JP5274157B2 - Magenta toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magenta toner free of cleaning failure even during printing in the initial stage at a high printing speed in a low temperature and low humidity environment. <P>SOLUTION: The magenta toner includes magenta toner particles containing at least: a binder resin; a release agent; a colorant having a specified structure; 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 under the conditions of 25&deg;C measurement temperature, a displacement amount (&mu;m) obtained after loading a single particle of the toner with the maximum of 2.94&times;10<SP>-4</SP>N at a loading speed of 9.8&times;10<SP>-5</SP>N/sec is finished, is denoted by a displacement amount X<SB>2</SB>; a displacement amount (&mu;m) obtained when the toner particle after finishing the maximum loading is left to stand for 0.1 second under the maximum load, is denoted by a maximum displacement amount X<SB>3</SB>; a displacement amount (&mu;m) obtained when the toner after left for the 0.1 second is unloaded down to zero at an unloading speed of 9.8&times;10<SP>-5</SP>N/sec, is denoted by a displacement amount X<SB>4</SB>; the difference between the maximum displacement X<SB>3</SB>and the displacement X<SB>4</SB>is denoted by an elastic displacement amount (X<SB>3</SB>-X<SB>4</SB>); and a percentage [(X<SB>3</SB>-X<SB>4</SB>)/X<SB>3</SB>&times;100, which defines a recovery rate] of the elastic displacement amount (X<SB>3</SB>-X<SB>4</SB>) with respect to the maximum displacement amount X<SB>3</SB>is denoted by Z(25) (%), Z(25) satisfies 60&le;Z(25)&le;90. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a magenta toner that reveals an electrostatic charge latent image.

  Conventionally, as an image forming method, many methods such as an electrophotographic method, that is, an electrostatic recording method, a magnetic recording method, and a toner jet method are known. Among them, as an electrophotographic method, a photoconductive substance is generally used, an electric latent image is formed on a photoreceptor by various means, and then the latent image is developed with toner to be visible. It is to be an image. Further, if necessary, toner is transferred to a transfer material such as paper, and then a toner image is fixed on the transfer material by heat, pressure or the like to obtain a copy. Toner that is not transferred and remains on the photoreceptor is cleaned by various methods, and the above-described steps are repeated.

  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. A heavy user demands high durability without deterioration in image quality even in the initial stage and a large number of copies or prints. In small offices and homes, there are demands for obtaining a high-quality image and miniaturizing the apparatus and lowering the fixing temperature from the viewpoint of saving space and energy. Various studies have been carried out from various viewpoints 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, with regard to toner cleaning, magenta toner tends to deteriorate in cleaning properties due to the influence of the colorant. As a result of investigations by the inventors about the reason, it has been clarified that when a colorant having a monoazo skeleton is used as the colorant, the initial chargeability of the toner tends to change greatly. It has been clarified that when a colorant having a monoazo skeleton is added to the toner particles, cleaning failure is likely to occur particularly in the initial stage of printing.
This is considered that when the pigment is used as a toner colorant, its own charging action affects the physical properties of the toner due to intramolecular polarization of the azo pigment. That is, since the charge amount of the azo pigment itself is high, the charge amount of the toner becomes excessive, and it is considered that cleaning failure is likely to occur.
Further, when the pigment is used as a toner colorant, the electrostatic charge of the toner, such as a toner carrying member, is increased due to an excessive charge amount of the toner. Has been found to cause toner contamination.

  Conventionally, it is known to use a quinacridone pigment, a thioindigo pigment, a xanthene pigment, a monoazo pigment, a perylene pigment, a diketopyrrolopyrrole pigment, or the like alone or in combination for the magenta toner. Among these, monoazo pigments have been widely used as colorants for toners because of their excellent weather resistance (light) resistance. Therefore, it is necessary to improve the toner cleaning property by using a colorant having a monoazo skeleton, and to further suppress toner contamination on the member.

On the other hand, there is a technique for improving the cleaning property by optimizing the toner shape (Patent Document 1). In Japanese Patent Laid-Open No. 2004-260688, toner surface cleanliness and toner chargeability are controlled by controlling the surface roughness of the toner. In addition to the toner shape, it has also been proposed to further improve the cleaning property by using a pigment surface-treated with a rosin resin.
However, the toner proposed in Patent Document 1 has several examples with different charge amounts, and a certain level of cleaning performance is satisfactory, but it is still at a satisfactory level in a low temperature and low humidity environment. Absent.

Further, there is a technique for improving the toner cleaning property by controlling the toner strength (Patent Document 2). In Patent Document 2, there is an inflection point in a test force-displacement graph obtained by performing a micro-compression test of toner particles, and the cleaning property is controlled by defining the strength. However, although the toner proposed in Patent Document 2 has sufficient cleaning performance after durability, the cleaning performance in the initial state is unclear. The present inventors have further investigated the cleaning performance when the printing speed is further increased and the initial toner has a high charge amount, and it has been found that the cleaning performance is still insufficient.
As described above, in order to improve the cleaning property in a toner containing a colorant having a monoazo skeleton, studies are made in consideration of the toner shape and strength. However, in the current situation where higher speeds and high-definition full-color images are required, it is the actual situation that a toner that sufficiently satisfies the cleaning property has not yet been obtained.
JP 2007-155926 A JP 2007-003694 A

  The problem to be solved by the present invention is to provide a toner that solves the above problems of the background art. That is, it is to provide a magenta toner that does not cause a cleaning failure even in initial printing at a high printing speed in a low temperature and low humidity environment. Furthermore, it is to provide a magenta toner in which the contamination of the member is suppressed even during long-term use.

［前記式（１）中、Ｒ_１〜Ｒ_３は、水素原子、若しくはハロゲン原子、又はアルキル基、アルコキシ基、ニトロ基、アニリド基、及びスルファモイル基からなる群より選ばれる置換基を示し、Ｒ_４は、−ＯＨ、−ＮＨ_２、

、及び

からなる群より選ばれる置換基を示し、Ｒ_５〜Ｒ_８は、水素原子、若しくはハロゲン原子、又はアルキル基、アルコキシ基、ニトロ基からなる群より選ばれる置換基を示す。］

The present invention, both a binder resin, a releasing agent, a colorant having the structure of Formula (1), central metal, Cr, Fe, Co, chosen from Zn, and M n or Ranaru group or a metal phthalocyanine and / or metal phthalocyanine derivative is a metal a magenta toner having magenta toner particles containing at least, in the microscopic compression test on the toner at a measurement temperature 25 ° C., loading rate on the toner 1 particles The displacement amount (μm) obtained when the maximum load of 2.94 × 10 ⁻⁴ N is finished at 9.8 × 10 ⁻⁵ N / sec is the displacement amount X ₂ , and after the maximum load is applied, Displacement amount (μm) obtained by leaving at the maximum load for 0.1 second is the maximum displacement amount X ₃ , and after leaving for 0.1 second, it is unloaded at the unloading speed of 9.8 × 10 ⁻⁵ N / sec. When the load becomes 0 The obtained displacement amount (μm) is the displacement amount X ₄ , the difference between the maximum displacement amount X ₃ and the displacement amount X ₄ is the elastic displacement amount (X ₃ -X ₄ ), and the elastic displacement amount (X ₃ -X _4). ) With respect to the maximum displacement amount X ₃ [ { (X ₃ −X ₄ ) / X ₃ } × 100: Restoration rate] is Z (25) (%), Z (25) is 60 ≦ The present invention relates to a magenta toner characterized by satisfying Z (25) ≦ 90.

[In the formula (1), R _{1 to} R ₃ represent a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of an alkyl group, an alkoxy group, a nitro group, an anilide group, and a sulfamoyl group; ₄ is —OH, —NH ₂ ,

,as well as

R _{5 to} R ₈ represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. ]

  According to the present invention, it is possible to obtain a magenta toner that does not cause a cleaning failure even in initial printing at a high printing speed in a low temperature and low humidity environment. Furthermore, it is possible to obtain a magenta toner in which member contamination is suppressed even after long-term use.

Hereinafter, the present invention will be described in detail.
In order to satisfactorily clean the transfer residual toner with the cleaning blade, it is important that a blocking layer is formed by the transfer residual toner at the abutting portion of the blade and the blocking layer is present stably. The blocking layer is a toner layer in which the transfer residual toner accumulates without passing through the cleaning blade at the blade abutting portion and continues to exist. By forming this layer, the subsequent transfer residual toner can be satisfactorily cleaned. become.
The formation of the blocking layer needs to be performed promptly at the initial stage of printing, and it is important that the charge amount of the toner is not excessive and that the toner surface has an appropriate deformation characteristic. If the charge amount of the toner is excessive, the surface energy of the toner also becomes excessive, and it is easy to slip through the cleaning blade. Further, even when the toner surface does not have an appropriate deformation characteristic, it is easy to slip through the cleaning blade.

  On the other hand, the contamination of the member by the toner causes the toner to adhere to the member, and then the toner is fused to the member by applying physical energy such as pressure. In order to suppress member contamination, it is important to suppress this phenomenon in the former stage. That is, the electrostatic force is the dominant factor in the adhesion of toner to a charge imparting member such as a developing roller. Therefore, in order to suppress the adhesion, it is necessary not to impart an excessive charge amount to the toner.

  Accordingly, the present inventors have paid attention to these matters, and in particular, in magenta toner, have intensively studied improvement of cleaning defects and member contamination, which are the problems of the present invention. As a result, it has been found that a magenta toner capable of improving the above-described problems can be obtained by containing a specific metal complex and imparting appropriate deformability to the toner.

［前記式（１）中、Ｒ_１〜Ｒ_３は、水素原子、若しくはハロゲン原子、又はアルキル基、アルコキシ基、ニトロ基、アニリド基、及びスルファモイル基からなる群より選ばれる置換基を示し、Ｒ_４は、−ＯＨ、−ＮＨ_２、

、及び

からなる群より選ばれる置換基を示し、Ｒ_５〜Ｒ_８は、水素原子、若しくはハロゲン原子、又はアルキル基、アルコキシ基、ニトロ基からなる群より選ばれる置換基を示す。］ That is, the magenta toner of the present invention (hereinafter also simply referred to as “toner”) includes a binder resin, a release agent, a colorant having a structure of the following formula (1), and a central metal [Cr, Fe, Co, Zn, and Mn] magenta toner having magenta toner particles containing at least metal phthalocyanine and / or metal phthalocyanine derivative selected from the group consisting of Co, Zn, and Mn, and measured in a micro compression test for the toner A displacement amount (μm) obtained when a maximum load of 2.94 × 10 ⁻⁴ N is applied to the toner particle at a load speed of 9.8 × 10 ⁻⁵ N / sec at a temperature of 25 ° C. X ₂ , after finishing the application of the maximum load, the displacement amount (μm) obtained by leaving for 0.1 second at the maximum load is the maximum displacement amount X ₃ , after leaving for 0.1 second, the unloading speed is 9. 8 × ¹⁰ -5 unloaded at an N / sec, resiliently displace the displacement amount obtained when a load becomes 0 ([mu] m) the displacement _{X 4,} and the maximum displacement _{X 3} and the displacement amount _{X 4} The amount (X ₃ −X ₄ ) and the percentage of the elastic displacement amount (X ₃ −X ₄ ) to the maximum displacement amount X ₃ [(X ₃ −X ₄ ) / X ₃ × 100: restoration rate] is Z ( 25) (%), Z (25) satisfies 60 ≦ Z (25) ≦ 90.

[In the formula (1), R _{1 to} R ₃ represent a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of an alkyl group, an alkoxy group, a nitro group, an anilide group, and a sulfamoyl group; ₄ is —OH, —NH ₂ ,

,as well as

R _{5 to} R ₈ represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. ]

  Examples of the colorant having a monoazo skeleton according to the present invention include a pigment composition represented by the following structural formula (1) from the viewpoint of the weather resistance (light) property of the toner, and these may be used alone or in combination. it can.

［前記式（１）中、Ｒ_１〜Ｒ_３は、水素原子、又はハロゲン原子、もしくはアルキル基、アルコキシ基、ニトロ基、アニリド基、及びスルファモイル基からなる群より選ばれる置換基を示し、Ｒ_４は、−ＯＨ、−ＮＨ_２、

、及び

からなる群より選ばれる置換基を示し、Ｒ_５〜Ｒ_８は、水素原子、若しくはハロゲン原子、又はアルキル基、アルコキシ基、ニトロ基からなる群より選ばれる置換基を示す。］

[In the formula (1), R _{1 to} R ₃ represent a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of an alkyl group, an alkoxy group, a nitro group, an anilide group, and a sulfamoyl group; ₄ is —OH, —NH ₂ ,

,as well as

R _{5 to} R ₈ represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. ]

In the present invention, in the toner particles, the central metal is [Cr, Fe, Co, Zn,
And Mn], by including a metal phthalocyanine and / or a metal phthalocyanine derivative selected from the group consisting of Mn], it is possible to suppress excessive toner charging even in a toner using a colorant having a monoazo skeleton. 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 phthalocyanine derivatives”, whose central metal is any one selected from the group consisting of [Cr, Fe, Co, Zn, and Mn] used in the present invention. Can be a pentacoordinate structure or a hexacoordinate 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 monoazo skeleton portion, and also suppress the overcharge of the toner by reducing the charge of the colorant having a monoazo skeleton by causing a charge interaction. The metal phthalocyanines also have an affinity with the binder resin and other toner constituent materials, so they exist uniformly throughout the toner particles without being unevenly distributed, so there is no local charge concentration and uniform charge distribution. It becomes.
In addition, when a toner is produced in an aqueous medium such as a suspension polymerization method, a colorant having a monoazo skeleton has a high polarity, so that the colorant is unevenly distributed near the toner particle surface. Although the toner charge amount tends to be excessive due to frictional charging of the toner, the above effect can be obtained by containing metal phthalocyanines, and the uneven distribution of the colorant near the toner particle surface is suppressed. Let As a result, the charge amount of the toner can be made good, and toner cleaning properties and contamination of the members are suppressed.

  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, the central metal is indispensable to be any one selected from the group consisting of [Cr, Fe, Co, Zn, and Mn] in consideration of easy incorporation of the axial ligand. Among these, Zn phthalocyanine (zinc phthalocyanine) having a central metal of Zn represented by the following structural formula [2] capable of taking a five-coordinate structure is particularly preferably selected. Zinc phthalocyanine has good adsorption to a colorant having a monoazo skeleton, and can particularly favorably reduce the charge of the colorant having a monoazo skeleton in the toner particles and prevent uneven distribution near the toner particle surface.

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. 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 described later as a constituent unit as a polymer ligand. And since it acts as a dispersing agent with respect to the coloring agent which has a monoazo skeleton, it becomes easy to acquire the effect of this invention by adding this polymer.
On the other hand, the amount of metal phthalocyanine added needs to be in a range where the influence of the coloring power of the metal phthalocyanine itself can be ignored. The specific addition amount is preferably such that the mass ratio of the content of the colorant having a monoazo skeleton and the metal phthalocyanine used simultaneously is 10 to 500. When the mass ratio of the content of the colorant having a monoazo skeleton and the metal phthalocyanines is less than 10, the magenta hue tends to change easily. Furthermore, the charge amount of the toner tends to decrease due to excessive charge relaxation of the colorant having a monoazo skeleton. On the other hand, when it exceeds 500, the charge relaxation of the colorant having a monoazo skeleton may be insufficient, and as a result, the charge amount of the toner tends to be excessive, and cleaning failure and member contamination may occur.

The metal phthalocyanines are preferably contained in the magenta toner particles in an amount of 0.001 to 1.000 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 is not exhibited, and the level of cleaning failure and member contamination tends to decrease. On the other hand, when the amount exceeds 1,000 parts by mass, the chargeability tends to decrease due to the influence of metal phthalocyanines, and the image density tends to decrease and fog tends to occur.

The specific conductivity of the colorant having the structure of the above formula (1) is preferably 40 to 60 μS / cm. When the specific conductivity is less than 40 μS / cm, it is difficult for the metal phthalocyanines to interact well with each other, and there is a tendency that cleaning failure and member contamination are likely to occur.
On the other hand, when it exceeds 60 μS / cm, it tends to be disadvantageous in the frictional charging characteristics of the toner and tends to cause adverse effects such as a decrease in charge amount due to long-term use.
The specific conductivity of the colorant having the structure of the above formula (1) is adjusted as follows. That is, the amount of calcium and magnesium in the colorant is adjusted by mixing the magenta colorant with an aqueous solution containing a calcium compound or a magnesium compound, followed by filtration and drying. At this time, the amount of calcium and magnesium in the colorant can be adjusted by the concentration of the calcium compound and the aqueous solution of the magnesium compound, the mixing time, or the amount of washing water and the number of washings after the filtration.

Moreover, the measurement of the specific conductivity of the colorant having the structure of the above formula (1) is performed as follows using an electric conductivity measuring instrument (TOA M-2A manufactured by Toa DKK Corporation) according to the operation manual of the measuring instrument. To do.
Weigh 5 g of colorant into an Erlenmeyer flask. Next, 5 ml of ethanol and 5 ml of purified water are added and stirred to wet the magenta colorant. Then, 90 ml of purified water is further added and shaken for 30 minutes to obtain a sample. The sample is filtered with a filter paper (Toyo Filter Paper Type No. 6), and the obtained filtrate is measured by the electric conductivity measurement.

Among the colorants having the structure of the above formula (1), examples of the colorant having a monoazo skeleton that has good interaction with metal phthalocyanines and can suppress excessive charging of the toner include C.I. I. Pigment Red 31, 146, 150, 185, 238, and 269 are preferable.
Of these, C.I. I. Pigment Red 238 and C.I. I. Pigment
Both of the structural formulas of Red 269 are as shown in the following formula (3), and the structures thereof are the same, and any of them may be used.

Next, a micro compression test of magenta toner will be described.
In the magenta toner of the present invention, it is an essential requirement that the value of the restoration rate Z (25) in the minute compression test of the toner is 60 ≦ Z (25) ≦ 90.
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 the stress received in the developing device, and the deformed toner contaminates the member and causes an image defect. On the other hand, if the value of Z (25) exceeds 90, the surface of the toner particles is difficult to deform, and it becomes difficult to form a blocking layer at the abutting portion of the cleaning blade, resulting in poor cleaning.
The present inventors consider this phenomenon as follows. That is, the toner particle surface is appropriately deformed at the abutting portion of the cleaning blade, so that the toner is slightly caught on the blade. Then, it is considered that the toner stays at the abutting portion without passing through the blade, and this leads to the prompt formation of the blocking layer.
The value of the restoration rate Z (25) is controlled by controlling the molecular weight and glass transition temperature (Tg) of the binder resin of the toner, the physical properties and addition amount of the wax, and the toner surface layer material. It is possible to adjust to.

Further, in the micro-compression test for the toner of the present invention, an index representing how much the toner surface layer returns to its original state after applying a load to one toner particle at a measurement temperature of 50 ° C. It is preferable to set the restoration rate Z (50) as 10 ≦ Z (50) ≦ 55 because the contamination of members and the cleaning property can be further improved.
When the value of Z (50) is less than 10, the member tends to be contaminated during long-term use, and when the value of Z (50) exceeds 55, cleaning failure tends to occur.
The value of the restoration rate Z (50) is determined by controlling the molecular weight and glass transition temperature (Tg) of the binder resin in the toner, the physical properties and addition amount of the wax, and the toner surface layer material. It is possible to adjust to the 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 an ultra micro hardness tester ENT1100 manufactured by Elionix Co., Ltd.
Follow the operation manual attached to the measurement device. In this test, the used indenter 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 amount of displacement 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, it is unloaded 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).
The restoration rate Z (25) is obtained as 100 × (X ₃ −X ₄ ) / X ₃ . Further, the value of the restoration rate Z (50) is a value measured in the same manner as the measurement method of Z (25) except that measurement is performed at a 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. From this, a toner having an aspect ratio [(major axis + minor axis) / 2] value 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. Use as Then, 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. Details of the measurement method are as follows.
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; o
-Styrene monomers such as (m-, p-) methylstyrene and 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, methacrylic acid 2 -Acrylic acid ester monomers such as ethylhexyl, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate ; 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). Use.

In the present invention, a crosslinking agent may be used when the binder resin is synthesized in order to increase the mechanical strength of the toner particles and to control the molecular weight of the binder resin of the toner.
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, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its 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 also a preferred form to add a polar resin. By setting the glass transition temperature (Tg) measured using a differential scanning calorimeter of this polar resin to 80 to 120 ° C., both durability and low-temperature fixability can be further improved. In the toner of the present invention, when the Tg value is less than 80 ° C., toner component contamination tends to occur, and when the Tg value exceeds 120 ° C., cleaning failure tends to occur.

When the toner particles of the present invention are directly produced by suspension polymerization, it is desirable 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 monoazo skeleton near the toner surface, so that the toner cleaning characteristics and member contamination 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 preferred 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. Can be sought. 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 2 to 5 mg, preferably 3 mg, in an aluminum pan, and an empty pan is set for control 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.
Thereafter, a sample processed filter (Mysholy disk H-25-2 manufactured by Tosoh Corporation, Excrodisk 25CR manufactured by Gelman Science Japan) is used as a GPC sample.
The molecular weight distribution of the sample and the molecular weight (Mp) of the main peak are measured using a GPC measuring device (HLC-8120G PC manufactured by Tosoh Corporation) under the following measurement conditions according to the operation manual of the device.
<Measurement conditions>
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 8

7 series of 06, 807 (made by Showa Denko)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
Moreover, 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-1 manufactured by Tosoh Corporation).
28, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500). Use a calibration curve.

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 winding property is improved by having an appropriate 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.
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, in the toner of the present invention, the addition of a charge control agent is not essential.

In the present invention, it is also preferable that the toner particles contain a polymer having a sulfonic acid group, a sulfonic acid group salt, or a sulfonic acid ester group for the purpose of charge control and stabilization of granulation in an aqueous medium. It is a form. When the toner of the present invention is produced by a suspension polymerization method, the addition of the polymer promotes the core-shell structure of the toner particles in the polymerization stage as well as stabilization of granulation. Therefore, the toner cleaning property and the member contamination suppressing property can be further enhanced.
Examples of the monomer having a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group for producing the polymer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 2-methacrylamide-2. -Methylpropane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid and their alkyl esters.
Among them, a monomer having an amide group in the molecule is a particularly preferable embodiment because it forms a polymer complex with the metal phthalocyanines of the present invention and acts as a dispersant for a colorant having a monoazo skeleton. .

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 having a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the binder resin. The amount is preferably 0.1 to 3.0 parts by mass.
When the blending amount of the polymer having a sulfonic acid group or the like is 0.01 to 5.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin, sufficient chargeability can be obtained and uniform. Transferability can be obtained. Furthermore, in the granulation step in an aqueous medium using a dispersion stabilizer having a positive component, a sharp distribution of toner particle size can be obtained in order to enhance the formation of an electric double layer.

The toner particles of the present invention are preferably externally added with inorganic fine powder as a fluidizing agent.
The inorganic fine powder added to the toner particles of the present invention is preferably silica, more preferably a silica fine powder having a number average primary particle size of 4 to 80 nm. 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 average circularity of the magenta toner of the present invention is preferably 0.970 to 0.995. If it is less than 0.970, toner component contamination tends to occur.
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, it is preferable to produce toner particles by a polymerization method so that the average circularity of the magenta toner of the present invention can be easily set in an optimal range and each material of the toner particles is optimally arranged.
Examples of a method for producing toner particles using a polymerization method include a direct polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion association polymerization method, and a seed polymerization method. Here, the magenta toner particles are preferably those obtained by producing them in an aqueous medium, and are produced by a suspension polymerization method from the viewpoint of easy balance of particle size and particle shape. More preferably. 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 (for example, an aqueous medium) containing a dispersion stabilizer using an appropriate stirrer, and a 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.

  In the case of obtaining toner particles using a polymerization method in the present invention, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably a substance that does not inhibit surface modification, for example, polymerization inhibition It is better to apply a hydrophobizing treatment to the colorant.

As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used.
Specifically, the following are mentioned as an inorganic dispersion stabilizer. 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 organic dispersion stabilizers 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.
The dispersion stabilizer used in the toner of the present invention is preferably an inorganic poorly water-soluble dispersion stabilizer, and more preferably a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid.

In the present invention, when an aqueous dispersion medium is prepared using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0. It is preferably 2 to 2.0 parts by mass. 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 dispersion stabilizer may be used as it is. In addition, in order to obtain dispersion stabilizer particles having a fine uniform particle size, an aqueous dispersion medium is prepared by generating a poorly water-soluble inorganic dispersion stabilizer as described above in a liquid medium such as water under high-speed stirring. May be. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

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.

Hereinafter, the present invention will be specifically described with reference to production examples and examples. In the examples and comparative examples, “part” and “%” are based on mass unless otherwise specified.

A production example of the toner of the present invention will be described.
<Production Example 1 of polymer having sulfonic acid group, sulfonic acid group or sulfonic acid ester group>
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts of methanol as a solvent, 150 parts of 2-butanone and 100 parts of 2-propanol, and styrene as a monomer 92.5 parts, 5 parts of 2-ethylhexyl acrylate, and 2.5 parts of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature with stirring. A solution obtained by diluting 0.30 part of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts of 2-butanone was added dropwise over 50 minutes, and stirring was continued for 5 hours. Further, t-butylperoxy was further added. A solution prepared by diluting 0.15 part of 2-ethylhexanoate with 20 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.
The polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained polymer is referred to as “sulfonic acid group-containing polymer 1”. The weight average molecular weight (Mw) of the polymer was 35,000.

<Production Example 2 of polymer having sulfonic acid group, sulfonic acid group or sulfonic acid ester group>
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts of methanol as a solvent, 150 parts of 2-butanone and 100 parts of 2-propanol, and styrene as a monomer 92.5 parts, 2-ethylhexyl acrylate 5 parts, and styrene sulfonic acid 2.5 parts were added and heated to reflux temperature with stirring. A solution obtained by diluting 0.30 part of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts of 2-butanone was added dropwise over 50 minutes, and stirring was continued for 5 hours. Further, t-butylperoxy was further added. A solution prepared by diluting 0.15 part of 2-ethylhexanoate with 20 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.
The polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained polymer is referred to as “sulfonic acid group-containing polymer 2”. The polymer had a weight average molecular weight (Mw) of 33,000.

<Manufacture of magenta colorant 1>
C. I. Pigment Red 31 was mixed with an aqueous calcium chloride solution and filtered and dried to obtain a pigment mixture. The calcium content of the pigment mixture after filtration and drying was 20 ppm. The specific conductivity of the pigment mixture was 43 μS / cm. The pigment mixture was designated as magenta colorant 1.

<Manufacture of magenta colorant 2>
In Production Example 1 of the magenta colorant, the calcium content of the pigment mixture after filtration and drying was adjusted to 40 ppm by adjusting the concentration and mixing time of calcium chloride. The specific conductivity of the pigment mixture at that time was 57 μS / cm. This pigment mixture was designated as magenta colorant 2.

<Manufacture of magenta colorant 3>
In Production Example 1 of the magenta colorant, the calcium content of the pigment mixture after filtration and drying was adjusted to 13 ppm by adjusting the concentration and mixing time of calcium chloride. The specific conductivity of the pigment mixture at that time was 38 μS / cm. This pigment mixture was designated as magenta colorant 3.

<Manufacture of magenta colorant 4>
In Production Example 1 of the magenta colorant, the calcium content of the pigment mixture after filtration and drying was adjusted to 50 ppm by adjusting the concentration and mixing time of calcium chloride. At that time, the specific conductivity of the pigment mixture was 63 μS / cm. The pigment mixture was designated as magenta colorant 4.

<Manufacture of magenta colorant 5>
In Production Example 1 of magenta colorant, C.I. I pigment red 31 is C.I. A pigment mixture was obtained in the same manner except that I Pigment Red 146 was used. This pigment mixture was designated as magenta colorant 5. The specific conductivity of the pigment mixture was 43 μS / cm.

<Manufacture of magenta colorant 6>
In Production Example 1 of magenta colorant, C.I. I pigment red 31 is C.I. A pigment mixture was obtained in the same manner except that I Pigment Red 150 was used. This pigment mixture was designated as magenta colorant 6. The specific conductivity of the pigment mixture was 43 μS / cm.

<Manufacture of magenta colorant 7>
In Production Example 1 of magenta colorant, C.I. I pigment red 31 is C.I. A pigment mixture was obtained in the same manner except that I Pigment Red 185 was used. This pigment mixture was designated as magenta colorant 7. The specific conductivity of the pigment mixture was 43 μS / cm.

<Manufacture of magenta colorant 8>
In Production Example 1 of magenta colorant, C.I. C.I. Pigment Red 31 is represented by C.I. A pigment mixture was obtained in the same manner except using I pigment red 238 and 269. The pigment mixture was designated as magenta colorants (8-1) and (8-2). The specific conductivity of the pigment mixture was 43 μS / cm.

構造式（３）

Structural formula (3)

<Manufacture of magenta colorant 9>
In Production Example 1 of magenta colorant, C.I. I pigment red 31 is C.I. A pigment mixture was obtained in the same manner except that I Pigment Red 22 was used. This pigment mixture was designated as magenta colorant 9. The specific conductivity of the pigment mixture was 43 μS / cm.

<Manufacture of magenta colorant 10>
In Production Example 1 of magenta colorant, C.I. I pigment red 31 is C.I. A pigment mixture was obtained in the same manner except that it was changed to I Pigment Red 3. The pigment mixture was designated as magenta colorant 10. The specific conductivity of the pigment mixture was 43 μS / cm.

<Manufacture of toner>
Each physical property value of the toner or toner particles was measured as follows.

[Average circularity]
(1) Average circularity of toner The average circularity of toner in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, flow particle image analyzer manufactured by Toago Medical Electronics Co., Ltd. Measurement is performed using “FPIA-3000”. Calculate the circularity (Ci) of each measured particle by the following formula (2), and further divide the total roundness of all measured particles by the total number of particles (m) as shown by the following formula (3). This value is defined as the average circularity (C).

In addition, "FPIA-3000" which is a measuring apparatus used in the present invention uses the following calculation method for calculating the average circularity and the mode circularity after calculating the circularity of each particle. That is, the particles are obtained by dividing the circularity from 0.400 to 1.000 into 61 divided classes according to the obtained circularity, and using a calculation method for calculating the average circularity using the center value and frequency of the dividing points. Yes. However, there is very little error between each value of the average circularity calculated by this calculation method and each value of the average circularity calculated by the above-described calculation formula that directly uses the circularity of each particle. Is negligible. In the present invention, for the reason of handling data such as a short calculation time and simplification of the calculation formula, the concept of the calculation formula that directly uses the circularity of each particle described above is used, and this is partially changed. Such a calculation method may be used.
The specific measurement method is as follows. A dispersion is prepared by dispersing about 5 mg of toner in 10 ml of water in which about 0.1 mg of a surfactant is dissolved, and the dispersion is irradiated with ultrasonic waves (20 kHz, 50 W) for 5 minutes. The average circularity is determined by measuring with the above device at 20,000 / μl. The average circularity in the present invention is an index of the degree of unevenness of the toner, and indicates 1.000 when the toner is a perfect sphere, and the average circularity becomes smaller as the toner surface shape becomes more complicated.

<Toner Production Example 1>
2.3 parts of tricalcium phosphate is added to 900 parts of ion-exchanged water heated to 60 ° C., and stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain an aqueous medium. It was.
on the other hand,
Styrene 65 parts n-butyl acrylate 35 parts styrene-methacrylic acid-methyl methacrylate (polar resin) 20 parts (styrene / methacrylic acid / methyl methacrylate = 95.85 / 1.65 / 2.50, Mp = 15000, Mw = 7900 Tg = 89 ° C., acid value = 10.9 mg KOH / g, Mw / Mn = 2.17)
Sulfonic acid group-containing polymer 1 1 part Aluminum salicylate compound (negative charge control agent) 1 part (Bontron E-88, manufactured by Orient Chemical Co., Ltd.)
Magenta Colorant 1 8 parts Zn Phthalocyanine 0.040 parts The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.). The polymerizable monomer composition was heated to a temperature of 60 ° C., and 14 parts of ester wax (mainly endothermic peak 65 ° C. in DSC measurement) mainly composed of stearyl stearate was added and dissolved therein. Then, 10 parts of a polymerization initiator lauroyl peroxide (10 hour half-life temperature 62 ° C.) was dissolved in this to prepare a polymerizable monomer composition.
The polymerizable monomer composition was put into the aqueous medium, and the mixture was granulated by stirring for 7 minutes at 10,000 rpm with a TK homomixer at a temperature of 60 ° C. in an N ₂ atmosphere.
Thereafter, the mixture was reacted at a temperature of 60 ° C. for 6 hours while stirring with a paddle stirring blade. Thereafter, the liquid temperature was raised to 80 ° C., and stirring was further continued for 4 hours. After completion of the reaction, the suspension was cooled at a cooling rate of 5 ° C./min.
Hydrochloric acid was added to the suspension cooled to room temperature (25 ° C.) to dissolve the calcium phosphate salt, followed by filtration and washing with water to obtain wet colored particles.
Next, the particles were dried at a temperature of 40 ° C. for 12 hours and then subjected to air classification to adjust the particle size to obtain magenta toner particles 1.
100 parts of the toner particles and 1.6 parts of hydrophobic silica fine powder having a BET value of 200 m ² / g as an external additive and a number average primary particle size of 12 nm were added to a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). Were mixed to obtain magenta toner 1. Table 1 shows the physical properties of the toner.

<Toner Production Example 2>
Magenta toner 2 was obtained in the same manner as in Toner Production Example 1 except that the amount of addition of the polymerization initiator lauroyl peroxide was changed to 6 parts. Table 1 shows the physical properties of the toner.

<Toner Production Example 3>
Magenta toner 3 was obtained in the same manner as in Toner Production Example 1 except that Zn phthalocyanine was changed to Cr phthalocyanine. Table 1 shows the physical properties of the toner.

<Toner Production Example 4>
Magenta toner 4 was obtained in the same manner as in Toner Production Example 1 except that Zn phthalocyanine was changed to Fe phthalocyanine. Table 1 shows the physical properties of the toner.

<Toner Production Example 5>
Magenta toner 5 was obtained in the same manner as in Toner Production Example 1 except that Zn phthalocyanine was changed to Co phthalocyanine. Table 1 shows the physical properties of the toner.

<Toner Production Example 6>
Magenta toner 6 was obtained in the same manner as in Toner Production Example 1 except that Zn phthalocyanine was changed to Mn phthalocyanine. Table 1 shows the physical properties of the toner.

<Toner Production Example 7>
In the same manner as in Toner Production Example 1, except that the addition part of the wax mainly composed of stearyl stearate is 20 parts and the reaction is performed at 60 ° C. for 6 hours and the reaction is performed at 75 ° C. for 6 hours. Magenta toner 7 was obtained. Table 1 shows the physical properties of the toner.

<Toner Production Example 8>
Magenta toner 8 was obtained in the same manner as in Toner Production Example 1 except that the amount of addition of the polymerization initiator lauroyl peroxide was changed to 4 parts. Table 1 shows the physical properties of the toner.

<Toner Production Example 9>
Magenta toner 9 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 2. Table 1 shows the physical properties of the toner.

<Toner Production Example 10>
Magenta toner 10 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 3. Table 1 shows the physical properties of the toner.

<Toner Production Example 11>
Magenta toner 11 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 4. Table 1 shows the physical properties of the toner.

<Toner Production Example 12>
Magenta toner 12 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 5. Table 1 shows the physical properties of the toner.

<Toner Production Example 13>
Magenta toner 13 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 6. Table 1 shows the physical properties of the toner.

<Toner Production Example 14>
Magenta toner 14 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 7. Table 1 shows the physical properties of the toner.

<Toner Production Example 15>
Magenta toner 15 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant (8-1). Table 1 shows the physical properties of the toner.

<Toner Production Example 16>
Magenta toner 15 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant (8-2). Table 1 shows the physical properties of the toner.

<Toner Production Example 17>
Magenta toner 17 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 9. Table 1 shows the physical properties of the toner.

<Toner Production Example 18>
A magenta toner 18 was obtained in the same manner as in Toner Production Example 1 except that the sulfonic acid group-containing polymer 1 was not added. Table 1 shows the physical properties of the toner.

<Toner Production Example 19>
A magenta toner 19 was obtained in the same manner as in Toner Production Example 1 except that the sulfonic acid group-containing polymer 1 was changed to the sulfonic acid group-containing polymer 2. Table 1 shows the physical properties of the toner.

<Toner Production Example 20>
In Toner Production Example 1, the polar resin was styrene-methyl methacrylate-acryloylmorpholine (styrene / methyl methacrylate / acryloylmorpholine = 3.00 / 30.00 / 66.70, Mp = 18,000, Mw) having a Tg of 128 ° C. = 102,000, Tg = 128 ° C., Mw / Mn = 5.66), and magenta toner 20 was obtained by the same method. Table 1 shows the physical properties of the toner.

<Toner Production Example 21>
In Toner Production Example 1, a polar resin having a Tg of 74 ° C., styrene-butyl acrylate-methyl methacrylate-monobutyl maleate (styrene / butyl acrylate / methyl methacrylate / monobutyl maleate = 82.35 / 13.50 / 2.50) /1.65, Mp = 15,000, Mw = 12,000, Tg = 74 ° C., Mw / Mn = 2.87) to obtain magenta toner 21 by the same method. Table 1 shows the physical properties of the toner.

<Toner Production Example 22>
In Toner Production Example 1, the polar resin was styrene-methyl methacrylate-acryloylmorpholine (styrene / methyl methacrylate / acryloylmorpholine = 10.00 / 30.00 / 60.00, Mp = 16,000, Mw) having a Tg of 118 ° C. = 103,000, Tg = 118 ° C., Mw / Mn = 5.50), magenta toner 22 was obtained by the same method. Table 1 shows the physical properties of the toner.

<Toner Production Example 23>
A magenta toner 23 was obtained in the same manner as in Toner Production Example 1 except that the amount of Zn phthalocyanine added was 0.800 parts and the amount of magenta colorant 1 added was 10 parts. Table 1 shows the physical properties of the toner.

<Toner Production Example 24>
A magenta toner 24 was obtained in the same manner as in Toner Production Example 1 except that the addition amount of Zn phthalocyanine was 0.0008 part and the addition amount of magenta colorant 1 was 0.4 part. Table 1 shows the physical properties of the toner.

<Toner Production Example 25>
Magenta toner 25 was obtained in the same manner as in Toner Production Example 1 except that the amount of Zn phthalocyanine added was 1.004 parts and the amount of magenta colorant 1 added was 12 parts. Table 1 shows the physical properties of the toner.

<Toner Production Example 26>
Magenta toner 26 was obtained in the same manner as in Toner Production Example 1 except that the amount of Zn phthalocyanine added was 0.200 parts and the amount of magenta colorant 1 added was 1.9 parts. Table 1 shows the physical properties of the toner.

<Toner Production Example 27>
Magenta toner 27 was obtained in the same manner as in Toner Production Example 1, except that the amount of Zn phthalocyanine added was 0.004 parts and the amount of magenta colorant 1 added was 2.2 parts. Table 1 shows the physical properties of the toner.

<Toner Production 28>
-Styrene / butyl acrylate copolymer produced by solution polymerization (glass transition temperature: 6
5 ° C., weight average molecular weight: 12500, Mw / Mn: 2.4) 100 parts. Styrene / acrylic acid copolymer produced by suspension polymerization method (glass transition temperature: 59 ° C.,
Weight average molecular weight: 573,000, Mw / Mn: 2.0) 100 parts · Aluminum salicylate compound (Bontron E-88; manufactured by Orient Chemical Co.) 4 parts · Sulphonic acid group-containing polymer 1 3 parts · Magenta colorant 1 8 parts Zn phthalocyanine 0.040 parts Styrene-methacrylic acid-methyl methacrylate 20 parts (styrene / methacrylic acid / methyl methacrylate = 95.85 / 1.65 / 2.50,
Mp = 15000, Mw = 7900, Tg = 89 ° C., acid value = 10.9 mgKOH / g, Mw / Mn = 2.17)
The above materials are mixed with a blender, melt-kneaded with a biaxial extruder heated to 110 ° C., the cooled kneaded product is coarsely pulverized with a hammer mill, and the coarsely pulverized product is finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.). The colored particles were obtained by air classification.
100 parts of the toner particles and 1.6 parts of hydrophobic silica fine powder having a BET value of 200 m ² / g treated with silicone oil and a number average primary particle size of 12 nm were added to a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). ) To obtain a magenta toner 28. The results are shown in Table 1.

<Toner Production Example 29>
[Preparation of resin dispersion A]
Styrene 312 parts Ethyl acrylate 64 parts 2-Ethylhexyl acrylate 24 parts Dodecyl mercaptan 10 parts Carbon tetrabromide 3 parts Styrene-methacrylic acid-methyl methacrylate 80 parts (styrene / methacrylic acid / methyl methacrylate = 95.85 / 1.65 / 2.50, Mp = 15000, Mw = 7900, Tg = 89 ° C., acid value = 10.9 mgKOH / g, Mw / Mn = 2.17)
The above components are mixed in advance and dissolved to prepare a solution (a). On the other hand, 7 parts of nonionic surfactant (trade name: Novonil, Sanyo Kasei Co., Ltd.) and 10 parts of anionic surfactant (trade name: Neogen R, Daiichi Kogyo Seiyaku Co., Ltd.) are added to 520 parts of ion-exchanged water. Dissolve to prepare solution (b). The solutions (a) and (b) were put into a flask, emulsified by dispersing, and slowly mixed for 10 minutes. Further, 70 parts of ion-exchanged water in which 2.5 parts of ammonium persulfate was dissolved was added to perform nitrogen replacement. Thereafter, while stirring the flask, the content was heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 6 hours. Then, this reaction liquid was cooled to room temperature, and a resin dispersion A having a volume average particle diameter: 152 nm, a glass transition temperature: 55 ° C., and a peak average molecular weight: 20000 was obtained.
[Preparation of Colorant Dispersion A]
Magenta Colorant 1 32 parts Anionic surfactant (trade name: Neogen, manufactured by Daiichi Kogyo Co., Ltd.) 3 parts Zn phthalocyanine 0.16 parts Ion-exchanged water 400 parts (Manufactured by Ultra Turrax) to obtain a colorant dispersion A in which a colorant having a volume average particle diameter of 150 nm is dispersed.
[Preparation of release agent dispersion A]
Polyethylene wax (trade name: POLYWAX655, melting point 93 ° C., manufactured by Toyo Petrolite Co., Ltd.) 100 parts anionic surfactant (trade name: Pionin A-45-D, manufactured by Takemoto Yushi Co., Ltd.): 2 parts 500 parts of ion-exchanged water After mixing and dissolving, the mixture was dispersed using a homogenizer (manufactured by IKA, Ultra Tarrax). Subsequently, it was subjected to dispersion treatment with a pressure discharge type homogenizer to obtain a release agent dispersion liquid (A) in which release agent fine particles (polyethylene wax) having a volume average particle diameter of 280 nm are dispersed.
[Manufacture of magenta toner 29]
Resin dispersion A 300 parts Colorant dispersion A 200 parts Release agent dispersion A 100 parts Bontron E-84 (manufactured by Orient Chemical Co.) 5 parts Polymer 1 containing sulfonic acid group 12 parts Rosin-modified maleic acid (softening point 139 ° C) 60 parts (8%) cationic surfactant (trade name: SANISOL B50, manufactured by Kao Corporation) 3 parts ion-exchanged water 500 parts The above components were homogenized in a round bottom stainless steel flask (trade name: ULTRA TALLAX T50) , Manufactured by IKA Co., Ltd.) to prepare a mixed solution, which was then heated to 50 ° C. with stirring in an oil bath for heating and held at 50 ° C. for 30 minutes to form aggregated particles.
50 parts of the resin dispersion A was gradually added to the liquid in which the aggregated particles were formed, and the mixture was further heated and stirred at 50 ° C. for 30 minutes to obtain an aggregated particle dispersion A.
Next, 6 parts of sodium dodecylbenzenesulfonate (trade name: Neogen SC, manufactured by Daiichi Kogyo Co., Ltd.) as an anionic surfactant is added to the aggregated particle dispersion A, heated to 97 ° C., and maintained for 9 hours. Then, the aggregated particles were fused. Thereafter, it was cooled to 45 ° C. at a descending rate of 1.0 ° C./min, filtered, sufficiently washed with ion-exchanged water, and further filtered through a 400 mesh sieve. This was dried with a vacuum dryer to obtain magenta toner particles 29.
100 parts of the toner particles and 1.6 parts of hydrophobic silica fine powder having a BET value of 200 m ² / g treated with silicone oil and a number average primary particle size of 12 nm were added to a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). ) To obtain a magenta toner 29. The results are shown in Table 1.

<Toner Comparative Production Example 1>
A comparative magenta toner 1 was obtained in the same manner as in Toner Production Example 1 except that Zn phthalocyanine was not added. Table 1 shows the physical properties of the toner.

<Toner Comparative Production Example 2>
A comparative magenta toner 2 was obtained in the same manner as in Toner Production Example 1 except that Zn phthalocyanine was changed to Mg phthalocyanine. Table 1 shows the physical properties of the toner.

<Toner Comparative Production Example 3>
Comparative Magenta Toner 3 was obtained in the same manner as in Toner Production Example 7 except that the polar resin was not added and the addition amount of the polymerization initiator lauroyl peroxide was changed to 13 parts. Table 1 shows the physical properties of the toner.

<Toner Comparative Production Example 4>
Comparative Magenta Toner 4 was obtained in the same manner as in Toner Production Example 8 except that the amount of polar resin added was 32 parts and the amount of polymerization initiator lauroyl peroxide added was changed to 2 parts. Table 1 shows the physical properties of the toner.

<Toner Comparative Production Example 5>
A comparative magenta toner 5 was obtained in the same manner as in Toner Production Example 1 except that magenta colorant 1 was changed to magenta colorant 10. Table 1 shows the physical properties of the toner.

Next, an image forming apparatus for evaluating the toner of the present invention will be described with reference to FIGS.
The configuration of the image forming apparatus is shown in FIG. FIG. 2 is a cross-sectional view of a tandem 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. 3 is an enlarged view of the developing unit of the apparatus.

In FIG. 2, 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. 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, yellow (Y) 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. Then, the photosensitive drum 101a is subjected to light image exposure by laser beam exposure means (hereinafter referred to as a scanner) 103a.
An electrostatic latent image of image information is formed on 1a.
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 the image forming method in 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. 3). In FIG. 3, the developing unit 13 is located in a developer container 23 containing a 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 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. This is supported by the regulating member support sheet metal 24 and is provided so that the vicinity of the free end side 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 more desirable in terms of toner layer regulation when the contact angle of the restricting member with respect to the tangent of the toner carrier at the contact point with the contact pressure is set to 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. And unevenness occurs on the image, which is not preferable.
The charging roller 29 is biased by a power source 27 between the toner carrier 14 and the latent image carrier 10 in a direct current (27 in FIG. 3), 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.

<Example 1>
The magenta toner 1 was a non-magnetic one-component developer, and the image was evaluated using the image forming apparatus shown in FIG. 2 in an extremely low temperature and low humidity environment (temperature 0 ° C., humidity 5% RH). Further, the evaluation of the cleaning property was also performed in a low temperature and low humidity environment (temperature 15 ° C., humidity 10% RH). The image forming apparatus will be described below.
FIG. 2 is a schematic view of a modified 600 dpi laser beam printer (manufactured by HEWLETT PACKARD: Color LaserJet CP4005) using a non-magnetic one-component contact development type electrophotographic process. In the present example, an apparatus additionally modified under the following conditions (a) to (g) was used.
(A) The rotational speed of the toner carrying member was driven in the same direction at the contact portion with the photosensitive member, and was 160% of the rotational peripheral speed of the photosensitive member.
(B) The process speed of the image forming apparatus in the present invention is 250 mm / sec, while the peripheral speed of the toner carrier is 400 mm / sec.
(C) As a means for applying the toner to the toner carrier, an application roller made of foamed urethane rubber was provided in the developing device and brought into contact with the toner carrier. A voltage of about −550 V is applied to the application roller.
(D) In order to control the coat layer of the toner on the toner carrier, a stainless steel blade coated with resin was used.
(E) Only the DC component (−450 V) was applied voltage during development.
A commercially available paint is applied very thinly on the surface of a rubber roller having the same diameter, the same hardness, and the same resistance as the toner carrier used in the image forming apparatus, and after temporarily assembling the image forming apparatus, the rubber roller is removed, The surface of the stainless steel blade was observed and the NE length was measured. The NE length was 1.30 mm.
(F) The cleaning blade contact pressure was set to 75% of the initial setting.
(G) Adjustment was made so that the machine could operate normally even if there was a station that did not contain a cartridge among the four color cartridge stations.
The electrophotographic apparatus was remodeled and process conditions were set as follows in order to conform to the remodeling of these process cartridges.
The modified device uses a roller charger (applying only direct current) to uniformly charge the image carrier. Subsequent to charging, an image portion is exposed with a laser beam to form an electrostatic latent image, and a visible image is formed with toner, and then the toner image is transferred to a transfer material by a roller to which a voltage of +700 V is applied.
As for the photosensitive member charging potential, the dark portion potential was set to -600V, and the bright portion potential was set to -150V.
Under the above conditions, when printing out an image with a printing ratio of 0.5% up to 10,000 sheets in an extremely low temperature and low humidity environment (0 ° C., 5% RH), the initial and 10,000 sheets After durability, the following image evaluation was performed.
Furthermore, the cleaning property was evaluated in a low temperature and low humidity environment (temperature 15 ° C., humidity 10% RH).
In the evaluation, the cartridge containing the magenta toner of the present invention and the comparative magenta toner was put in the magenta station of the image forming apparatus.

(1) Image Density Using a normal copying machine plain paper (75 g / m ² ) transfer material, output a solid image and measure its density (upper right, lower right, center, upper left, lower left average of 5 points) ). The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: Image density is 1.45 or more B: Image density is 1.30 or more and less than 1.45 C: Image density is 1.15 or more and less than 1.30 D: Image density is less than 1.15 In evaluation, A is the most Well, D is the worst.

(2) Fog For the measurement of fog, the reflectance of the non-image part of the standard paper and the printout image was measured using a reflection densitometer manufactured by Tokyo Denshoku Co., Ltd. and REFECTECTOMER MODEL TC-6DS. A green filter was used as a filter used in the measurement. The fog was calculated from the measurement results by the following formula and evaluated according to the following criteria.
Fog (reflectance:%) = reflectance on standard paper (%) − reflectance of sample non-image area (%)
A: Fog (reflectance) is less than 0.5% B: Fog (reflectance) is 0.5% or more and less than 1.0% C: Fog (reflectance) is 1.0% or more, 2.0% Less than D; fog (reflectance) is 2.0 or more
In evaluation, A is the best and D is the worst.

(3) Evaluation of cleaning property The cleaning property was evaluated after the toner and the evaluation machine were allowed to stand for 8 hours or more in the low temperature and low humidity environment and in the extremely low temperature and low humidity environment. In the evaluation method, one solid image and a halftone image were continuously printed in the initial stage, and then image defects due to defective cleaning were visually evaluated from the obtained halftone images. The cleaning member was also observed and evaluated. Evaluation was performed according to the following criteria.
A: The cleaning property on the image is good. The back of the cleaning member is also very beautiful.
B: The cleaning property on the image is good. Some toner contamination is confirmed on the back surface of the cleaning member.
C: The level of cleanability on the image is not a problem for practical use. A large amount of toner contamination is confirmed on the back surface of the cleaning member.
D: The image is poorly cleaned and has a practically problematic level. A large amount of toner contamination is confirmed on the back surface of the cleaning member.

(4) Contamination of developer carrier After completion of the 10,000-sheet printout test, the appearance of toner on the surface of the developer carrier and the effect on the obtained image were visually observed, and the following criteria It was evaluated with.
A: Not generated (no sticking)
B: Adhering occurs slightly, but the influence on the image is small. C: Toner adhering occurs and image unevenness is slightly caused by this, but there are few problems in practical use.
D: There is a large amount of toner fixing, and image unevenness is caused by this. There are also practical problems.

  When the magenta toner 1 was evaluated under the above conditions, it was found that the density was high and there was no fog. Also, the cleaning property and developer carrier contamination were good. Detailed results are shown in Table 2.

<Examples 2-29>
Magenta toner 2 to magenta toner 29 were evaluated under the same conditions as in Example 1. Detailed results are shown in Table 2.

<Comparative Examples 1-5>
When the comparative magenta toners 1 to 5 were evaluated under the same conditions as in Example 1, a decrease in density was observed and the fog level was also poor. Furthermore, the developer carrier contamination was also bad. Detailed results are shown in Table 2.

It is a load-displacement curve in the micro compression test of toner. 2 is a cross-sectional view of an electrophotographic apparatus used for evaluating the toner of the present invention. FIG. It is an enlarged view of the developing unit of the electrophotographic apparatus.

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 (10)

A binder resin, a releasing agent, a colorant having the structure of Formula (1), central metal, Cr, Fe, Co, Zn, and in any of the metal selected from M n or Ranaru group A magenta toner having magenta toner particles containing at least a metal phthalocyanine and / or a metal phthalocyanine derivative,
Obtained when a maximum load of 2.94 × 10 ⁻⁴ N was applied to one particle of the toner at a measurement temperature of 25 ° C. and a loading speed of 9.8 × 10 ⁻⁵ N / sec in a 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 (25) (%), Z (25) is 60 ≦ Z ( 25) A magenta toner characterized by satisfying ≦ 90.

[In the formula (1), R _{1 to} R ₃ represent a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of an alkyl group, an alkoxy group, a nitro group, an anilide group, and a sulfamoyl group; ₄ is —OH, —NH ₂ ,

,as well as

R _{5 to} R ₈ represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. ] 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 the relationship of 50) ≦ 55 is satisfied. The magenta toner according to claim 1, wherein a specific conductivity of the colorant having the structure of the formula (1) is 40 to 60 μS / cm. The colorant having the structure of the formula (1) is C.I. I. 4. The magenta toner according to claim 1, wherein the red toner is Pigment Red 31, 146, 150, 185, 238, or 269. 5. The magenta toner according to any one of claims 1 to 4, wherein the magenta toner particles contain a polymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. The magenta toner according to any one of claims 1 to 5, wherein the magenta toner particles contain a polar resin, and the glass transition temperature of the polar resin is 80 to 120 ° C. The metal phthalocyanine and / or metal phthalocyanine derivative is contained in 0.001 to 1.000 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 the structure of the formula (1) and the metal phthalocyanine and / or the metal phthalocyanine derivative contained in the magenta toner particles is 10 to 500. 9. The magenta toner according to any one of items 8 to 8. 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. magenta toner according to any one of claims 1 to 9, characterized in that the toner particles obtained by.

Images