JP2005221840A - Nonmagnetic toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide nonmagnetic toner to be used for an image forming method by which a digital latent image can be accurately developed and the initial performance can be maintained even when the toner is continuously used for a long time. <P>SOLUTION: The nonmagnetic toner contains at least a binder resin, a colorant and a charge controlling agent, wherein the charge controlling agent is a resin obtained by polymerizing monomers having at least a sulfonate group, and (1) the resin has a first acid value (A) and a second acid value (B) measured by potentiometric titration, (2) the first acid value (A) ranges 2 to 10 mg/mgKOH; and (3) the first acid value (A) and the second acid value (B) satisfy 1.20≤A/B≤2.00, and the binder resin has a polyester structure. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a non-magnetic toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method.

  In recent years, there have been various demands from the market, such as multifunctional copying machines and printers, higher image quality, higher speed, and from black and white machines to color machines. As a developing method applied to a copying machine or a printer, a one-component developing method is preferable in terms of downsizing, durability stability, and low running cost.

  In the above situation, further improvement is required for the characteristics required of the toner. In particular, various studies have been made on the charge control agent for toner, and as a charge control agent not containing a heavy metal, there is a negative charge control agent resin copolymerizing a sulfonic acid monomer (Patent Document 1). ). However, in the charge control agent resin of Patent Document 1, since a polymerization stabilizer such as an emulsifier is added at the time of polymerization, when the toner is used, the above-mentioned emulsifier remaining in the toner results in insufficient toner charging characteristics. In some cases, the image quality may be adversely affected, and further improvement has been demanded.

  Further, as seen in Patent Document 2, there is an application for a toner containing a negative charge control agent resin copolymerizing a sulfonic acid monomer. However, the toner may adversely affect image quality, and further improvement has been demanded.

JP 2002-23426 A JP 2003-43742 A

  An object of the present invention is to provide a non-magnetic toner used in an image forming method capable of performing development faithfully to a digital latent image.

  Still another object is to provide a non-magnetic toner used in an image forming method that maintains the initial performance even when the toner is continuously used over a long period of time.

  Still another object is to provide a non-magnetic toner for use in an image forming method for reproducing a stable image that is not easily affected by changes in temperature and humidity.

In the present invention, in a non-magnetic toner containing at least a binder resin, a colorant and a charge control agent,
The charge control agent is a resin obtained by polymerizing at least a monomer having a sulfonic acid group, and
1) having a first acid value A and a second acid value B, measured by potentiometric titration,
2) The first acid value A is 2 mg / mg KOH to 10 mg / mg KOH,
3) The first acid value A and the second acid value B are represented by the following formula (1)
1.20 ≦ A / B ≦ 2.00 (1)
And
The present invention relates to a nonmagnetic toner, wherein the binder resin is a binder resin having a polyester structure.

  In the present invention, the dispersion state formed by stirring the charge control agent for 5 minutes at a shear rate of 10 (1 / sec) is phase-separated into at least two phases within 20 seconds to 60 minutes without stirring. The present invention relates to a nonmagnetic toner, which is a charge control agent obtained by a production method in which polymerization is performed in a suspended state and having at least a monomer having a sulfonic acid group and a plurality of vinyl monomers.

  The present invention also relates to a non-magnetic toner, wherein the charge control agent in the toner is a charge control agent which is a production method in which polymerization is performed without adding a water-soluble dispersion stabilizer.

  The present invention also relates to a nonmagnetic toner, wherein the charge control agent in the toner is a charge control agent that is a production method in which polymerization is performed using a water-insoluble polymerization initiator.

  The present invention also relates to a non-magnetic toner wherein the charge control agent has a weight average molecular weight (Mw) of 10,000 to 100,000.

The present invention also relates to a non-magnetic toner wherein the charge control agent has a weight average molecular weight W (Mw) and a number average molecular weight N (Mn) satisfying the following formula (2).
1.2 ≦ W / N ≦ 3.5 (2)

In the present invention, the non-magnetic toner has a particle size of 3 μm or more and 90% or more of particles having a circularity a obtained from the following formula (3) of 0.900 or more in terms of the number-based cumulative value. And a non-magnetic toner.
Circularity a = L ₀ / L (3)
[Where L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image]

  Further, the present invention relates to the nonmagnetic toner, wherein the nonmagnetic toner contains 10 to 500 particles per 5 g of toner that do not pass through a mesh having an opening of 34 μm.

  According to the present invention, development that is faithful to a digital latent image can be performed, and the initial performance is maintained even when the toner is continuously used over a long period of time, and it is hardly affected by changes in temperature and humidity. A nonmagnetic toner used in an image forming method for reproducing a stable image can be provided.

In the present invention, in a non-magnetic toner containing at least a binder resin, a colorant and a charge control agent,
The charge control agent is a resin obtained by polymerizing at least a monomer having a sulfonic acid group, and
1) having a first acid value A and a second acid value B, measured by potentiometric titration,
2) The first acid value A is 2 mg / mg KOH to 10 mg / mg KOH,
3) The first acid value A and the second acid value B are represented by the following formula (1)
1.20 ≦ A / B ≦ 2.00 (1)
And
The present invention relates to a nonmagnetic toner, wherein the binder resin is a binder resin having a polyester structure.

  Regarding the first acid value A and the second acid value B of the charge control agent in the present invention, the acid value measured first when the acid value is measured twice by potentiometric titration is the first acid value. The acid value measured for the second time is called the second acid value B.

  The reason why the acid value data gives a plurality of results when the acid value of the charge control agent in the present invention is measured twice is unclear, but the sulfonic acid group is produced by the specific production method of the present invention. It is presumed that the change in physical properties of the contained monomer in the resin appears.

  By using the charge control agent of the present invention in a toner together with a binder resin having a polyester structure, it is possible to stably obtain an image having good image density, good image flow characteristics, and good fog. . Although details of this reason are unknown, it is considered that the chargeability of the toner is further stabilized and the balance between charge accumulation and discharge in the toner particles is improved.

  As a result, the adhesion between the toner classified product and the toner external additive is stabilized and the slipping property with respect to the photosensitive member is improved. Therefore, the characteristics of the image flow as a negative effect that seems to be caused by the charging of the charging member to the photosensitive member. Is estimated to improve.

  In the present invention, the first acid value A of the charge control agent needs to be 2 mg / mg KOH to 10 mg / mg KOH. When the first acid value A of the charge control agent is less than 2 mg / mg KOH, the chargeability of the toner tends to be low, and the image density is liable to deteriorate. If the first acid value A of the charge control agent exceeds 10 mg / mg KOH, the chargeability of the toner will be excessively increased, and the toner charge amount on the sleeve will increase. And fog are likely to deteriorate.

In the present invention, the first acid value A and the second acid value B of the charge control agent are represented by the following formula (1):
1.20 ≦ A / B ≦ 2.00 (1)
It is necessary to satisfy. In the present invention, when the value of the relational expression A / B between the first acid value A and the second acid value B of the charge control agent is less than 1.2, the chargeability as a toner tends to be lowered, and the image density The decline tends to get worse. In the present invention, when the value of the relational expression A / B between the first acid value A and the second acid value B of the charge control agent exceeds 2.0, the chargeability as a toner is excessively increased. The characteristics of image flow and fog are likely to deteriorate because the toner charge amount on the sleeve increases.

  In the present invention, the binder resin needs to be a binder resin having a polyester structure. In the present invention, if the binder resin does not have a polyester structure as the binder resin, the chargeability as a toner tends to be low even when the charge control resin in the present invention is used, and the decrease in image density tends to deteriorate. .

  In the present invention, in the method in which the charge control agent polymerizes at least a monomer having a sulfonic acid group and a plurality of vinyl monomers in a solvent containing water to obtain a copolymer, a shear of 10 (1 / sec) More preferably, the dispersion is formed by stirring at a speed of 5 minutes, and the polymerization is performed in a suspension state in which the phase is separated into at least two phases within 20 seconds to 60 minutes without stirring. As the image characteristics of the toner, the image flow characteristics and the fog characteristics are improved.

  In the present invention, the charge control agent is preferably a production method in which polymerization is carried out without adding a water-soluble dispersion stabilizer, and as a result, image flow characteristics and fog characteristics are better as toner image characteristics. It becomes.

  In the present invention, the charge control agent is preferably a production method in which a water-insoluble polymerization initiator is used for polymerization, and as a result, the image flow characteristics and fog characteristics are better as toner image characteristics. It becomes.

  In the present invention, it is more preferable that the charge control agent has a weight average molecular weight (Mw) of 10,000 to 100,000. As a result, image flow characteristics and fog characteristics are improved as toner image characteristics. Further, as the image characteristics of the toner, the resolution is good. The reason for this is a presumed state, but it is thought that the variation in the charge amount distribution of the toner is reduced.

In the present invention, the weight average molecular weight W (Mw) and the number average molecular weight N (Mn) of the charge control agent satisfy the following formula (2): 1.2 ≦ W / N ≦ 3.5 (2)
More preferably, as a result, the image flow characteristic and the fog characteristic are improved as the image characteristic of the toner. Further, as the image characteristics of the toner, the resolving power is good. The reason for this is a presumed state, but it is thought that the variation in the charge amount distribution of the toner is reduced.

In the present invention, the non-magnetic toner has a particle size of 3 μm or more and 90% or more of particles having a circularity a obtained by the following formula (3) of 0.900 or more in terms of the number-based cumulative value. Circularity a = L ₀ / L (3)
[Where L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image]
As a result, the image flow characteristics and fog characteristics are improved as the image characteristics of the toner. Further, as image characteristics of the toner, the resolution and the nail mark in a solid black image are good. The reason for this is a presumed state, but it is thought that the variation in the toner charge amount distribution is further reduced and the flatness of the toner image transferred onto the paper is made more uniform.

  In the present invention, the non-magnetic toner preferably contains 10 to 500 particles that do not pass through a mesh having a mesh size of 34 μm per 5 g of the toner. The characteristics are better. Further, as image characteristics of the toner, the resolution and the nail mark in a solid black image are good. The reason for this is a presumed state, but it is thought that the variation in the toner charge amount distribution is further reduced and the flatness of the toner image transferred onto the paper is made more uniform.

  As the monomer having a sulfonic acid group constituting the charge control agent used in the present invention, a sulfonic acid-containing acrylamide monomer is particularly preferable, for example, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid. 2-acrylamide-n-hexanesulfonic acid, 2-acrylamide-n-octanesulfonic acid, 2-acrylamide-n-dodecanesulfonic acid, 2-acrylamide-n-tetradecanesulfonic acid, 2-acrylamido-2-methylpropanesulfone Acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-acrylamido-2,2,4-trimethylpentanesulfonic acid, 2-acrylamido-2-methylphenylethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) )Professional Sulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2-acrylamido-2- (2-pyridyl) propanesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 3-acrylamido-3-methylbutanesulfone An acid, 2-methacrylamide-n-decanesulfonic acid, 2-methacrylamide-n-tetradecanesulfonic acid, etc. can be mentioned. Preferably, 2-acrylamido-2-methylpropanesulfonic acid is used.

  Examples of the vinyl monomer copolymerized with the monomer having a sulfonic acid group include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p -Styrene such as methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof; ethylene unsaturated such as ethylene, propylene, butylene, isobutylene Monoolefins; unsaturated polyenes such as butadiene and isoprene Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl Α-methylene aliphatics such as n-butyl acid, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Monocarboxylic acid esters: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethyl acrylate Acrylic esters such as ruhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether: vinyl methyl ketone, vinyl hexyl ketone, methyl isoprohenyl ketone Vinyl ketones such as: N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide Etc.

  Examples of the polymerization initiator used in producing the charge control agent of the present invention include azo polymerization initiators such as azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (4-methoxy-2). , 4-dimethylvaleronitrile), azobis (2-methylbutyronitrile), azobis (cyclohexane-1-carbonitrile) and azobiscyanovaleric acid; organic peroxide polymerization initiators such as isobutyryl peroxide, octanoyl peroxide Oxide, lauroyl peroxide, tert-butylperoxy 2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, 1,1-bis (tert-peroxy) 3,3,5-trimethylcyclo Hexane, tert-butyl peroxyl Propyl monocarbonate, tert- butylperoxy benzoin benzoate, dicumyl peroxide, di -t- butyl peroxide and t- butyl hydroperoxide, and the like.

As a water-soluble polymerization initiator in the production of the charge control agent of the present invention, 2,2′-Azobis [2- (2-imidazolin-2-yl) propane] disulfate manufactured by Wako Pure Chemical Industries, Ltd. dihydrate
2,2′-Azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate 2,2′-Azobis [N- (2-carboxyethyl) -2-methylpropionamide] hydrate
2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate 2,2′-Azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride
2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride 2,2′-Azobis (1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride
2,2'-azobis (1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]
2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]
2,2′-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride
2,2′-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride 2,2′-Azobis (2-methylpropionamide) dihydrochloride
2,2′-Azobis (2-methylpropionamidine) dihydrochloride 2,2′-Azobis [2- (2-imidazolin-2-yl) propane]
2,2′-azobis [2- (2-imidazolin-2-yl) propane]
2,2′-Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}
Etc.

  As the water-soluble dispersion stabilizer in the production of the charge control agent of the present invention, polyvinyl alcohol (PVA), polyethylene oxide (PEO), sodium polyacrylate, natural water-soluble polymer polysaccharide, anionic water-soluble cellulose ether And natural cellulosic polysaccharides.

  The method for producing a charge control agent according to the present invention is unstable in that it is dispersed when subjected to shearing such as stirring in a mixture of a monomer and a solvent before polymerization and phase-separated into at least two phases when left unsheared. A method in which polymerization is carried out in a suspended state is preferred.

  By carrying out the polymerization in the suspended state, the copolymer after polymerization is dispersed and precipitated in the solvent, so that separation from the solvent becomes easy. Preferably, a method is preferred in which the polymerization is carried out under the condition that the suspension formed by stirring at a step speed of 10 (1 / sec) for 5 minutes is phase-separated into at least two phases within 20 seconds to 60 minutes without stirring. .

  By setting this condition, a copolymer having an appropriate dispersion diameter can be easily obtained.

  About the weight average molecular weight W (Mw) and the number average molecular weight N (Mn) of the charge control agent of this invention, it measures on condition of the following using measuring apparatus: HLC-8120GPC (made by Tosoh Corporation).

  The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min.

  When the sample is a binder resin raw material, a material obtained by passing the binder resin raw material through a roll mill (130 ° C., 15 minutes) is used. When the sample is toner, the toner is dissolved in THF, filtered through a 0.2 μm filter, and the filtrate is used as a sample.

Measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6 mass%. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used, and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, in order to accurately measure the molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, μ-styragel 500, 10 ³ , manufactured by Waters, A combination of 10 ⁴ and 10 ^{5 and} a combination of shodex KA801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK are preferable.

  In the present invention, the method for measuring the acid value by potentiometric titration of the charge control agent is measured by the following measurement.

The acid value of the charge control agent in the present invention is measured in accordance with the measurement method described in JIS K0070.
Measuring apparatus: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics Co., Ltd.)
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 25 ° C
Sample preparation: 1.0 g of toner is added to 120 ml of toluene and dissolved by stirring with a magnetic stirrer at room temperature (about 25 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
Measurement operation:
1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. The pulverized sample 0.5 to 2.0 (g) is precisely weighed, and the weight of the polymer component is defined as W (g). For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (4/1) is added and dissolved.
3) Titrate with a potentiometric titrator using a 0.1 mol / l ethanol solution of KOH (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette. Automatic titration using can be used).
4) The amount of KOH solution used at this time is S (ml), and a blank is measured at the same time. The amount of KOH solution used at this time is B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

  Next, in the toner of the present invention, a method for containing 10 to 500 particles that do not pass through a mesh having an opening of 34 μm per 5 g of the toner is not particularly limited. It is preferable to use a mechanical pulverizer as shown because the powder raw material can be pulverized and surface-treated to improve efficiency. In this pulverizer, the surface property of the toner can be controlled by adjusting the temperature during pulverization.

  Hereinafter, the mechanical pulverizer shown in FIGS. 1, 2 and 3 will be described. FIG. 1 shows a schematic cross-sectional view of an example of a mechanical pulverizer used in the present invention, FIG. 2 shows a schematic cross-sectional view along the line DD ′ in FIG. 1, and FIG. The perspective view of the rotor 214 shown in FIG. 1 is shown. As shown in FIG. 1, the apparatus includes a casing 213, a jacket 216, a distributor 220, and a plurality of grooves on a surface that rotates within a casing 213 and includes a rotating body attached to a central rotating shaft 215. The provided rotor 214, the stator 210 provided with a number of grooves on the outer periphery of the rotor 214, which is arranged at regular intervals, and the raw material input for introducing the raw material to be treated It is comprised from the port 211 and the raw material discharge port 202 for discharging the powder after a process.

  As the base material of the rotor 214 and the stator 210 of these mechanical grinders, carbon steel such as S45C or chromium molybdenum steel such as SCM material is often used, but there is a problem in wear resistance performance, and rotation Since there is a problem in that the frequency of replacement of the core and the stator is high, it is preferable to use these surfaces coated with a wear-resistant plating in order to obtain stable toner surface properties.

  By coating with a wear-resistant plating, the surface hardness is high, the wear resistance is high, and a long-life rotor or stator is obtained. It is possible to finish the surface uniformly and smoothly by plating, to reduce the coefficient of friction and improve the wear resistance, and to obtain a toner with higher uniformity in the quality of the pulverized toner. It becomes possible. After the plating process, a polishing process such as buffing or a blasting process such as shot blasting may be performed to adjust the surface roughness of the rotor or stator.

  The surface hardness of the rotor and / or stator is preferably HV 400 to 1300 (Vickers hardness 400 to 1300). Further preferable surface hardness is HV500 to 1250, and particularly preferable is HV900 to 1230. The surface hardness in the present invention was measured under the condition that a load of 0.4903 N was held for 30 seconds.

  When the surface hardness is in the range of HV400 to 1300, the amount of wear on the pulverized surface can be reduced as much as possible, and the replacement frequency of the rotor and stator can be reduced. If the surface hardness is less than HV400, the wear resistance starts to deteriorate, the pulverization ability cannot be improved, and the surface property of the toner tends to be uneven. When the surface hardness exceeds HV1300, the surface is too hard and brittle, so peeling and cracking are likely to occur, and the replacement frequency of the rotor and stator starts to increase.

  When the surface of the rotor and / or stator is pulverized by a mechanical pulverizer coated with a wear-resistant plating as described above, the wear of the pulverized surface of the rotor and / or stator is reduced. In addition to prolonging the service life, it is possible to further stabilize the toner quality, particularly the chargeability and environmental stability resulting from the toner surface.

  The method for obtaining the toner having the characteristics of the present invention is not particularly limited. For example, the temperature of the raw material discharge port 202 is set to −25 to 25 from the glass transition point Tg of the binder resin. An example is a method in which pulverization is performed at a temperature of -20 ° C to -20 ° C of the glass transition point Tg of the binder resin in an actual pulverized state. By this method, the presence distribution of the raw material on the toner surface tends to be an appropriate value, which is a preferable method for obtaining the toner that is the feature of the present invention.

  Examples of the mechanical pulverizer preferably used as the pulverizing means used in the toner production method of the present invention include Kawasaki Heavy Industries, Ltd. pulverizer KTM, Kryptron, and Turbo Industries, Ltd. turbo mill. These devices are preferably used as they are or after being appropriately improved.

  Counting the number of particles that do not pass through a mesh having a mesh size of 34 μm can be easily performed using a jig as shown in FIG. A mesh 3 having a predetermined opening is sandwiched and fixed between the jig upper portion 1 and the jig lower portion 2. As the mesh having a mesh opening of 34 μm, a commercially available mesh as 400 mesh can be used. From the lower part of the jig 2, the toner 5 g is sucked from the sample toner suction port 4 while sucking the toner having a particle diameter smaller than the mesh opening of the mesh 3 by means such as a suction hose 5. Throw gently. After completely sucking, the jig upper part 1 is gently removed, and the particles on the mesh are sampled by taping. A taped sample is pasted on paper, magnified with a magnifying glass or microscope, and counted.

That is, the toner preferably used in the present invention contains at least a binder resin and a wax, and particles having a circularity a of 0.900 or more obtained from the following formula (3) among particles of 3 μm or more of the toner. It is preferable that the cumulative value based on the number is 90% or more.
Circularity a = L ₀ / L (3)
[In the formula, L ₀ represents the circumference of a circle having the same projected area as the particle image, and L represents the circumference of the particle image. ]

  In the present invention, the manufacturing method for the circularity toner represented by the above formula (3) is not particularly limited, but the peripheral speed, load, or rotor of the cooling device, the rotor in the mechanical crusher, or the rotor Examples thereof include a method of finely adjusting the minimum distance from the stator in the pulverizer and a method of controlling the circularity by a method of manufacturing by controlling the supply feed amount at the time of pulverization.

  In the present invention, the particle size distribution was performed by the following method.

  The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was performed using a multisizer of a Coulter counter.

  As a measuring device, a multisizer II type or IIE type (manufactured by Coulter Co., Ltd.), a Coulter counter, is connected to an interface (manufactured by Nikkiki) that outputs a number distribution / volume distribution and a general personal computer. A 1% NaCl aqueous solution is prepared using special grade or first grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measured using a Coulter counter Multisizer II type with a 100 μm aperture. The volume and number of toners are measured to calculate a volume distribution and a number distribution, and a weight-based weight average diameter obtained from the volume distribution is obtained.

The circularity in the present invention is used as a simple method for quantitatively expressing the particle shape. In the present invention, the circularity is measured by using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. The circularity of the obtained particles is obtained by the following equation (3).
Circularity a = L ₀ / L (3)
[In the formula, L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents a particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). The perimeter of is shown. ]

  The circularity used in the present invention is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the circularity.

  Furthermore, the measurement device used in the present invention, “FPIA-2100”, has a thinner sheath flow (7 μm → 4 μm) than “FPIA1000” which has been used to calculate the shape of the toner. ) And the magnification of the processed particle image, and further improved the processing resolution of the captured image (256 × 256 → 512 × 512), so that the accuracy of toner shape measurement has been improved, thereby more reliably capturing fine particles. It is a device that has achieved. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

  As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impurities in the container have been removed in advance, and a measurement sample is 0. Add about 1-0.5g. The suspension in which the sample is dispersed is irradiated with ultrasonic waves (50 kHz, 120 W) for 1 to 3 minutes, the dispersion concentration is set to 1.2 to 2 million pieces / μl, and the flow type particle image measurement apparatus is used. The circularity distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.

  The outline of the measurement is as follows.

  The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat flow cell (thickness: about 200 μm). The strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to form an optical path that passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.

  In the present invention, the binder resin for the toner is preferably a resin having a polyester structure.

  The resin having a polyester structure is not particularly limited, and a conventionally known resin having a polyester structure can be used.

  As the monomer constituting the resin having a polyester structure, conventionally known substances described below can be used, but are not limited thereto.

  Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and diols such as bisphenol derivatives represented by the following formula (4) Kind.

（式中Ｒはエチレン又はプロピレン基であり、ｘ、ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  In addition, as the acid component, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or acid anhydrides thereof, dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or acid anhydrides thereof And aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.

  Further, trivalent or higher alcohols include glycerin, sorbit, sorbitan, etc., and trivalent or higher acids include trimellitic acid, pyromellitic acid, and the acid anhydrides thereof.

  Moreover, the manufacturing method of resin which has a polyester structure used by this invention is not specifically limited, A conventionally well-known manufacturing method is applied.

  As the binder resin for the toner, in addition to the resin having a polyester structure, a styrene-acrylic resin, a styrene-vinyl methyl ether copolymer, a styrene-butadiene copolymer, a styrene-vinyl methyl ketone copolymer, and a styrene-acrylonitrile. -Styrene copolymer of styrene and other vinyl monomers such as indene copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, phenol resin, fat Aliphatic or alicyclic hydrocarbon resins, petroleum resins, chlorinated paraffins, and the like can be mixed and used.

  In the present invention, if necessary, other charge control agents can be contained, and conventionally known charge control agents can be used in combination.

  The following are examples of charge control agents known in the art today.

  For example, organometallic complexes and chelate compounds are effective, and there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid, and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts, anhydrides, esters thereof; phenol derivatives such as bisphenol.

  In the present invention, it is preferable to use an organometallic compound as the charge control agent, and those containing an organic compound rich in vaporization and sublimation as a ligand or counter ion are particularly useful. As such an organometallic compound, an azo metal complex compound is preferably used from the viewpoint of chargeability. Examples of the azo metal complex compounds include metal complexes of azo dyes described in JP-B Nos. 41-20153, 42-27596, 44-6397, and 45-26478. . In particular, from the viewpoint of dispersibility and chargeability, an azo metal complex compound represented by the following general formula (5) is preferable, and an azo metal complex compound whose central metal is iron is particularly preferable. More preferably, an azo metal complex compound represented by the following general formula (6) is used.

  In the present invention, it is preferable to contain a compound having an azo structure. The compound having an azo structure is not particularly limited in the present invention, but the above general formulas (5) and (6) It is preferable to contain the azo type metal complex compound shown by this.

［式中、Ｍは、Ｃｒ、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ、Ｔｉ及びＡｌからなるグループから選択される配位中心金属を示す。Ａｒは、ニトロ基、ハロゲン基、カルボキシル基、アニリド基、炭素数１乃至１８のアルキル基及び炭素数１乃至１８のアルコキシ基からなるグループから選択される置換基を有しても良いアリール基を示す。Ｘ、Ｘ’、Ｙ及びＹ’は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ₂₆−（Ｒ₂₆は炭素数１乃至４のアルキル基）を示す。Ａ⁺は、水素、ナトリウムイオン、カリウムイオン、アンモニウムイオン又は脂肪族アンモニウムイオンを示す。］

[Wherein M represents a coordination center metal selected from the group consisting of Cr, Co, Ni, Mn, Fe, Ti and Al. Ar represents an aryl group which may have a substituent selected from the group consisting of a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Show. X, X ′, Y and Y ′ each represent —O—, —CO—, —NH— or —NR ₂₆ — (R ₂₆ represents an alkyl group having 1 to 4 carbon atoms). A ⁺ represents hydrogen, sodium ion, potassium ion, ammonium ion or aliphatic ammonium ion. ]

［式中、Ｘ₁及びＸ₂は水素原子、低級アルキル基、低級アルコキシ基、ニトロ基又はハロゲン原子を示し、Ｘ₁とＸ₂は同じであっても異なっていても良い。ｍ及びｍ’は１乃至３の整数を示す。Ｒ₁₂及びＲ₁₄は水素原子、炭素数１乃至１８のアルキル、アルケニル、スルホンアミド、メシル、スルホン酸、カルボキシエステル、ヒドロキシ、炭素数１乃至１８のアルコキシ、アセチルアミノ、ベンゾイルアミノ基又はハロゲン原子を示し、Ｒ₁₂とＲ₁₄は同じであっても異なっていても良い。ｎ及びｎ’は１乃至３の整数を示す。Ｒ₁₃及びＲ₁₅は水素原子又はニトロ基を示す。Ａ₁ ⁺はアンモニウムイオン、水素イオン、ナトリウムイオン、カリウムイオン及びそれらの混合イオンからなるグループから選択されるカチオンイオンを示す。］

[Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different. m and m ′ each represent an integer of 1 to 3. R ₁₂ and R ₁₄ are each a hydrogen atom, alkyl having 1 to 18 carbon atoms, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy having 1 to 18 carbon atoms, acetylamino, benzoylamino group or halogen atom. R ₁₂ and R ₁₄ may be the same or different. n and n ′ represent an integer of 1 to 3. R ₁₃ and R ₁₅ represent a hydrogen atom or a nitro group. A ₁ ⁺ represents a cation ion selected from the group consisting of ammonium ion, hydrogen ion, sodium ion, potassium ion and mixed ions thereof. ]

  In the present invention, the wax is added for the purpose of improving the offset resistance at the time of hot roll fixing and controlling the contact angle of the toner. As the wax used in the present invention, as the wax having an endothermic peak in DSC measurement at 60 to 150 ° C., for example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are used. Can be mentioned.

  Examples of the aliphatic hydrocarbon wax include low molecular weight alkylene polymers obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure, alkylene polymers obtained by thermally decomposing high molecular weight alkylene polymers, carbon monoxide. A wax such as a synthetic hydrocarbon obtained from a distillation residue of hydrocarbons obtained from the synthesis gas comprising hydrogen by the age method or by hydrogenation of these can be used. Furthermore, the thing which fractionated hydrocarbon wax by the use of the press perspiration method, the solvent method, vacuum distillation, or a fractional crystallization system can be used.

  An example of the aliphatic hydrocarbon wax is an endothermic onset temperature in the range of 50 to 110 ° C. with respect to an endothermic peak at the time of temperature rise and an exothermic peak at the time of temperature drop in a DSC curve measured by a differential scanning calorimeter. And an aliphatic hydrocarbon wax having at least one endothermic peak in a temperature range of 70 to 130 ° C., and having a maximum exothermic peak when the temperature falls within the range of the peak temperature ± 9 ° C. of the endothermic peak. Can do.

  The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems), for example, the jintole method, hydrocol method (fluidized catalyst bed) Or hydrocarbons with up to several hundred carbon atoms obtained by the Age method (using a fixed catalyst bed) that can produce a large amount of wax-like hydrocarbons, and hydrocarbons obtained by polymerizing alkylenes such as ethylene with Ziegler catalysts. Can be used. In addition, a wax synthesized by a method not based on polymerization of alkylene can be used.

  Further, the wax used in the present invention includes an oxide of an aliphatic hydrocarbon wax such as an oxidized polyethylene wax, or a block copolymer thereof, a wax having a structure having an ester bond such as a carnauba wax or a montanic ester wax. , And esters obtained by partially or fully deoxidizing esters such as deoxidized carnauba wax can be used.

  In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol, linoleic acid amides, oleic acid amides, fatty acid amides such as lauric acid amides, methylenebisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides Saturated fatty acid bisamides such as hexamethylenebisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dio Unsaturated fatty acid amides such as irsevacinamide; aromatic bisamides such as m-xylene bis stearamide, N, N′-distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Fatty acid metal salts (generally referred to as metal soaps); graft waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acid and polyhydric alcohol moieties such as behenic acid monoglyceride Examples of esterified products include methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

Furthermore, examples of the wax-like substance used in the present invention include aliphatic alcohol waxes and alkyl monocarboxylic acid waxes. The aliphatic alcohol wax is represented by the following general formula (7). The alkyl monocarboxylic acid wax is represented by the following general formula (8).
CH ₃ (CH ₂ ) _{X 3} CH ₂ OH (7)
(Wherein X ₃ represents an average value and is 20 to 250)
CH ₃ (CH ₂ ) _{Y 4} CH ₂ COOH (8)
(In the formula, Y ₄ represents an average value and is 20 to 250)

  The addition amount of the wax-like substance used in the present invention to the binder resin can be 0.1 to 20 parts by mass per 100 parts by mass of the binder resin.

  As the colorant that may be used in the toner used in the present invention, various colorants can be used depending on the color of the toner, and any appropriate pigment or dye can be used. Toner colorants are well known, and examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, Bengala, phthalocyanine blue, and induslen blue. These can be used in an amount necessary and sufficient to maintain the optical density of the fixed image. The addition amount is 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the binder resin. . Further, a dye can be further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, and the like, and the addition amount is 0.1 to 20 parts by weight, preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the binder resin. Good.

  The toner of the present invention preferably contains an inorganic fine powder in order to improve charging stability, developability, fluidity and durability, and silica fine powder is preferably externally added as such an inorganic fine powder.

The fine silica powder used in the present invention gives a good result when the specific surface area by nitrogen adsorption measured by the BET method is in the range of 30 m ² / g or more (particularly 50 to 400 m ² / g). The silica fine powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner.

  In addition, the silica fine powder used in the present invention is optionally made of silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, functional groups for the purpose of hydrophobization and chargeability control. It is also preferable that the surface is treated with a silane coupling agent having silane, other treating agents such as an organosilicon compound, and the like. Particularly in the present invention, it is preferable to treat the surface of the silica fine powder with silicone oil.

  Furthermore, as other additives, for example, a lubricant such as polyfluorinated ethylene, zinc stearate, polyvinylidene fluoride, and the like can be used. Abrasives such as cerium oxide, silicon carbide, and strontium titanate can be used, and among these, strontium titanate is preferable. Alternatively, a fluidity-imparting agent such as titanium oxide or aluminum oxide is used, and among them, a hydrophobic one is particularly preferable. An appropriate amount of an anti-caking agent, or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide or tin oxide, or white and black fine particles having opposite polarity can also be used as a developability improver.

  The toner of the present invention may be mixed with a carrier and used as a two-component developer.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated. Examples of the resin covering the carrier surface include styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, silicone resin, fluorine-containing resin, and polyamide resin. , Ionomer resin, polyphenylene sulfide resin, or a mixture thereof can be used.

  As the magnetic material for the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, or alloys thereof can be used. Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done.

  The toner according to the present invention is not particularly limited as long as it has the above-described physical properties, but can be manufactured using a so-called pulverization method. That is, a binder resin, and if necessary, a pigment or dye as a colorant, a charge control agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then heated rolls, kneaders, extruders. The composite particles of the present invention are obtained by dispersing or dissolving the pigments and dyes in the melted, kneaded and ground meat using a heat kneader such as Can be sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner according to the present invention.

  Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

The evaluation items in the examples of the present invention were evaluated by the following methods. 1) Image density after endurance 10000 sheets of image endurance under ambient conditions of normal temperature and humidity (23.5 ° C., 60%) After completion of the evaluation, the image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to the printout image of the white background portion having a document density of 0.00.

2) Fog Evaluation Method Using A4 paper, a solid white copy image was formed, and the fog value was evaluated by the difference in reflectance between the paper passed through the copying machine and the paper of the same lot.

  The reflectance was measured for any nine points on the paper using a Tokyo Denshoku reflection densitometer TC-6MC, and the average value for the nine points was used as the fog value.

  The evaluation criteria for fogging are as follows.

3) Resolving power The resolving power of a copied image was evaluated by the following method after the end of image printing endurance.

  It is a pattern consisting of five fine lines with the same line width and spacing, and 2.8, 3.2, 3.6, 4.0, 4.5, 5.0, 5.6, 6.3 in 1 mm. , 7.1, 8.0, 9.0, 10.0 Create an original image drawn.

  An image obtained by copying an original document having these 12 types of line images under appropriate copying conditions is observed with a magnifying glass, and the number of images (lines / mm) in which fine lines are clearly separated is used as an evaluation means. It was.

  Here, the greater the value of the number of images (lines / mm) in which fine lines are clearly separated, the better the level of blurring of the line image of the copied image, the higher the resolution, and the higher the image quality. It is.

  The evaluation criteria for resolving power are as shown in the following table.

4) Evaluation method of image flow Using paper of 10% moisture absorption at 33 ° C. and 95% relative humidity (moisture absorption was measured using MOISTEX MX5000 manufactured by Infrared Engineering). 5000 sheets of A4 image originals with 12 E characters arranged in 15 rows × 12 columns were continuously fed, and the 5000th sheet was used for image flow evaluation. The occurrence of the image flow occurs such that the E character on the copy image is blurred and the E character of the copy image cannot be discriminated. The evaluation criteria for image flow are as follows.

5) Nail mark measurement method with solid black images Leave the copier used for image endurance evaluation under ambient temperature and humidity (23.5 ° C, 60%) environmental conditions with the power outlet unplugged overnight. Immediately after turning on the power outlet, the main switch of the copier main body used in the image endurance evaluation is turned on, and immediately after the main body is ready for operation, five A3 solid black images are taken in succession. The length of the fixing nail trace generated at the tip of the solid black image is measured. The longer the length of the fixing nail mark generated at the tip of the fifth A3 solid black image, the worse the level of the nail mark in the solid black image. The evaluation criteria for the level of nail marks in a solid black image are as follows.

(Production Example 1 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 40 parts by mass Polymerization was performed for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the following temperature conditions took 70 minutes to phase separate into two phases after no stirring. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent A in the present invention.

(Production Example 2 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 40 parts by mass Polymerization was performed for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the following temperature conditions took 30 minutes to phase separate into two phases after no stirring. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent B in the present invention.

(Production Example 3 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitryl) 40 parts by mass Polymerization was carried out for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under temperature conditions took 45 minutes to phase separate into two phases after no stirring.

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent C in the present invention.

(Production Example 4 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitryl) 40 parts by mass Polymerization was carried out for 5 hours under stirring conditions in which the dispersion state formed when stirring at a shear rate of 10 (1 / sec) under temperature conditions for 5 minutes was 50 minutes with a time for phase separation into two phases after no stirring.

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent D in the present invention.

(Production Example 5 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitryl) 40 parts by mass Water-soluble dispersion stabilizer When 5 parts by weight of polyvinyl alcohol is stirred for 5 minutes at a shear rate of 10 (1 / sec) under a temperature condition of 80 ° C., the time for phase separation into two phases after stirring is 70 minutes Polymerization was performed for 5 hours under the following stirring conditions.

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent E in the present invention.

(Production Example 6 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass 2,2′-azobis [2- (2-imidazoline-2- Yl) propane] disulfate dihydrate Time for 30 parts by mass of the dispersed state formed when stirring at a shear rate of 10 (1 / sec) at 80 ° C. for 5 minutes to phase-separate into two phases after no stirring Was polymerized for 5 hours under stirring conditions of 70 minutes.

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent F in the present invention.

(Production Example 7 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 65 parts by mass Polymerization was performed for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the following temperature conditions took 70 minutes to phase separate into two phases after no stirring. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent G in the present invention.

(Production Example 8 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 120 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 90 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 5 parts by mass Polymerization was performed for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the following temperature conditions took 70 minutes to phase separate into two phases after no stirring. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent H in the present invention.

(Production Example 9 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 90 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 30 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 40 parts by mass Polymerization was performed for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the temperature conditions of 80 minutes was 80 minutes. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent I in the present invention.

(Production Example 10 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 150 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 140 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 40 parts by mass Polymerization was performed for 5 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the temperature conditions of 80 minutes was 80 minutes. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent J in the present invention.

(Production Example 11 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 100 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 15 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 40 parts by mass Polymerization was carried out for 2 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the temperature conditions was 80 minutes for phase separation into two phases after no stirring. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent K in the present invention.

(Production Example 12 of Charge Control Agent)
Isopropyl alcohol 290 parts by mass Styrene 780 parts by mass n-butyl acrylate 200 parts by mass 2-acrylamido-2-methylpropanesulfonic acid 160 parts by mass Water 2600 parts by mass Azobis (2-methylbutyronitrile) 40 parts by mass Polymerization was carried out for 2 hours under stirring conditions in which the dispersion state formed when stirring for 5 minutes at a shear rate of 10 (1 / sec) under the temperature conditions was 80 minutes for phase separation into two phases after no stirring. .

  Thereafter, the obtained polymer was dried under reduced pressure to obtain a charge control agent L in the present invention.

(Toner developer production example 1)
Binder resin (polyester resin glass transition point Tg 60 ° C.) 100 parts by mass Carbon black 3 parts by mass Charge control agent A 2 parts by mass Wax (polyethylene wax, softening point 100 ° C.) 5 parts by mass The mixture was melt kneaded with a twin screw extruder heated to 125 ° C., and the cooled kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill type T-250 manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. Toner classification product A of 5 μm was obtained.

  To 100 parts by mass of toner classification product A, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner A.

  The weight average particle diameter of the toner A was 7.5 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 5. The toner A contained 85% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  Toner A and silicon coat carrier were mixed to obtain developer A.

(Toner developer production example 2)
In toner production example 1, except that charge control agent A is changed to charge control agent B, the same material as in toner production example 1 is melt-kneaded under the same kneading conditions as in toner production example 1 and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill type T-250 manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product B of 7 μm was obtained.

  0.4 parts by mass of hydrophobic silica fine powder was added to 100 parts by mass of the toner classification product B, and mixed with a Henschel mixer to obtain toner B.

  The weight average particle diameter of the toner B was 7.7 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 5. Toner B contained 85% of the number-based cumulative value of particles having a circularity a of 0.900 or more in the formula (3).

  Toner B and silicon coat carrier were mixed to obtain developer B.

(Toner developer production example 3)
In toner production example 1, except that charge control agent A is changed to charge control agent C, the same material as toner production example 1 is melt-kneaded under the same kneading conditions as toner production example 1, and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill type T-250 manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. Toner classification product C of 4 μm was obtained.

  To 100 parts by mass of the toner classification product C, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner C.

  The weight average particle diameter of Toner C was 7.4 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of toner was 5. The toner C contained 85% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  Toner C and silicon coat carrier were mixed to obtain developer C.

(Toner developer production example 4)
In toner production example 1, except that charge control agent A is changed to charge control agent D, the same material as in toner production example 1 is melt-kneaded under the same kneading conditions as in toner production example 1 and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill type T-250 manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. Toner classification product D of 8 μm was obtained.

  0.4 parts by mass of hydrophobic silica fine powder was added to 100 parts by mass of the toner classified product D, and mixed with a Henschel mixer to obtain toner D.

  The weight average particle diameter of Toner D was 7.8 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of toner was 5. The toner D contained 85% of particles having a circularity a in the formula (3) of 0.900 or more in terms of the number-based cumulative value.

  The toner D and the silicon coat carrier were mixed to obtain a developer D.

(Toner developer production example 5)
In Toner Production Example 4, except that the pulverization conditions in the turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd., which is a mechanical pulverizer shown in FIG. 1, are changed to the pulverization conditions shown in Table 6. A toner classified product E having a weight average particle diameter of 7.2 μm was obtained under the same production conditions as in No. 4.

  To 100 parts by mass of the toner classification product E, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner E.

  The weight average particle diameter of the toner E was 7.2 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 15. The toner E contained 82% of particles having a circularity a in the formula (3) of 0.900 or more in terms of the number-based cumulative value.

  The toner E and a silicon coat carrier were mixed to obtain a developer E.

(Toner developer production example 6)
In Toner Production Example 4, except that the pulverization conditions in the turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd., which is a mechanical pulverizer shown in FIG. 1, are changed to the pulverization conditions shown in Table 6. A toner classified product F having a weight average particle diameter of 7.3 μm was obtained under the same production conditions as in No. 4.

  To 100 parts by mass of toner classification product F, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner F.

  The weight average particle diameter of the toner F was 7.3 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of toner was 6. The toner F contained 92% of particles having a circularity a of 0.900 or more in formula (3) in terms of the number-based cumulative value.

  The toner F and the silicon coat carrier were mixed to obtain a developer F.

(Toner developer production example 7)
In Toner Production Example 4, except that the pulverization conditions in the turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd., which is a mechanical pulverizer shown in FIG. 1, are changed to the pulverization conditions shown in Table 6. A toner classified product G having a weight average particle diameter of 7.1 μm was obtained under the same production conditions as in No. 4.

  To 100 parts by mass of the toner classification product G, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner G.

  The weight average particle diameter of the toner G was 7.1 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 20. The toner G contained 95% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner G and a silicon coat carrier were mixed to obtain a developer G.

(Toner developer production example 8)
In the toner production example 1, except that the charge control agent A is changed to the charge control agent E, the same material as the toner production example 1 is melt-kneaded under the same kneading conditions as the toner production example 1 and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill type T-250 manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. Toner classification product H of 2 μm was obtained.

  To 100 parts by mass of the toner classification product H, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner H.

  The weight average particle diameter of the toner H is 7.2 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner is 6. The toner H contained 84% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner H and the silicon coat carrier were mixed to obtain a developer H.

(Toner developer production example 9)
In the toner production example 1, except that the charge control agent A is changed to the charge control agent F, the same material as the toner production example 1 is melt kneaded and cooled under the same kneading conditions as the toner production example 1. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A 1 μm toner classification product I was obtained.

  0.4 parts by mass of hydrophobic silica fine powder was added to 100 parts by mass of the toner classification product I, and mixed with a Henschel mixer to obtain toner I.

  The weight average particle diameter of the toner I was 7.1 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 7. The toner I contained 83% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner I and a silicon coat carrier were mixed to obtain a developer I.

(Toner developer production example 10)
In toner production example 1, except that charge control agent A is changed to charge control agent G, the same material as toner production example 1 is melt-kneaded under the same kneading conditions as toner production example 1, and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product J of 4 μm was obtained.

  To 100 parts by mass of the toner classification product J, 0.4 part by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner J.

  The weight average particle diameter of Toner J was 7.4 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of toner was 5. The toner J contained 86% of particles having a circularity a of 0.900 or more in formula (3) in terms of the number-based cumulative value.

  The toner J and a silicon coat carrier were mixed to obtain a developer J.

(Production Example 11 of Toner Developer)
In toner production example 1, except that charge control agent A is changed to charge control agent H, the same material as in toner production example 1 is melt-kneaded under the same kneading conditions as in toner production example 1, and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product K of 3 μm was obtained.

  To 100 parts by mass of the toner classification product K, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner K.

  The weight average particle diameter of the toner K was 7.3 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 6. The toner K contained 86% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner K and a silicon coat carrier were mixed to obtain a developer K.

(Toner Developer Production Example 12)
In Toner Production Example 1, except that the pulverization conditions in the turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd., which is a mechanical pulverizer shown in FIG. 1, are changed to the pulverization conditions shown in Table 6. A toner classified product L having a weight average diameter of 7.2 μm was obtained under the same production conditions as in Example 1.

  To 100 parts by mass of the toner classification product L, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner L.

  The weight average particle diameter of the toner L was 7.2 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 521. The toner L contained 85% of particles having a circularity a in the formula (3) of 0.900 or more in terms of the number-based cumulative value.

  The toner L and a silicon coat carrier were mixed to obtain a developer L.

(Comparative Production Example 1 of Toner Developer)
In the toner production example 1, except that the charge control agent A is changed to the charge control agent I, the same material as the toner production example 1 is melt kneaded and cooled under the same kneading conditions as the toner production example 1. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product M of 8 μm was obtained.

  To 100 parts by mass of the toner classification product M, 0.4 part by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner M.

  The weight average particle diameter of the toner M was 7.8 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 6. The toner M contained 81% of particles having a circularity a in the formula (3) of 0.900 or more in terms of the number-based cumulative value.

  The toner M and a silicon coat carrier were mixed to obtain a developer M.

(Comparative Production Example 2 of Toner Developer)
In toner production example 1, except that charge control agent A is changed to charge control agent J, the same material as toner production example 1 is melt-kneaded under the same kneading conditions as toner production example 1, and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverization conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product N of 7 μm was obtained.

  To 100 parts by mass of the toner classified product N, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner N.

  The weight average particle diameter of the toner N was 7.7 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of toner was 5. The toner N contained 83% of particles having a circularity a of 0.900 or more in Formula (3) in terms of the number-based cumulative value.

  The toner N and silicon coat carrier were mixed to obtain developer N.

(Comparative Production Example 3 of Toner Developer)
In toner production example 1, except that charge control agent A is changed to charge control agent K, the same material as toner production example 1 is melt-kneaded under the same kneading conditions as toner production example 1, and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product O of 5 μm was obtained.

  0.4 parts by mass of hydrophobic silica fine powder was added to 100 parts by mass of the toner classified product O, and mixed with a Henschel mixer to obtain toner O.

  The weight average particle diameter of the toner O was 7.5 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of the toner was 5. The toner O contained 82% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner O and a silicon coat carrier were mixed to obtain a developer O.

(Comparative Production Example 4 of Toner Developer)
In toner production example 1, except that charge control agent A is changed to charge control agent L, the same material as toner production example 1 is melt-kneaded under the same kneading conditions as toner production example 1, and cooled. The kneaded product was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product P of 2 μm was obtained.

  To 100 parts by mass of the toner classification product P, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner P.

  The weight average particle diameter of the toner P was 7.2 μm, and the number of magnetic particles that did not pass through a mesh having an opening of 34 μm per 5 g of toner was 6. The toner P contained 87% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner P and the silicon coat carrier were mixed to obtain a developer P.

(Comparative Production Example 5 of Toner Developer)
In Toner Production Example 1, the same materials as in Toner Production Example 1 are kneaded in the same manner as in Toner Production Example 1 except that the binder resin (polyester resin) is changed to a binder resin (styrene acrylic resin). The kneaded material that had been melt-kneaded and cooled under conditions was coarsely pulverized with a hammer mill.

  The coarsely pulverized product is pulverized under the pulverizing conditions shown in Table 6 using a turbo mill T-250 type manufactured by Turbo Industry Co., which is a mechanical pulverizer shown in FIG. A toner classification product Q of 6 μm was obtained.

  To 100 parts by mass of the toner classification product Q, 0.4 parts by mass of hydrophobic silica fine powder was added and mixed with a Henschel mixer to obtain toner Q.

  The weight average particle diameter of the toner Q was 7.6 μm, and the number of magnetic particles not passing through a mesh having an opening of 34 μm per 5 g of toner was 7. The toner Q contained 84% of particles having a circularity a of 0.900 or more in the formula (3) in terms of the number-based cumulative value.

  The toner Q and silicon coat carrier were mixed to obtain developer Q.

<Example 1>
Developer A is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 2>
Developer B is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and is used in an environment of room temperature and normal humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 3>
Developer C is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 4>
The developer D is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 5>
Developer E is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 6>
The developer F is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 7>
The developer G is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 8>
Developer H is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 9>
Developer I was applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment was normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 10>
Developer J is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 11>
Developer K is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Example 12>
The developer L is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Comparative Example 1>
The developer M is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Comparative example 2>
Developer N is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Comparative Example 3>
Developer O is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C, 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Comparative example 4>
The developer P is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

<Comparative Example 5>
The developer Q is applied to a Canon copier CLC5000 modified to remove the fixing oil application function by replacing the silicon fixing roller with a fluorine fixing roller, and the environment is normal temperature and humidity (23.5 ° C., 60%). Under the conditions, the above-described various evaluations were made on the endurance evaluation of 100,000 images and the image quality. Table 7 shows the evaluation results.

It is a schematic explanatory drawing of a mechanical grinder. It is a schematic sectional drawing in the D-D 'surface of FIG. It is a perspective view of the rotor of a mechanical grinder. It is explanatory drawing of the jig | tool for magnetic particle number count.

Explanation of symbols

DESCRIPTION OF SYMBOLS 201 Mechanical grinder 210 Stator 212 Swirl chamber 213 Casing 214 Rotor 215 Rotating shaft 216 Jacket 219 Pipe 220 Distributor 222 Bag filter 224 Suction blower 229 Collection cyclone 235 Fixed amount feeder 1 Jig upper part 2 Jig lower part 3 Mesh 4 Sample toner suction port 5 Suction hose

Claims (8)

In a non-magnetic toner containing at least a binder resin, a colorant and a charge control agent,
The charge control agent is a resin obtained by polymerizing at least a monomer having a sulfonic acid group, and
1) having a first acid value A and a second acid value B, measured by potentiometric titration,
2) The first acid value A is 2 mg / mg KOH to 10 mg / mg KOH,
3) The first acid value A and the second acid value B are represented by the following formula (1)
1.20 ≦ A / B ≦ 2.00 (1)
And
A nonmagnetic toner, wherein the binder resin is a binder resin having a polyester structure.   The dispersion was formed by stirring the charge control agent at a shear rate of 10 (1 / sec) for 5 minutes, and the polymerization was performed in a suspension state in which phase separation into at least two phases within 20 seconds to 60 minutes without stirring. The nonmagnetic toner according to claim 1, wherein the nonmagnetic toner is a charge control agent having at least a monomer having a sulfonic acid group and a plurality of vinyl monomers, which is obtained by the production method performed.   The non-magnetic toner according to claim 1, wherein the charge control agent is a charge control agent produced by a polymerization method without adding a water-soluble dispersion stabilizer.   The nonmagnetic toner according to claim 1, wherein the charge control agent is a charge control agent produced by a method of polymerizing using a water-insoluble polymerization initiator.   The nonmagnetic toner according to claim 1, wherein the charge control agent has a weight average molecular weight (Mw) of 10,000 to 100,000. 6. The nonmagnetic toner according to claim 1, wherein a weight average molecular weight W (Mw) and a number average molecular weight N (Mn) of the charge control agent satisfy the following formula (2).
1.2 ≦ W / N ≦ 3.5 (2) 2. The non-magnetic toner according to claim 1, wherein the non-magnetic toner has 90% or more of particles having a circularity a of 0.900 or more obtained from the following formula (3) in terms of a number-based cumulative value when the particle diameter is 3 μm or more. The nonmagnetic toner as described in any one of 1 to 6: Circularity a = L ₀ / L (3)
[Where L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image] The nonmagnetic toner according to any one of claims 1 to 7, wherein the nonmagnetic toner contains 10 to 500 particles that do not pass through a mesh having an opening of 34 µm per 5 g of toner.

Images