JP5025357B2 - Toner and image forming method - Google Patents

Description

  The present invention relates to a toner used for electrophotography, an image forming method for developing an electrostatic image, and a toner used for a toner jet.

  In recent years, devices using electrophotography have begun to be used in printers for output of computers, facsimiles, etc., in addition to copying machines for copying original documents. As a result, smaller, lighter, faster, and more reliable are being sought, and machines are becoming simpler in various ways. As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, a better machine cannot be realized.

  As a general electrophotographic image forming method, for example, a photoconductive material is used, an electric latent image is formed on an electrostatic latent image carrier by various means, and then the latent image is developed into a developing device. It is visualized by developing it into a toner image. Next, a method is known in which a toner image is transferred to a transfer material such as paper as necessary, and then fixed by heating, pressure, heating and pressing, or solvent vapor to obtain a toner image.

  As a developing device in such an electrophotographic method, a rubber or metal toner regulating blade as a toner layer thickness regulating member for regulating the toner coating amount is generally provided on the surface of a toner carrying body as a toner carrying body. A device having a configuration of contacting is known.

  The toner is given a positive or negative charge by friction between the toner regulating blade and the toner and / or friction between the toner carrier and the toner. In addition, a toner control blade generally develops a toner carrier with a thin toner applied on the surface thereof, by causing the toner to fly onto and adhere to an electrostatic latent image on the surface of the electrostatic latent image carrier facing the toner carrier. Has been done.

  As the technical direction of image forming apparatuses in recent years, in addition to high definition, high quality, and high image quality, further high speed and long-term high reliability are required. In order to achieve a high-resolution and high-definition development system, development of toners having high development characteristics such as toner spheroidization, particle size reduction, and particle size distribution sharpening is progressing.

  When such a highly developable toner is applied to a conventional developing device, the behavior of the toner in the developing device becomes important due to the difference in powder characteristics and the like.

  Patent Documents 1 and 2 disclose a technique for modifying the shape and surface properties of a toner produced by a pulverization method by mechanical impact. However, even if the shape of the toner is modified by these methods, the developability in long-term durability may not be sufficient.

  Patent Document 3 discloses a technique for making a toner shape close to a sphere by a polymerization method. However, both of these techniques require large-scale equipment for toner production, which is not preferable in terms of production efficiency, but may be insufficient in durability stability and image quality of development characteristics.

  Patent Document 4 proposes a toner regulating blade member that defines the surface roughness of the surface that rubs against the toner carrier. In the toner regulating blade of this invention, it is disclosed that in the examples, using one-component magnetic toner having an average particle diameter of 8 μm is effective in character thickening and charging stability. However, the developer characteristics are not sufficiently mentioned, and the durability stability and the image quality may be insufficient particularly when the toner having the high development characteristics as described above is applied.

JP-A-2-87157 JP-A-8-184987 JP-A-4-102862 JP 2000-330376 A

  An object of the present invention is to provide a toner and an image forming method that solve the above-mentioned problems of the prior art.

  An object of the present invention is to provide a toner and an image forming method that have excellent fluidity even under conditions of high temperature and high humidity, maintain good developability even in long-term use, suppress fogging, and further suppress tailing. There is to do.

The present invention includes toner particles containing at least a binder resin and a magnetic material, a toner having an inorganic fine particles externally added to the toner particles, the toner particles satisfies the following relation (1), (2 The present invention relates to a toner that satisfies the following.
2400mJ ≦ Et (1) ≦ 3000mJ (1)
800 mJ ≦ Et (1) −Et (3) ≦ 1800 mJ (2)
[However, Et (1), said toner particles after compaction with 40N, vertically enters the toner particles powder layers in the container while the peripheral speed of the outermost edge of the propeller blade was rotated at 10 mm / sec The total of the rotational torque and the vertical load obtained when the measurement is started from a position 100 mm from the bottom surface of the powder layer and moved to a position 10 mm from the bottom surface is represented. Measurement from the position of 100 mm from the bottom surface of the powder layer in the third measurement is performed by repeating the operation from the entry to the extraction of the propeller blade in the same manner, and the operation from the entry to the extraction of the propeller blade is repeated in the same manner. And the sum of the rotational torque and the vertical load obtained when entering the position 10 mm from the bottom is Et (3). ]
The present invention also provides an image forming method in which a toner is carried on a toner carrier, a layer thickness of the toner carried on the toner carrier is regulated by a toner regulating blade, and the regulated toner is conveyed to a development area. A method,
The ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrier is 5.0 μm or more and 25.0 μm or less,
The average spacing Sm of the irregularities measured with a laser microscope on the surface of the toner regulating blade on the side in contact with the toner carrier is 5.0 μm or more and 200.0 μm or less,
The toner includes toner particles containing at least a binder resin and a magnetic material, and inorganic fine particles externally added to the toner particles, and the toner particles satisfy the relational expressions (1) and (2). The present invention relates to an image forming method.

  The toner of the present invention is a toner with suitable powder characteristics, has excellent fluidity even under conditions of high temperature and high humidity, and can maintain good developability, fogging and tailing even under long-term use. It is. In addition, it is more effective for image formation using a toner control blade with appropriately controlled properties.

As a result of intensive studies, the present inventors have developed a toner having toner particles and inorganic fine particles containing at least a binder resin and a magnetic material,
2400mJ ≦ Et (1) ≦ 3000mJ
(Preferably 2500 mJ ≦ Et (1) ≦ 2900 mJ) (1)
800 mJ ≦ Et (1) −Et (3) ≦ 1800 mJ
(Preferably 1000 mJ ≦ Et (1) −Et (3) ≦ 1600 mJ) (2)
[However, Et (1) allows toner particles to be compacted with 40 N and then vertically entered into the toner particle powder layer in the container while rotating the peripheral speed of the outermost edge of the propeller blade at 10 mm / sec. , Represents the sum of the rotational torque and the vertical load obtained when measurement starts from a position 100 mm from the bottom of the powder layer and enters the position 10 mm from the bottom. Measurement from the position of 100 mm from the bottom surface of the powder layer in the third measurement is performed by repeating the operation from the entry to the extraction of the propeller blade in the same manner, and the operation from the entry to the extraction of the propeller blade is repeated in the same manner. And the sum of the rotational torque and the vertical load obtained when entering the position 10 mm from the bottom is Et (3). ]
By controlling the toner particles so as to satisfy the above relational expressions (1) and (2), the toner can be efficiently filled in the cartridge, the cartridge can be reduced in size, and it can be used under high temperature and high humidity. It has been found that it has excellent fluidity even under the above conditions, maintains good developability and fog suppression even for long-term use, and can also improve tailing.

<Measuring method of Et (1) and Et (3)>
In the present invention, Et (1) and Et (3) are measured by using a powder rheology analyzer powder rheometer FT-4 (manufactured by Freeman Technology) (hereinafter sometimes abbreviated as FT-4). To do.

  Specifically, the measurement is performed by the following operation. In all operations, the propeller blade is a 48 mm diameter blade dedicated to FT-4 measurement (see Fig. 1). There is a rotation axis in the normal direction at the center of the blade plate of 48 mm x 10 mm. The outer edge portion (24 mm from the rotation axis) is smoothly twisted counterclockwise such that the outer edge portion (24 mm from the rotation axis) is 70 °, and the 12 mm portion from the rotation axis is 35 °, and the material is made of SUS. May be abbreviated as blade).

  Dedicated for FT-4 measurement, split container (model number: C203, height 82mm from the bottom of the container to the split part. Material is glass, hereinafter may be abbreviated as container), 23 ° C, 60mm A toner particle powder layer is formed by adding 100 g of toner particles that have been left in a% environment for 3 days or more.

(1) Consolidation operation of toner 35 g of toner particles are added to the above-mentioned cell dedicated for FT-4 measurement. A compression piston dedicated to FT-4 measurement is attached and consolidation is performed at 40N for 20 seconds. Further, 35 g of toner particles are added, and compaction is similarly performed with a compression piston at 40 N for 20 seconds. This operation is repeated for a total of four times to bring a total of 140 g of consolidated toner particles into a dedicated cell.

(2) Split operation A toner powder layer having the same volume is formed by scraping the toner powder layer at the split portion of the above-described cell dedicated to FT-4 measurement and removing the toner on the powder layer.

(3) Measurement operation (i) Measurement of Et (1) In the clockwise rotation direction (the direction in which the powder layer is not pushed in by rotation of the blade) with respect to the powder layer surface, the blade rotation speed is 10 mm / sec. The approach speed in the vertical direction to the powder layer is entered at a speed of 5 degrees from the bottom surface of the toner powder layer to a position of 10 mm. Then, in the clockwise rotation direction with respect to the powder layer surface, the blade rotation speed is 10 mm / sec, and the vertical entry speed to the powder layer is 2 deg. After performing an operation to enter the position 1 mm from the bottom, the angle at which the blade rotation speed is 10 mm / sec in the clockwise rotation direction with respect to the powder layer surface, and the vertical extraction speed from the powder layer However, extraction is performed from the bottom surface of the powder layer to a position of 100 mm at a speed of 5 deg. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.

  In the above measurement, the propeller blade is rotated and vertically entered into the toner particle powder layer in the container. The measurement is started from a position of 100 mm from the bottom surface of the powder layer, and is advanced from the bottom surface to a position of 10 mm. Let Et (1) be the sum of the rotational torque and vertical load obtained at the time.

(Ii) Measurement of Et (3) The same operation as (i) above is repeated twice more.

  In the third measurement, while rotating the propeller blade, the toner particle vertically enters the toner particle powder layer in the container, and the measurement is started from a position 100 mm from the bottom surface of the powder layer to a position 10 mm from the bottom surface. Let Et (3) be the sum of the rotational torque and the vertical load obtained when entering.

In a toner in which an external additive is externally added to toner particles, it is necessary to remove the external additive when measuring the fluidity of the toner particles. Specific examples of the method include the following methods.
-Add alkali to the toner and stir for 4 hours. The alkali is preferably a 0.1N sodium hydroxide aqueous solution.
・ Suction filtration separates toner particles and external additives.
-The obtained toner particles are sufficiently dried at room temperature in a vacuum dryer.

  The toner particles from which the external additive has been removed are observed with a scanning electron microscope, and after confirming that the external additive has disappeared, it can be used for measurement of fluidity. When the external additive has not been sufficiently removed, the above operation can be repeated until the external additive is sufficiently removed, and then used for fluidity measurement.

  In the case of 2400 mJ ≦ Et (1) ≦ 3000 mJ, it is indicated that a large amount of energy is required to loosen the state in which the toner particles are consolidated. In other words, it is thought that it has the property of being easily clogged.

  In the case of 800 mJ ≦ Et (1) −Et (3) ≦ 1800 mJ, it indicates that the energy applied when the toner particles recover the fluidity is smaller than the energy when the toner particles are released from the compacted state. . In other words, the fluidity can be easily recovered from the consolidated state.

  Therefore, the toner of the present invention can efficiently fill the cartridge with the toner, and the size of the cartridge can be reduced. In addition, even in an environment where toner deterioration is accelerated under conditions of high temperature and high humidity, it is thought that good fluidity can be maintained at all times, so that stable images can be produced without fading even during long-term use. Easy to obtain concentration.

  In addition, although the toner coated on the toner carrier forms spikes, it is easy to take a compacted state, so that the toner can be densely coated on the toner carrier, so that a sufficient image density can be obtained. Cheap. Further, since the fluidity can be recovered immediately from the compacted state, tailing can be improved because it is easy to disperse even from the state of the ears tightened by magnetic force during development.

  In the case of 2400 mJ ≧ Et (1), it is indicated that the energy required to loosen the state where the toner particles are consolidated is small. In other words, it is thought that it has the property that it is hard to clog. For this reason, the cartridge cannot be efficiently filled with toner, and it is difficult to reduce the size of the cartridge. In addition, the toner on the toner carrying member is difficult to take a compacted state, the coating amount becomes insufficient, and the image density may be lowered.

  In the case of 3000 mJ ≦ Et (1), it is indicated that very large energy is required to loosen the state where the toner particles are consolidated. In other words, it is thought that it has the property of being easily clogged. Therefore, fading is likely to occur under conditions of high temperature and high humidity, and the image density is likely to decrease.

  When 800 mJ ≧ Et (1) −Et (3), it is shown that there is no significant difference in fluidity between the state where the toner particles are compacted and the state where the fluidity is restored. There is a possibility that the toner coating amount on the toner carrier and the ease of spreading during development cannot be achieved at the same time. For this reason, the image density or tailing tends to deteriorate.

  The toner of the present invention comprises: a developing container that contains toner; a toner carrier that carries the toner contained in the developing container and transports it to the developing region; and a layer thickness of the toner that is carried on the toner carrier It is used in an image forming method using a toner regulating blade that regulates toner.

  Here, the arithmetic mean roughness Ra value of the irregularities on the surface of the toner carrier used in the present invention is 0.1 or more and 2.5 μm or less, preferably 0.8 or more and 1.8 μm or less. It is preferable for obtaining an effect. Since the Ra value of the sleeve is 0.1 or more and 2.5 μm or less, the toner of the present invention can be thinned even in long-term use, and the toner can be charged well, under low temperature and low humidity. The fog is also improved. Furthermore, since the toner of the present invention tends to be in a dense state, the image density can be satisfied even with a thinner coating.

  If Ra is less than 0.1 μm, the toner coating amount on the toner carrying member becomes extremely small, and it becomes easy to charge up, and the image density may decrease. When Ra exceeds 2.5 μm, the toner coating on the toner carrier may be uneven, and the image density may be lowered due to insufficient charging, resulting in deterioration of fog.

  In the present invention, the surface roughness is measured using a surface roughness meter SE-3300H manufactured by Kosaka Laboratory, and the measurement conditions are a cutoff of 0.8 mm, a specified distance of 8.0 mm, and a feed rate of 0.5 mm / s. The average of 12 measured values was taken.

  In order to obtain the effect of the present invention, the toner regulating blade used in the present invention is pressed against the surface of the toner carrier with a pulling pressure of 10 to 40 gf / cm, preferably 18 to 35 gf / cm. preferable. When the extraction pressure of the toner regulating blade against the surface of the toner carrier is 10 or more and 40 gf / cm or less, the toner of the present invention can be thinned even in long-term use, and the charging of the toner is improved. Further, the fog can be improved. Furthermore, since the toner of the present invention tends to be in a dense state, the image density can be satisfied even with a thinner coating.

  If the drawing pressure is less than 10 gf / cm, the toner cannot be properly regulated on the toner carrier, and the image density is lowered. When the pulling pressure exceeds 40 gf / cm, the amount of toner coating on the toner carrying member becomes extremely small, and it becomes easy to charge up, the image density is lowered, and the fog may be deteriorated.

  The drawing pressure is such that three 20 μm-thick SUS thin plates are inserted into the pressure nip portion of the blade portion, and one of the SUS thin plates is pulled out with a spring balance. At that time, the mass (g) displayed on the spring balance is extracted from the SUS thin plate. The value divided by the width (mm).

  In the present invention, the toner regulating blade may be roughened. When the surface is roughened, the toner regulating blade has irregularities on the surface, so that the charge imparting power to the toner coated on the toner carrier can be further increased. Further, since the image density becomes good even after long-term use and the chargeability of the toner is good, it is easy to obtain an excellent image quality with less fog.

  The effect of the present invention can be easily obtained when the ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrier is 5.0 μm or more and 25.0 μm or less. Preferably they are 5.0 micrometers or more and 20.0 micrometers or less, More preferably, they are 5.0 micrometers or more and 15.0 micrometers or less.

  Further, the average spacing Sm of the irregularities measured by a laser microscope on the surface of the toner regulating blade on the side in contact with the toner carrying member is 5.0 μm or more and 200.0 μm or less, preferably 20.0 μm or more and 180.0 μm or less. If it exists, the effect of this invention will be easy to be acquired.

  In the present invention, the ten-point average roughness Rz and the average spacing Sm of the surface of the portion of the toner regulating blade that is in contact with the toner carrier are non-contact type using a laser microscope (VK-8500, manufactured by Keyence Corporation). It is measured by the measuring method.

  In many conventional inventions, a contact-type surface roughness measuring device is used to adjust the surface roughness of the toner layer thickness regulating member. In contact-type measurement, the tip radius of the stylus is determined according to the measurement force, but the tip radius may be affected by the shape of the irregularities on the surface of the toner regulating blade. However, different cross-sectional curves may be obtained due to the difference in tip radius. The surface roughness adjustment method using a contact-type measuring device is strict about the vertical direction and the planar direction of the unevenness, especially when the density of the unevenness in the planar direction is relatively higher than the roughness in the vertical direction. It was difficult to adjust to the desired surface properties defined.

  Below, the specific example of the non-contact measuring method in this invention is shown.

<Measuring method of ten-point average roughness Rz and average interval Sm of unevenness of toner regulating blade surface>
1) Preparation of sample Cut the toner regulating blade into a size of about 1 cm square. However, as long as there is a sufficient area for irradiating the laser in the observation with a laser microscope, the size to be cut is not particularly limited.
2) Measurement conditions Set parameters for measurement as follows.
Objective lens magnification: 20 × Optical zoom magnification: 1 × Digital zoom magnification: 1 × RUN MODE: Color super depth LASER (gain): 594
LASER (offset): -1328
Camera settings (shutter): 158
Camera setting (white balance): 3200k
Camera setting (gain): 0
3) Setting of the sample The cut toner regulating blade is set on the stage of the laser microscope so that the portion in contact with the toner carrier becomes the observation surface.
4) Measurement The surface of the toner regulating blade is measured with a measurement PITCH of 0.1 μm.
5) Image processing In order to correct the overall distortion and inclination of the image obtained by the measurement, the following processing was performed.

[1. Tilt correction]
Correction method: Surface correction (automatic)
Process target: Height The following process was performed in order to remove fine noise components in the image obtained by the measurement.

[2. Filter processing]
Process target: Smoothing (height data)
Size: 7x7
Number of executions: 1
File Type: Median

[3. Filter processing]
Process target: Smoothing (height data)
Size: 3x3
Number of executions: 1
File type: Simple average 6) Analysis Height data is used for analysis. A scale is drawn on the obtained height data image, a range of 200 μm × 260 μm is selected, and the ten-point average roughness Rz and the average interval Sm of the irregularities in this range are used as measurement results.

[Ten point average roughness Rz]
The value obtained in the surface roughness measurement mode.

[Average interval Sm of unevenness]
In line roughness measurement mode, draw 5 straight lines in any horizontal direction and 5 straight lines in any vertical direction, and 2 upper and lower limit values out of the average interval Sm of 10 irregularities obtained from a total of 10 straight lines And the average of the remaining 8 points.

  Examples of the method for roughening the toner regulating blade include a sandblast method, a shot blast method, a method using a sand paper, and the like as physical methods. Examples of the chemical method include an etching method and a method of forming a film containing coarse particles.

  Among them, in the present invention, it is preferable to mold using a drum mold such as a centrifugal molding method or a continuous injection molding method. That is, the mold is rotating in the process of injecting the toner regulating blade forming liquid into the mold and molding the toner regulating blade while rotating. For this reason, centrifugal force works, air etc. in the toner regulating blade forming liquid escapes inward, and the toner regulating blade forming liquid is pressed against the mold surface, so that the unevenness of the mold is accurately transferred without mixing in air etc. A toner regulating blade can be obtained. At this time, as a method for forming irregularities on the inner peripheral surface of the mold, a method of using a bead blast method with roughened particles on the mold surface, or a mold release layer on the inner peripheral surface of the mold, A method in which a surface roughening agent such as spherical graphite fluoride is included in the surface layer portion of the mold layer is preferable. The height (depth) of the concavo-convex portion and the concavo-convex interval can be controlled by the particle size and content of the roughened particles. For example, as shown in the model diagram of FIG. 2, the toner regulating blade 12 transferred from the die 11 that has been bead-blasted with roughened particles has a convex portion with a smooth rounded arc shape, By adjusting the diameter and the discharge pressure, the ratio (ratio) and depth (height) of the concave and convex portions can be controlled. On the other hand, as shown in the model diagram of FIG. 3, in the toner regulating blade 23 transferred from the mold surface 21 formed with the release layer 22 containing the roughening treatment agent, the convex portion is relatively It becomes a flat shape, and the recess can obtain a relatively deep surface shape. Also in this case, the ratio (ratio) and depth (height) of a recessed part and a convex part are controllable by adjusting the particle size and content of a roughening processing agent. Then, by configuring the toner regulating blade so that the uneven surface (mold surface) of the toner regulating blade thus obtained is on the contact surface side with the toner carrier, the toner layer thickness regulation is performed. I do.

  The toner regulating blade member used in the present invention is not particularly limited. For example, urethane rubber, polyamide resin, polyamide elastomer, silicone rubber, silicone resin, or the like can be used. It is preferable to use urethane rubber for obtaining the effects of the present invention. The support member of the toner regulating blade is preferably made of a metal flat plate, a resin flat plate, more specifically, a stainless steel plate, a phosphor bronze plate, an aluminum plate, or the like. An additive such as a conductive material can be added to the main material of the blade member. In addition, the support member and the blade member can be bonded by, for example, an adhesive such as hot melt.

  When a rubber material is used as the toner regulating blade member, the rubber hardness is preferably 40 ° or more and 100 ° or less in (JIS) A. More preferably, (JIS) A 45 ° to 95 ° is preferable. More preferably, (JIS) A is 50 ° or more and 90 ° or less. If the rubber hardness is less than 40 °, the contact pressure with respect to the toner carrying member tends to be insufficient, and the toner may not be sufficiently charged and the image density may be lowered. On the other hand, when the angle exceeds 100 °, the contact pressure becomes too high, causing toner deterioration and easily causing poor charging, so that the image density is likely to decrease.

  Next, a toner particle manufacturing method using a surface modification step will be described as a preferred method for obtaining toner particles characterized by the present invention.

  As the surface modification device, the following devices are used. A pulverizer or the like can also be used as the toner particle surface modifying apparatus of the present invention. Faculty (manufactured by Hosokawa Micron), Mechano-Fusion (manufactured by Hosokawa Micron), Nobilta (manufactured by Hosokawa Micron), Hybridizer (manufactured by Nara Machinery Co., Ltd.), Inomizer (manufactured by Hosokawa Micron Co., Ltd.), Examples include mechano mill (Okada Seiko Co., Ltd.), kryptron (Kawasaki Heavy Industries Co., Ltd.), super rotor (Nisshin Engineering Co., Ltd.), turbo mill (Turbo Industry Co., Ltd.), tornado mill (Nikkiso Co., Ltd.) and the like. In the surface modification of the toner particles, the treatment may be repeated twice or more with the same apparatus, or two or more kinds of surface modification apparatuses may be combined.

  In the surface modification apparatus, for example, Faculty (manufactured by Hosokawa Micron Corporation) has a function of removing fine powder components simultaneously with the surface modification of toner particles in the toner particle surface modification step. When the surface modification of the toner particles is performed by the surface modification apparatus capable of removing the fine powder component at the same time as the surface modification of the toner particles as described above, the raw material toner particles finely divided in the vicinity of a desired particle diameter in advance are converted into an air flow type. It is preferable to remove the fine powder and coarse powder to some extent using a classifier, and then to modify the surface of the toner particles with a surface modification device. In this case, the toner particles from which fine powder has been removed by the airflow classifier have a cumulative value of the number average distribution of toner particles of less than 4 μm in a particle size distribution measured using a Coulter counter method of 10% or more and less than 50%. It is preferably 15% or more and less than 45%, more preferably 15% or more and less than 40%. Examples of the airflow classifier used in the present invention include Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.).

  Hereinafter, the binder resin used in the present invention will be described in detail.

  As the binder resin used in the present invention, various resin compounds conventionally known as binder resins can be used. Examples of such resins include vinyl resins, phenol resins, natural resin-modified phenol resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, Examples include furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumaroindene resins, and petroleum resins. In particular, a polyester resin and a vinyl resin are more preferable in terms of chargeability and fixability, and more preferably, a polyester resin is preferably used for obtaining the toner of the present invention. As the binder resin, these resins can be used alone or in combination of two or more.

  The following are mentioned as a polyester-type monomer used for this invention.

  As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Examples include diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, bisphenol A hydride, bisphenol derivatives represented by the following formula (A), and diols represented by the following formula (B).

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less.)

  Examples of the acid component include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or anhydrides thereof; Examples thereof include succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or an anhydride thereof.

  The polyester resin of the present invention is preferably a polyester resin containing a trivalent or higher polyvalent carboxylic acid or anhydride thereof and / or a trihydric or higher polyhydric alcohol, which makes it easier to control the molecular weight and viscosity. Examples of the trivalent or higher polyvalent carboxylic acid or anhydride thereof include 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid. And acid anhydrides or lower alkyl esters thereof. Examples of the trihydric or higher polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol and the like. In the binder resin of the present invention, aromatic alcohols having high stability due to environmental fluctuations are particularly preferable, and examples thereof include 1,2,4-benzenetricarboxylic acid and anhydrides thereof.

  The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type resin.

  Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene such as styrene, pn-butyl styrene, p-tert butyl styrene, pn hexyl styrene, pn octyl styrene, pn nonyl styrene, pn decyl styrene, pn dodecyl styrene and derivatives thereof Styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate; Vinyl such as vinyl propionate and vinyl benzoate Stealth; methyl methacrylate, ethyl methacrylate, propyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, n octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamino methacrylate Α-methylene aliphatic monocarboxylic acid esters such as ethyl and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic Acrylic acid esters such as 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether, Vinyl ethers such as vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone Vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated 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, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated dibasic acid ester such as dimethyl fumaric acid; acrylic acid, Α, β-unsaturated acids such as phosphoric acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride, the α, β-unsaturated acids and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Furthermore, 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) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl resin 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 acrylate, and 1,6-hexane. Examples include diol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate. Examples of diacrylate compounds linked by 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, Examples include dipropylene glycol diacrylate, and those obtained by replacing the acrylate relay of the above compounds with methacrylate. Examples of diacrylate compounds entrapped by a chain containing an aromatic group and an ether bond include, for example, polyoxyethylene (2) -2,2-bis (4hydroxyphenyl) propane diacrylate, polyoxyethylene (4)- Examples include 2,2-bis (4hydroxyphenyl) propane diacrylate and those obtained by replacing acrylate of the above compound with methacrylate. Examples of the polyester diacrylate compounds include trade name MANDA (Nippon Kayaku).

  Examples of the polyfunctional cross-linking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate; And lucyanurate and triallyl trimellitate.

  These crosslinking agents can be used in an amount of 0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) with respect to 100 parts by mass of other monomer components.

  Among these crosslinkable monomers, those which are preferably used in the binder resin from the viewpoint of fixability and offset resistance are bonded with aromatic divinyl compounds (particularly divinylbenzene), chains containing aromatic groups and ether bonds. And diacrylate compounds.

  Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azopis (-2methylptyronitrile), dimethyl-2,2′-azobisisoptylate, 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-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexane Ketone peroxides such as Sanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, denoyl peroxide Peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di n-propyl peroxydicarbonate, di-2-engineered tooxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t- Butyl peroxyacetate, t-butyl peroxyisoptylate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl perokine Benzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy 2-ethylhexanoate, di-t-butylperoxyhexahydride Terephthalate, di -t- butyl peroxy azelate and the like.

  In the present invention, the binder resin preferably has an acid value. When the acid value of the binder resin is 1 to 30 mgKOH / g, more preferably the acid value is 1 to 20 mgKOH / g, and still more preferably the acid value is 1 to 10 mgKOH / g, the effect of the present invention is obtained. Surface properties suitable for the toner, and tends to be advantageous for the formation of toner spikes.

  When the acid value of the binder resin is less than 1 mgKOH / g, the chargeability of the toner becomes insufficient, the developability tends to deteriorate, and the staying toner tends to decrease. On the other hand, when it exceeds 30 mgKOH / g, the moisture absorption of the binder resin tends to be high, the chargeability of the toner becomes unstable, and the developability tends to deteriorate.

  The acid value of the binder resin is determined, for example, by the operations 1) to 5) below. The basic operation belongs to JIS K0070.

  1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the content of components other than the binder resin in the sample is obtained. Weigh precisely 0.5 to 2.0 g of the pulverized product of magnetic toner or binder resin. The mass of the binder resin component at this time is defined as W (g).

  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) Using an ethanol solution of 0.1 mol / l KOH, measurement is performed using a potentiometric titrator. For this titration, for example, an automatic titration using a potentiometric titration measuring device AT-400 (winworkstation) of Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.

  4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).

5) Calculate the acid value according to the following formula. In the following formula, f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

  The acid value of the binder resin can be adjusted by, for example, the types of monomers constituting the binder resin and their blending amounts.

  In the present invention, other resins such as rosin, modified rosin, aliphatic or alicyclic hydrocarbon resin can be mixed with the above-described binder resin as necessary. When two or more kinds of resins are mixed and used as a binder resin, as a more preferable form, those having different molecular weights are preferably mixed at an appropriate ratio.

  Furthermore, the glass transition temperature (Tg) of the binder resin used in the present invention is preferably 45 to 80 ° C., more preferably 55 to 70 ° C., and the peak molecular weight is preferably 2,000 to 30,000.

  The peak molecular weight of the binder resin is measured by gel permeation chromatography (GPC) using the solution obtained by dissolving the binder resin in tetrahydrofuran (THF). It can be obtained from the count value (retention time) which is a measured value and the logarithmic value of a calibration curve prepared using several types of monodisperse polystyrene standard samples. Further, the molecular weight of the binder resin can be adjusted by polymerization conditions, use of a crosslinking agent, kneading of the binder resin, and the like.

  The glass transition temperature of the binder resin is generally determined so that the theoretical glass transition temperature described in the publication Polymer Handbook 2nd edition III-p139-192 (John Wiley & Sons) is 45 to 80 ° C. It can be adjusted by selecting the constituent material (polymerizable monomer) of the adhesion resin. The glass transition temperature of the binder resin can be measured according to ASTM D3418-82 using a differential scanning calorimeter, for example, DSC-7 manufactured by PerkinElmer or DSC2920 manufactured by TA Instruments Japan. When the glass transition temperature of the binder resin is lower than the above range, the toner may have insufficient storability. When the glass transition temperature of the binder resin is higher than the above range, the toner may have insufficient fixability. It may become.

  The method for synthesizing the binder resin containing the vinyl polymer or copolymer is not particularly limited, and various conventionally known production methods can be used. For example, polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. When a carboxylic acid monomer or an acid anhydride monomer is used, it is preferable to use a bulk polymerization method or a solution polymerization method because of the properties of the monomer.

  In the present invention, it is preferable to use a mixture of a polyester resin and a vinyl resin as a binder resin in terms of chargeability, fixability, and storage stability, and further contains a hybrid resin component in which both partially react. It is particularly preferred. Since this hybrid resin is uniformly dispersed with two types of resins that are inherently poorly compatible, not only can the properties of both resins be utilized, but also excellent compatibility with other internal additives such as wax, The mold releasability can be improved and the charge amount distribution tends to be uniform.

  That is, it is preferable that the vinyl copolymer component and / or the polyester resin component contain a monomer component capable of reacting with both resin components. Examples of the monomer constituting the polyester resin component that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl resin and a polyester resin, a polymer containing a monomer component capable of reacting with each of the vinyl resin and the polyester resin listed above is present. A method obtained by polymerizing a resin is preferred.

  Although the above binder resins may be used alone, two or more binder resins having different softening points may be mixed and used.

  The toner of the present invention preferably contains a charge control agent.

  Examples of the toner that controls the negative charge include the following compounds.

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

  Among these, an azo metal complex represented by the following general formula (1) is preferable.

  In particular, the central metal is preferably Fe, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, an alkali metal, ammonium or aliphatic ammonium. A mixture of complex salts having different counter ions is also preferably used.

  Alternatively, a basic organic acid metal complex represented by the following general formula (2) is also preferable as a charge control agent that imparts negative chargeability.

  In particular, Fe, Cr, Si, Zn or Al is preferred as the central metal, alkyl groups, anilide groups, aryl groups and halogens are preferred as substituents, and hydrogen, ammonium and aliphatic ammonium are preferred as counter ions.

  The following compounds are used to control the toner to be positively charged.

  Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts thereof. And these lake pigments, triphenylmethane dyes and these lake pigments. Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Such diorgano tin borate of Suzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used. Moreover, general formula (3)

［式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換または未置換のアルキル基（好ましくはＣ₁以上Ｃ₄以下）を示す。］
で表わされるモノマーの単重合体：前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合これらの荷電制御剤は、結着樹脂（の全部または一部）としての作用をも有する。

[Wherein, R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C ₁ or more and C ₄ or less). ]
Monomers of monomers represented by: A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, these charge control agents also have an action as a binder resin (all or a part thereof).

  In particular, a compound represented by the following general formula (4) is preferred as the positive charge control agent of the present invention.

  As a method for adding the charge control agent to the toner, there are a method of adding the toner inside the toner particles and a method of adding the toner outside the toner particles. The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method. Therefore, although not uniquely limited, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may contain a wax. The waxes used in the present invention include the following. For example, paraffin wax and derivatives thereof, montan wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, carnauba wax and derivatives thereof, and the like. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

  In the toner of the present invention, the total content of these waxes is 0.1 to 15 parts by mass, preferably 0.5 to 12 parts by mass with respect to 100 parts by mass of the binder resin. It is effective.

  These waxes have a melting point measured using a differential thermal analyzer (DSC) of 60 ° C. or higher and lower than 130 ° C., preferably 60 ° C. or higher and lower than 120 ° C., more preferably 60 ° C. or higher and lower than 110 ° C., more preferably. It is preferable that it is 65 degreeC or more and less than 100 degreeC. When a wax having such a melting point is contained in the toner particles, the toner particles can have an appropriate hardness, and the toner particles having a desired fluidity can be effectively used in the surface modification process of the toner particles. Therefore, the effects of the present invention can be obtained more easily. When the melting point of the wax is less than 65 ° C., the storage stability of the toner may be deteriorated. When the melting point of the wax exceeds 130 ° C., the toner particles become too hard and the productivity of the surface-modified toner may deteriorate.

In the present invention, the melting point of the wax is determined by the following method.
Sample: 0.5 to 2 mg Measurement method: Place the sample in an aluminum pan, and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. to 180 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (180 ° C. to 10 ° C., temperature drop rate 10 ° C./min)
Temperature increase II (10 ° C to 180 ° C, temperature increase rate 10 ° C / min)

  The endothermic peak temperature measured at the temperature elevation II in the temperature curve is defined as the melting point.

  The toner of the present invention contains a magnetic material. The magnetic material can also serve as a colorant. Magnetic materials used in the toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Examples include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

These magnetic materials preferably have a number average particle diameter of 0.05 to 1.0 μm, and more preferably 0.1 to 0.5 μm. A magnetic material having a BET specific surface area of 2 to 40 m ² / g (more preferably 4 to 20 m ² / g) is preferably used. There is no restriction | limiting in particular in a shape, The thing of arbitrary shapes is used. As magnetic characteristics, the saturation magnetization is 10 or more and 200 Am ² / kg or less (more preferably 70 or more and 100 Am ² / kg or less) under a magnetic field of 795.8 kA / m, and the residual magnetization is 1 or more and 100 Am ² / kg or less (more preferably). 2 to 20 Am ² / kg) and those having a coercive force of 1 to 30 kA / m (more preferably 2 to 15 kA / m) are preferably used. These magnetic materials are used in an amount of 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin. Preferably it is used in 40-150 mass parts.

  The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope or the like with a digitizer or the like. The magnetic properties of the magnetic material can be measured under an external magnetic field of 795.8 kA / m using a “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.). The specific surface area can be calculated by using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.

  Other colorants that can be used in the toner of the present invention include any suitable pigment or dye. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, Bengala, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image. The amount added is from 0.1 to 20 parts by weight, preferably from 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin. Is good. Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes. The addition amount of the dye is 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, with respect to 100 parts by mass of the binder resin.

  The toner particles of the present invention are preferably externally added with inorganic fine powder or hydrophobic inorganic fine powder. For example, silica fine powder, titanium oxide fine powder, or a hydrophobized product thereof can be used. They are preferably used alone or in combination.

  Examples of the silica fine powder include both a dry process produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica, and wet silica produced from water glass or the like. Dry silica with fewer silanol groups on the surface and inside and no production residue is preferred.

  Further, the silica fine powder is preferably hydrophobized. The hydrophobizing treatment is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. Preferable methods include a method in which a dry silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with a silane compound or with a silane compound and simultaneously with an organosilicon compound such as silicone oil.

  The silane compounds used for the hydrophobization treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethyl. Chlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane , Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Examples thereof include siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organosilicon compound include silicone oil. As a preferable silicone oil, one having a viscosity at 25 ° C. of about 30 to 1,000 mm ² / s is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are preferred.

  Silicone oil treatment can be performed by directly mixing silica powder treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, or spraying silicone oil onto the base silica. It may be by the method. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, and then mixed with the base silica fine powder to remove the solvent.

  As a preferable hydrophobizing treatment of the silica fine powder, there is a method of preparing by treating with hexamethyldisilazane and then treating with silicone oil.

  As described above, it is preferable to treat the silica fine powder with the silane compound and then oil-treat it later, so that the degree of hydrophobicity can be effectively increased.

  The silica fine powder is preferably subjected to a hydrophobization treatment, and further, an oil treatment applied to the titanium oxide fine powder, similarly to the silica-based one.

  To the toner particles of the present invention, additives other than silica fine powder or titanium oxide fine powder may be externally added as necessary.

  Examples thereof include resin fine particles and inorganic fine particles that act as charging aids, conductivity imparting agents, fluidity imparting agents, anti-caking agents, mold release agents at the time of hot roll fixing, lubricants, and abrasives.

  As the resin fine particles, those having an average particle size of 0.03 to 1.0 μm are preferable. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivatives; acrylic acid; methacrylic acid; methyl acrylate , Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acrylic acid esters such as: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, Lil, phenyl methacrylate, dimethylaminoethyl methacrylate, such as methacrylic acid esters of diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, and the like monomers acrylamide.

  Examples of the polymerization method include suspension polymerization, emulsion polymerization, and soap-free polymerization. More preferably, particles obtained by soap-free polymerization are good.

  Other fine particles include lubricants such as poly (ethylene fluoride), zinc stearate and polyvinylidene fluoride (polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide and strontium titanate (especially strontium titanate). Fluidity-imparting agents such as titanium oxide and aluminum oxide (especially hydrophobic ones are preferred); anti-caking agents; and conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide. . Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the toner may be used as a developability improver.

  The resin fine particles, inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is used in an amount of 0.01 to 5 parts by mass (preferably 0.01 to 3 parts by mass) with respect to 100 parts by mass of the toner. good.

  The toner of the present invention preferably has a weight average particle diameter of 2.5 to 10.0 μm, preferably 5.0 to 9.0 μm, more preferably 5.0 to 7.0 μm. It is easy to obtain fluidity and a compacted state suitable for obtaining the effects of the invention.

  The weight average particle diameter and particle size distribution of the toner are determined using a Coulter counter method. For example, a Coulter Multisizer (manufactured by Coulter Inc.) can be used.

  The toner of the present invention can be used as a two-component developer in combination with a carrier. As the carrier for use in the two-component development method, a conventionally known carrier can be used. Specifically, particles having an average particle size of 20 to 300 μm formed of metal such as surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, and alloys or oxides thereof are used as carrier particles. Is done. The surface of the carrier particles is preferably coated with a substance such as styrene resin, acrylic resin, silicone resin, fluorine resin, or polyester resin.

  In order to produce the toner according to the present invention, the toner constituent materials as described above are sufficiently mixed by a ball mill or other mixer, and then kneaded well using a heat kneader such as a hot roll, a kneader or an extruder, and cooled. A method in which after the solidification and coarse pulverization, fine pulverization and classification, and then surface modification of the toner particles using a surface modification device is preferable. Furthermore, the toner according to the present invention can be produced by sufficiently mixing the desired additives with a mixer such as a Henschel mixer, if necessary.

  For example, as a mixer, Henschel mixer (made by Mitsui Mining); Super mixer (made by Kawata); Ribocorn (made by Okawara Seisakusho); Nauter mixer, turbulizer, cyclomix (made by Hosokawa Micron); Spiral pin mixer (Manufactured by Taiheiyo Kiko Co., Ltd.); Ladige mixer (manufactured by Matsubo Co., Ltd.), and kneaders: KRC kneader (manufactured by Kurimoto Iron Works Co.); bus co kneader (manufactured by Buss); TEM type extruder (Manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho Co., Ltd.); Mining company); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) It is below.

  As a fine pulverizer after kneading, cooling and solidifying and coarsely pulverizing, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industrial Co., Ltd.) Cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.); SK jet o-mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); ); Super rotor (manufactured by Nisshin Engineering Co., Ltd.).

Classifiers include: Classy, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turbo Flex (ATP), TSP Separator (manufactured by Hosokawa Micron) Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).
As a sieving device used to screen coarse particles, Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Deoksugaku Kojo Co., Ltd.); Vibrasonic System (Dalton Co., Ltd.); Soniclean (Shinto) (Industry company); Turbo screener (Turbo industry company); Micro shifter (Ogino industry company); Circular vibration sieve, etc.

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

  Table 1 shows the binder resin used, Table 2 shows the magnetic material, and Table 3 shows the wax.

[Preparation of Toner 1]
Binder resin 1 100 parts by mass Magnetic substance 1 95 parts by mass Monoazo iron complex: T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass Wax 1 4 parts by mass After premixing the above mixture with a Henschel mixer, The mixture was melt-kneaded with a biaxial extruder heated to 110 ° C., and the cooled kneaded product was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner product. The obtained coarsely pulverized product was coated with a mechanical pulverizer turbo mill (manufactured by Turbo Kogyo Co., Ltd .; coated with chromium alloy plating containing chromium carbide on the rotor and stator surfaces (plating thickness 150 μm, surface hardness HV1050)). Based on the condition table of Table 4, the air temperature at the inlet and outlet is adjusted and mechanically pulverized to finely pulverize. The resulting finely pulverized product is a multi-division classifier using the Coanda effect (Nittetsu Mining Co., Ltd.). Fine powder and coarse powder were simultaneously classified and removed by an elbow jet classifier. The weight average particle diameter (D ₄ ) measured by the Coulter counter method of the raw material toner particles thus obtained was 5.9 μm, and the cumulative value of the number average distribution of toner particles of less than 4 μm was 27.3%.

The raw toner particles were subjected to surface modification and fine powder removal using a surface modification device faculty (manufactured by Hosokawa Micron). At that time, the rotational peripheral speed of the dispersion rotor is 140 m / sec, the input amount of the finely pulverized product is 8.6 kg per cycle, and the surface modification time (= cycle time, the discharge valve opens after the raw material supply is completed) Time) was 82 sec. The temperature at the time of discharging the toner particles was 42 ° C. Furthermore, surface modification and fine powder removal were performed again using the surface modification equipment faculty under exactly the same conditions. Through the above steps, the negatively chargeable toner particles 1 having a cumulative value of 24.8% of the number average distribution of toner particles having a weight average particle diameter (D ₄ ) of 5.8 μm and less than 4 μm measured by the Coulter counter method are obtained. Obtained. Table 5 shows the Et (1) value and the Et (1) -Et (3) value of the toner particles 1 measured by FT-4.

  100 parts by weight of the toner particles and 1.3 parts by weight of hydrophobic silica fine powder treated with hexamethyldisilazane and then treated with dimethylsilicone oil were mixed with a Henschel mixer to prepare negatively charged toner 1. .

[Preparation of Toners 2 to 4 and 7]
The binder resin, magnetic material and wax to be used are changed as shown in Table 4, and the finely pulverizing conditions of the turbo mill are changed as shown in Table 4, the classification conditions in the multi-division classifier are changed, and the surface reformer Toners 2 to 4 were obtained in the same manner as in Toner 1 except that the conditions for faculty (manufactured by Hosokawa Micron) were as shown in Table 4. Table 5 shows the Et (1) value and Et (1) -Et (3) value of toner particles 2 to 4 and 7 measured by FT-4.

[Preparation of Toner 5]
The binder resin, magnetic material and wax to be used are changed as shown in Table 4, and the finely pulverizing conditions of the turbo mill are changed as shown in Table 4, the classification conditions in the multi-division classifier are changed, and the surface reformer A toner 5 was obtained in the same manner as the toner 1 except that the surface modification was not performed. Table 5 shows the Et (1) value and the Et (1) -Et (3) value measured by FT-4 for the toner particle toner 5.

[Preparation of Toner 6]
As shown in Table 4, the binder resin, magnetic material and wax to be used were used in a multi-division classifier using a jet stream crusher IDS type mill (manufactured by Nippon Pneumatic Industry Co., Ltd.) without using a mechanical crusher. Toner 6 was obtained in the same manner as toner 1 except that the classification conditions were changed and the surface modification by the surface modification apparatus was not performed. Table 5 shows the Et (1) value and the Et (1) -Et (3) value measured by FT-4 for the toner particle toner 6.

[Examples 1 to 7, Comparative Examples 1 to 4]
Next, the prepared toner was used for evaluation by the following method.

  The laser beam printer Laser Jet 4350n manufactured by Hewlett-Packard Co. was modified to A4 size 60 sheets / minute (process speed 380 mm / sec), and the capacity of the toner filling portion was increased 1.5 times, and the following evaluation was performed. Table 6 shows the properties and evaluation results of the toner, toner carrier and toner regulating blade used.

(1) Image density Plain paper for copying machines under a high temperature and high humidity environment (32.5 ° C., 80% RH) at a printing speed of 2 sheets / 10 seconds and a printing ratio of 5% (A4 size: 75 g / m ² ) The image printing test was performed at 4000 sheets / day, a total of 28000 sheet printing tests were performed, and the image density at 28000 sheets was measured.

  For the image density, a “Macbeth reflection densitometer” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having an original density of 0.00.

(2) Tailing In a high-temperature and high-humidity environment (32.5 ° C, 80% RH), a pattern in which 4-dot horizontal lines are printed in a 20-dot space is drawn out. Judgment was made visually according to the standards.
A: No tailing has occurred.
B: Good image with slight tailing.
C: Although there is tailing, there is no problem in practical use.
D: An image having a bad tail and not practically preferable.

(3) Fog 4000 sheets / printing paper (A4 size: 75 g / m ² ) at a printing speed of 2 sheets / 10 seconds and a printing ratio of 5% in a low-temperature, low-humidity environment (15 ° C., 10% RH) The image-drawing test was conducted in one day, and a total of 28,000 image-drawing tests were carried out, and the fog after 28000 sheets was measured.

The image quality of the fog was evaluated on the white background on the test chart. The fog was evaluated by calculating the fog density (%) from the difference between the whiteness of the white portion of the fixed image and the whiteness of the transfer material measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.).
Unused paper reflectance-image white area reflectance = fog%
A: Fog less than 0.8% B: Fog 0.8 or more and less than 2.0% C: Fog 2.0 or more to less than 3.2% D: Fog 3.2% or more

It is explanatory drawing of the external appearance (a) of the propeller-type blade of a powder fluidity | liquidity analyzer, and the twist angle (b) of a blade outermost edge part. It is a model figure of the method of roughening a toner control blade using the metal mold | die blasted by the roughening particle | grains. FIG. 3 is a model diagram of a method for roughening a toner regulating blade using a mold layer on which a release layer containing a roughening treatment agent is formed.

Claims (3)

Toner particles containing at least a binder resin and a magnetic material, a toner having an inorganic fine particles externally added to the toner particles, the toner particles of the following equation (1), (2) are satisfied Toner characterized by the above.
2400mJ ≦ Et (1) ≦ 3000mJ (1)
800 mJ ≦ Et (1) −Et (3) ≦ 1800 mJ (2)
[However, Et (1), said toner particles after compaction with 40N, vertically enters the toner particles powder layers in the container while the peripheral speed of the outermost edge of the propeller blade was rotated at 10 mm / sec The total of the rotational torque and the vertical load obtained when the measurement is started from a position 100 mm from the bottom surface of the powder layer and moved to a position 10 mm from the bottom surface is represented. Measurement from the position of 100 mm from the bottom surface of the powder layer in the third measurement is performed by repeating the operation from the entry to the extraction of the propeller blade in the same manner, and the operation from the entry to the extraction of the propeller blade is repeated in the same manner. And the sum of the rotational torque and the vertical load obtained when entering the position 10 mm from the bottom is Et (3). ] An image forming method for carrying toner on a toner carrier, regulating a layer thickness of the toner carried on the toner carrier by a toner regulating blade, and transporting the regulated toner to a development region,
The ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrier is 5.0 μm or more and 25.0 μm or less,
The average spacing Sm of the irregularities measured with a laser microscope on the surface of the toner regulating blade on the side in contact with the toner carrier is 5.0 μm or more and 200.0 μm or less,
The toner has toner particles containing at least a binder resin and a magnetic material, and inorganic fine particles externally added to the toner particles, and the toner particles satisfy the following relational expressions (1) and (2): An image forming method.
2400mJ ≦ Et (1) ≦ 3000mJ (1)
800 mJ ≦ Et (1) −Et (3) ≦ 1800 mJ (2)
[However, Et (1) enters the toner particle powder layer in the container vertically while rotating the peripheral speed of the outermost edge of the propeller blade at 10 mm / sec after compacting the toner particles with 40 N The total of the rotational torque and the vertical load obtained when the measurement is started from a position 100 mm from the bottom surface of the powder layer and moved to a position 10 mm from the bottom surface is represented. Measurement from the position of 100 mm from the bottom surface of the powder layer in the third measurement is performed by repeating the operation from the entry to the extraction of the propeller blade in the same manner from the entry to the extraction of the propeller blade. And the sum of the rotational torque and the vertical load obtained when entering the position 10 mm from the bottom is Et (3). ] 3. The image forming method according to claim 2, wherein an arithmetic average roughness Ra of irregularities on the surface of the toner carrier is 0.1 μm or more and 2.5 μm or less.

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