JP5344551B2 - Magenta toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magenta toner having improved durability relating to developability and transfer properties, and further is improved in fixability. <P>SOLUTION: The magenta toner comprises magenta toner particles containing at least a binder resin, a release agent, a colorant having a quinacridone skeleton, and a metal phthalocyanine and/or a metal phthalocyanine derivative having a center metal selected from a group consisting of Cr, Fe, Co, Zn and Mn. In a micro-compression test on the toner at a measurement temperature of 25&deg;C, the recovery rate of the toner particles obtained by a displacement amount and unloading conditions satisfies the relation: 60&le;(recovery rate)&le;90. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a magenta toner used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, or the like.

  Conventionally, many methods are known as electrophotographic methods. In general, a photoconductive substance is used, and an electric latent image is formed on the photoreceptor by various means. Next, the latent image is developed with toner to form a visible image. After the toner is transferred to a recording material (transfer material) such as paper, the toner image is fixed on the recording material with heat and pressure, and a copy is made. Is what you get.

  In recent years, with the development of computers and multimedia, there is a demand for means for outputting further high-definition full-color images in a wide range of fields from offices to homes. In particular, heavy users demand high durability without deterioration in image quality even when a large number of copies or prints are made, and studies have been made from various viewpoints in order to achieve these objects.

In particular, in recent years, there is a tendency for full-color copying or printing. In full-color image formation, an electrostatic latent image is generally developed using magenta toner, cyan toner, yellow toner, and black toner, and a multicolor image is reproduced by superimposing the toner images of each color. Yes.
In order to form a full color image, magenta toner, cyan toner, yellow toner and black toner are necessary. These toners are generally produced by changing the colorant added to the toner particles.
Therefore, the characteristics of the toner may change greatly depending on the added colorant. In particular, regarding toner durability, magenta toner tends to deteriorate in durability due to the influence of a colorant. As a result of the study by the present inventors on the reason, it has been clarified that when a colorant having a quinacridone skeleton is used as the colorant, the hardness of the toner particles tends to change greatly. When a colorant having a quinacridone skeleton is added to the toner particles, the colorant functions as a filler in the toner binder, so that the toner particles tend to be hard. As a result, the brittleness of the toner particles is deteriorated and the durability is considered to be lowered. In particular, when the toner is produced in an aqueous medium such as suspension polymerization, the colorant having a quinacridone skeleton tends to be unevenly distributed in the vicinity of the surface of the toner particles, and the decrease in durability tends to be remarkable.

Since the colorant having a quinacridone skeleton is generally excellent in light resistance and color, it is widely used as a toner colorant. Therefore, it is necessary to improve the durability of the toner by using a colorant having a quinacridone skeleton.
In general, from the viewpoint of improving the durability of the toner, the viscoelasticity and melt viscosity of the toner are often discussed. Since the toner deteriorates due to mechanical friction in the developing device, it is advantageous to increase the viscoelasticity and melt viscosity of the toner. In addition, the storage stability of the toner in an environment around 50 ° C. is also deteriorated. On the other hand, in the fixing step, the viscoelasticity and melt viscosity of the toner must be lowered in order to realize low-temperature fixing and image glossiness. In addition, it is preferable that the wax component in the toner particles easily exudes instantaneously (bleeding property) in the fixing step because the releasability from the fixing roller is improved. As described above, durability and fixability are contradictory performances, but many techniques have been studied so far to satisfy both of them.

As another attempt to improve the durability, there is one that focuses on the DSC curve of toner in a differential scanning calorimeter (DSC). In an image forming toner containing at least a binder resin and a colorant, at least one near the glass transition point of the binder resin in the second temperature rising process of the DSC curve of the toner measured by a differential scanning calorimeter An image forming toner characterized by the presence of an exothermic peak has been proposed (Patent Document 1).
Fixing property can be improved by this method. However, in general, when the durability related to the development characteristics near room temperature is taken into consideration, sufficient performance cannot be exhibited.

On the other hand, in order to improve the durability by taking into account the internal structure of the toner particles, it is necessary to discuss the durability and fixability of each toner particle unit. ) Is an effective indicator. The hardness (micro compression hardness) of the toner particles indicates the degree of deformation (elasticity / plasticity) of the toner particles. Therefore, in a transfer process in which toner particles can be deformed by applying pressure as in contact transfer, the micro-compression hardness of the toner can be an effective index for transferability in addition to durability and fixability.
For example, there is also a proposal for a capsule toner composed of a heat-meltable core (core) made of a thermoplastic resin having a low glass transition point and an outer shell (shell) mainly composed of amorphous polyester (core-shell structure). Has been done. Among these proposals, it is disclosed that the durability is improved by defining the relationship between the amount of displacement compressed when a load is applied to one toner particle and the load within a specific range (Patent Literature). 2, Patent Document 3).
Since this capsule toner has a structure in which a core material having a low glass transition point is covered with a relatively thick shell layer, it is effective in a heat and pressure fixing process. However, since the compatibility between the core material and the shell material is low, the shell part is detached from the toner particles in durability, and the chargeability of the toner tends to be low.

Further, an association method toner is disclosed in which toner particles are given a certain hardness by making the toner binder resin have a high molecular weight body and a low molecular weight body (Patent Document 4).
In this non-magnetic one-component developing system, this associative toner is excellent in durability stability without causing any harmful effects due to the frictional charging action of the toner carrier and the toner layer regulating member. This associative toner can be obtained through a step of salting out / fusing resin particles and colorant particles. However, in this associative toner, the resin particle structure is controlled so that the molecular weight of the resin constituting each layer becomes smaller as it goes from the central part to the surface layer, and there is a concern about storage stability and high-temperature offset resistance.

Further, the load-displacement curve obtained by performing a micro-compression test of toner particles has an inflection point, and the load at the inflection point is larger than the load received by the toner in the developing device. The use of toner is disclosed (Patent Document 5).
By this method, the toner is easily crushed in the fixing step, but the toner has excellent durability in the developing unit and stable charging characteristics can be obtained. However, this toner can satisfy the fixability in the fixing process, but it cannot satisfy the low-temperature fixability and can obtain a high image glossiness when dealing with a light load or high speed of the fixing process. Can not.

Many studies have been made for the purpose of improving the dispersibility of the colorant present in the toner. In order to improve the transparency of the magenta toner, the use of a quinacridone pigment having an average particle size of 0.5 μm or less is disclosed (Patent Document 6).
The transparency of the toner is determined by the pigment and the resin, the dispersion method in the resin and the degree thereof, and a magenta toner having a high transparency has not necessarily been obtained. Further, sufficient effects were not obtained with respect to the durability of the toner.

Furthermore, although a method for producing a toner while applying heat and pressure in a kneader is disclosed, this method is preferable for dispersing a colorant, but the molecular chain of the binder resin constituting the toner is strong. Cutting by the kneading load promotes partial reduction in molecular weight in the polymer. Therefore, high temperature offset is likely to occur in the fixing process (Patent Document 7, Patent Document 8, and Patent Document 9).
In particular, in full-color copying, three- or four-color toners are layered and fixed, so the high temperature offset latitude is much more severe than for black and white toners, and there is a slight molecular break in the polymer. This can easily cause high temperature offset. In addition, when the toner is produced in an aqueous medium such as suspension polymerization, it is difficult to use the above method.

In addition, as a method for dispersing the colorant, a resin and an aqueous presscake of a pigment are charged into a kneader and heated and kneaded to achieve dispersion of the pigment into the resin (Patent Document 10).
Although this method is preferable for dispersing the pigment, the pigment considering the color and reproducibility of the toner is not mentioned at all. Also, the durability of the toner is not sufficient.

As described above, in order to improve durability and fixability in a toner containing a colorant having a quinacridone skeleton, many studies have been made in consideration of the internal structure of the toner particles and the dispersibility of the colorant. However, in the current situation where higher speeds and high-definition full-color images are demanded, it is the actual situation that a toner that sufficiently satisfies high durability while maintaining fixability has not yet been obtained.
JP 2004-184561 A Patent No. 0300318 Patent No. 03391931 JP 2004-109601 A JP-A-2005-300937 JP-A-1-154161 Japanese Patent Laid-Open No. 4-39671 JP-A-4-39672 Japanese Patent Laid-Open No. 4-242752 JP-A-5-34978

  An object of the present invention is to provide a magenta toner having improved durability with respect to developability and transferability, and further improved fixability.

Metal phthalocyanine and / or metal, wherein the binder resin, the release agent, the colorant having a quinacridone skeleton, and the central metal is any metal selected from the group consisting of Cr, Fe, Co, Zn, and Mn A magenta toner having magenta toner particles containing at least a phthalocyanine derivative, the magenta toner particles obtained by manufacturing in an aqueous medium , and measured at a measurement temperature of 25 in a micro compression test for the magenta toner. ℃, the amount of displacement obtained when finished applying a maximum load of the one magenta toner over grain child loading rate ^{9.8 × 10 -5 N / sec 2.94} × 10 -4 N to ([mu] m) Displacement amount X ₂ , the displacement amount (μm) obtained by leaving for 0.1 second at the maximum load after finishing the application of the maximum load is the maximum displacement amount X ₃ , 0.1 After leaving for 2 seconds, unloading is performed at an unloading speed of 9.8 × 10 ⁻⁵ N / sec, and the displacement amount (μm) obtained when the load becomes 0 is defined as displacement amount X ₄ and the maximum displacement amount X ₃ . the difference between the displacement _{X 4} and the elastic displacement _(X 3 -X _4), percentage of the maximum displacement amount _{X 3} of the elastic displacement _{(X 3 -X 4) [{} (X 3 -X 4) / The present invention relates to a magenta toner characterized in that Z (25) satisfies 60 ≦ Z (25) ≦ 90 when X ₃ } × 100: Restoration rate] is Z (25) (%).

According to the present invention, in a toner containing a colorant having a quinacridone skeleton, the toner particles contain at least a specific metal phthalocyanine and / or a metal phthalocyanine derivative, and the toner particles have a specific displacement curve in a micro compression test. As a result, a magenta toner having good durability and fixing property can be provided.

The magenta toner of the present invention (hereinafter also simply referred to as toner) is composed of a binder resin, a release agent, a colorant having a quinacridone skeleton, and a central metal consisting of [Cr, Fe, Co, Zn, and Mn]. A magenta toner having magenta toner particles containing at least a metal phthalocyanine and / or a metal phthalocyanine derivative selected from the group, wherein the toner 1 particle is measured at a measurement temperature of 25 ° C. in a micro compression test for the toner. The displacement amount (μm) obtained when the maximum load of 2.94 × 10 ⁻⁴ N is finished at a load speed of 9.8 × 10 ⁻⁵ N / sec is the displacement amount X ₂ , and the maximum load is finished. after the maximum displacement amount obtained was left for 0.1 second under a load ([mu] m) the maximum displacement _{X 3,} after leaving the 0.1 seconds, unloading speed 9.8 × ¹⁰ -5 N / s unloaded at an c, the displacement amount obtained when the load becomes 0 ([mu] m) the displacement X _4, elastic displacement of a difference between the maximum displacement X ₃ and the displacement amount X ₄ (X ₃ -X ₄ ), and the percentage [(X ₃ −X ₄ ) / X ₃ × 100: restoration rate] of the elastic displacement amount (X ₃ −X ₄ ) with respect to the maximum displacement amount X ₃ is Z (25) (%). Z (25) satisfies the following condition: 60 ≦ Z (25) ≦ 90.

  Examples of the colorant having a quinacridone skeleton according to the present invention include a pigment composition represented by the following structural formula [1] from the viewpoint of light resistance and color of the toner, and these may be used alone or in combination. it can. Furthermore, it is also a preferred method to be used in combination as a mixed crystal.

［上記構造式（１）中、Ｘ_１とＸ_２は、水素原子、もしくはハロゲン基、アルキル基、及びアルコキシ基の群から選ばれる置換基を示す。］

[In the structural formula (1), X ₁ and X ₂ represent a hydrogen atom or a substituent selected from the group consisting of a halogen group, an alkyl group, and an alkoxy group. ]

  Among these, examples of the colorant having a quinacridone skeleton that has good interaction with the metal phthalocyanine and / or metal phthalocyanine derivative described below and can improve dispersibility include C.I. I. Pigment Red 122, 192, 202, C.I. I. Pigment Violet 19 is preferable.

In the present invention, the toner particles may contain a metal phthalocyanine and / or a metal phthalocyanine derivative whose central metal is selected from the group consisting of [Cr, Fe, Co, Zn, and Mn]. It is possible to prevent the colorant having a quinacridone skeleton in the particles from being unevenly distributed near the toner particle surface. Regarding this reason, the present inventors consider as follows.
That is, a metal phthalocyanine and / or a metal phthalocyanine derivative (hereinafter referred to as “metal phthalocyanines”) whose central metal used in the present invention is any one selected from the group consisting of [Cr, Fe, Co, Zn, Mn]. Is capable of adopting a 5-coordinate structure or a 6-coordinate structure capable of coordinating a ligand in the axial direction with respect to the phthalocyanine ring which is a compound.
The metal phthalocyanines used in the present invention exhibit good affinity with the quinacridone skeleton portion, and the polymer site not only exhibits affinity with the binder resin and other toner constituent materials, but also reaggregates due to steric hindrance. Can be prevented. Further, when the toner is produced in an aqueous medium such as a suspension polymerization method, the colorant having a quinacridone skeleton in the toner particles is less likely to be unevenly distributed in the vicinity of the toner particle surface. As a result, the brittleness of the toner particle surface can be made good, and the durability of the toner is improved.

  The metal phthalocyanines used in the present invention have a divalent metal or a trivalent or tetravalent substituted metal as a central metal because of the necessity of a pentacoordinate structure or a hexacoordinate structure. Specifically, considering the ease of incorporation of the axial ligand, it is essential that the selected ligand is any one selected from the group consisting of [Cr, Fe, Co, Zn, and Mn]. Zn phthalocyanine (zinc phthalocyanine) having a central metal of Zn represented by the following structural formula [2] capable of taking a coordinate structure is particularly preferably selected. Zinc phthalocyanine has good adsorption to a colorant having a quinacridone skeleton, and can prevent the colorant having a quinacridone skeleton in the toner particles from being unevenly distributed in the vicinity of the toner particle surface.

構造式〔２〕

Structural formula [2]

  Known metal phthalocyanines used in the present invention can be used. That is, it is not particularly limited as long as it has a phthalocyanine skeleton. For example, four isoindole moieties into which substituents such as carboxylic acid and sulfonic acid are introduced, aromatics, aliphatics, ethers, alcohols Those introduced with a substituent such as. However, it is not preferable that itself affects the adsorptivity of the phthalocyanine ring and the colorant and the ease of incorporation of the axial ligand.

  In the present invention, the metal phthalocyanines form a polymer complex using a polymer containing a specific polymerizable monomer having an amide group, which will be described later, as a constituent unit as a polymer ligand, and a dispersant for the colorant Therefore, the object can be achieved with a very small addition amount. On the other hand, when the addition amount is too large, the influence of the coloring power of the metal phthalocyanine itself needs to be in a range that can be ignored. The specific addition amount is preferably such that the mass ratio of the content of the colorant having a quinacridone skeleton and the metal phthalocyanine used simultaneously is 10 to 500. When the mass ratio of the content of the colorant having a quinacridone skeleton and the metal phthalocyanines is less than 10, the magenta hue tends to change easily. Furthermore, the dispersion of the colorant having a quinacridone skeleton is excessively increased, and the amount of the colorant having a quinacridone skeleton in the toner particles is increased, so that the durability tends to be lowered. On the other hand, when it exceeds 500, it tends to be difficult to sufficiently prevent the colorant having a quinacridone skeleton from being unevenly distributed near the surface in the toner particles.

In addition, the metal phthalocyanines are preferably contained in the magenta toner particles in an amount of 0.001 to 3000 parts by mass with respect to 100 parts by mass of the binder resin. When the addition amount of the metal phthalocyanines is less than 0.001 part by mass, a sufficient effect as dispersibility tends to be hardly exhibited. On the other hand, when it exceeds 3.000 parts by mass, the chargeability tends to decrease due to the influence of metal phthalocyanines.

In the magenta toner particles, the colorant having a quinacridone skeleton is present in a good state in the toner particles. Specifically, since the colorant having a quinacridone skeleton is not unevenly distributed in the vicinity of the surface of the toner particles, the vicinity of the toner surface layer (shell portion) is characterized by having an appropriate hardness. Therefore, the restoration rate shows a good value, the brittleness in the vicinity of the toner surface layer is greatly improved, and the durability of the toner is improved.

In the magenta toner of the present invention, the value of the restoration rate Z (25) is in a range satisfying 60 ≦ Z (25) ≦ 90 [preferably 60 ≦ Z (25) ≦ 80] in a minute compression test for the toner. By adjusting, the durability can be improved.
In the measurement method of micro compression in the present invention, the hardness near the toner surface and the recovery rate are evaluated by applying a small load such as 2.94 × 10 ⁻⁴ N to the toner as compared with the conventional measurement method. Is to measure.
The value of the restoration rate Z (25) in the toner of the present invention represents how much the toner surface layer is restored to the original state after applying a load to one toner particle at a temperature of 25 ° C. It is an indicator.

  When Z (25) is less than 60, the toner is easily deformed by stress applied in the developing device, and developability and transferability are deteriorated. On the other hand, if the value of Z (25) exceeds 90, the toner particle surface becomes difficult to be deformed, so that the external additive is less likely to adhere to the toner particle surface. Is easily released, and developability and transferability deteriorate.

The magenta toner of the present invention has a restoration rate Z (50) value of 10 ≦ Z (50) ≦ 50 [more preferably, 20 ≦ Z (50) ≦ 50] in a minute compression test for the toner. It is preferable to adjust the range to satisfy the range because the fixability can be further improved. If the value of Z (50) is less than 10, hot offset tends to occur during fixing, and if the value of Z (50) exceeds 90, the gloss tends to decrease.
In addition, the value of the said restoration rate Z (25) and the value of the restoration rate Z (50) adjust the addition amount of the coloring agent which has a quinacridone skeleton, and metal phthalocyanine and / or a metal phthalocyanine derivative, and the ratio of those addition amounts. Thus, it is possible to adjust to the above range.

Next, a measurement method of the micro compression test will be described with reference to FIG.
FIG. 1 is a profile (displacement curve) obtained in a micro compression test for the toner of the present invention. In the figure, the horizontal axis represents the amount of displacement of the toner, and the vertical axis represents the amount of load applied to the toner.
The micro compression test in the present invention is carried out using an ultra micro hardness tester ENT1100 manufactured by Elionix Co., Ltd., according to an operation manual attached to the measuring instrument. In this test, the indenter used is a 20 μm × 20 μm square flat indenter. (1-1) in the figure is the initial state before starting the test. From this state, a load is applied at a speed of 9.8 × 10 ⁻⁵ N / sec with respect to the maximum load of 2.94 × 10 ⁻⁴ N. Immediately after reaching the maximum load, the state is (1-2), and the displacement amount at this time is X ₂ (μm). In the state of (1-2), leave with the load for 0.1 sec. The state immediately after the end of standing is (1-3). The maximum displacement at this time is X ₃ (μm), and after the maximum load, unloading is performed at a speed of 9.8 × 10 ⁻⁵ N / sec. When the load becomes 0, the state is (1-4). The amount of displacement at this time is X ₄ (μm)
And
The restoration rate Z (25) is obtained as 100 × (X ₃ −X ₄ ) / X ₃ . Further restoration rate Z (50)
The value of is a value measured in the same manner as the measurement method of Z (25) except that measurement is performed at a measurement temperature of 50 ° C.

In actual measurement, a toner is applied on a ceramic cell, and minute air is blown so that the toner is dispersed on the cell. The cell is set in the apparatus and measured.
In the measurement, the cell is brought into a temperature-controllable state, and the temperature of the cell is set as a measurement temperature. That is, Z (25) is measured at a cell temperature of 25 ° C., and Z (50) is measured at a cell temperature of 50 ° C. In the micro compression test according to the present invention, the toner is dispersed on the cell, and then the cell is placed on the main body. Thereafter, after the cell reaches the measurement temperature, it is left for 10 minutes or more, and then the measurement is started.
For the measurement, while looking through the microscope attached to the apparatus, select the measurement screen (horizontal width: 160 μm, vertical width: 120 μm) in which one toner exists. In order to eliminate the displacement error as much as possible, a toner having a number average particle diameter (D1) of ± 0.2 μm is selected and measured. An arbitrary toner is selected from the measurement screen, and the toner particle diameter measuring means on the measurement screen measures the major and minor diameters of the toner particles using the software attached to the microhardness meter ENT1100. A toner having a value of aspect ratio [(major axis + minor axis) / 2] determined from them of D1 of ± 0.2 μm is selected and measured.
Regarding measurement data, 100 arbitrary particles were selected and measured, and the remaining 80 data obtained by excluding 10 from the maximum and minimum values for Z (25) and Z (50) obtained as the measurement results were used as data. And Z (25) and Z (50) are obtained as the 80 arithmetic mean values.

The method for measuring the number average diameter (D1) of the toner is as follows.
A Coulter Multisizer (manufactured by Beckman Coulter) is connected to an interface (manufactured by Nikka) and a PC 9801 personal computer (manufactured by NEC) for outputting the number distribution and volume distribution, and used for measurement.
A 1% NaCl aqueous solution (electrolytic aqueous solution) is prepared using primary sodium chloride (ISOTON R-II (manufactured by Coulter Scientific Japan) may be used). 20 mg of a measurement sample (toner) is added to 150 ml of the electrolytic aqueous solution. The electrolytic aqueous solution in which the sample is suspended is dispersed for 3 minutes with an ultrasonic disperser to prepare a sample for measurement. The measurement sample is measured by the Coulter Multisizer equipped with a 100 μm aperture, and the volume and number of toner particles of 2.0 μm or more are measured to determine the number average particle diameter (D1).

  Examples of the binder resin used in the present invention include styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, and styrene-butadiene copolymers. As the polymerizable monomer for forming the polymer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

The following are mentioned as a polymerizable monomer used for binder resin. Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.
These may be used alone or in general by appropriately mixing monomers with reference to the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-p139 to 192 (manufactured by John Wiley & Sons). Used.

In the production of the toner of the present invention, it is preferable to add a low molecular weight polymer in order to obtain a preferable molecular weight distribution of the toner of the present invention. The low molecular weight polymer can be added at the time of melt kneading with a binder resin or the like when the toner is produced by a pulverization method, and the polymerizable single monomer is produced when the toner is produced by a suspension polymerization method. It can be added to the body composition.
The low molecular weight polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 2,000 to 5,000, and Mw / Mn of less than 4.5, preferably Those less than 3.0 are preferred.
Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.

In the present invention, in order to increase the mechanical strength of the toner particles and control the molecular weight of the binder resin of the toner, a crosslinking agent may be used when the binder resin is synthesized.
Examples of the crosslinking agent used in the present invention include the following as the bifunctional crosslinking agent.
Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.
The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer.

  In the toner of the present invention, it is possible to achieve both durability and fixability by setting the Tg of the toner itself including the polar resin described later to 35 to 60 ° C.

In the present invention, it is preferable to use a polar resin such as a polyester resin or a polycarbonate resin together with the above-described binder resin. Of this polar resin
By setting the glass transition temperature (Tg) in the differential scanning calorimeter to 80 to 120 ° C., both durability and low-temperature fixability can be further enhanced. In the toner of the present invention, when the Tg value is less than 80 ° C., the durability of the toner tends to decrease, and when the Tg value exceeds 120 ° C., the low-temperature fixability tends to decrease.

  When the toner particles of the present invention are directly produced by suspension polymerization, it is preferable to add a polar resin during the polymerization reaction from the dispersion step to the polymerization step. Thereby, the added polar resin can form a thin core on the surface of the toner particles in accordance with the balance of polarity exhibited by the polymerizable monomer composition serving as the toner particles and the aqueous dispersion medium. In addition, the presence state of the polar resin can be controlled so that the presence ratio of the polar resin is large on the surface of the toner particles and the presence ratio of the polar resin is decreased as going to the center of the toner particles. That is, the strength of the shell part of the core-shell structure can be freely controlled by adding the polar resin. Furthermore, there is an effect of suppressing the uneven distribution of the colorant having a quinacridone skeleton near the toner surface, so that the durability and fixability of the toner can be optimized. In order to form the core-shell structure, the acid value of the polar resin is preferably 5 to 25 mgKOH / g in the present invention.

A preferable addition amount of the polar resin is 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the presence of the polar resin in the toner particles tends to be non-uniform, and the triboelectric charge distribution of the toner tends to be broad. Conversely, if the amount exceeds 30 parts by mass, the polar resin is formed on the surface of the toner particles. The thin layer becomes thicker and the fixability tends to decrease.
Specific examples of the polar resin used in the present invention include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, styrene-methacrylic acid copolymers and styrene-acrylic acid copolymers having a peak molecular weight of 3,000 to 50,000 are preferable as polar resins because the amount added during toner production can be freely controlled. Further, when a styrene-methacrylic acid copolymer or a styrene-acrylic copolymer is used as the polar resin, the compatibility of the toner with the binder resin is improved. As a result, the presence of the polar resin can be controlled so that the presence of the polar resin is large on the surface of the toner particles and the proportion of the polar resin is decreased as it goes to the center of the toner particles. Adhesion with the layer is increased, and the durability of the toner is improved.

The glass transition temperature (Tg) of the toner particles and the polar resin in the present invention is measured by using a differential scanning calorimeter (DSC measuring apparatus; “DSC-7” manufactured by Perkin Elmer Co.) according to ASTM D3418-82. Desired. As a detailed measurement method, a modulated mode is used, measurement is performed under the following conditions, and the midpoint method is obtained from the peak position of the DSC curve at the first temperature increase. A sample to be measured is precisely weighed 10 mg in an aluminum pan, and an empty pan is set for measurement and measured.
<Measurement conditions>
• Equilibrate at a temperature of 20 ° C for 5 minutes.
・ Modulation of 1.0 ° C / min was applied, and the temperature was increased to 140 ° C at 1 ° C / min. • Equilibrate at 140 ° C for 5 minutes.
・ Temperature drop to 20 ℃.

On the other hand, the method for measuring the molecular weight of the polar resin in the present invention is such that the polar resin to be measured and THF are mixed at a concentration of 5 mg / ml, left at room temperature for 5 hours, and then sufficiently shaken to prepare the THF and sample. Are mixed well (until the sample is no longer united), and further left at room temperature for 24 hours.
Then, what passed the sample processing filter (Maishori disk H-25-2 Tosoh company make, Excro disk 25CR Gelman Science Japan company make) is prepared as a sample of GPC.
The molecular weight distribution of the prepared sample and the molecular weight (Mp) of the main peak are measured using a GPC measurement apparatus (HLC-8120G PC manufactured by Tosoh Corporation) according to the operation manual of the apparatus under the following measurement conditions.
<Measurement conditions>
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, a calibration curve was obtained from standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F- manufactured by Tosoh Corporation). 20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

The acid value of the polar resin in the present invention is determined by the following operations (1) to (5). The basic operation follows JIS K 0070.
(1) The measurement sample is precisely weighed. Let the mass of the sample at this time be W (g).
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (toluene mass / ethanol mass = 4/1) is added and dissolved.
(3) Measurement is performed using a potentiometric titration apparatus using an ethanol solution of 0.1 (mol / l) KOH. For this titration, for example, an automatic titration using a potentiometric titration measuring device AT-400 (winworkstation) of Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.
(4) The amount of KOH ethanol solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH ethanol solution used at this time is defined as B (ml).
(5) The acid value is calculated by the following formula. In the following formula, f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

  The following are mentioned as a mold release agent used for this invention. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; carnauba wax Natural waxes such as candelilla wax and derivatives thereof. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. Further, in the toner of the present invention, it is more preferable to use a hydrocarbon wax in order to easily control the core-shell structure and to easily exhibit the effects of the present invention.

  The release agent is preferably contained in an amount of 4 to 25 parts by mass with respect to 100 parts by mass of the binder resin. When the release agent is 4 to 25 parts by mass with respect to 100 parts by mass of the binder resin, the wrapping property is improved by having a moderate release agent bleeding property when the toner is heated and pressurized. Further, even when the toner is subjected to stress during development or transfer, exposure of the release agent to the toner surface is small and uniform triboelectric chargeability of each toner can be obtained.

In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By blending the charge control agent, the charging characteristics are stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.
As the charge control agent, a known charge control agent can be used in a known addition amount. In particular, a charge control agent that has a high frictional charging speed and can stably maintain a constant triboelectric charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.
Examples of charge control agents include those that control the toner to be negatively charged, such as organometallic compounds and chelate compounds. Specific examples include a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid, and a dicarboxylic acid-based metal compound. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.
Examples of charge control agents include those that control the toner to be positively charged. Nigrosine modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Some onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid , Ferricyanides, ferrocyanides); metal salts of higher fatty acids; resin-based charge control agents.
The toner of the present invention can contain these charge control agents alone or in combination of two or more.
Among these charge control agents, a metal-containing salicylic acid-based compound is preferable in order to sufficiently exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium.
The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.
A preferable blending amount of the charge control agent is 0.01 to 20 parts by mass, more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention.

In the present invention, the toner particles contain a polymer or copolymer of a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group for the purpose of charge control and stabilization of granulation in an aqueous medium. Is also a preferred form. When the toner of the present invention is produced by a suspension polymerization method, the addition of the polymer or copolymer promotes the core-shell structure of the toner particles in the polymerization stage as well as stabilizing the granulation. Therefore, it is possible to further improve both the durability and the fixing property of the toner. Further, by adding metal phthalocyanines to the toner particles as in the present invention, it is possible to prevent the toner from being poorly charged which tends to occur.
Examples of the monomer having a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group for producing the polymer or copolymer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2- Examples include methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid, and alkyl esters thereof.
The polymer containing a sulfonic acid group, a sulfonic acid group salt, or a sulfonic acid ester group used in the present invention may be a homopolymer of the monomer, but the monomer and other monomer It may be a copolymer with a body. Examples of the monomer that forms a copolymer with the monomer include vinyl polymerizable monomers, and monofunctional polymerizable monomers or polyfunctional polymerizable monomers can be used. .
A preferable blending amount of the polymer or copolymer having a sulfonic acid group, a sulfonic acid group salt, or a sulfonic acid ester group is 0.1 to 5 parts by mass, and more preferably, 0.1 parts by mass with respect to 100 parts by mass of the binder resin. 1 to 1 part by mass.

The toner particles of the present invention are preferably externally added with inorganic fine powder as a fluidizing agent.
As the inorganic fine powder added to the toner particles of the present invention, silica is preferable, and silica fine powder having a number average primary particle size of 4 to 80 nm is preferable. In the present invention, when the number average primary particle size is in the above range, the fluidity of the toner is improved and the storage stability of the toner is also improved.

The number average particle diameter of the inorganic fine powder is measured using a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.). The photographing magnification is 100,000 times, and the photographed photograph is further doubled, and then 300 samples of inorganic fine powder are randomly extracted from the photograph image. Then, the maximum particle size is the major axis, the minimum particle size is the minor axis, and the number average particle size is determined based on the major axis.

As the inorganic fine powder, silica and fine powder such as titanium oxide, alumina, or a double oxide thereof can be used in combination. The fine powder used in combination with silica is preferably titanium oxide.
The silica includes both dry silica produced by vapor phase oxidation of silicon halides or dry silica called fumed silica, and wet silica produced from water glass. As the inorganic fine powder used in the present invention, dry silica having less silanol groups on the surface and inside of the silica fine powder and less production residue of Na ₂ O and SO ₃ ²⁻ is preferable. In addition, dry silica can be used in the production process to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds. is there. The silica includes them.

The inorganic fine powder is preferably added for improving the fluidity of the toner and making the toner particles triboelectrically charged. In addition, the inorganic fine powder can be hydrophobized by imparting functions such as adjustment of the triboelectric charge amount of the toner, improvement of environmental stability, and improvement of characteristics in a high humidity environment. It is more preferable to use a treated inorganic fine powder. This is because when the inorganic fine powder added to the toner absorbs moisture, the triboelectric charge amount as the toner decreases, and the developability and transferability tend to decrease.
Examples of the treatment agent for the hydrophobic treatment of the inorganic fine powder include the following. Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination.
Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is hydrophobized with a coupling agent at the same time or after the treatment, and the hydrophobized inorganic fine powder treated with silicone oil maintains a high triboelectric charge amount of the toner particles even in a high humidity environment. It is good for reducing selective developability.

  The method for producing the toner of the present invention can use a pulverization method or a polymerization method, and is not particularly limited. However, in view of ease of drawing out the characteristics of the present invention, the magenta toner particles are preferably obtained by producing them in an aqueous medium, which means that it is easy to balance the particle size and particle shape. In that respect, it is more preferable that it is produced by a suspension polymerization method. In particular, the magenta toner particles are prepared by dispersing and granulating a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a release agent in an aqueous medium, thereby polymerizing the polymerizable monomer. The toner particles obtained by doing so are preferred.

In this suspension polymerization method, a colorant and a release agent, and if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed in a polymerizable monomer. Let it be a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed and granulated in a continuous layer containing a dispersant (for example, an aqueous medium) using an appropriate stirrer, and the polymerization reaction of the polymerizable monomer is performed. To obtain toner particles having a desired particle size. When toner particles are produced by this suspension polymerization method, since the individual toner particle shapes are almost spherical, the charge amount distribution is relatively uniform, and a toner having satisfactory development characteristics can be easily obtained.
On the other hand, in the present invention, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibition property and water phase transfer property of the colorant, and preferably, surface modification, for example, polymerization inhibition It is better to give the colorant a hydrophobizing treatment with no substances.

As the dispersant used in the preparation of the aqueous medium, known inorganic and organic dispersants can be used.
Specifically, examples of the inorganic dispersant include the following. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Is mentioned. Examples of the organic dispersant include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, and starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.
As the dispersant, an inorganic poorly water-soluble dispersant is preferable, and it is more preferable to use a poorly water-soluble inorganic dispersant that is soluble in an acid.

In the present invention, when preparing a water-based dispersion medium using a hardly water-soluble inorganic dispersant, the amount of these dispersants used is 0.2 to about 100 parts by mass of the polymerizable monomer. It is preferable that it is 2.0 mass parts. In the present invention, it is preferable to prepare an aqueous dispersion medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.
In the present invention, when preparing an aqueous dispersion medium in which the poorly water-soluble inorganic dispersant as described above is dispersed, a commercially available dispersant may be used as it is. Further, in order to obtain dispersant particles having a fine uniform particle size, a water-based dispersion medium can be prepared by generating a poorly water-soluble inorganic dispersant as described above in a liquid medium such as water under high-speed stirring. Good. For example, when tricalcium phosphate is used as a dispersant, a preferred dispersant can be obtained by mixing aqueous sodium phosphate solution and aqueous calcium chloride solution at high speed to form fine particles of tricalcium phosphate. .

Moreover, the following are mentioned as said polymerization initiator. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.
The amount of these polymerization initiators used varies depending on the desired degree of polymerization, but is generally 3 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

Next, an example of the image forming method used in the present invention will be described with reference to FIGS.
The configuration of the image forming apparatus is shown in FIG. FIG. 3 is a sectional view of a tandem type color LBP (color laser printer) as an example of an image forming apparatus used in the image forming method according to the present invention. FIG. 2 is an enlarged view of the developing unit of the apparatus.
In FIG. 3, reference numeral 101 (101a to 101d) denotes a drum-type electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) as a latent image carrier that rotates in a direction indicated by an arrow (counterclockwise) at a predetermined process speed. . The photosensitive drums 101a, 101b, 101c, and 101d sequentially share the yellow (Y) component, magenta (M) component, cyan (C) component, and black (Bk) component of the color image.
Hereinafter, the Y, M, C, and Bk image forming apparatuses are referred to as a unit a, a unit b, a unit c, and a unit d, respectively.
These photosensitive drums 101a to 101d are rotationally driven by a drum motor (DC servo motor) (not shown), but independent driving sources may be provided for the respective photosensitive drums 101a to 101d. The rotational drive of the drum motor is controlled by a DSP (digital signal processor) (not shown), and other controls are performed by a CPU (not shown).
The electrostatic adsorption conveyance belt 109a is stretched around a driving roller 109b, fixed rollers 109c and 109e, and a tension roller 109d. The electrostatic adsorption conveyance belt 109a is rotationally driven by the driving roller 109b in the direction indicated by the arrow in FIG. To do.

Hereinafter, unit a (yellow) of the four colors will be described as an example.
The photosensitive drum 101a is uniformly charged to a predetermined polarity and potential by the primary charging means 102a during its rotation. The photosensitive drum 101a is exposed to a light image by a laser beam exposure means (hereinafter referred to as a scanner) 103a, and an electrostatic latent image of image information is formed on the photosensitive drum 101a.
Next, a toner image is formed on the photosensitive drum 101a by the developing unit 104a, and the electrostatic latent image is visualized. Similar steps are performed for the other three colors (magenta (B), cyan (C), and black (Bk)).
Thus, the four-color toner images are synchronized by the registration roller 108c that stops and re-transports the recording medium S conveyed by the paper feed roller 108b at a predetermined timing. Then, the toner images are sequentially transferred to the recording medium S at the nip portion between the photosensitive drums 101a to 101d and the electrostatic adsorption conveyance belt 109a. At the same time, the photosensitive drums 101a to 101d after the transfer of the toner image to the recording medium S are subjected to repeated image formation by removing residual deposits such as transfer residual toner by the cleaning means 106a, 106b, 106c and 106d. .
The recording medium S on which the toner images are transferred from the four photosensitive drums 101a to 101d is separated from the surface of the electrostatic attraction / conveying belt 109a by the driving roller 109b and sent to the fixing device 110. Then, after the toner image is fixed in the fixing device 110, the toner image is discharged onto the discharge tray 113 by the discharge roller 110c.

Next, a specific example of an image forming method using the non-magnetic one-component contact developing method applied as the present invention will be described with reference to an enlarged view of the developing portion (FIG. 2). In FIG. 2, the developing unit 13 is located in a developer container 23 containing non-magnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23. A photosensitive drum) 10 and a toner carrier 14 disposed opposite to each other. The electrostatic latent image on the latent image carrier 10 is developed and visualized. The latent image carrier contact charging member 11 is in contact with the latent image carrier 10. The bias of the latent image carrier contact charging member 11 is applied by a power source 12.
The toner carrier 14 is horizontally provided with the substantially right half-periphery surface shown in the drawing through the opening into the developer container 23 and the left substantially half-periphery surface exposed outside the developer container 23. The surface exposed to the outside of the developer container 23 is in contact with the latent image carrier 10 located on the left side of the developing unit 13 in the drawing as shown in FIG.
The toner carrier 14 is rotationally driven in the direction of arrow B, the peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is 1 to 2 with respect to the peripheral speed of the latent image carrier 10. It is rotating at twice the peripheral speed.
At a position above the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate of SUS or phosphor bronze having spring elasticity, and a contact surface side to the toner carrier 14. There is a regulating member 16 made of a rubber material or the like adhered thereto. The restricting member 16 is supported by a restricting member supporting metal plate 24 and is provided so that the vicinity of the free end is brought into contact with the outer peripheral surface of the toner carrier 14 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support sheet metal 24, and the contact pressure (linear pressure) with respect to the toner carrier 14 is appropriately set. is there. The contact pressure is preferably 20 to 300 N / m. The measurement of the contact pressure is converted from a value obtained by inserting three metal thin plates with known friction coefficients into the contact portion and pulling out the central one with only a spring. The regulating member 16 having a rubber material or the like bonded to the abutting surface is desirable in terms of adhesion to the toner, and can suppress the fusion and fixing of the toner to the regulating member in long-term use. Further, the restricting member 16 can be in contact with the toner carrier 14 by edge contact with which the tip is in contact. In the case of edge contact, it is more desirable in terms of toner layer regulation to set the contact angle of the regulating member with respect to the tangent of the toner carrying body at the contact with the toner carrying body to be 40 degrees or less.
The toner supply roller 15 is in contact with the contact portion of the regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. The contact width of the toner supply roller 15 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.
The charging roller 29 is not essential for the image forming method of the present invention, but is preferably installed. The charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the charging member 29 on the toner carrier 14 by the suppressing member 30 is set to 0.49 to 4.9N. Due to the contact of the charging roller 29, the toner layer on the toner carrier 14 is finely filled and uniformly coated. The longitudinal positional relationship between the regulating member 16 and the charging roller 29 is preferably arranged so that the charging roller 29 can reliably cover the entire contact area of the regulating member 16 on the toner carrier 14.
Further, for the driving of the charging roller 29, a driven or the same peripheral speed is indispensable between the charging roller 29 and the toner carrier 14, and if a peripheral speed difference occurs between the charging roller 29 and the toner carrier 14, the toner coat becomes uneven. This is not preferable because unevenness occurs on the image.
The bias of the charging roller 29 is applied by a power source 27 between the toner carrier 14 and the latent image carrier 10 in a direct current (27 in FIG. 2), and the nonmagnetic toner 17 on the toner carrier 14 is charged by the charging roller. From 29, charge is applied by discharge.
The bias of the charging roller 29 is a bias equal to or higher than the discharge start voltage having the same polarity as that of the nonmagnetic toner, and is set so that a potential difference of 1000 to 2000 V is generated with respect to the toner carrier 14.
After being charged by the charging roller 29, the toner layer formed as a thin layer on the toner carrier 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 10.
In this developing unit, the toner layer formed as a thin layer on the toner carrier 14 is transferred to the latent image by a DC bias applied between the toner carrier 14 and the latent image carrier 10 by the power source 27 shown in FIG. The electrostatic latent image on the carrier 10 is developed as a toner image.

  The present invention will be specifically described with reference to the following examples. A method for producing toner particles will be described below. In the examples and comparative examples, “part” and “%” are all based on mass unless otherwise specified.

Example 1
A polymerized toner was produced according to the following procedure.
9 parts by mass of tricalcium phosphate was added to 1300 parts by mass of ion-exchanged water heated to 60 ° C., and the mixture was stirred at 10,000 r / min using a TK homomixer (manufactured by Tokushu Kika Kogyo). . Thereafter, 11 parts by mass of 10% hydrochloric acid was added to adjust pH to prepare an aqueous medium.
Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
・ Styrene 69.0 parts by mass ・ N-butyl acrylate 31.0 parts by mass ・ Sulphonic acid group-containing resin (Acrybase FCA-1001-NS, manufactured by Fujikura Kasei)
0.7 parts by mass of styrene-methacrylic acid-methyl methacrylate (styrene / methacrylic acid / methyl methacrylate = 95.85 / 1.65 / 2.50, Mp
= 15,000, Mw = 7,900, Tg = 89 ° C., acid value = 10.9
mgKOH / g, Mw / Mn = 2.17)
20.0 parts by mass Next, the following materials were added to the solution.
・ C. I. Pigment Red 122 (PR122) 7.0 parts by mass, Zn phthalocyanine 0.0375 parts by mass, negative charge control agent (Bontron E-88, manufactured by Orient Chemical) 1.0 part by mass, hydrocarbon wax having a melting point of 77 ° C. HNP-51 (manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Thereafter, the mixture was heated to a temperature of 60 ° C. and then TK type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 5 at 9,000 r / min. Stir for hours, dissolve and disperse.
Into this, 8.0 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was put into the aqueous medium and stirred at 12,000 r / min for 10 minutes at a temperature of 60 ° C. using a TK homomixer, and granulated.
Thereafter, the mixture was transferred to a propeller type stirring device and reacted at a temperature of 70 ° C. for 5 hours while stirring at 100 r / min, and then heated to a temperature of 80 ° C. and further reacted for 5 hours to produce toner particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain toner particles. Hydrophobic silica fine powder (number average 1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. A toner (A) was obtained by mixing 2.0 parts by mass of a secondary particle size of 10 nm and a BET specific surface area of 170 m ^{2 /} g with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes. Table 1 shows the physical properties of Toner (A).

(Example 2)
A toner (B) was obtained in the same manner as in Example 1 except that PR122 was changed to 5 parts by mass in Example 1 and 3 parts by mass of PR150 was added as a colorant. Table 1 shows the physical properties of Toner (B).

(Example 3)
A toner (C) was obtained in the same manner as in Example 1 except that PR122 was changed to PR192 in Example 1. Table 1 shows the physical properties of Toner (C).

Example 4
A toner (D) was obtained in the same manner as in Example 1 except that PR122 was changed to PR202 in Example 1. Table 1 shows the physical properties of Toner (D).

(Example 5)
In Example 1, (a mass ratio PR122: PV19 = 75: 25) to PR122 PR122 and mixed crystals of PV19 except to change, prepared in the same manner as in Example 1, to obtain a toner (E) It was. Table 1 shows the physical properties of Toner (E).

(Example 6)
A toner (F) was obtained in the same manner as in Example 1 except that Zn phthalocyanine was changed to Cr phthalocyanine in Example 1. Table 1 shows the physical properties of Toner (F).

(Example 7)
A toner (G) was produced in the same manner as in Example 1 except that Zn phthalocyanine was changed to Fe phthalocyanine in Example 1. Table 1 shows the physical properties of Toner (G).

(Example 8)
A toner (H) was obtained in the same manner as in Example 1 except that Zn phthalocyanine was changed to Co phthalocyanine in Example 1. Table 1 shows the physical properties of Toner (H).

Example 9
A toner (I) was obtained in the same manner as in Example 1 except that Zn phthalocyanine was changed to Mn phthalocyanine in Example 1. Table 1 shows the physical properties of Toner (I).

(Example 10)
A toner (J) was obtained in the same manner as in Example 1 except that the amount of PR122 added was changed to 3 parts by mass and the amount of Zn phthalocyanine added was changed to 0.0015 parts by mass in Example 1. . Table 1 shows the physical properties of Toner (J).

(Example 11)
A toner (K) was obtained in the same manner as in Example 1 except that the amount of Zn phthalocyanine added in Example 1 was changed to 2.8 parts by mass. Table 1 shows the physical properties of Toner (K).

(Example 12)
A toner (L) was obtained in the same manner as in Example 1 except that the amount of PR122 added was changed to 33 parts by mass and the amount of Zn phthalocyanine added was changed to 3.05 parts by mass in Example 1. . Table 1 shows the physical properties of Toner (L).

(Example 13)
In Example 1, except that the amount of PR122 added was changed to 0.4 parts by mass and the amount of Zn phthalocyanine added was changed to 0.0009 parts by mass, the toner (
M) was obtained. Table 1 shows the physical properties of Toner (M).

(Example 14)
In Example 1, the polar resin was styrene / butyl acrylate / methyl methacrylate / monobutyl maleate having a Tg of 74 ° C. (styrene / butyl acrylate / methyl methacrylate / monobutyl maleate = 82.35 / 13.50 / 2.50 / 1). .65, Mp = 15
The toner (N) was produced in the same manner as in Example 1 except that the toner was changed to 12,000, Mw = 12,000, Tg = 74 ° C., Mw / Mn = 2.87). Table 1 shows the physical properties of Toner (N).

(Example 15)
In Example 1, the polar resin was styrene-methyl methacrylate-acryloylmorpholine (styrene / methyl methacrylate / acryloylmorpholine = 3.
00 / 30.00 / 67.00, Mp = 18,000, Mw = 102,000, Tg = 128 ° C., Mw / Mn = 5.66). The toner (O) was obtained. Table 1 shows the physical properties of Toner (O).

(Example 16)
A toner (P) was obtained in the same manner as in Example 1, except that the reaction was performed at a temperature of 70 ° C. for 5 hours in Example 1 except that the reaction was performed at a temperature of 85 ° C. for 5 hours. Table 1 shows the physical properties of Toner (P).

(Example 17)
A toner (Q) was obtained in the same manner as in Example 1 except that the reaction in Example 1 was performed at a temperature of 70 ° C. for 5 hours, except that the reaction was performed at a temperature of 45 ° C. for 5 hours. Table 1 shows the physical properties of Toner (Q).

(Example 18)
A toner (R) was obtained in the same manner as in Example 1 except that the sulfonic acid group-containing resin was not added. Table 1 shows the physical properties of Toner (R).

(Example 19)
In Example 19, a toner was produced by the emulsion aggregation method described below.
(Preparation of resin fine particle dispersion)
Styrene 69.0 parts by mass n-butyl acrylate 31.0 parts by mass sulfonic acid group-containing resin (Acrybase FCA-1001-NS, manufactured by Fujikura Kasei))
0.7 parts by mass The above ingredients are mixed and dissolved, while the nonionic surfactant (Nonipol 400, manufactured by Kao)
What melt | dissolved 6 mass parts and 10 mass parts of anionic surfactant (Neogen SC, Daiichi Kogyo Seiyaku Co., Ltd.) in 500 mass parts of ion-exchange water was accommodated in the flask. Then, the above mixed solution was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 4 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath until the temperature reached 70 ° C. while stirring, and emulsion polymerization was continued for 5 hours. Thereby, an anionic resin fine particle dispersion was obtained.
(Preparation of colorant particle dispersion)
-PR122 7.0 parts by mass-Zn phthalocyanine 0.0375 parts by mass-Nonionic surfactant (Nonipol 400, manufactured by Kao) 1.0 part by mass-Ion-exchanged water 100.0 parts by mass The above components are mixed and dissolved. Dispersion was carried out for 10 minutes using a homogenizer (Ultra Turrax manufactured by IKA) to obtain a colorant particle dispersion.
(Preparation of release agent particle dispersion)
-8.0 parts by mass of hydrocarbon wax (HNP-51, Nippon Seiwa Co., Ltd.) having a melting point of 77 ° C-5.0 parts by mass of cationic surfactant (Sanisol B50, manufactured by Kao)-Ion-exchanged water 200. 0 part by mass The above components were heated to a temperature of 95 ° C. and sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge homogenizer to obtain a release agent particle dispersion.
[Preparation of fine particle dispersion for shell formation]
20.0 parts by mass of the polar resin used in Example 1 was dissolved in 50.0 parts by mass of ethyl acetate. The emulsified solution was emulsified with IKA Ultra Turrax T50, and the solvent was removed by heating at 80 ° C. and holding for 6 hours to obtain a shell-forming fine particle dispersion.
[Creation of toner particles]
The resin fine particle dispersion, the colorant particle dispersion, the release agent particle dispersion, and 1.2 parts by mass of polyaluminum chloride are mixed, and an IKA Ultra Turrax T50 is prepared in a round stainless steel flask. After sufficiently mixing and dispersing, the flask was heated to a temperature of 51 ° C. while stirring the flask in a heating oil bath. After maintaining at a temperature of 51 ° C. for 60 minutes, the above-mentioned fine particle dispersion for shell formation was added thereto. Then, after adjusting the pH in the system to 6.5 using a sodium hydroxide aqueous solution having a concentration of 0.5 mol / L, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while stirring was continued. Heated to a temperature of 97 ° C. and held for 3 hours. After completion of the reaction, the reaction mixture was cooled, filtered, sufficiently washed with ion exchange water, and solid-liquid separation was performed by Nutsche suction filtration. This was further redispersed with 3 L of ion-exchanged water at a temperature of 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 5 times, and then No. 1 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner particles. The following toner particle processing method was produced in the same manner as in Example 1 to obtain toner (R). Table 1 shows the physical properties of Toner (R).

(Comparative Example 1)
A toner (a) was obtained in the same manner as in Example 1 except that Zn phthalocyanine was not added. Table 1 shows the physical properties of Toner (a).

(Comparative Example 2)
A toner (b) was produced in the same manner as in Example 1 except that the amount of Zn phthalocyanine added was 4 parts by mass and no polar resin was added. Table 1 shows the physical properties of Toner (b).

(Comparative Example 3)
A toner (c) was obtained in the same manner as in Example 1 except that Zn phthalocyanine was changed to Mg phthalocyanine in Example 1. Table 1 shows the physical properties of Toner (c).

The evaluation method and evaluation criteria of the present invention will be described below.
<Evaluation for developability>
(1) Fog / Image Density In the image forming apparatus of the contact single component development system shown in FIG. 2, a developer is charged with 250 g of the toner described in the examples and comparative examples, and the normal temperature and humidity (temperature 23 ° C., Leave in a 60% RH environment for 24 hours. At this time, the transfer paper is also left as it is. In the evaluation regarding developability, Xerox 4200 (75 g / m ² paper) was used as the transfer paper. Thereafter, the image forming apparatus of the contact one-component developing system shown in FIG. 2 is installed in the unit b portion of FIG. 3 in an environment of normal temperature and normal humidity (temperature 23 ° C., humidity 60% RH), and the process speed in the magenta single color mode. Was carried out at 250 mm / s. Under this condition, continuous output is performed on a chart with a printing ratio of 2%. Evaluation on developability is carried out at the time of initial / 10,000 sheets / 20,000 sheets, and image density / fogging is confirmed by the following method.

(1-1) Fog As for the fog evaluation method, an image having a white background portion was output, and measurement was performed by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku). From the difference between the whiteness (reflectance Ds (%)) of the white background portion of the printout image and the whiteness of the transfer paper (average reflectance Dr (%)), the fog density (%) (= Dr (%) − Ds ( %)) And image fog at the end of durability evaluation was evaluated. An amberlite filter was used as the filter. A, B, and C are levels that do not cause a problem in use, while D is a level that causes a problem in use.
A: Less than 0.5% B: 0.5% or more and less than 1.0% C: 1.0% or more and less than 1.5% D: 1.5% or more and less than 5.0%

(1-2) Image Density For the image density, a “Macbeth reflection densitometer RD918” (manufactured by Macbeth) was used to measure a relative density with respect to an image of a white background portion having an original density of 0.00. A, B, and C are levels that do not cause a problem in use, while D is a level that causes a problem in use.
A: 1.40 or more B: 1.30 or more, less than 1.40 C: 1.20 or more, less than 1.30 D: 1.10 or more, less than 1.20

<Evaluation on transferability>
(2) Transfer Efficiency / Transfer Uniformity Similar to the evaluation of developability, in the image forming apparatus of the contact single component development system shown in FIG. Leave in a high humidity (temperature 30 ° C./humidity 85% RH) environment for 24 hours. At this time, the transfer paper is also left as it is. After that, the image forming apparatus of the contact one-component developing system shown in FIG. 2 is installed in the unit b part of FIG. It implemented as 200 mm / s. Continuous output is performed using a chart with a print ratio of 2%. Evaluation of transfer efficiency / transfer uniformity was performed at the initial stage / 10,000 sheets / 20,000 sheets.

(2-1) Transfer efficiency Xerox 4200 (75 g / cm ² paper) is used as the transfer paper, and the entire body is forcibly output during the output (during the transfer process) of a single solid image (toner paste amount 0.55 mg / cm ² ). power off.
Then, the weight per unit area of the toner before transfer on the photosensitive drum and the toner transferred to the transfer material is measured, and the transfer efficiency is measured by the following equation. A, B, and C are levels that do not cause a problem in use, while D is a level that causes a problem in use.
Transfer efficiency = 100 × (toner transferred to transfer material / toner before transfer on photosensitive drum)
A: 90% or more B: 82% or more and less than 90% C: 75% or more and less than 82% D: Less than 75%

(2-2) Transfer Uniformity A half-tone entire image with a toner applied amount of 0.20 mg / cm ² is used as transfer paper with Xero.
Evaluation was performed using x4200 (75 g / cm ² paper) and Fox River Bond (90 / cm ² paper). The criteria are shown below.
A: Both Xerox 4200 and Fox River Bond show good transfer uniformity, and there is no problem in use.
B: Although the transfer uniformity of the Fox River Bond is slightly inferior, there is no problem in use.
C: Although the transfer uniformity of the Fox River Bond is slightly inferior, it is less likely to cause a problem in use.
D: Since the transfer uniformity of the Fox River Bond is inferior, it is likely to cause a problem in use.

<Evaluation on fixability>
(3) Low-temperature fixability / image glossiness In the image forming apparatus of the contact one-component development system shown in FIG. 2, the developer is filled with 250 g of the toner described in the examples and comparative examples, and the normal temperature and humidity (temperature (23 ° C., humidity 60% RH). At this time, the transfer paper is also left as it is. Thereafter, the image forming apparatus of the contact one-component developing system shown in FIG. 2 is installed in the unit b portion of FIG. 3 in an environment of normal temperature and normal humidity (temperature 23 ° C., humidity 60% RH), and the process speed in the magenta single color mode. An unfixed image was output at 200 mm / s.

(3-1) Low-temperature fixability A plain paper for a copying machine (64 g / m ² paper) was used as a transfer material, and an unfixed image on which a solid image with a toner applied amount of 0.6 mg / cm ² was obtained was obtained. This was fixed at a process speed of 250 mm / s using a fixing machine of IRC3200 (manufactured by Canon Inc.). The fixing temperature was in the range of 130 to 200 ° C. at intervals of 5 ° C. The image was reciprocated five times with sylbon paper applied with a load of 4.9 kPa, and the temperature at which the density reduction rate was 20% or more was evaluated as the minimum fixing temperature. A, B, and C are levels that do not cause a problem in use, while D is a level that causes a problem in use.
A: Fixing lower limit temperature is less than 145 ° C. B: Fixing lower limit temperature is 145 ° C. or more and less than 155 ° C. C: Fixing lower limit temperature is 155 ° C. or more and less than 165 ° C. D: Fixing lower limit temperature is 165 ° C. or more, 175 Less than ℃

(3-2) Image Glossiness Xerox 4200 (75 g / m ² paper) was used as a transfer material, and an unfixed image on which a solid image with a toner applied amount of 0.5 mg / cm ² was placed was obtained. This was fixed at a process speed of 100 mm / s and a fixing temperature of 180 ° C. using a fixing machine of IRC3200 (manufactured by Canon Inc.). Using “PG-3D” (manufactured by Nippon Denshoku Industries Co., Ltd.), the image glossiness at a measurement optical part angle of 75 ° was measured. A, B, and C are levels that do not cause a problem in use, while D is a level that causes a problem in use.
A: 25 or more B: 20 or more, less than 25 C: 18 or more, less than 20 D: 15 or more, less than 18

(Evaluation Test 1)
As a result of performing the above evaluation on the toner (A), good results were obtained in each item. The evaluation results are shown in Table 2.

(Evaluation test 2)
As a result of carrying out the above evaluation on the toner (B), good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 3)
As a result of carrying out the above evaluation on the toner (C), good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 4)
As a result of carrying out the above evaluation on the toner (D), good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 5)
As a result of carrying out the above evaluation on the toner (E), good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 6)
As a result of carrying out the above evaluation on the toner (F), generally good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 7)
As a result of performing the above evaluation on the toner (G), generally good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 8)
As a result of carrying out the above evaluation on the toner (H), generally good results were obtained in each item. The evaluation results are shown in Table 2.

(Evaluation Test 9)
As a result of carrying out the above evaluation on the toner (I), generally good results were obtained in the respective items. The evaluation results are shown in Table 2.

(Evaluation Test 10)
As a result of performing the above evaluation on the toner (J), the fixing property deteriorated. The reason for this is considered to be that the ratio of the addition amount of the colorant having a quinacridone skeleton and the metal phthalocyanine is too large. The evaluation results are shown in Table 2.

(Evaluation Test 11)
As a result of performing the above evaluation on the toner (K), the developability deteriorated. The reason for this is thought to be that the ratio of the colorant having a quinacridone skeleton and the metal phthalocyanines is too small. The evaluation results are shown in Table 2.

(Evaluation Test 12)
As a result of performing the above evaluation on the toner (L), the developability and transferability deteriorated. The reason for this is considered to be that the amount of Zn phthalocyanine added is too large. The evaluation results are shown in Table 2.

(Evaluation Test 13)
As a result of performing the above evaluation on the toner (M), the developability deteriorated. The reason for this is considered to be that the amount of metal phthalocyanines added is too small. The evaluation results are shown in Table 2.

(Evaluation Test 14)
As a result of performing the above evaluation on the toner (N), the fixing property was deteriorated. This reason is considered to be because the Tg of the polar resin is too low. The evaluation results are shown in Table 2.

(Evaluation Test 15)
As a result of carrying out the above evaluation on the toner (O), the developability and the fixability deteriorated. The reason for this is considered that the Tg of the polar resin is too high. The evaluation results are shown in Table 2.

(Evaluation Test 16)
As a result of performing the above evaluation on the toner (P), the fixing property (image glossiness) was deteriorated. The reason for this is considered that the glossiness of the image deteriorates due to the occurrence of high temperature offset because the value of Z (50) of the toner is too low. The evaluation results are shown in Table 2.

(Evaluation Test 17)
As a result of performing the above evaluation on the toner (Q), the fixing property deteriorated. This is considered to be because the value of Z (50) of the toner is too high. The evaluation results are shown in Table 2.

(Evaluation Test 18)
As a result of carrying out the above evaluation on the toner (R), the developability and transferability deteriorated. The reason for this is thought to be that charging failure of the toner occurred because the sulfonic acid group-containing resin was not added. The evaluation results are shown in Table 2.

(Evaluation Test 19)
As a result of performing the above evaluation on the toner (S), good results were obtained in each item even when the toner was produced by the emulsion aggregation method. The evaluation results are shown in Table 2.

(Comparative evaluation test 1)
As a result of carrying out the above evaluation on the toner (a), the developability was remarkably deteriorated. This is probably because no Zn phthalocyanine was added. The evaluation results are shown in Table 2.

(Comparative evaluation test 2)
As a result of performing the above evaluation on the toner (b), the fixability was remarkably deteriorated in the initial stage. Therefore, the printout evaluation for 20,000 sheets was not performed. The evaluation results are shown in Table 2.

(Comparative evaluation test 3)
As a result of performing the above evaluation on the toner (c), the developability and transferability were remarkably deteriorated. This is considered to be due to the use of Mg phthalocyanine. The evaluation results are shown in Table 2.

It is a load-displacement curve in the micro compression test of toner. It is an enlarged view of the developing unit of the electrophotographic apparatus. 3 is an electrophotographic apparatus used for evaluating the toner of the present invention.

Explanation of symbols

Reference Signs List 10 latent image carrier 11 latent image carrier contact charging member 12 power supply 13 developing unit 14 toner carrier 15 toner supply roller 16 regulating member 17 nonmagnetic toner 23 developer container 24 regulating member support sheet metal 29 charging roller 30 suppressing member 101a d Photosensitive drums 102a to d Primary charging means 103a to d Laser beam exposure means 104a to d Developing sections 106a to d Cleaning means 108b Paper feed roller 108c Registration roller 109a Electrostatic adsorption transport belt 109b Drive roller 109c, e Fixed roller 109d Tension roller 110 Fixing device 110c Discharge roller 113 Discharge tray S Recording medium

Claims (9)

Metal phthalocyanine and / or metal, wherein the binder resin, the release agent, the colorant having a quinacridone skeleton, and the central metal is any metal selected from the group consisting of Cr, Fe, Co, Zn, and Mn A magenta toner having magenta toner particles containing at least a phthalocyanine derivative,
The magenta toner particles are obtained by manufacturing in an aqueous medium,
In the micro compression test for the magenta toner, at a measurement temperature of 25 ° C., applying a maximum load of 2.94 × ^{10 -4} N at a loading rate 9.8 × ¹⁰ -5 N / sec to one the magenta toner over particle child The amount of displacement (μm) obtained when finished is the amount of displacement X ₂ , and after the maximum load is applied, the amount of displacement (μm) obtained by leaving for 0.1 second at the maximum load is the amount of maximum displacement X ₃ After leaving for 0.1 seconds, the unloading speed is 9.8 × 10 ⁻⁵ N / sec, and the displacement amount (μm) obtained when the load becomes 0 is expressed as the displacement amount X ₄ , the maximum elastic displacement of the difference between the displacement _{X 3} and displacement _{X 4 (X} 3 -X ₄₎ and then, the elastic displacement _(X 3 -X ₄₎ percentage of the maximum displacement amount _{X 3} of _{[{(X 3} −X ₄ ) / X ₃ } × 100: Restoration rate] is Z (25) (%), Z (25 ) Satisfies 60 ≦ Z (25) ≦ 90. Obtained when a maximum load of 2.94 × 10 ⁻⁴ N was applied to one particle of the toner at a measurement temperature of 50 ° C. and a loading speed of 9.8 × 10 ⁻⁵ N / sec in the micro-compression test for the toner. The displacement amount (μm) obtained is the displacement amount X ₂ , the displacement amount (μm) obtained by leaving the maximum load for 0.1 second after the maximum load is applied, and the maximum displacement amount X ₃ , 0.1 After leaving for 2 seconds, unloading is performed at an unloading speed of 9.8 × 10 ⁻⁵ N / sec, and the displacement amount (μm) obtained when the load becomes 0 is defined as displacement amount X ₄ and the maximum displacement amount X ₃ . the difference between the displacement _{X 4} and the elastic displacement _(X 3 -X _4), percentage of the maximum displacement amount _{X 3} of the elastic displacement _{(X 3 -X 4) [{} (X 3 -X 4) / X ₃ } × 100: Restoration rate] is Z (50) (%), Z (50) is 10 ≦ Z ( The magenta toner according to claim 1, wherein 50) ≦ 50 is satisfied. The colorant having the quinacridone skeleton is C.I. I. Pigment Red 122, 192, 202, or C.I. I. The magenta toner according to claim 1, wherein the toner is Pigment Violet 19. The magenta toner according to any one of claims 1 to 3, wherein the magenta toner particles contain a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. 5. The magenta toner according to claim 1, wherein the magenta toner particles contain a polar resin, and the glass transition temperature of the polar resin is 80 to 120 ° C. 6. 6. The metal phthalocyanine and / or the metal phthalocyanine derivative is contained in 0.001 to 3000 parts by mass with respect to 100 parts by mass of the binder resin in the magenta toner particles. The magenta toner according to any one of the above. The magenta toner according to claim 1, wherein a central metal of the metal phthalocyanine and / or metal phthalocyanine derivative is Zn. The mass ratio of the content of the colorant having a quinacridone skeleton and the metal phthalocyanine and / or metal phthalocyanine derivative contained in the magenta toner is 10 to 500. The magenta toner according to item. The magenta toner particles are obtained by dispersing and granulating a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a release agent in an aqueous medium to polymerize the polymerizable monomer. The magenta toner according to any one of claims 1 to 8 , wherein the toner particles are obtained by toner particles.

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