JP2006106534A - Method for manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing toner to obtain an excellent toner which ensures no color irregularity and a wide color reproduction range even in a light pressure fixing system, does not cause faulty fixing even at high speed, can be fixed without problems even on transfer materials of different sizes, and requires neither cleaning means nor waste toner box. <P>SOLUTION: In the method for manufacturing the toner, a step of simultaneously carrying out surface modification and classification is carried out using a simultaneous surface modification-classification apparatus to obtain toner particles, and in a step of externally adding an inorganic fine powder to the toner particles to obtain toner, mixing and surface modification of the toner particles with the external additive are carried out using a simultaneous mixing-surface modification apparatus with impellers to obtain the objective toner. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method and a toner jet method, particularly a toner suitable for oilless.

  In full-color copying machines and printers, cyan toner, magenta toner, yellow toner, black toner, etc. are used and developed by superimposing each color toner using the subtractive color mixing action, and each color toner image formed by development The toner image is finally superimposed and transferred onto a transfer material such as an OHP sheet or plain paper, and a toner image superimposed on the transfer material is fixed on the transfer material, thereby forming a desired color image. For this reason, when color toners are mixed, it is necessary to uniformly apply heat and pressure to the upper toner layer and the lower toner layer to create an image having no color unevenness. If color unevenness occurs because the heat and pressure cannot be applied uniformly to the toner, the gloss unevenness will be severe, and when the toner is overlaid, the color of the lower toner will not appear and the color reproduction range will be narrow. End up. In black and white apparatuses and printers, in recent years, the speed has been remarkably increased, and the amount of heat given to the toner at the time of fixing is steadily decreasing due to the shortening of the fixing time as the speed increases. If heat and pressure cannot be uniformly applied to the toner, an image with poor fixing is likely to appear.

  As a fixing method, an on-demand fixing method that hardly uses electric power during standby is preferably used from the viewpoint of ecology in recent years. On-demand fixing tends to be light-pressure fixing compared to normal high-pressure roller fixing, and it becomes difficult to apply heat and pressure uniformly to the toner, so it tends to be inferior to fixing performance and color unevenness. . In order to improve this, contrivances such as the viscoelastic design of the resin of the toner and the presence state of the release agent have been made (for example, see Patent Document 1).

  In order to respond to various user needs, it is also necessary to support a variety of transfer materials, and in particular, it is important that different sizes can be fixed without problems. If the size is different, the temperature at the fixing machine is different between the place where the paper is passed and the place where it is not, that is, the temperature distribution is generated in the fixing device, which causes fixing failure. This is not a complete solution with current technology. In order to avoid fixing failure, it takes a long time to fix (down time) to eliminate temperature unevenness, and there is a problem in fixing different sizes continuously without downtime. .

  In recent years, copiers and printers have been sought to be smaller, lighter, faster, and more reliable due to demands for space and energy, and machines are simpler elements in various ways. It has come to be composed of. As a result, the performance required for the toner becomes higher, and an excellent main body configuration cannot be realized unless the toner performance can be improved.

Among them, when an intermediate transfer member is used, it is necessary to increase the toner transfer efficiency, and methods for increasing the toner transfer efficiency by various methods as described below have been proposed. For example, a toner that has been proposed to increase the transfer efficiency by rounding the shape of the toner using a manufacturing apparatus (see, for example, Patent Document 2), an increase in transfer efficiency by an external additive, and a charge control agent on the surface of toner particles There have been proposed improvements in image quality by controlling the amount of the image (for example, see Patent Documents 3 and 4). Although these various proposals are excellent as a single improvement measure, they satisfy the above-mentioned fixing property at the same time and can achieve a transfer property that does not require a cleaning device or a waste toner box. The transfer residual toner can not be reused.

That is, the conventional fixing unit and toner have the following problems. (1) In a light pressure fixing system, gloss unevenness is likely to occur, so the color unevenness and color reproduction range tend to be narrow, and fixing failure is likely to occur at high speeds. (2) In the on-demand fixing method,
Different sizes cannot be fixed continuously without downtime. (3) Although the toner is improved to increase the transfer efficiency, a cleaning device and a waste toner box are required, and therefore the space for the electrophotographic apparatus main body cannot be reduced.
JP 2002-351143 A Japanese Patent Application Laid-Open No. 2002-233787 Japanese Patent Application Laid-Open No. 2002-214825 Japanese Patent Application Laid-Open No. 2002-268280

  The problem of the present invention is that there is no color unevenness in the light pressure fixing system, the color reproduction range is wide, fixing failure does not occur even at a high speed, and it is possible to fix a transfer material of a different size without any problem. And a toner manufacturing method for obtaining an excellent toner that does not require waste toner BOX.

As a result of intensive studies, the present inventors have found that the presence of toner on the transfer material is important for good fixing in a small light pressure fixing device, and have reached the present invention.
That is, the present invention is as follows.
A toner having toner particles having at least a binder resin, a colorant and a release agent, and an inorganic fine powder,
The inorganic fine powder is an inorganic fine powder having at least one maximum value in a region having a particle size of 90 nm to 350 nm in the number distribution particle size on the toner particle surface,
The toner is a method for producing a toner having an average circularity of 0.935 to 0.975 in particles having an equivalent circle diameter of 3 μm or more,
A step (i) in which a composition having at least a binder resin, a colorant and a release agent is melt-kneaded, the obtained kneaded product is cooled and solidified, and the cooled solidified product is finely pulverized to obtain a finely pulverized product; At least a step (ii) of obtaining a toner particle by simultaneously performing a surface modification treatment and a classification treatment of the finely pulverized product, and a step (iii) of obtaining a toner by externally adding an inorganic fine powder to the toner particle,
The step (ii) includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less in the finely pulverized product to the outside of the system, and subjecting the treated particles from which fine powder has been removed by the classifying means to mechanical impact force. A surface treatment means for modifying the surface by use, a first space provided between the classification means and the surface treatment means for introducing the particles to be treated into the classification means, and the particles to be treated Is carried out using a batch-type classifying simultaneous surface reforming apparatus having a second space for introducing the gas into the surface treatment means, a guide means for partitioning the first space and the second space, and the classification In the simultaneous surface modification treatment apparatus, the finely pulverized product is introduced into the first space, and the fine powder having a predetermined particle size or less is continuously discharged and removed from the apparatus by the classification means, while the second space is removed. To the surface treatment means using mechanical impact force Perform surface modification treatment by entering a re-by circulating the first space to obtain a toner particle by repeating a surface modification treatment using a fixed time classification and a mechanical impact force,
The step (iii) includes a processing tank having a spherical upper part, a rotating shaft that vertically penetrates the center of the tank bottom of the processing tank, and a stirring blade that is provided on the rotating shaft and discharges a processed material along the inner wall of the processing tank And a mixing simultaneous surface modification apparatus having an exhaust pipe disposed in the tank from the upper part of the processing tank, and the mixing speed of the stirring blade is 80 m / s or more, and the toner particles and the external additive are mixed. And a method for producing a toner, wherein the toner is obtained by surface modification.

  Even in a light pressure fixing system, there is no color unevenness, a wide color reproduction range, no fixing failure occurs even at high speed, and it can be fixed without problems even with different transfer material sizes, and a cleaning means and a waste toner box are required. An excellent toner manufacturing method is provided.

  In order to satisfy various user needs, it has been described that a small light pressure fixing is desirable. However, as described above, it is important to apply uniform heat and pressure to the toner in order to improve the fixing property.

  The toner according to the present invention is a toner that is preferably used in an image forming method having a fixing step of performing heat and pressure fixing while pressing a rotary pressure member at a linear pressure of 380 to 1140 N / m. If the linear pressure is less than 380 N / m, the pressure for pressing the toner is too small, so that the thermal conductivity to the toner in the lower layer is poor, and the color mixing property and the fixing performance at low temperature are inferior. Also, if the linear pressure exceeds 1140 N / m, the member used for fixing must be strengthened so that it can withstand the high pressure, and it is necessary to increase the size and heat capacity by increasing the thickness of the member and adding auxiliary reinforcing members. Become. As a result, the thermal power source is also increased in size, which increases the size of the apparatus itself, increases the cost, and requires a large amount of heat capacity, and cannot be fixed on demand. Accordingly, the linear pressure of the fixing device is preferably 380 to 1140 N / m, and more preferably 500 to 1000 N / m.

  As the toner used in the light pressure fixing method, it is considered that the presence state of the toner on the transfer material becomes important. Since the toner is crushed during high-pressure fixing, the presence state is almost irrelevant, but during light-pressure fixing, if the toner is uneven and not evenly present on the transfer material, the heat and pressure will be non-uniform, and as a result The gloss unevenness tends to be poor, and the color toner has poor color reproducibility due to poor color mixing.

  If the toners are stacked like densely packed, the air layer in which heat is difficult to pass is reduced and the thermal conductivity is improved, so that the fixing performance, for example, low temperature fixing property is excellent. To achieve these, the circularity of the toner plays a major role. By increasing the circularity, the transfer performance can be improved, the toner layer can be easily formed uniformly on the transfer material, and the fine packing can be easily performed.

The circularity is preferably 0.935 to 0.975 for particles having an equivalent circle diameter of 3 μm or more. If it is less than 0.935, it is difficult to obtain the above-mentioned uniform and fine packing effect, and if it is more than 0.975, the release effect is too strong and the problem of scattering occurs. Therefore, the average circularity is preferably 0.935 to 0.975, and more preferably 0.945 to 0.970.

In order to improve the fixing property and transfer property at light pressure, not only the circularity but also the size and state of the inorganic fine powder existing on the toner particles are important.
In the present invention, a preferable inorganic fine powder has at least one maximum value in the number average distribution particle diameter on the toner particle surface, and the maximum value exists in a region having a particle diameter of 90 nm to 350 nm. It is preferable. If the number average distribution particle size of the inorganic fine powder existing on the toner particle surface satisfies the above range, the composition of silica, alumina, titanium oxide and the like is not particularly limited. For example, in the case of silica, those produced by a conventionally known technique obtained by any method such as a gas phase decomposition method, a combustion method, a deflagration method can be used.
When there is only one maximum value of the number distribution particle size of the inorganic fine powder existing on the toner particle surface, if the maximum value is larger than 350 nm, a gap is formed between the toners because it is difficult to be crushed during light pressure fixing. As a result, the fixing performance is deteriorated. Conversely, when there is only one maximum value of the number distribution particle size of the inorganic fine powder existing on the toner particle surface, and the maximum value is less than 90 nm, the deterioration of the inorganic fine powder is so great that the initial toner and The developing performance is different from that of the toner that has been developed and transferred to the developing device again in the developing simultaneous cleaning process, and fog and scattering are poor. Preferably, an inorganic fine powder having at least one maximum value in a region of a particle size of 100 nm or more and 300 nm or less in the number distribution particle size on the toner particle surface is suitable.
As the inorganic fine powder of the toner according to the present invention, a first inorganic fine powder having a maximum maximum value of 5 nm or more and less than 90 nm and a second inorganic fine powder having a maximum maximum value of 90 nm or more and 350 nm or less in the number distribution. More preferably used in combination.

  The surface of the inorganic fine powder is preferably hydrophobized. As the hydrophobizing agent for hydrophobizing inorganic fine powder, silane compounds are preferably used, monosilanol compounds such as hexamethyldisilazane, trimethylsilanol and triethylsilanol, monochlorosilanes such as trimethylchlorosilane and triethylchlorosilane, Examples thereof include monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane, monoaminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine, and monoacyloxysilanes such as trimethylacetoxysilane.

In the toner of the present invention, the amount of the inorganic fine powder added is 0.3 to 4.0 parts by mass, more preferably 0.5 to 3.0 parts by mass with respect to the toner particles.
In the number average distribution particle size on the toner particle surface, the inorganic fine powder having at least one maximum value in the region of the particle size of 90 nm or more and 350 nm or less is less likely to adhere to the toner particles because it has a larger particle size than usual. Even if it is initially attached, it often comes off due to an impact in the developing device. If it is removed, it will be difficult to obtain the effect of continuous transferability improvement, and it will become an interface between the fixing member and the toner layer at the time of fixing, which will cause a decrease in fixing performance, for example, low temperature fixing performance. In the case of different size papers that can be distributed in temperature by the fixing device, fixing failure occurs.
Therefore, in order to reduce the inorganic fine powder released from the toner, it is necessary to make the toner particles easy to adhere to the inorganic fine powder, and it is necessary to strongly adhere the inorganic fine powder to the toner particles.

  The composition of the toner particle surface is related to the adhesion of the inorganic fine powder, and the more the release agent is on the surface of the toner particle, the more easily the inorganic fine powder is released from the toner particle. Therefore, it is necessary to increase the circularity of the toner, but a manufacturing method in which the release agent is not present on the toner particle surface as much as possible is required. Represented by conventional hybridization systems manufactured by Nara Machinery Co., Ltd., mechano-fusion systems manufactured by Hosokawa Micron Co., Ltd., kryptron systems manufactured by Kawasaki Heavy Industries, Ltd., super rotor manufactured by Nissin Engineering Co., Ltd., etc. Although it seems that the material that gives mechanical impact force while being pulverized at first glance, it seems that the amount of heat is not so much, but in reality, when trying to create the desired spherical shape, it gives a considerable amount of heat and separates it on the toner particle surface. The reality is that a large amount of mold is present.

  Therefore, in the present invention, an apparatus for simultaneously performing classification and surface modification treatment using mechanical impact force (hereinafter referred to as “classified simultaneous surface modification treatment apparatus”) as shown in FIGS. 1 and 2 is used. Thus, the classified fine powder having a predetermined particle size or less is continuously discharged and removed out of the apparatus, so that the dust concentration in the toner particles can be suppressed and the toner particles are not continuously impacted. By efficiently removing the heat generated from the particles themselves, the amount of the release agent on the surface of the toner particles is improved.

  Toner particles that could not be achieved in the past by using a simultaneous classification surface modification device to increase the flow velocity inside the device, for example, by increasing cold air, reducing the gap between the hammer and the liner, and reducing the gap to the classification part. It becomes possible to achieve both control of the surface release agent and circularity. This is because the time required to pass between the hammer and the liner is shortened by increasing the internal flow rate, but the number of passes is increased to make the toner particle treatment uniform, while the flow rate is increased to increase the cooling effect. It is considered that this can be achieved by carrying out the spheronization step with a uniform and large cooling effect.

  However, merely obtaining toner particles using the simultaneous classification surface modification treatment apparatus does not provide toner particles that easily adhere to the inorganic fine powder. That is, in order to externally add inorganic fine powder to the toner particles obtained using the simultaneous classification surface modification apparatus, conventional mixing apparatuses such as a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, and a Henschel Even if external mixing is performed using a mixer, a Nauta mixer or the like, the desired performance cannot be satisfied. As a parameter for maintaining the adhesion of the inorganic fine powder to the toner particles, when the toner particles and the inorganic fine powder are externally added and mixed, the number of collisions (mixing time) between the toner particles and the inorganic fine powder is increased more than once. Good energy is good. That is, no matter how long mixing is performed at the peripheral speed as in the conventional case, the improvement effect is small.

  In the present invention, toner particles and inorganic fine powder are mixed at a peripheral speed of 80 m / s or higher by an apparatus as shown in FIG. 3 (hereinafter, also referred to as “mixed simultaneous surface modification apparatus”). More preferably, the mixing and the surface modification treatment are performed at a peripheral speed of 100 m / s or more. In the mixed simultaneous surface modification treatment device, by putting something that disturbs the powder flow into the device, the adhesion of the inorganic fine powder to the toner particles that cannot be obtained only at a high flow rate is improved, and a small amount of the inorganic fine powder. However, it can be uniformly dispersed.

  The average circularity of particles having an equivalent circle diameter of 3 μm or more for use in a light pressure fixing method is 0.935 to 0.975, and a maximum value is obtained in a region having a number distribution particle size of 90 nm to 350 nm on the toner particle surface. In order to obtain the toner having the toner, it is important to use the simultaneous classification surface modification apparatus shown in FIG. 1 and the mixed simultaneous surface modification apparatus shown in FIG. 3 in the toner production method. If only the mixed simultaneous surface modification processing apparatus is used without using the classification simultaneous surface modification processing apparatus, the improvement effect is small and not all the effects can be satisfied. Both devices and various improvements are provided to the present invention.

  In particular, in an image forming method having a simultaneous development cleaning step (specifically, a step of collecting a transfer residual toner by contacting a cleaning means such as a blade on the image carrier and collecting a transfer residual toner at a developing unit). It is a very effective means to use a toner produced by using the simultaneous classification surface modification apparatus shown in FIG. 1 and the mixed simultaneous surface modification apparatus shown in FIG.

  Collecting the toner in the developing unit means reusing it, and the untransferred toner and the unused toner must have almost the same characteristics. Otherwise, the charge becomes non-uniform and long-term printing causes fatal effects such as fogging, scattering, and image density change. For this purpose, it is necessary that the amount of the inorganic fine powder existing on the toner particles hardly changes and the adhesion state of the inorganic fine powder on the toner particle surface hardly changes.

The toner production method of the present invention makes it difficult to separate the inorganic fine powder from the toner particles and does not change the toner characteristics by using the simultaneous classification surface modification apparatus and the simultaneous mixing surface modification apparatus. . Further, by reducing the release agent present on the surface of the toner particles by the simultaneous classification surface modification apparatus, the hardness of the surface of the toner particles can be increased, and the inorganic fine powder can be hardly buried. When these effects overlap, the simultaneous development cleaning process in which the transfer residual toner is collected at the developing unit is effective only for the first time. The simultaneous classification surface modification treatment apparatus shown in FIG. 1 and the mixed simultaneous surface modification treatment apparatus shown in FIG. 3 will be described later.

The binder resin used for the toner particles in the present invention includes (a) a polyester resin; (b) a hybrid resin having a polyester unit and a vinyl polymer unit; (C) a mixture of a hybrid resin and a vinyl polymer; (d) a mixture of a polyester resin and a vinyl polymer; (e) a mixture of a hybrid resin and a polyester resin; (f) a polyester resin and a hybrid resin; and A resin selected from any of a mixture with a vinyl polymer is preferable. The molecular weight distribution measured by gel permeation chromatography (GPC) of the binder resin component preferably has a main peak in the region of molecular weight 3,500 to 30,000, more preferably molecular weight 5,000. It is having in the area | region of -20,000, and it is preferable that Mw / Mn is 5.0 or more.

  When the main peak is in a region having a molecular weight of less than 3,500, the hot offset resistance of the toner tends to be insufficient. On the other hand, when the main peak is in the region where the molecular weight exceeds 30,000, it is difficult to obtain sufficient low-temperature fixability of the toner, and application to high-speed fixing becomes difficult. Moreover, when Mw / Mn is less than 5.0, it becomes difficult to obtain good offset resistance.

  In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. Examples of the polyester monomer constituting the polyester unit include a polyvalent carboxylic acid component and a polyhydric alcohol component, and examples of the monomer constituting the vinyl polymer unit include a vinyl monomer having a vinyl group.

  As the monomer constituting the polyester resin or the polyester unit, polyester monomers such as alcohol and carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester can be used. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

Examples of the acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with an alkyl group or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;

Among these, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it has good charging characteristics as a color toner.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 1,4-naphthalene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomer.

  When a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved release agent dispersibility, low-temperature fixability, and offset resistance can be expected. The “hybrid resin” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, and preferably a vinyl polymer. A graft copolymer (or a block copolymer) is formed by using as a trunk polymer and a polyester unit as a branch polymer.

The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type polymer and a vinyl-type polymer unit. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; Halogenation of vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc. Cycloalkenyl like; vinyl acetate,
Vinyl esters such as vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, Acrylic acid such as isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Ters; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole N-vinyl compounds such as N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride and alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester, and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acrylic acid, Methacrylic acid, Croto Α, β-unsaturated acids such as acids and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, anhydrides of the α, β-unsaturated acid and lower fatty acids Monomers having a carboxylic acid ester group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, anhydrides thereof, and monoesters thereof are also exemplified as vinyl monomers.

  Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) Hexyl) styrene derivatives having a hydroxy group such as styrene; can also be mentioned as vinyl monomers.

  In the present invention, the vinyl polymer and vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6 hexanediol. Examples include diacrylate, neopentyl glycol diacrylate and those obtained by replacing acrylate of the above compound with methacrylate. Examples of the diacrylate compound linked with an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. The thing which replaced the acrylate of glycol diacrylate and the above compound with the methacrylate is mentioned. Examples of the diacrylate compound linked by a chain containing an aromatic group and an ether bond include, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2. , 2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing acrylate of the above compound with methacrylate.

  The vinyl polymer and the vinyl polymer unit may have a structure crosslinked with a polyfunctional crosslinking agent. Examples of the polyfunctional crosslinking agent used at that time include pentaerythritol triacrylate, trimethylolethane triacrylate, Trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; triallyl cyanurate and triallyl trimellitate.

  Examples of the polymerization initiator used in producing the vinyl polymer and vinyl polymer unit in the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy). -2,4-dimethylvaleronitrile), 2,2'-azobis (-2,4-dimethylvaleronitrile), 2,2'-azobis (-2methylbutyronitrile), dimethyl-2,2'-azo Bisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo -2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetyl Ketone peroxides such as acetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethyl Syl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetyl Cyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate , T-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate Di -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

Examples of the production method capable of preparing the hybrid resin used for the toner particles in the present invention include the following production methods (1) to (5).
(1) A method in which a vinyl polymer and a polyester resin are separately produced, dissolved and swollen in a small amount of an organic solvent, an esterification catalyst and an alcohol are added, and the ester exchange reaction is performed by heating to produce.
(2) A method for producing a polyester unit and a hybrid resin in the presence of a vinyl polymer after the production thereof. The hybrid resin comprises a reaction between a vinyl polymer unit (adding a vinyl monomer if necessary) and either a polyester monomer (polyhydric alcohol, polycarboxylic acid) or a polyester unit, or both. Produced by reaction. An organic solvent can be appropriately used.

(3) A method for producing a vinyl polymer unit and a hybrid resin in the presence of the polyester resin after the production. The hybrid resin is produced by a reaction between a polyester unit (added with a polyester monomer if necessary) and one or both of a vinyl polymer unit and a vinyl monomer. An organic solvent can be appropriately used.

(4) After producing a vinyl polymer unit and a polyester unit, a hybrid is obtained by adding one or both of a vinyl monomer and a polyester monomer (polyhydric alcohol, polycarboxylic acid) in the presence of these polymer units. A method for producing a resin. An organic solvent can be appropriately used.
(5) Manufacture vinyl polymer units, polyester units and hybrid resins by mixing vinyl monomers and polyester monomers (polyhydric alcohols, polycarboxylic acids) and continuously performing addition polymerization and condensation polymerization reactions. how to. An organic solvent can be appropriately used.

  In the production methods (1) to (5), a plurality of types of polymer units having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer unit and the polyester unit. In the present invention, the vinyl polymer means a vinyl monopolymer or a vinyl copolymer, and the vinyl polymer unit means a vinyl monopolymer unit or a vinyl copolymer unit. To do.

  The glass transition temperature of the binder resin contained in the toner particles in the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. When the glass transition temperature of the binder resin satisfies the above range, it is preferable because fixability and blocking resistance are improved. The acid value of the binder resin is preferably 1 to 40 mgKOH / g. When the acid value of the binder resin satisfies the above range, it is preferable because the environmental stability and offset resistance of the toner are improved.

The toner in the present invention may contain a known charge control agent. For example, other organic metal complexes, metal salts, monoazo metal complexes which are chelate compounds, acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, polyol metal complexes and the like can be mentioned. In addition, carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic acid anhydrides and carboxylic acid esters, and condensates of aromatic compounds are also included. In addition, phenol derivatives such as bisphenols and calixarenes are also used, but preferably, a metal compound of an aromatic carboxylic acid is preferable from the viewpoint of rising of charge.
The addition amount of the charge control agent used in the present invention is 0.2 to 10 parts by mass, preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the binder resin. When the amount is less than 0.2 parts by mass, the effect of charging rise cannot be obtained, and when the amount is more than 10 parts by mass, the environmental fluctuation increases.

  Examples of the release agent used in the toner of the present invention include the following. Low molecular weight polyethylene having a number average molecular weight of 1,000 to 50,000, low molecular weight polypropylene having a number average molecular weight of 1,000 to 5,000, olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxidized polyethylene wax, etc. Aliphatic hydrocarbon wax oxides; block copolymers of aliphatic hydrocarbon waxes; waxes based on fatty acid esters such as carnauba wax and montanic acid ester wax; and fatty acid esters such as deoxidized carnauba wax And those obtained by deoxidizing a part or all of the above.

A partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oil or the like, and the like can also be mentioned as a release agent. Particularly preferred release agents are aliphatic hydrocarbon waxes such as paraffin wax, polyethylene, and Fischer-Tropsch wax, which have a short molecular chain and little steric hindrance and excellent mobility.

  In the molecular weight distribution by GPC of the release agent, the main peak is preferably in the region of molecular weight 350-2400, and more preferably in the region of 400-2000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.

  The endothermic curve in the differential thermal analysis (DSC) measurement of the release agent used in the present invention has one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C., and the temperature of the maximum endothermic peak in the endothermic peak. Tsc is preferably 60 ° C. <Tsc <110 ° C., more preferably 70 ° C. <Tsc <90 ° C. When the temperature is 60 ° C. or lower, the anti-blocking property is inferior. When the temperature is 110 ° C. or higher, the desired low-temperature fixing cannot be performed sufficiently, and a load requiring pressure is required even in the fixing configuration. is there.

  The addition amount of the release agent used for the toner in the present invention is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the binder resin. If the amount is less than 1 part by mass, the amount for coming out on the surface of the toner particles at the time of melting and exhibiting the releasability is small, so that a considerable amount of heat and pressure must be used. On the other hand, if the amount exceeds 10 parts by mass, the amount of the release agent in the toner particles is too large, so that the transparency and charging characteristics tend to be inferior.

  Examples of the toner colorant used in the toner of the present invention include the following. Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 202, 206, 207, 209, 269, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Such a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 are listed.

  Examples of other color pigments include cyan color pigments. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 155, 180, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned.

  The amount of the colorant used in the magenta / cyan / yellow toner is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  Further, as the black colorant, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black is used. Magnetic powder such as magnetite and ferrite, or yellow / magenta / cyan / The thing adjusted to black using the black coloring agent can be utilized. The amount of the colorant used in the black toner is preferably 0.1 to 60 parts by mass, and more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin.

Next, a procedure for manufacturing toner will be described.
The method for producing a toner of the present invention comprises melt-kneading a composition having at least a binder resin, a colorant and a release agent, cooling and solidifying the obtained kneaded product, and finely pulverizing the cooled solidified product to obtain a finely pulverized product. Step (i) for obtaining toner particles, Step (ii) for obtaining toner particles by simultaneously performing surface modification treatment and classification treatment on the obtained finely pulverized product, and obtaining toner by externally adding inorganic fine powder to the toner particles Step (iii
).
The step (ii) includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less in the finely pulverized product to the outside of the system, and subjecting the treated particles from which fine powder has been removed by the classifying means to mechanical impact. Surface treatment means for surface modification using force, a first space provided between the classification means and the surface treatment means for introducing the particles to be treated into the classification means, and the target The surface modification is carried out using a batch type surface modification device having a second space for introducing treated particles into the surface treatment means, and a guide means for partitioning the first space and the second space. The quality device introduces the finely pulverized material into the first space, and continuously discharges and removes fine powder having a predetermined particle size or less from the device by the classification means, through the second space, Introduced into the surface treatment means using mechanical impact force to perform surface modification treatment Is again by circulating the first space, by repeating the surface modification treatment using a fixed time classification and a mechanical impact force, to obtain toner particles.
Further, in the step (iii), the processing tank having a spherical shape at the top, a rotating shaft penetrating vertically through the center of the bottom of the processing tank, and a processed material discharged along the inner wall of the processing tank provided on the rotating shaft. This is carried out using a disperser having a stirring blade and an exhaust pipe disposed in the tank from the upper part of the treatment tank. When the peripheral speed of the stirring blade is 80 m / s or more, mixing of toner particles and external additives and surface modification are performed. It is a process of obtaining a toner by performing quality.

  Before the step of melt-kneading the composition having at least a binder resin, a colorant and a release agent, there may be a step of weighing, mixing and mixing a predetermined amount of raw materials to be used. Examples of the mixing apparatus used for the mixing include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  The mixed toner raw material composition is melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin-screw extruder manufactured by Kobe Steel, Ltd., manufactured by Toshiba Machine Co., Ltd. A TEM type twin-screw extruder, a twin-screw extruder manufactured by Kay C.K., Co. kneader manufactured by Buss, etc. are generally used. Further, the kneaded material obtained by melt-kneading the toner raw material composition is rolled with a two-roll or the like and cooled by water cooling or the like to perform a cooling step for obtaining a cooled solidified product.

  Next, a step of coarsely pulverizing the cooled solidified product and then finely pulverizing the coarsely pulverized product to obtain a finely pulverized product is performed. In the step of obtaining a finely pulverized product, an air jet pulverizer or the like is used.

After obtaining the finely pulverized product, a step of simultaneously performing the surface modification treatment and the classification treatment is performed in order to obtain toner particles satisfying the above-described circularity. The step may be performed by a mechanical pulverization method. However, as described above, the spheronization by the mechanical pulverization method applies a heat amount more than necessary, and a large amount of a release agent is present on the surface of the obtained toner particles. End up. In the present invention, toner particles having a weight average particle diameter of 3 to 11 μm are obtained using a simultaneous classification surface modification treatment apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force shown in FIGS. 1 and 2. Is preferred. Then, if necessary, a sieving machine such as a high-voltage winder sieve (manufactured by Shin Tokyo Machine Co., Ltd.) may be used.

  The classification simultaneous surface modification apparatus used in the present invention will be described in detail. As shown in FIG. 1, in the simultaneous classification surface modification processing apparatus, the casing 30, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, and the surface modification means are located in the casing 30 and attached to the central rotating shaft. A plurality of square discs or cylindrical pins 40 on the upper surface, and a dispersion rotor 36 that is a rotating body on a disk that rotates at a high speed, and is arranged on the outer periphery of the dispersion rotor 36 at regular intervals. Liner 34 provided with a large number of grooves on the surface thereof (there is no need to have grooves on the liner surface), and means for classifying the surface-modified finely pulverized product into a predetermined particle size The classifying rotor 31, the cold air inlet 35 for introducing the cold air, the raw material supply port 33 for introducing the finely pulverized material, and the surface modification time can be freely opened and closed. Like A discharge valve 38, a powder discharge port 37 for discharging the processed powder, and a space between the classification rotor 31 as classification means and the dispersion rotor 36-liner 34 as surface modification means Is a cylinder that is a guide means for partitioning the first space 41 before being introduced into the classifying means and the second space 42 for introducing the particles to be treated, from which fine powder has been classified and removed by the classifying means, into the surface treatment means And a guide ring 39 having a shape. A gap portion between the dispersion rotor 36 and the liner 34 is a surface modification zone, and a classification rotor 4 and a rotor peripheral portion are classification zones.

  In the classifying simultaneous surface modification treatment apparatus configured as described above, when a finely pulverized product is introduced from the raw material supply port 33 with the discharge valve 38 closed, the introduced finely pulverized product is first blower (illustrated). Not classified) and classified by the classification rotor 31. At that time, the classified fine powder having a predetermined particle diameter or less is continuously discharged and removed out of the apparatus, and the coarse powder having a predetermined particle diameter or more passes along the inner periphery (second space 42) of the guide ring 39 by centrifugal force. The circulating flow generated by the dispersion rotor 36 is guided to the surface modification zone. The coarse powder guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 36 and the liner 34. The surface-modified particles to be treated are guided to the classification zone along the outer periphery (first space 41) of the guide ring 39 by the cold air passing through the inside of the machine, and the fine powder is again removed from the machine by the classification rotor 4. The coarse powder is circulated and returned to the surface modification zone and repeatedly undergoes surface modification. After a certain period of time, the discharge valve 38 is opened and the surface modified particles are recovered from the discharge port 37.

  In the toner of the present invention, a predetermined amount of the toner particles classified and surface-modified by the simultaneous classification and surface modification treatment apparatus shown in FIG. 1 and the inorganic fine powder described above are blended, and the mixed simultaneous surface modification shown in FIG. It is obtained by stirring and mixing using a quality treatment device. If necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Kikai Co., Ltd.) may be used.

  The toner obtained by the toner production method of the present invention is suitably used for one-component development.

The mixed simultaneous surface modification treatment apparatus used in the present invention will be described in detail. As shown in FIG. 3, the processing tank 51 has a spherical shape having a relatively large horizontal disk-shaped tank bottom, and is provided with a flange 57 at the center so that it can be divided into two vertically.
Further, the entire spherical portion is provided with a jacket 55 and has a double structure, and the processed material can be heated or cooled by flowing a heat medium therethrough. In the upper part of the processing tank 51, an opening 56 to which a furnace cloth is attached for pressure release is provided, and in the lower part, an outlet 58 for discharging the product is provided.

In the center of the disk-shaped tank bottom, a drive shaft 52 penetrates as a rotation shaft and can be rotated by external power. A stirring blade 53 is provided on the drive shaft 52. And processing tank 51
A plate 54 whose size, angle, etc. can be adjusted is provided along the inner surface. The peripheral speed represents the peripheral speed at the tip of the stirring blade 53. In the present invention, the peripheral speed of the stirring blade of the simultaneous mixing surface modification apparatus shown in FIG. 3 may be set to 80 m / s, for example.

  When the toner of the present invention is used as a two-component developer, the toner is used by mixing with a magnetic carrier. Examples of the magnetic carrier include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, and ferrite. Can be used.

  A coated carrier in which the magnetic carrier particles are used as a carrier core and the surface thereof is coated with a resin is particularly preferably used in a developing method in which an AC bias is applied to the developing sleeve. Conventional coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the carrier core, a method in which the magnetic carrier core and the coating material are mixed with powder, and the like. Known methods can be applied.

  The magnetic carrier is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. When the two-component developer of the present invention is prepared, good results are usually obtained when the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  Various methods for measuring physical properties used in the present invention will be described below.

(1) Measurement of maximum endothermic peak of release agent The maximum endothermic peak of the release agent is a differential scanning calorimeter (DSC measuring device), DCS-7 (manufactured by PerkinElmer) or DSC2920 (manufactured by TA Instruments Japan). Used and measured according to ASTM D3418-82.
The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. It is put in an aluminum pan, an empty aluminum pan is used as a reference, and measurement is performed at normal temperature and humidity with a measurement range of 30 to 200 ° C. and a temperature increase rate of 10 ° C./min.
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C to 200 ° C, temperature increase rate 10 ° C / min)

(2) Molecular weight measuring device for release agent: GPC-150C (Waters)
Column: GMH-HT 30 cm, 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% by mass ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% by mass of wax Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the release agent. Furthermore, the molecular weight of the release agent is calculated by converting to polyethylene based on a conversion formula derived from the Mark-Houwink viscosity formula.

(3) Measurement of molecular weight distribution of toner binder resin by GPC The molecular weight distribution of toner binder resin by GPC is as follows, using a THF soluble component obtained by dissolving the binder resin in a THF solvent. Then, it is measured by GPC.

  That is, the binder resin is put in THF, allowed to stand for several hours, and then shaken sufficiently, mixed well with THF (until the sample is no longer united), and further allowed to stand for 12 hours or more. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corporation, Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.) can be used. Is a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The GPC measurement of the sample prepared by the above method was performed by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min as a solvent at this temperature. About 50 to 200 μl of a THF sample solution of a binder resin adjusted to 0.05 to 0.6% by mass is injected and measured. 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 (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. The molecular weights made are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ⁴ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8 It is suitable to use a standard polystyrene sample of at least about 10 points, using .6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ . An RI (refractive index) detector is used as the detector.

As a column, in order to accurately measure a 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, shodex GPC KF-801, 802 manufactured by Showa Denko K.K. , 803, 804, 805, 806, and 807, and combinations of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters.

(4) Measurement of Toner Particle Size In the present invention, the average particle size of the toner is measured using a Coulter Multisizer (manufactured by Beckman Coulter). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan Co., Ltd.) can be used. 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 the volume and number of toner particles having a particle diameter of 2.00 μm or more are measured using the 100 μm aperture as the aperture by the measuring device. The volume distribution and the number distribution are calculated. Then, the weight average particle diameter (D4) obtained from the volume distribution according to the present invention (the median value of each channel is used as the representative value for each channel) is obtained.

  As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

(5) Method for measuring softening point of binder resin This refers to a method of measuring with a Koka flow tester in accordance with JIS K 7210. A specific measurement method is shown below. Using a Koka type flow tester (manufactured by Shimadzu Corporation), a sample of 1 cm ³ was heated at a heating rate of 6 ° C./min, and a load of 1960 N / m ² (20 kg / cm ² ) was applied by a plunger. A nozzle having a diameter of 1 mm and a length of 1 mm is pushed out, whereby a plunger descending amount (flow value) -temperature curve is drawn, and when the height of the S-shaped curve is h, it corresponds to h / 2. The temperature (temperature at which half of the resin flows out) is defined as the softening point (Tm) of the resin.

(6) Measuring method of glass transition temperature of binder resin The glass transition temperature of binder resin is measured by DSC method. As a differential thermal analyzer (DSC measuring device), DSC-7 (manufactured by Perkin Elmer) or DSC2920 (manufactured by TA Instruments Japan) can be used, and measurement is performed under the following conditions.
Sample: 5-20 mg, preferably 10 mg
Temperature curve: Temperature increase I (20 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
Temperature drop I (180 ° C. → 10 ° C., temperature drop rate 10 ° C./min.)
Temperature increase II (10 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
Tg measured at the temperature elevation II is taken as the measured value.
Measurement procedure: Place the sample in an aluminum pan and use an empty aluminum pan as a reference. The intersection between the line of the midpoint of the base line before and after the endothermic peak and the differential heat curve is defined as the glass transition temperature Tg.

(7) Measurement of Toner Average Circularity The average circularity of toner is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and is calculated using the following equation.

Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).
In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.
The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  Further, the circularity standard deviation SD is calculated from the following equation where the average circularity C, the circularity ci of each particle, and the number of measured particles are m.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity and the circularity standard deviation. The degree 0.4 to 1.0 is divided into classes equally divided every 0.01, and the average circularity and the circularity standard deviation are calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the circularity of the toner particles, the flow type particle image measuring device is used, and the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. Measure more than one. After the measurement, data having an equivalent circle diameter of less than 3 μm is cut using this data, and the average circularity of the toner particles is obtained.

  Furthermore, the measurement device used in the present invention, “FPIA-2100”, has a thinner sheath flow (7 μm →) than “FPIA-1000”, which has been used to calculate the shape of the toner. 4μm) and improved processing particle image magnification, and further improved processing resolution of the captured image (256 × 256 → 512 × 512), the accuracy of toner shape measurement has been improved, thereby ensuring more reliable capture of 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.

(8) Number distribution particle size on toner particles of inorganic fine powder The number distribution particle size on the toner particle surface was measured using a scanning electron microscope S-4700 (manufactured by Hitachi, Ltd.). The photographic magnification is 100,000 times, and after further expanding the photographed photograph twice, 200 to 500 samples are randomly extracted from this photographic image, the maximum particle diameter is the longest diameter, the minimum particle diameter is the shortest diameter, The distribution of the number particle diameter and the maximum value particle diameter as the number distribution particle diameter were obtained on the basis of the major axis. The particle size distribution was divided into 90 to 400 nm every 10 nm, and the maximum value was determined. Each of less than 90 nm and 400 nm or more was combined.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited only to these Examples.

<Example 1>
[Manufacture of binder resin]
(Example of hybrid resin production)
As monomers of the vinyl copolymer, styrene: 2.0 mol, 2-ethylhexyl acrylate: 0.21 mol, fumaric acid: 0.14 mol, α-methylstyrene dimer: 0.03 mol, and dicumyl as a polymerization initiator Peroxide: 0.05 mol was placed in a dropping funnel. Moreover, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 7.0 mol, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 3.0 mol, terephthalic acid: 3.0 mol, trimellitic anhydride: 1.9 mol, fumaric acid: 5.0 mol and 0.2 g of dibutyltin oxide are placed in a 4-liter four-necked flask made of glass, thermometer, stirring A rod, condenser and nitrogen inlet tube were attached and placed in the mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the monomer of the vinyl copolymer and the polymerization initiator were added from the previous dropping funnel over 4 hours while stirring at a temperature of 145 ° C. And dripped. This was heated to 200 ° C. and reacted for 4 hours to obtain a hybrid resin. The obtained hybrid resin had Mw = 82,000 and Mp = 16,000 in the molecular weight measurement, and Tm = 110 ° C. in the softening point measurement.

[Production of toner]
Toner 1 was prepared by the following method.
-100 parts by weight of the above hybrid resin-6 parts by weight of purified normal paraffin (maximum endothermic peak temperature 78 ° C)-0.2 parts by weight of 1,4-di-t-butylsalicylic acid aluminum compound-Cyan pigment (Pigment Blue 15: 3) 5 Parts by mass

Preliminarily mix the above formulation with a Henschel mixer, melt knead with a twin-screw extrusion kneader, cool and coarsely pulverize to about 1 to 2 mm using a hammer mill, then use an air jet fine pulverizer. A finely pulverized product was obtained by pulverizing to a particle size of 20 μm or less. The resulting finely pulverized product is subjected to simultaneous classification and surface modification treatment equipment (hereinafter referred to as “apparatus (1)”) that simultaneously performs classification and surface modification treatment using mechanical impact force as shown in FIGS. Then, classification and surface treatment were performed to obtain cyan toner particles 1 (classified product).

Vapor-phase silica fine powder (surface treated product of 10 wt% of HMDS treatment and 10 wt% of 50 cs silicon oil) having a particle size of 20 nm on the toner particles is 1.2 wt% with respect to the cyan toner particles, Vapor phase silica fine powder (HMDS) with a particle size of 150 nm
Toner 1 is obtained by externally adding 1.5 wt% of the surface treated product (processed 8 wt%) at a peripheral speed of 100 m / s using a mixed simultaneous surface reforming apparatus (hereinafter referred to as “apparatus (2)”) shown in FIG. Got. Toner 1 had a weight average particle diameter of 6.3 μm and an average circularity of 0.955. Table 1 shows the production conditions of the toner 1 and the physical properties of the obtained toner.

[Evaluation of development performance and fixability]
One-component development evaluation was performed using toner 1. The device is an iRC-3200 (manufactured by Canon Inc.) improved for one-component development, using an original document with an image area ratio of 5% in a single color mode under a normal temperature and low humidity environment (23 ° C./5%), The printing durability test of 3000 sheets of development performance was evaluated. As shown in Table 2, there was little fogging after 3000 sheets, and there was no scattering.

The evaluation method is as follows.
(Fog measurement)
The fog (Fog [%]) in the endurance test is a reflectometer (Tokyo Denshoku Co., Ltd.) equipped with an amber filter for the average reflectance Dr (%) of plain paper before image output for cyan and black images. (Reflectometer Model TC-6DS) manufactured on the other hand, a solid white image was drawn on plain paper, and then the reflectance Ds (%) of the solid white image was measured and calculated from the following formula. The above measurement was performed with a green filter for magenta and black images, and a blue filter for yellow images.
Fog [%] = Dr [%] − Ds [%]
The evaluation criteria are as follows.
A: Good with less than 0.7% B: Good with 0.7 or more and less than 1.2% C: Good with 1.2 or more and less than 1.5% No practical problem D: 1.5 or more and 2.0 Less than% is practically problematic E: Poor at 2.0% or more

Next, fixability was evaluated using a fixing unit of LBP-2410 (manufactured by Canon Inc.) that was modified so that the speed, temperature, linear pressure, etc. could be adjusted manually. In this embodiment, the fixing width is good because the fixing speed is 100 mm / s and 150 mm / s at a linear pressure of 900 N / m, and the low-temperature fixing property is excellent. Also, in the continuous paper fixing evaluation of different sizes, fixing was possible with almost no waiting time, and a good image was obtained.
A specific evaluation method will be described below.

(Toner fixable area)
Using a modification unit of a fixing unit of LBP-2410 (manufactured by Canon Inc.), the fixing unit was manually fixed at a fixing temperature, speed, linear pressure, and a fixing belt provided with an elastic layer, and a fixing test was conducted.
Using LBP-2410, the development contrast was adjusted so that the applied toner amount on paper was 1.2 mg / cm ² in a single color mode in a normal temperature and normal humidity environment (23 ° C./60%), and an unfixed image was created. . An image is formed on A4 (recommended paper EW-500) with an image area ratio of 25%. In a room temperature and normal humidity environment (23 ° C./60%), the temperature range was raised by 10 ° C. in order from 120 ° C., and the temperature range at which no offset (same as fog evaluation) or wrapping occurred was defined as the fixable region.
In the evaluation of the magnetic toner in Example 7 described later, non-magnetic except that LBP-1210 (manufactured by Canon Inc.) was used and the applied amount of toner on the paper was 1.0 mg / cm ^2. Evaluation was performed in the same manner as the toner.
The evaluation criteria are as follows.
A: The fixing width is 40 ° C. or more.
B: The fixing width is 30 ° C. or more and less than 40 ° C.
C: The fixing width is 20 ° C. or more and less than 30 ° C.
D: The fixing width is less than 20 ° C., which is problematic in practice.
E: There is no fixing width at all.

(Fixing evaluation of toner of different sizes)
Similar to the toner fixable region, an image was formed on A4 size plain paper (recommended paper EW-500) at an image area ratio of 25%. Similarly, an image was formed on a B5 size plain paper with an image area ratio of 25%. After fixing five sheets of B5 paper continuously at 170 ° C under normal temperature and humidity conditions (23 ° C / 60%), A4 paper was fixed after a lapse of a predetermined time, and the time when the offset disappeared, that is, the downtime was measured. .
In the evaluation of magnetic toner in Example 7 to be described later, nonmagnetic toner is used except that the fixing unit is LBP-1210 (manufactured by Canon Inc.) and the toner loading on the paper is 1.0 mg / cm ^2. The same evaluation was performed. The evaluation criteria are as follows.
A: The downtime is 0 to 2 seconds or less, and it is excellent.
B: The downtime is greater than 2 and within 4 seconds, which is good.
C: Downtime is greater than 4 and within 7 seconds, and is practically usable.
D: The downtime is required to be greater than 7 and within 10 seconds, which is problematic in practical use.
E: Downtime is further required than 10 seconds, which is bad.

  The evaluation results in this example are shown in Table 2.

<Example 2>
As shown in Table 1, a toner 2 was obtained in the same manner as in Example 1 except that the production conditions of the device (1) were changed. Various evaluations of development performance and fixability were made in the same manner as in Example 1. As shown in Table 2, the fixable area at 150 mm / s was a little inferior, but was good.

<Example 3>
As shown in Table 1, the same as in Example 1 except that silica having a maximum particle size of 350 nm in the number distribution particle size of the inorganic fine powder existing on the toner particle surface and the production conditions of the apparatus (1) are changed. Thus, Toner 3 was obtained. Various evaluations of development performance and fixability were made in the same manner as in Example 1. As shown in Table 2, the fixable area at 150 mm / s, the fog and scattering after 3000 sheets were slightly inferior, but were good results. .

<Example 4>
As shown in Table 1, silica having a maximum particle size of 90 nm in the number distribution particle size of the inorganic fine powder existing on the toner particle surface is externally treated in the apparatus (2) at a peripheral speed of 80 m / s. Toner 4 was obtained in the same manner as in Example 1 except that the above was changed. When the linear pressure of the fixing unit was set to 500 N / m and various evaluations of development performance and fixability were performed in the same manner as in Example 1, as shown in Table 2, the evaluation of continuous paper-fixing in a fixable area and different sizes was slightly inferior The fogging and scattering after 3000 sheets were inferior but usable.

<Example 5>
As shown in Table 1, the toner 5 is the same as in Example 4 except that the manufacturing conditions of the apparatus (1) are changed.
Got. As in Example 4, various evaluations of development performance and fixability were made. As shown in Table 2, the evaluation of continuous paper fixing of the fixable area and different sizes was inferior, and the fog after 3000 sheets was slightly inferior, but usable. It was a level.

<Comparative Example 1>
As shown in Table 1, a toner 6 was obtained in the same manner as in Example 4 except that the external device was not a device (2) but a Henschel mixer (H / M) and mixed at a peripheral speed of 40 m / s. As shown in Table 2, the evaluation of development performance and fixability in the same manner as in Example 4 showed that the continuous paper fixing evaluation of different sizes and the fogging and scattering after 3000 sheets were bad.

<Comparative example 2>
As shown in Table 1, a toner 7 is obtained in the same manner as in Example 4 except that the classification device is not an apparatus (1) but an elbow jet classifier (E / J) is used and classification is performed at a peripheral speed of 40 m / s. It was. As in Example 4, various evaluations of development performance and fixability were made. As shown in Table 2, the fixable area, evaluation of continuous paper fixing of different sizes, and fogging and scattering after 3000 sheets were bad. It was.

<Comparative Example 3>
As shown in Table 1, a toner 8 was obtained in the same manner as in Comparative Example 2 except that silica having a maximum particle size of 400 nm in the number distribution particle size of the inorganic fine powder existing on the toner particle surface was used. As in Comparative Example 2, various evaluations were made on development performance and fixability.

<Comparative example 4>
As shown in Table 1, a toner 9 was obtained in the same manner as in Comparative Example 2 except that silica having a maximum particle size of 90 nm or more in the number distribution particle size of the inorganic fine powder existing on the toner particle surface was not used. As shown in Table 2, the development performance and the fixability were evaluated in the same manner as in Comparative Example 2.

<Comparative Example 5>
As shown in Table 1, a toner 10 was obtained in the same manner as in Comparative Example 2 except that the pulverizing apparatus was not pulverized by a super-rotor manufactured by Nisshin Engineering Co., Ltd. instead of an air jet fine pulverizer. As shown in Table 2, fogging and scattering after 3,000 sheets were poor as a result of various evaluations of development performance and fixability as in Comparative Example 2.

<Comparative Example 6>
As shown in Table 1, a toner 11 was obtained in the same manner as in Comparative Example 2 except that a hybridization system (hybrid) manufactured by Nara Machinery Co., Ltd. was used as the surface treatment apparatus. When various evaluations were made on the development performance and fixability in the same manner as in Comparative Example 6, as shown in Table 2, continuous paper fixing evaluation of different sizes, fogging and scattering after 3000 sheets were poor.

<Comparative Example 7>
As shown in Table 1, various evaluations of development performance and fixability were made in the same manner as in Comparative Example 6 except that the linear pressure of the fixing unit was changed to 330 N / m. .

<Comparative Example 8>
As shown in Table 1, the development performance and fixability were evaluated in the same manner as in Comparative Example 6 except that the linear pressure of the fixing unit was 1290 N / m. As a result, the fixing unit was damaged because it could not withstand the pressure. .

<Example 6>
Using toner 1 was evaluated in two-component developer. Resin carrier particles whose surface is coated with a silicone resin (average particle size 40 μm) are mixed with toner 1 so that the toner concentration becomes 8.0% by mass.
To obtain a two-component developer. Using this two-component developer, the device is an iRC-3200 (manufactured by Canon Inc.) modified for two-component development, and the image area in a single color mode in a room temperature and low humidity environment (23 ° C./5%). Using an original document with a ratio of 5%, a printing durability test of 3000 sheets of development performance was evaluated. The evaluation method is as described above. As shown in Table 2, there was little fogging after 3000 sheets, and there was no scattering.

  Next, the fixing property of the fixing unit of LBP-2410 (manufactured by Canon Inc.) was modified so that the speed, temperature, linear pressure, etc. could be adjusted manually, and the fixing property was evaluated as described above. In this embodiment, the linear pressure was 1140 N / m, and the fixing speed was 100 mm / s and 150 mm / s. Also, in the continuous paper fixing evaluation of different sizes, fixing was possible with almost no waiting time, and a good image was obtained.

<Example 7>
A magnetic toner as a magnetic one-component developer was prepared and evaluated as follows. Toner 12 was produced as a magnetic toner as follows.
-Hybrid resin 100 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 7 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Magnetic iron oxide 90 parts by mass (average particle size: 0) .18 μm, Hc (coercive force): 9.6 kA / m, σs (saturation magnetization): 81 Am ² / kg, σr (residual magnetization): 13 Am ² / kg)
The above material was manufactured in the same manner as in Example 1 except that the manufacturing conditions of the device (1) were changed, and a magnetic toner 12 was obtained. With respect to this magnetic toner, a cleaner unit of a digital copying machine IR6000 (manufactured by Canon Inc.) was removed, and various evaluations of development performance and fixability were performed at a linear pressure of 380 N / m. As shown in Table 2, the fixable area, the evaluation of continuous paper fixing of different sizes, and the fog after 3000 sheets were at a practical level although slightly inferior.

It is a schematic block diagram of the classification simultaneous surface modification processing apparatus used for the manufacturing method of the toner of this invention. It is a figure which shows the dispersion | distribution rotor of the classification simultaneous surface modification processing apparatus used for the manufacturing method of the toner of this invention. It is a schematic block diagram of the mixing simultaneous surface modification processing apparatus used for the manufacturing method of the toner of this invention.

Explanation of symbols

31: Classification rotor 32: Fine powder recovery 33: Raw material supply port 34: Liner 35: Cold air introduction port 36: Dispersion rotor 37: Powder discharge port 38: Discharge valve 39: Guide ring 40: Square disk 41: First space 42: second space 51: treatment tank 52: drive shaft 53: stirring blade 54: plate 55: jacket 56: exhaust pipe (furnace attachment port)
57: Flange 58: Discharge port

Claims (1)

A toner having toner particles having at least a binder resin, a colorant and a release agent, and an inorganic fine powder,
The inorganic fine powder is an inorganic fine powder having at least one maximum value in a region having a particle size of 90 nm to 350 nm in the number distribution particle size on the toner particle surface,
The toner is a method for producing a toner having an average circularity of 0.935 to 0.975 in particles having an equivalent circle diameter of 3 μm or more,
A step (i) in which a composition having at least a binder resin, a colorant and a release agent is melt-kneaded, the obtained kneaded product is cooled and solidified, and the cooled solidified product is finely pulverized to obtain a finely pulverized product; At least a step (ii) of obtaining a toner particle by simultaneously performing a surface modification treatment and a classification treatment of the finely pulverized product, and a step (iii) of obtaining a toner by externally adding an inorganic fine powder to the toner particle,
The step (ii) includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less in the finely pulverized product to the outside of the system, and subjecting the treated particles from which fine powder has been removed by the classifying means to mechanical impact force. A surface treatment means for modifying the surface by use, a first space provided between the classification means and the surface treatment means for introducing the particles to be treated into the classification means, and the particles to be treated Is carried out using a batch-type classifying simultaneous surface reforming apparatus having a second space for introducing the gas into the surface treatment means, a guide means for partitioning the first space and the second space, and the classification In the simultaneous surface modification treatment apparatus, the finely pulverized product is introduced into the first space, and the fine powder having a predetermined particle size or less is continuously discharged and removed from the apparatus by the classification means, while the second space is removed. To the surface treatment means using mechanical impact force Perform surface modification treatment by entering a re-by circulating the first space to obtain a toner particle by repeating a surface modification treatment using a fixed time classification and a mechanical impact force,
The step (iii) includes a processing tank having a spherical upper part, a rotating shaft that vertically penetrates the center of the tank bottom of the processing tank, and a stirring blade that is provided on the rotating shaft and discharges a processed material along the inner wall of the processing tank And a mixing simultaneous surface modification apparatus having an exhaust pipe disposed in the tank from the upper part of the processing tank, and the mixing speed of the stirring blade is 80 m / s or more, and the toner particles and the external additive are mixed. And a method for producing a toner, wherein the toner is obtained by surface modification.

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