispersion and dispersion stability of the conductive powder particles when producing the coating resin solution.

The dynamic electric resistance of the carrier used in the present invention is determined as follows. 1. A flat electrode having an area of 3 cm ² was placed on a developing roll having a diameter of 4 cm and a length of 10 cm in the axial direction.
The magnetic brush is formed by placing the carrier on a developing roll facing the flat plate electrode at a distance of 5 mm. At this time, the weight of the carrier per unit area is about 40 mg / c.
The weight of the carrier was adjusted to m ^2. 120r
A voltage is applied between the developing roll and the plate electrode while rotating the developing roll at a rotation speed of pm, and the current flowing at that time is measured. From the obtained current-voltage characteristics, the electrical resistance is obtained using the equation of Ohm's law. Note that between the applied voltage E and the current density J at this time, logJ∝E
It is well known that there is a ^1/2 relationship. (Japanese
Journal of Applied Physicals, vol.19, No.12, p.241
3)

When the electric resistance is low as in the carrier used in the present invention, a large electric current may flow in a high electric field of 1000 v / cm or more and measurement may not be performed. In such a case, three or more points are measured in a low electric field and extrapolated to an electric field of 10 ⁴ v / cm by the least squares method using the above relational expression.

[0059] dynamic electrical resistance of the carrier of the present invention is 10 ⁰
A range of from 10 to 10 ⁸ Ωcm is appropriate. Below the 10 ⁰ [Omega] cm, will brush marks are likely to occur, also leaks between the carrier and the photosensitive member under high temperature and high humidity,
The photoconductor is damaged. On the other hand, if it exceeds 10 ⁸ Ωcm, toner filling of a solid image in toner development becomes worse.

The toner used in the developer of the present invention contains a polyester binder resin and a coloring material. As pigments used in color toners, at least CI Pigmentable 15: 3 as a cyan coloring material, CI Pigment Red 57-1, 122 as a magenta coloring material, CI Pigment Yellow-180 as a yellow coloring material, 185 and 17 are preferably used as the black color material, a color material selected from carbon black.

The carbon black used in the present invention has an average primary particle diameter of at least 35 and no more than 50 n as observed by an electron microscope.
Those having a range of less than m are used. The average primary particle size is
When the thickness is less than 35 nm, the color rendering properties, that is, the color tone changes when the light source is changed, and the gray reproduction color changes depending on the light source, so that a stable texture cannot be obtained. Also, 50n
When carbon black of m or more is used, the coloring power is inferior. Therefore, it is necessary to add a large amount of carbon black to the toner, and as a result, it becomes difficult to obtain an appropriate charge amount. On the other hand, carbon black is usually produced by the furnace method. In this case, in order to produce particles having a particle size of 50 nm or more, the heating temperature must be kept low. However, if the heating temperature is kept low, the carcinogenic substance tends to remain, which causes a problem in safety. The amount of the carbon black can be appropriately set, but is usually 2.0 to 10% by weight, preferably 3.0 to 10% by weight.
A range of 6.0% by weight is suitable.

In the present invention, the binder resin used in the color toner for development of electrostatic charge and the black toner contains at least a polyester resin, and in particular, a polyoxyalkylenebisphenol type diol, and Preferably a polyoxyethylene bisphenol type diol and / or a polyoxypropylene bisphenol type diol,
Aromatic dicarboxylic acid or its anhydride, its ester as the main monomer component, and further alkyl succinic acid or its anhydride, its ester, and alkenyl succinic acid or its anhydride, at least selected from its ester One of them contains 2 to 25 mol% of the total monomer amount.

The content of the succinic acid derivative monomer in the toner binder resin is suitably in the range of 2 to 25 mol%. If the amount is less than 2 mol%, the powder characteristics of the toner deteriorate. If it exceeds 25 mol%, it is difficult to obtain a desired value of Tg of the binder resin, and the resin has a strong coloring property, which is not preferable particularly when transparency such as OHP is required.

Polyoxyethylene bisphenol type diol and polyoxypropylene bisphenol type diol
Is an ethoxylated or propoxylated bisphenol, which has 2 to 3 moles of oxyethylene or oxypropylene per mole of bisphenol. Is shown.

[0065]

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(In the formula, 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.)

As a specific example, 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. 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 of the ethoxylated bisphenol type diol to the propoxylated bisphenol type diol is from 1:10 to 1
It is preferably in the range of 0: 1, especially 1: 4 to 4: 1.

The polyester in the present invention may be used as other alcohol components as long as the characteristics of the present invention are not impaired, such as ethylene glycol, propylene glycol and 1,4-.
Butanediol, 1,5-pentanediole, 1,6-
Aliphatic polyols such as hexanediol, glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, and 1,4-cyclohexanediol
And alicyclic alcohols such as 1,4-cyclohexanedimethanol.

On the other hand, examples of the aromatic dicarboxylic acid include aromatic carboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid. Further, as those esters, low molecular alcohol esters of the above dicarboxylic acids,
For example, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate and the like can be mentioned.

Examples of the alkyl succinic acid and alkenyl succinic acid, anhydrides and esters thereof include, for example, n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenylsuccinic acid, n-dodecylsuccinic acid,
n-Dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, anhydrides thereof, lower alkyl esters and the like. These components can suppress the cohesiveness of the toner powder and contribute to the prevention of the penetration of the fixed image into the paper at the time of fixing.

The polyhydric carboxylic acid having a valency of 3 or more, its acid anhydride or its lower alkyl ester used in the present invention includes 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2, 5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,
3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,
7,8-octanetetracarboxylic acid, trimesic acid, pyromellitic acid, and acid anhydrides or lower alkyl ester compounds thereof and the like, particularly trimellitic acid,
Trimesic acid, pyromellitic acid, or their acid anhydrides, methyl ester compounds and ethyl ester compounds are preferred.

The alcohol component having three or more valences used in the present invention includes sorbitol, 1,2,3,6-hexanetetate
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanthrol, 1,2,5-pentantriol, glycerol -
Diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanthrol, trimethylolethane,
Trimethylolpropane, 1,3,5-hydroxymethylbenzene and the like are used.

At least one selected from the above trivalent or higher polycarboxylic acids, their acid anhydrides or lower alkyl esters, and / or the trivalent or higher alcohol components has a total monomer amount of 10%. Used in less than mole%. The amount of addition is adjusted so as to be in the following molecular weight range.

The range of the molecular weight of the polyester resin of the present invention selected from the above monomers is as follows. The weight-average molecular weight as a THF solvent-soluble component is Mw: 20,000 to 150,000, preferably 30,000 to 120,000. preferable. When Mw is less than 20,000, the intensity of the fixed image becomes weak, and there is a problem particularly in the preservability of the fixed image of the color image. On the other hand, if it is larger than 150,000, a large amount of heat energy is required at the time of fixing the toner image, the load on the fixing device becomes large, and it becomes difficult to output a stable fixed image.

The acid value of the toner binder resin of the present invention is 20 mg
It is appropriate that the KOH / g or less and the hydroxyl value be 30 mgKOH / g or less. If the acid value exceeds 20 mgKOH / g and the hydroxyl value exceeds 30 mgKOH / g, the developer under low temperature and low humidity and under high temperature and high humidity Is large, which is not practically preferable.

The Tg of the toner binder resin of the present invention is suitably 60 ° C. or higher. If the Tg is lower than 60 ° C., the storage stability of the toner deteriorates, and for example, long-term storage such as warehouse storage is difficult. In addition, the frictional heat in the developing machine causes the toners to fuse with each other, thereby deteriorating the image quality. Further, the melt viscosity of the toner binder resin is 1
The temperature at which the pressure reaches 000 Pas is suitably in the range of 115 to 150 ° C. If the temperature is lower than 115 ° C., a fixing failure occurs, and 1
If the temperature exceeds 50 ° C., a large amount of heat energy is required in the step of melting and kneading the toner.

The color toner for developing an electrostatic image and the black toner according to the present invention include a toner powder having improved fluidity, developability and transferability, and frictional charge control between the toner and the carrier. Therefore, it is necessary to add an external additive. As the external additive, any known ones such as titanium oxide, silica, and alumina can be used.Particularly, titanium oxide fine particles, hydrophobic titanium oxide fine particles having a silica fine particle surface treated with a hydrophobizing agent, and hydrophobic silica It is preferable to externally add fine particles. As the above-mentioned hydrophobizing agent, known ones can be used, but preferably those which react with hydroxyl groups on the surface of titanium oxide fine particles and silica fine particles are used. For example,
Silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconium coupling agents, silicone oils and the like can be used. Among these, 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)
Represents an alkyl group or a perfluoroalkyl group, and OR ₁ represents an alkoxy group such as a methoxy group or an ethoxy group. The following can be specifically mentioned. _{(CH 3) 2 Si (NCO} ) 2 CH 3 Si (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

Incidentally, in the above general formula, those where x is 3 are preferable in that the charge amount increases. For the same reason, R is preferably an alkyl group having 7 to 16 carbon atoms or a perfluoroalkyl group. As the silicone oil, modified silicone oil can be used in addition to dimethylsilicon, methylphenylsilicone, monomethylsilicone and the like.

The full-color toner for developing an electrostatic image of the present invention
When added externally, the hydrophobic fine particles are added in an amount of 0.2 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The optimum addition amount is determined by the fluidity and charging characteristics of the toner powder. As the size of the hydrophobic fine particles, those having an average particle size in the range of 5 to 500 nm are suitable. The external additive can be attached to the toner particle surface by, for example, a high-speed mixer. Specifically, a Henschel mixer or a V-type blender
The toner particles and the external additive may be mixed using the method described above.

The toner concentration in the developer of the present invention is 3 to 8
If the amount is less than 3% by weight, brush marks and insufficient image density appear, which is not preferable. On the other hand, if it exceeds 8% by weight, sufficient chargeability cannot be obtained, and fogging on the copy background becomes severe.

[0082]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.

Production Example of Toner Binder Resin (Binder Resin-1) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2 , 2) -2,2-Bis (4-hydroxyphenyl) propane: 1.6 mol ・ terephthalic acid: 1.4 mol ・ n-dodecenylsuccinic acid: 0.7 mol ・ trimellitic acid: 0.2 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out in a nitrogen stream while heating with a mantle heater. Was. The degree of polymerization was monitored at a softening point according to a ring and ball softening point measurement method (JIS-K2531), and the reaction was terminated when the softening point reached 140 ° C.
After the completion of the reaction, the resultant was gradually cooled to room temperature. The obtained resin had a succinic acid derivative monomer content of 15.2 mol%,
Acid value is 12mgKOH / g, hydroxyl value is 17mgKOH
/ G, the glass transition point Tg is 67 ° C., and the temperature at which the melt viscosity of the resin becomes 1000 Pa · s is 150 ° C.
Met.

(Binder Resin-2) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2,2) -2,2 -Bis (4-hydroxyphenyl) propane: 1.6 mol-Terephthalic acid: 1.5 mol-Isododecenyl succinic acid: 0.7 mol-Trimellitic acid: 0.1 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the mixture was reacted at about 170 ° C. in the first half while heating in a nitrogen stream while heating with a mantle heater.
The reaction was performed under reduced pressure at 20 ° C. The degree of polymerization was monitored at a softening point according to a ring and ball softening point measurement method (JIS-K2531), and 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. The obtained resin had a succinic acid derivative monomer content of 15.2 mol%, an acid value of 8 mg KOH / g and a hydroxyl value of 15 mg KOH / g.
The glass transition point Tg was 65 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 115 ° C.

(Binder Resin-3) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 1.6 mol Polyoxypropylene (2,2) -2,2 -Bis (4-hydroxyphenyl) propane: 0.7 mol-Terephthalic acid: 1.4 mol-n-dodecenylsuccinic acid: 0.7 mol-Trimellitic acid: 0.2 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored at a softening point according to a ring and ball softening point measurement method (JIS-K2531), 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. The obtained resin had a succinic acid derivative monomer content of 15.2 mol%, an acid value of 17 mgKOH / g, and a hydroxyl value of 20 mgKOH / g.
g, the glass transition point Tg was 63 ° C., and the temperature at which the resin had a melt viscosity of 1,000 Pa · s was 130 ° C.

(Binder Resin-4) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 1.6 mol Polyoxypropylene (2,2) -2,2 -Bis (4-hydroxyphenyl) propane: 0.7 mol-Terephthalic acid: 2.0 mol-n-dodecenylsuccinic acid: 0.1 mol-Trimellitic acid: 0.2 mol

The above raw material compounds were placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored by a softening point according to a ring and ball softening point measurement method (JIS-K2531), and the reaction was terminated when the softening point reached 130 ° C.
After the completion of the reaction, the resultant was gradually cooled to room temperature. The obtained resin had a succinic acid derivative monomer content of 2.2 mol%, an acid value of 12 mg KOH / g and a hydroxyl value of 13 mg KOH / g.
The glass transition point Tg was 67 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 130 ° C.

(Binder Resin-5) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 1.6 mol Polyoxypropylene (2,2) -2,2 -Bis (4-hydroxyphenyl) propane: 0.7 mol-Terephthalic acid: 0.95 mol-n-dodecenyl succinic acid: 1.10 mol-Trimellitic acid: 0.2 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored at a softening point according to a ring and ball softening point measurement method (JIS-K2531), and the reaction was terminated when the softening point reached 140 ° C.
After the completion of the reaction, the resultant was gradually cooled to room temperature. The resulting resin had a succinic acid derivative monomer content of 24.2 mol%, an acid value of 19 mg KOH / g, and a hydroxyl value of 14 mg KOH / g.
g, the glass transition point Tg was 61 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 140 ° C.

(Comparative Binder Resin-1) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2,2) -2, 2-bis (4-hydroxyphenyl) propane: 1.6 mol ・ terephthalic acid: 1.6 mol ・ n-dodecenyl succinic acid: 0.7 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored by a softening point according to a ring and ball softening point measurement method (JIS-K2531), and 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 obtained resin had a succinic acid derivative monomer content of 15.2 mol%, an acid value of 30 mg KOH / g, and a hydroxyl value of 33 mg KOH / g.
g, the glass transition point Tg was 64 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 120 ° C.

(Comparative Binder Resin-2) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2,2) -2, 2-bis (4-hydroxyphenyl) propane: 1.6 mol ・ terephthalic acid: 1.6 mol ・ trimellitic acid: 0.7 mol

The above raw material compound was placed in a glass two-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored at a softening point according to a ring and ball softening point measurement method (JIS-K2531), and 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 obtained resin had a succinic acid derivative monomer content of 0 mol%, an acid value of 9 mg KOH / g, a hydroxyl value of 45 mg KOH / g, a glass transition point Tg of 68 ° C., and a melt viscosity of the resin. Was 1000 Pa · s at 120 ° C.

(Comparative Binder Resin-3) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2,2) -2, 2-bis (4-hydroxyphenyl) propane: 1.6 mol ・ terephthalic acid: 1.6 mol ・ n-dodecenylsuccinic acid: 0.4 mol ・ trimellitic acid: 0.5

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored by a softening point according to a ring and ball softening point measurement method (JIS-K2531), and 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 resulting resin had a succinic acid derivative monomer content of 8.3 mol%, an acid value of 25 mg KOH / g, and a hydroxyl value of 26 mg KOH / g.
The glass transition point Tg was 64 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 120 ° C.

(Comparative Binder Resin-4) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2,2) -2, 2-bis (4-hydroxyphenyl) propane: 1.6 mol ・ terephthalic acid: 1.2 mol ・ n-dodecenylsuccinic acid: 0.6 mol ・ trimellitic acid: 0.5 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas introducing tube, and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced to 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored by a softening point according to a ring and ball softening point measurement method (JIS-K2531), and the reaction was terminated when the softening point reached 145 ° C. After the completion of the reaction, the resultant was gradually cooled to room temperature. The obtained resin has a succinic acid derivative monomer content of 13.0 mol%, an acid value of 10 mgKOH / g, and a hydroxyl value of 26 mgK.
OH / g, the glass transition point Tg is 65 ° C., and the temperature at which the melt viscosity of the resin becomes 1000 Pa · s is 15 ° C.
5 ° C.

(Comparative Binder Resin-5) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 0.7 mol Polyoxypropylene (2,2) -2, 2-bis (4-hydroxyphenyl) propane: 1.6 mol ・ terephthalic acid: 1.4 mol ・ n-dodecenylsuccinic acid: 0.7 mol ・ trimellitic acid: 0.2 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored at a softening point according to a ring and ball softening point measurement method (JIS-K2531), and the reaction was terminated when the softening point reached 103 ° C.
After the completion of the reaction, the resultant was gradually cooled to room temperature. The obtained resin had a succinic acid derivative monomer content of 15.2 mol%, an acid value of 10 mg KOH / g, and a hydroxyl value of 17 mg KOH / g.
g, the glass transition point Tg was 63 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 113 ° C.

(Comparative Binder Resin-6) Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 1.6 mol Polyoxypropylene (2,2) -2, 2-bis (4-hydroxyphenyl) propane: 0.7 mol ・ terephthalic acid: 0.9 mol ・ n-dodecenylsuccinic acid: 1.2 mol ・ trimellitic acid: 0.2 mol

The above raw material compound was placed in a glass 2-liter four-necked flask, and a stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer were set, and the mixture was set in a mantle heater. After the inside of the reaction vessel was replaced with nitrogen gas, 1 g of dibutyltin oxide was added, and the reaction was carried out at about 180 ° C. in the first half and reduced at 220 ° C. in the second half while heating with a mantle heater in a nitrogen stream. I let it. The degree of polymerization was monitored by a softening point according to a ring and ball softening point measurement method (JIS-K2531), and 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. The obtained resin had a succinic acid derivative monomer content of 26.1 mol%, an acid value of 22 mg KOH / g, and a hydroxyl value of 35 mg KOH / g.
g, the glass transition point Tg was 58 ° C., and the temperature at which the melt viscosity of the resin reached 1,000 Pa · s was 113 ° C.

Production Example of Flushing Pigment ( Production Example of Flushing Cyan Pigment-1) Binder Resin-1
To 100 parts of a cyan pigment having a water content of 30% by weight (C.I.
Add 60 parts of I. Pigmentable-15: 3) and add about 120 ° C.
The rotor is rotated at 20 cm / sec while pressurizing at a pressure of 1 kgf / cm ² with a pressurized kneader heated to a temperature of ² kPa, and melt-kneading and water removal are repeated to obtain a flushing cyan pigment having a pigment content of 30%. -1 was obtained.

(Production Example of Flushing Magenta Pigment-1) Water content is 30% by weight based on 100 parts of binder resin-1.
60 parts of magenta pigment (CI Pigment Red 57: 1) is added, and 1 kg is applied with a pressure kneader heated to about 120 ° C.
While pressurizing at a pressure of f / cm ^2, the rotor is set at 20 cm /
The mixture was rotated for 2 seconds to repeat the melt-kneading and water removal to obtain a flushing magenta pigment-1 having a pigment content of 30%.

(Production Example of Flushing Yellow-Pigment-1) Water content is 30% by weight based on 100 parts of binder resin-1.
60 parts of cyan pigment (CI Pigment Yellow-17), and add 1 kgf with a pressure kneader heated to about 120 ° C.
/ Cm ² while applying pressure at a pressure of 20 cm / s
The mixture was rotated at ec to repeatedly perform melt-kneading and water removal to obtain a flushing yellow pigment-1 having a pigment content of 30%.

Production Example of External Additive for Toner (Production Example 1 of Hydrophobized Titanium Oxide) Methanol containing 10 g of titanium oxide (MT150A, manufactured by Teica) having an average particle diameter of 15 nm and 1.5 g of decyltrimethoxysilane added. The mixture was stirred for 30 minutes with a stirrer and dispersed for 30 minutes while applying ultrasonic waves. Then, the dispersion medium was removed with an evaporator, dried, and then cured at a temperature of 120 ° C. And crushed in a mortar to obtain hydrophobic titanium oxide.

(Production Example 2 of Hydrophobized Titanium Oxide) 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 is subjected to a hydrophobic treatment with octyltrimethoxysilane. (Manufactured by Nippon Aerosil Co., Ltd., T805) was used.

(Example of Method for Producing Hydrophobized Silicon Oxide) Average Particle Size 4
0 nm silicon oxide (OX50, manufactured by Nippon Aerosil Co., Ltd.) 1
0 g was added to a methanol solution to which 1.5 g of decyltrimethoxysilane was added, and the mixture was stirred with a stirrer and dispersed for 30 minutes while applying ultrasonic waves. Then, the evaporator was used.
Then, the dispersion medium was removed, dried, and then cured at a temperature of 120 ° C., and crushed in a mortar to obtain hydrophobic silicon oxide.

Production Example of Coating Resin for Carrier (Coating Resin-1) Compound No. 1 of the above general formula (1) was prepared. No. 2 monomer: 2.64 g (16.8 mmol) Methacrylic acid methyl ester: 85.0 g (850 mmol) The above components were dissolved in 300 g of toluene, and a polymerization initiator AI
1.64 g of BN (manufactured by Wako Pure Chemical Industries, V-60) (10 mmo
l) was added and the reaction was carried out at 60 ° C. for 40 hours in a nitrogen stream.
After completion of the reaction, the precipitate is precipitated in methanol, filtered, and dried in vacuum. When the molecular weight of the obtained polymer was measured by gel permission chromatography, it was a weight average molecular weight (Mw: 30,000). The content of the monomer (No. 2), which is an amino group-containing monomer, was 1.9 mol%.

(Coating Resin-2) Compound No. 1 represented by the above general formula (1) 2 monomer: 0.84 g (5.3 mmol) methacrylic acid methyl ester: 85.0 g (850 mmol) The above components were dissolved in 300 g of toluene, and a polymerization initiator AI
1.64 g of BN (manufactured by Wako Pure Chemical Industries, V-60) (10 mmo
l) was added and the reaction was carried out at 60 ° C. for 40 hours in a nitrogen stream.
After completion of the reaction, the precipitate is precipitated in methanol, filtered, and dried in vacuum. When the molecular weight of the obtained polymer was measured by gel permission chromatography, it was a weight average molecular weight (Mw: 32000). The content of the monomer (No. 2), which is an amino group-containing monomer, was 0.6 mol%.

(Coating Resin-3) Compound No. 1 of the above general formula (2) Monomer 9: 2.4 g (15 mmol) Styrene: 100.0 g (960 mmol) The above components were dissolved in 300 g of toluene, and a polymerization initiator AI
1.64 g of BN (manufactured by Wako Pure Chemical Industries, V-60) (10 mmo
l) was added and the reaction was carried out at 60 ° C. for 48 hours in a nitrogen stream.
After completion of the reaction, the precipitate is precipitated in methanol, filtered, and dried in vacuum. When the molecular weight of the obtained polymer was measured by gel permission chromatography, it was a weight average molecular weight (Mw: 45000). The content of the monomer (No. 9), which is an amino group-containing monomer, was 1.5 mol%.

(Comparative Coating Resin-1) Compound No. 1 of the general formula (1) No. 2 monomer: 3.0 g (19 mmol) Methacrylic acid methyl ester: 85.0 g (850 mmol) The above components were dissolved in 300 g of toluene, and a polymerization initiator AI
1.64 g of BN (manufactured by Wako Pure Chemical Industries, V-60) (10 mmo
l) was added and the reaction was carried out at 60 ° C. for 40 hours in a nitrogen stream.
After completion of the reaction, the precipitate is precipitated in methanol, filtered, and dried in vacuum. The molecular weight of the obtained polymer was measured by gel permission chromatography and found to be a weight average molecular weight (Mw: 28,000). The content of the monomer (No. 2), which is an amino group-containing monomer, was 2.2 mol%.

(Comparative Coating Resin-2) Compound No. 1 of the above general formula (1) No. 2 monomer: 0.56 g (3.5 mmol) Methacrylic acid methyl ester: 85.0 g (850 mmol) The above components were dissolved in 300 g of toluene, and a polymerization initiator AI
1.64 g of BN (manufactured by Wako Pure Chemical Industries, V-60) (10 mmo
l) was added and the reaction was carried out at 60 ° C. for 40 hours in a nitrogen stream.
After completion of the reaction, the precipitate is precipitated in methanol, filtered, and dried in vacuum. When the molecular weight of the obtained polymer was measured by gel permission chromatography, it was a weight average molecular weight (Mw: 34000). The content of the monomer (No. 2), which is an amino group-containing monomer, was 0.4 mol%.

< Evaluation of Carrier > [Carrier Production Example 1] Toluene: 100 parts by weight Coating resin-1: 9 parts by weight (amino group-containing monomer content: 1.9 mol%) Tin oxide-based conductive powder: 27 parts by weight (Made by Mitsui Kinzoku Co., Ltd., Pastran Type-IV (specific resistance: 10 ⁴ Ωcm) Volume average particle diameter 100 nm) Bead for media mill (diameter 1 mm): 200 parts by weight The above components except magnetite are put in a sand mill and dispersed. After that, the medium mill was removed to prepare a dispersion.

The above-mentioned dispersion liquid: 18.8 parts by weight Magnetite (MX030A, manufactured by Fuji Electric Chemical Co., Ltd.): 100 parts by weight (dynamic electric resistance 4 × 10 ⁻⁵ Ωcm, volume average particle diameter 50 μm) Place in a mold kneader and heat the tank
The mixture was stirred at ℃ and stirred for 30 minutes under reduced pressure to remove the solvent, and the aggregates were removed with a 75 μm mesh sieve to obtain a coated carrier having an average particle size of about 50 μm. The thickness of the resin coating layer was about 0.8 μm. The electric resistance of this carrier was measured in the form of a magnetic brush, and the resistance value when extrapolated to an electric field of 10 ⁴ V / cm was 5 × 10 ⁶ Ωcm.

[Carrier Production Example 2] Toluene: 100 parts by weight Coating resin-2: 9 parts by weight (amino group-containing monomer content: 0.6 mol%) Tin oxide-based conductive powder: 10 parts by weight (manufactured by Mitsui Kinzoku Co., Ltd.) , Pastoran Type-IV (with specific resistance of 10 ⁴ Ωcm) Volume average particle diameter 100 nm) Needle-shaped conductive titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., FS-10P): 17 parts by weight (specific resistance 3 Ωcm, long axis average value 1000 nm) ) Beads for media mill (diameter 1 mm): 200 parts by weight The above components except magnetite were placed in a sand mill, dispersed, and then the media mill was removed to prepare a dispersion.

Dispersion: 20 parts by weight Magnetite (MX030A, manufactured by Fuji Electric Chemical Co., Ltd.): 100 parts by weight (dynamic electric resistance: 4 × 10 ⁻⁵ Ωcm, volume average particle diameter: 50 μm) -Put the temperature in the bath about 50
The mixture was stirred at ℃ and then stirred for 30 minutes under reduced pressure to remove the solvent and obtain a coated carrier. The thickness of the resin coating layer was about 1 μm. The electric resistance of the carrier was measured in the form of a magnetic brush, and the resistance value when extrapolated to an electric field of 10 ⁴ V / cm was 2 × 10 ³ Ω · cm.

[Carrier Production Example 3] Toluene: 100 parts by weight Coating resin-1: 9 parts by weight (amino group-containing monomer content: 1.9 mol%) Tin oxide conductive powder: 15 parts by weight (manufactured by Mitsui Kinzoku Co., Ltd.) Pastran Type-IV (with specific resistance of 10 ⁴ Ωcm) Volume average particle diameter 100 nm) Bead for medium mill (diameter 1 mm): 200 parts by weight The above components except magnetite are put in a sand mill, dispersed, and then put into a medium mill. This was removed to produce a dispersion.

The above dispersion: 18.8 parts by weight Magnetite (manufactured by Fuji Electric Chemical Co., Ltd., MX030A): 100 parts by weight (dynamic electric resistance 4 × 10 ⁻⁵ Ωcm, volume average particle diameter 50 μm) Place in a mold kneader and heat the tank
The mixture was stirred at ℃ and then stirred for 30 minutes under reduced pressure to remove the solvent to obtain a coated carrier. The thickness of the resin coating layer was about 0.8 μm. The electric resistance of this carrier was measured in the form of a magnetic brush, and the extrapolated resistance to an electric field of 10 ⁴ V / cm was 5 × 10 ⁷ Ω · cm.

[Comparative Example 1 for Carrier Production] Toluene: 100 parts by weight Comparative coating resin-2: 9 parts by weight (amino group-containing monomer content: 0.4 mol%) Tin oxide-based conductive powder: 27 parts by weight (Mitsui Metals) Made by Pastoran Type-IV (specific resistance: 10 ⁴ Ωcm) Volume average particle diameter 100 nm) Bead for media mill (diameter 1 mm): 200 parts by weight After dispersing the above components except magnetite in a sand mill Then, the medium mill was removed to prepare a dispersion.

The above dispersion: 18.8 parts by weight Magnetite (manufactured by Fuji Electric Chemical Co., Ltd., MX030A): 100 parts by weight (dynamic electric resistance: 4 × 10 ⁻⁵ Ωcm, volume average particle diameter: 50 μm) Place in a mold kneader and heat the tank
The mixture was stirred at ℃ and stirred for 30 minutes under reduced pressure to remove the solvent to obtain a coated carrier. The thickness of the resin coating layer was about 0.8 μm. The electric resistance of this carrier was measured in the form of a magnetic brush, and the extrapolated resistance up to an electric field of 10 ⁴ V / cm was 5 × 10 ⁶ Ω · cm.

[Comparative Example 2 for Carrier Production] Toluene: 100 parts by weight Comparative coating resin-1: 9 parts by weight (amino group-containing monomer content: 2.2 mol%) Tin oxide-based conductive powder: 27 parts by weight (Mitsui Metals) Made by Pastoran Type-IV (with a specific resistance of 10 ⁴ Ωcm) Volume average particle diameter 100 nm) Bead for media mill (diameter 1 mm): 200 parts by weight After dispersing the above components except magnetite in a sand mill, The dispersion was prepared by removing the media mill.

The above dispersion: 18.8 parts by weight Magnetite (manufactured by Fuji Electric Chemical Co., Ltd., MX030A): 100 parts by weight (dynamic electric resistance: 4 × 10 ⁻⁵ Ωcm, volume average particle diameter: 50 μm) Put it in a mold kneader and put the temperature in the tank
, And then stirred for 30 minutes under reduced pressure to remove the solvent and obtain a coated carrier. The thickness of the resin coating layer was about 0.8 μm. The electric resistance of this carrier was measured in the form of a magnetic brush, and the extrapolated resistance up to an electric field of 10 ⁴ V / cm was 5 × 10 ⁶ Ω · cm.

[Carrier Production Comparative Example 3] Toluene: 100 parts by weight Coating resin-2: 7 parts by weight (amino group-containing monomer content: 0.6 mol%) Tin oxide conductive powder: 10 parts by weight (manufactured by Mitsui Kinzoku Co., Ltd.) , Passtran Type-IV (resistivity 10 ⁰ [Omega] cm ones) volume average particle diameter 100 nm) needle-shaped conductive titanium oxide (manufactured by Ishihara Sangyo Kaisha, Ltd., FS-10P): 25 parts by weight (specific resistance 3Omucm, the major axis average 1000nm ) Beads for media mill (diameter: 1 mm): 200 parts by weight The above components except magnetite were placed in a sand mill and dispersed, and then the media mill was removed to prepare a dispersion.

Dispersion: 20 parts by weight Magnetite (MX030A, manufactured by Fuji Electric Chemical Co., Ltd.): 100 parts by weight (dynamic electric resistance: 4 × 10 ⁻⁵ Ωcm, volume average particle diameter: 50 μm) -Put the temperature in the bath about 50
The mixture was stirred at ℃ and stirred for 30 minutes under reduced pressure to remove the solvent to obtain a coated carrier. The thickness of the resin coating layer was about 0.5 μm. The electric resistance of the carrier was measured in the form of a magnetic brush, and the resistance value when extrapolated to an electric field of 10 ⁴ V / cm was 5 × 10 ⁻¹ Ω · cm.

[Comparative Example 4 for Carrier Production] Toluene: 100 parts by weight Coating resin-1: 13 parts by weight (amino group-containing monomer content: 1.9 mol%) Tin oxide-based conductive powder: 5 parts by weight (manufactured by Mitsui Kinzoku Co., Ltd.) Pastran Type-IV (with specific resistance of 10 ⁴ Ωcm) Volume average particle diameter 100 nm) Beads for media mill (diameter 1 mm): 200 parts by weight The above components except magnetite are dispersed in a sand mill and then dispersed in a media mill. Was removed to prepare a dispersion.

The above dispersion: 18.8 parts by weight Ferrite (EFC-50B, manufactured by Powder Tech): 100 parts by weight (dynamic electric resistance: 1 × 10 ² Ωcm, volume average particle diameter: 50 μm) Approximately 50
The mixture was stirred at ℃ and stirred for 30 minutes under reduced pressure to remove the solvent to obtain a coated carrier. The thickness of the resin coating layer was about 0.8 μm. The electric resistance of this carrier was measured in the form of a magnetic brush, and the extrapolated resistance to an electric field of 10 ⁴ V / cm was 6 × 10 ⁸ Ω · cm.

[Toner Production Example 1] (Cyan toner) Flushing cyan pigment: 16.7 parts by weight Binder resin-1: 83.7 parts by weight After the above components were preliminarily mixed, they were melt-kneaded with an extruder. Then, after cooling and coarse pulverization, the mixture was pulverized by a jet mill and classified to carry out a volume average particle diameter D _{50 of} 6.8 μm with a cyan pigment content of 4% by weight and a volume particle size distribution D ₁₆ (vo
l) A cyan toner of / D ₈₄ (vol) = 1.6 was obtained.

The above-mentioned cyan toner: 100 parts by weight Hydrophobic titanium oxide (hydrophobic titanium oxide production method 1): 1.0 parts by weight The above-mentioned hydrophobic silicon oxide: 1.0 parts by weight The above components were mixed with a Henschel mixer. A toner of Example 1 was prepared.

A developer was prepared by combining the thus prepared toner of Example 1 with the above carrier, and the charging characteristics and the image quality characteristics were evaluated. Carrier characteristics and charging characteristics,
Table 3 shows the results of the image quality characteristics.

Evaluation Method of Carrier ( Evaluation of Image Quality Characteristics) Toner (6 parts by weight) in toner production example 1, 100 parts by weight of carriers in carrier production examples 1 to 3 and comparative examples 1 to 4 were subjected to a V blender. A cyan developer for evaluation was prepared by blending for 30 minutes, and 30% to 100% with an Acolor 635 modified machine at normal temperature and normal humidity.
Was prepared and a sensory evaluation was performed on the image. A: Solid and uniform image quality. B: There are some brush marks and missing images, but they are not so noticeable. C: A brush mark or partial image omission (toner is not developed) is conspicuous, and the image quality is rough.

(Evaluation of Charging Characteristics) 6 parts by weight of the toner of Production Example 1 and 100 parts by weight of the carriers of Production Examples 1 to 3 and Comparative Examples 1 to 4 were weighed and placed in a glass reagent bottle. With the lid open, one day and night under each environment (low temperature and low humidity: 10 ° C, 20% RH, high temperature and high humidity: 30 ° C,
After being seasoned at 80% RH), the lid was closed, and blending was carried out for 30 minutes with a table mill to measure blow-off tribo. The value at that time and the environmental charge amount ratio were calculated and evaluated.

(Blow-off tribo) ：: When the blow-off tribo is in the range of 20 to 35 μC / g, the image density is high and no fog occurs. ×: When the value is outside the above range, the image density is reduced,
Fog occurs.

(Environmental Charging Ratio) ：: When the environmental charging ratio is in the range of 0.5 to 1.0, there is little environmental dependency and no image quality defect occurs. ×: When the value is out of the range of ○, the image quality changes depending on the environment or an image quality defect occurs.

[0137]

[Table 3]

As is clear from Table 3, the content of the amino group monomer in the coating resin was within the range of the present invention and was 10 ⁴ V /
The carriers of Examples 1 to 3 whose dynamic electric resistance under an electric field of 1 cm were within the range of the present invention were replaced with the toner of Example 1.
When used together with the above toner, uniform and stable image quality could be obtained, there was little environmental dependence on the charging property, and no image quality defect was observed. On the other hand, the carriers of Comparative Examples 1 to 4 whose amino group monomer content in the coating resin is out of the range of the present invention or whose dynamic electric resistance is out of the range of the present invention have brush marks or partial marks. Image omission was observed, and in particular, environmental dependency of chargeability was high, and image quality defects were observed.

< Evaluation of Toner > [Toner Production Example 2] In the preparation of the flushing cyan pigment-1, the binder resin-1 was replaced by the binder resin-2, and the melt-kneading temperature was changed to about 110.degree. In the same manner as in toner example 1, a cyan toner was prepared by using the binder resin-2 instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Toner Production Example 2.

[Toner Production Example 3] In the above-mentioned preparation of the flushing cyan pigment-1, the binder resin-1 was replaced by the binder resin-3, and the melting and kneading temperature was changed to about 120 ° C. In the preparation of cyan toner, binder resin-3 was used instead of binder resin-1.
, A cyan toner was produced in the same manner as in toner example 1, and hydrophobic titanium oxide and hydrophobic silicon oxide were externally added in the same manner as in toner example 1 to obtain a toner of toner production example 3. Was.

[Toner Production Example 4] In the above-mentioned preparation of the flushing cyan pigment-1, the binder resin-1 was changed to the binder resin-4, and the melting and kneading temperature was changed to about 125 ° C. In the preparation of cyan toner, binder resin-4 was used instead of binder resin-1.
, A cyan toner was produced in the same manner as in toner example 1, and hydrophobic titanium oxide and hydrophobic silicon oxide were externally added in the same manner as in toner example 1 to obtain a toner of toner production example 4. Was.

[Toner Production Example 5] In the preparation of the flushing cyan pigment-1 described above, the binder resin-1 was replaced by the binder resin-5, and the melting and kneading temperature was changed to about 130 ° C. 5 in the production of the cyan toner, the binder resin -5 was used instead of the binder resin -1.
, A cyan toner was produced in the same manner as in toner example 1, and hydrophobic titanium oxide and hydrophobic silicon oxide were externally added in the same manner as in toner example 1 to obtain a toner of toner production example 5. Was.

[Comparative Example 1 for Toner Production] In the preparation of the flushing cyan pigment-1, the binder resin-1 was replaced with the comparative binder resin-1, and the melt-kneading temperature was changed to about 110 ° C. for comparison. A flushing cyan pigment-1 was produced, and a cyan toner was produced in the same manner as in toner example 1 except that the comparative binder resin-1 was used instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Comparative Example 1 for toner production.

[Comparative Example 2 for Toner Production] In the preparation of the flushing cyan pigment-1, the binder resin-1 was replaced with the comparative binder resin-2, and the melt-kneading temperature was changed to about 110.degree. A flushing cyan pigment-2 was produced, and a cyan toner was produced in the same manner as in toner example 1, except that the comparative binder resin-2 was used instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Comparative Example 2 for toner production.

[Comparative Example 3 for Toner Production] In the preparation of the flushing cyan pigment-1, the binder resin-1 was replaced with the comparative binder resin-3, and the melt-kneading temperature was changed to about 110.degree. A flushing cyan pigment-3 was produced, and a cyan toner was produced in the same manner as in toner example 1 except that the comparative binder resin-3 was used instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Comparative Example 3 for toner production.

[Comparative Example 4 for Toner Production] In the preparation of the above flushing cyan pigment-1, the binder resin-1 was replaced with the comparative binder resin-4, and the melt-kneading temperature was changed to about 130 ° C. for comparison. A flushing cyan pigment-4 was produced, and a cyan toner was produced in the same manner as in toner example 1 except that the comparative binder resin-4 was used instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Comparative Example 4 for toner production.

[Comparative Example 5 for Toner Production] In the preparation of the flushing cyan pigment-1, the binder resin-1 was replaced with the comparative binder resin-5, and the melt-kneading temperature was changed to about 110.degree. A flushing cyan pigment-5 was produced, and a cyan toner was produced in the same manner as in toner example 1, except that the comparative binder resin-5 was used instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Comparative Example 5 for toner production.

[Comparative Example 6 for Toner Production] In the preparation of the flushing cyan pigment-1, the binder resin-1 was replaced with the comparative binder resin-6, and the melt-kneading temperature was changed to about 110.degree. A flushing cyan pigment-6 was produced, and a cyan toner was produced in the same manner as in toner example 1, except that the comparative binder resin-6 was used instead of the binder resin-1. In the same manner as in Example 1, hydrophobic titanium oxide and hydrophobic silicon oxide were externally added to obtain a toner of Comparative Example 6 for toner production.

Evaluation Method of Toner 100 parts by weight of the carrier of Carrier Production Example 2 and 5 parts by weight of the toners of Toner Production Examples 1 to 6 and Comparative Examples 1 to 6 were blended with a V blender for about 30 minutes for evaluation. A cyan developer was prepared. For fixing evaluation, a Fuji Xerox A Color 635 fixing device was modified to enable temperature control.

The evaluation items were environmental charge ratio, gloss (gloss), and gloss unevenness, and the fixing characteristics were examined. The results are shown in Table 4. The paper used for the evaluation was L paper manufactured by Fuji Xerox Co., Ltd. The environmental charge ratio was determined in the same manner as in the evaluation of the carrier. The glossiness (gloss) was measured at 75 to 75 degrees: using a 3GM-260 Type manufactured by Murakami Color Research Laboratory, and the fixing temperature was 12
The degree of gloss (gloss) when the temperature was changed from 0 ° C. to 180 ° C. was measured. If the gloss is less than 30, the surface of the color toner fixed image becomes rough and light scattering occurs on the surface, so that sufficient color development cannot be obtained. Gloss spots were evaluated as x when a 180 ° C temperature was applied, and x when no gloss spot was generated.

[0151]

[Table 4]

As is clear from Table 4, the content of the succinic acid derivative in the polyester resin as the binder resin is within the range of the present invention, and the values of Tg, melt viscosity, acid value and hydroxyl value are different from those of the present invention. When the toners of the toner production examples 1 to 6 falling within the range are used together with the carrier of the carrier production example 1, the toner has little environmental dependence on the chargeability, no image quality defect is observed, and glossiness, gloss spots and the like are reduced. Excellent image quality was obtained.

On the other hand, if the content of the succinic acid derivative in the polyester resin is out of the range of the present invention, Tg, melt viscosity,
Any one of the acid value and the hydroxyl value is out of the range of the present invention, and the toner of Comparative Example for toner production has a high environmental dependency on chargeability, and has an image quality defect or poor glossiness. In addition, gloss spots were generated, and excellent image quality could not be obtained.

[Test of Dependence of Developer on Toner Concentration] Using the carrier of Carrier Example 2 and the toner of Toner Example 1, the developer was adjusted to have the toner concentration shown in Table 5, and the carrier was evaluated. Evaluate the image quality characteristics in the same way as
The background fog was visually evaluated, and a comprehensive evaluation was performed from both.

[0155]

[Table 5]

As is apparent from Table 5, when the toner density is 3
The developer in the range of ８8% by weight has a uniform and stable image quality including the solid edge portion, or is hardly conspicuous even if there is a brush mark or image omission, and there is no problem with background fog at all. Was. However, the developer having a toner concentration of 2% by weight had no problem of background fog, but brush marks and image omission were conspicuous and the image quality was rough. The toner concentration is 9% by weight.
The developer had no brush mark or missing image, and the image quality was stable, but background fog was conspicuous.

[Comparative experiment of Karatona-developer kit] (Cyanatona-developer) Toner-The cyan toner of Example 1 and the carrier of Example 1 were blended in a weight ratio of 6:94. Mixing was performed for 10 minutes with a blender to obtain a cyan developer.

(Magenta toner developer) In the preparation of the above-mentioned cyan toner developer, the flushing cyan pigment
A magenta developer was prepared in the same manner as the cyan toner developer except that flushing magenta pigment-1 was used instead of 1.

(Yellow Developer) A yellow developer was prepared in the same manner as the cyan toner developer except that the flushing yellow pigment-1 was used in place of the flushing cyan pigment-1 in the above-mentioned preparation of the cyan toner developer. did.

(Black toner developer) Carbon black (primary particle size: 40 nm, manufactured by Mitsubishi Chemical Corporation, # 25B) 4
A black toner developer was prepared in the same manner as for the cyan toner developer except that 96 parts by weight of the binder resin-1 was preliminarily mixed with 96 parts by weight of the binder resin-1.

(Comparative Example of Color Developer) In the above color developer, the individual toner flushing pigments were replaced with ordinary commercial pigments which were not pre-kneaded. Carbon black had a primary particle diameter of 25 nm. Cyan, magenta, yellow, and black toner color comparative example developers were prepared in the same manner as in the cyan toner developer, except that Mogar L manufactured by Cabot Corp. was used.

(Evaluation of Image Quality with Coloraton Developer) The above coloraton kit developer was placed in a remodeling machine of Acolor 635 (manufactured by Fuji Xerox Co., Ltd.) and 1000 sheets, 5000 sheets
, 10,000 and 50,000 copies, and a full-color image were prepared, and the image quality and image quality stability were evaluated.

(Image Quality Evaluation Criteria) な し: No background fog. Image quality is stable. Δ: Fog on the background was observed, but there was no practical problem. ×: Background fog is severe, and image quality is partially rubbed.

[0164]

[Table 6]

In the above-mentioned copy, the charge amount of the toner of Example was stable, and the obtained full-color image had no background fog, was transparent, and had an image quality giving a clear impression. . On the other hand, the charge amount of the color toner developer of the comparative example was significantly reduced as the number of copies increased, and the obtained full-color image exceeded 10,000 sheets, and the background fog was severe and blurred. The image quality was a certain level. In particular, the color reproduction of the black portion was poor, the color became reddish black, and the image quality was outdated.

[0166]

According to the present invention, a CMB carrier and a developer which are excellent in proper charge imparting property, charge maintaining property and environmental resistance to a toner by employing the above-described structure in a CMB developing system are provided. No brush mark or fog, excellent transparency, color reproducibility, detail image reproducibility, clarity, and color balance, color images can be formed stably, and stable for a long time Full color
It is now possible to provide copy images.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03G 9/10 321 361 (72) Inventor Kazuhiko Yanagita 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. (72) Invention Person Ryosaku Igarashi 1600 Takematsu, Minamiashigara-shi, Kanagawa F-term in Fuji Xerox Co., Ltd. (Reference) 2H005 AA01 AA08 AA21 BA06 BA07 CA08 CA21 CA28 CB04 CB07 CB13 DA09 EA01 EA03 EA05 EA07 EA10 FA02

Claims (14)

[Claims] 1. An electrophotographic carrier for developing a conductive magnetic brush having a resin coating layer on a core material, wherein the resin coating layer contains 0.5 to 2 mol% of a monomer having an amino group.
And a conductive powder having a specific resistance of 10 ⁰ to 10 ⁶ Ωcm, and wherein the carrier is a magnetic brush in a dynamic state under an electric field of 10 ⁴ V / cm. An electrophotographic carrier having an electric resistance in the range of 10 ⁰ to 10 ⁸ Ωcm. 2. The electrophotographic carrier according to claim 1, wherein a metal oxide powder is blended in the resin coating layer as the conductive powder in a range of 30 to 85% by weight. 3. The resin coating layer has a thickness of 0.3 to 5.0.
3. The electrophotographic carrier according to claim 1, wherein the carrier is in a range of μm. 4. The carrier has an average particle size of 10 to 80.
The electrophotographic carrier according to any one of claims 1 to 3, wherein the carrier is in a range of µm. 5. The dynamic resistance value of the core material is 10 ⁻⁵ to 10 ^2.
The carrier for electrophotography according to any one of claims 1 to 4, wherein the carrier is ferrite in a range of Ωcm. 6. An electrophotographic developer for electroconductive magnetic brush development comprising the electrophotographic carrier according to claim 1, and a toner containing a binder resin and a colorant. An electrophotographic developer comprising a polyester resin as the toner binder resin. 7. The polyester resin comprising a polyoxyalkylenebisphenol-type diol and an aromatic dicarboxylic acid, an acid anhydride thereof, or an ester thereof as a main monomer component, further comprising an alkyl succinic acid, an acid anhydride thereof, 7. The electron according to claim 6, wherein the ester comprises one or more succinic acid derivatives selected from the group consisting of an alkenyl succinic acid, an acid anhydride thereof, and an ester thereof as a monomer. Photographic developer. 8. The electrophotographic developer according to claim 7, wherein the polyester resin contains the succinic acid derivative in a range of 2 to 25 mol%. 9. The polyester resin further comprises a trivalent or higher polycarboxylic acid, an acid anhydride thereof, an ester thereof,
And 1 selected from the group of trihydric or higher polyhydric alcohols
9. The electrophotographic developer according to claim 7, wherein the developer contains at least 10% by mole of a kind or two or more kinds of monomers. 10. The toner according to claim 6, wherein the toner is a color toner, and the polyester resin has an acid value of 20 mg KOH / g or less and a hydroxyl value of 30 mg KOH / g or less. Item 8. The electrophotographic developer according to item 1. 11. The polyester resin has a glass transition temperature of 60 ° C. or higher, and a temperature at which the melt viscosity of the polyester resin becomes 1000 Pa · s is 115 to 150.
The electrophotographic developer according to any one of claims 6 to 10, wherein the developer temperature is in the range of ° C. 12. The electrophotographic device according to claim 6, wherein the toner contains, as an external additive, silicon oxide fine particles or titanium compound fine particles subjected to hydrophobic treatment. Developer. 13. The electrophotographic developer according to claim 6, wherein the toner is blended in a range of 3 to 8% by weight. 14. A step of forming an electrostatic latent image on a latent image carrier, a step of developing the electrostatic latent image by a conductive magnetic brush developing method using a developer, and a step of transferring the developed toner image to a transfer material. An electrostatic latent image developer according to any one of claims 6 to 13, wherein the image forming method comprises: a step of transferring the toner image on the transfer member; and a fixing step of heating and fixing the toner image on the transfer member. An image forming method characterized by using: