JP4854645B2 - Image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner having a small particle diameter and sharp particle diameter distribution and an image forming apparatus using the toner capable of giving high-level picture quality with excellent minute dot reproducibility, to provide a toner and an image forming apparatus using the toner having excellent cleanability and low-temperature fixability and less adhesion of a toner component on a carrier even in long-term use, and causing no degradation in chargeability of the carrier, and to provide an image forming apparatus capable of decreasing reduction in transfer efficiency upon transferring and generation of abnormal images due to void defects, and moreover, decreasing a problem about turned up of a cleaning blade. <P>SOLUTION: The image forming apparatus includes an image carrier where a toner image according to image information is formed, an intermediate transfer member to be in contact with the image carrier, a primary transfer means transferring the toner image on the image carrier onto the intermediate transfer member, and a secondary transfer means to be press-contact with the intermediate transfer member and collectively transferring toner images transferred and held on the intermediate transfer member onto a recording medium. The apparatus is characterized in that the surface friction coefficient of the image carrier is lower than the surface friction coefficient of the intermediate transfer member and that the toner used shows an aspect ratio of from 0.80 to 0.90. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and an image forming apparatus using the toner.

  In recent years, the strong demand for higher image quality / energy saving from the market has spurred the development of toners and developers suitable for them. As a toner corresponding to high image quality, it is essential that the toner has a small particle size and a sharp particle size distribution. When the particle diameters of the toners are uniform and the particle diameter distribution is sharp, the behavior during development of the individual toners is uniform, and the fine dot reproducibility is remarkably improved. In recent years, a polymerized toner method has attracted attention as a method for producing such a toner having a uniform particle diameter. As the polymerized toner method, there are an emulsion polymerization method, a dissolution suspension method, and the like that are relatively easy to be modified, as well as suspension polymerization.

For low-temperature fixing of toner, use of a polyester resin having excellent low-temperature fixability and relatively good heat-preserving stability has been attempted in place of the styrene-acrylic resin that has been widely used. At this time, for further low-temperature fixing, it is necessary to control the thermal characteristics of the resin. However, if the glass transition point (Tg) is lowered too much, the heat-resistant storage stability is lowered, and the softening temperature T (F1 / 2). If the temperature is too low, there is a problem that the temperature at which hot offset occurs is lowered. For this reason, even if the thermal characteristics of a polyester resin excellent in low-temperature fixability are controlled, a toner having excellent low-temperature fixability and high hot offset occurrence temperature has not been obtained. Furthermore, because the developer in the copying machine is stirred for a long time due to the long-time image output, the release agent in the toner and the low melting point polyester resin adhere to the carrier, reducing the charging ability of the carrier, There is a strong tendency for the charge amount of the developer to decrease.
As for the shape of the toner, when unevenness is formed, the adhesion of the silica added as a fluidizing agent to the concave portion is weak, or the silica moves to the concave portion. The toner tends to adhere to the fixing roller.

  On the other hand, the dissolution suspension method has an advantage that a polyester resin that can be fixed at low temperature can be used. However, in order to achieve oil-less fixing, the resin or colorant is dissolved or dissolved in a solvent. In the dispersing step, a high molecular weight component is added. For this reason, liquid viscosity rises and it becomes easy to generate | occur | produce the problem on productivity. Patent Document 1 (Japanese Patent Application Laid-Open No. 9-15903) discloses a step of mixing a binder resin and a colorant in a solvent that is not miscible with water, and the resulting composition in an aqueous system in the presence of a dispersion stabilizer. An electrostatic charge image comprising a step of dispersing in a medium, a step of removing the solvent from the resulting suspension by heating and / or decompression to form particles having irregularities on the surface, and a step of spheroidizing or deforming by heating. A method for producing a developing toner is disclosed. However, since it is an irregularly shaped toner having no regularity, charging stability is lacking, and furthermore, a high molecular weight design for ensuring basic durability and releasability has not been made.

  As a known document disclosing a technique for evaluating a toner for developing an electrostatic charge image and an electrophotographic developer, Patent Document 2 (Japanese Patent Laid-Open No. 2004-177371) discloses a flow of a powder toner composed of at least a resin and a pigment. Is measured by measuring the torque or load generated when the conical rotor moves in the powder phase by rotating the conical rotor while rotating the conical rotor. Patent Document 3 (Japanese Patent Application Laid-Open Publication No. 2003-208443) describes a technique that measures torque or load under the condition of speed (mm / min) / rotational speed (rpm) of the conical rotor being 2/1 to 20/1. No. 2004-177850), by rotating the conical rotor into the powder phase while rotating, and measuring the torque or load generated when the conical rotor moves in the powder phase. Although the technology is described in which the conical rotor is rotated in advance and then penetrates into the powder phase, it is described as a further improvement of the technology of these patent documents. In Document 4 (Japanese Patent Laid-Open No. 2006-78257), there is a method suitable for evaluating differences between toners because the torque is small even when measuring a material having good fluidity, such as toner, and it is strongly influenced by measurement variations. Proposed.

  2. Description of the Related Art Conventionally, an intermediate transfer type image forming apparatus that transfers a toner image formed on an image carrier to an intermediate transfer member and collectively transfers the toner image transferred to the intermediate transfer member onto a recording medium is already known. As this type of image forming apparatus, the image carrier carries a toner image according to image information, for example, a photoconductor is used, and the intermediate transfer member is an endless member that is stretched around, for example, a plurality of rollers. An intermediate transfer belt is used. Also, as a primary transfer means for transferring the toner image on the photoreceptor to the intermediate transfer belt, a transfer electric field formed between the photoreceptor and the intermediate transfer belt is used for the primary transfer, and the toner image on the intermediate transfer belt is transferred to the recording medium. The secondary transfer means uses a transfer electric field formed between the intermediate transfer belt and the transfer material. The primary transfer unit is required to faithfully and stably transfer the toner image formed on the photosensitive member to the intermediate transfer member. Similarly, the secondary transfer unit is required to faithfully and stably transfer the toner image formed on the intermediate transfer member to the recording medium. That is, in order to realize the performance required for the primary transfer unit and the secondary transfer unit, it is necessary to perform stable transfer with high transfer efficiency.

  In such an image forming apparatus, there may occur a so-called worm-eating phenomenon in which the transfer efficiency is lowered or the center of the image (particularly the center of the line portion or character portion) is lost during the primary transfer. In order to solve this problem, a method of applying a lubricant to the photosensitive member and lowering the coefficient of friction to weaken the adhesion between the toner and the toner (Patent Document 5), the coefficient of friction of the photosensitive member and the intermediate transfer belt Has been proposed (Patent Documents 6 and 7) for defining the relationship between the friction coefficient and the friction coefficient.

  However, the friction coefficient is closely related not only to the transferability but also to the turning-up of the cleaning blade for removing the toner that could not be transferred. As a method for solving this blade turning, a method of supplying a lubricant to a cleaning target is effective and widely known (for example, Patent Documents 8 to 10). Therefore, a lubricant application condition and a friction coefficient condition are necessary to solve both the insect worm and the turning of the cleaning blade.

JP 9-15903 A JP 2004-177371 A JP 2004-177850 A JP 2006-78257 A Japanese Unexamined Patent Publication No. 8-21755 JP-A-6-332324 JP 2000-19858 A Japanese Unexamined Patent Publication No. 57-17793 JP 7-271142 A JP 2001-75449 A

The subject of this invention is as follows.
(1) To provide a toner having a small particle size and a sharp particle size distribution capable of obtaining a high-quality image having excellent fine dot reproducibility, and an image forming apparatus using the toner.
(2) Toner that has excellent cleaning properties and low-temperature fixability, has less toner component adhesion to the carrier even during long-term use, and does not deteriorate charging ability, and an image forming apparatus using the toner.
(3) To provide an image forming apparatus capable of reducing the transfer efficiency during transfer, reducing the occurrence of abnormal images due to insect erosion, and reducing the problem of turning over the cleaning blade.

The above problems are solved by the present invention described below.
(1) “An image carrier on which a toner image corresponding to image information is formed, an intermediate transfer member in contact with the image carrier, and a primary for transferring a toner image on the image carrier to the intermediate transfer member In the image forming apparatus, comprising: a transfer unit; and a secondary transfer unit that press-contacts the intermediate transfer member and transfers the toner image transferred and held on the intermediate transfer member to a recording medium. The surface friction coefficient is lower than the surface friction coefficient of the intermediate transfer member, and the toner has an aspect ratio of 0.80 or more and 0.90 or less, and toner containing paraffin wax in the base particle is used. Image forming apparatus ",
(2) “The toner has a base particle containing a paraffin wax having a melting point of 60 ° C. or higher and 90 ° C. or lower and a binder resin, and the base particle has an endothermic peak derived from the paraffin wax in an endothermic peak in DSC measurement. The image forming apparatus according to (1) above, wherein the heat quantity is 3.5 J / g or more and 5.5 J / g or less, and the average circularity is 0.950 or more and 0.980 or less.
(3) “The toner base particle is a water-based dispersion in which at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, the paraffin wax and an inorganic filler are dispersed in an organic solvent. It is obtained by dispersing in a medium and subjecting the polyester prepolymer to a crosslinking reaction and / or elongation reaction, and the base particles have a shape factor SF1 of 130 or more and 160 or less, and a shape factor SF2 of 110 or more and 140 or less. The image forming apparatus according to item (1) or (2), wherein:
(4) “The toner has a weight average particle diameter of 3 μm or more and 8 μm or less, and a ratio of the weight average particle diameter to the number average particle diameter of 1.00 or more and 1.30 or less. The image forming apparatus according to any one of items 1) to (3) ",
(5) "The image forming apparatus according to any one of (1) to (4) above, wherein the inorganic filler in the toner is montmorillonite or a modified product of montmorillonite",
(6) “The image forming apparatus according to any one of (1) to (5), wherein the toner has a glass transition point of 40 ° C. or more and 60 ° C. or less”,
(7) “The toner contains 1% by number or more and 10% by number or less of the base particles having a particle diameter of 2 μm or less, according to any one of (1) to (6),” The image forming apparatus described herein.

  According to the present invention, it is possible to provide a small particle size and sharp particle size distribution toner capable of obtaining a high quality image with excellent fine dot reproducibility, and an image forming apparatus using the same, and a cleaning property and a low temperature fixing property. In addition, the toner component does not adhere to the carrier even in long-term use and does not deteriorate the charging ability, and an image forming apparatus using the toner can be provided. Therefore, it is possible to provide an image forming apparatus that can reduce the occurrence of the occurrence of the cleaning blade and the problem of turning the cleaning blade.

(Particle size distribution)
Next, the toner suitably used in the image forming apparatus of the present invention will be described.
In order to reproduce minute dots of 600 dpi or more, the toner preferably has a weight average particle diameter (D4) of 3 to 8 μm. The ratio (D4 / Dn) of the weight average particle diameter (D4) to the number average particle diameter (Dn) is preferably in the range of 1.00 to 1.30. The closer the (D4 / Dn) is to 1.00, the sharper the particle size distribution. For the same reason, it is preferable that 1 to 10% by number of particles of 2 μm or less. Such a toner having a small particle size and a narrow particle size distribution makes the toner charge amount distribution uniform and can provide a high-quality image with little background fogging. In addition, the electrostatic transfer system has a high development efficiency. can do. On the other hand, the problem when reducing the toner particle size is that the non-electrostatic adhesion to the carrier is larger than that of the larger particle size, so it stays on the carrier surface for a long time and is easily subjected to agitation stress and adheres to the carrier surface. It causes the charging ability of the carrier to decrease. In order to prevent such a problem, the number of particles of 2 μm or less is preferably 1 to 10% by number.

In the present invention, the toner particle size distribution is measured by the Coulter counter method. Examples of the measuring device by the Coulter counter method include Coulter counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 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 measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(FPIA, average circularity, aspect ratio)
For measurement of ultra-fine toner having an aspect ratio, average circularity of 2 μm or less, measurement is performed using a flow type particle image analyzer (FPIA-3000; manufactured by Sysmex Corporation), and analysis is performed using analysis software attached to the same machine. It was. Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using the FPIA-3000, the dispersion was measured for toner shape and distribution until a density of 5000 to 15000 / μl was obtained. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. It will be enough. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.
As analysis conditions, an aspect ratio and an average circularity obtained by analyzing the measurement target particle size limit of 2 to 200 μm and the amount of super fine toner of 2 μm or less were obtained. The average circularity and aspect ratio are defined as follows.
Average circularity = (salt circumference equal to particle area) / (particle circumference)
Aspect ratio = (Maximum vertical length) / (Maximum length)
The average circularity is a shape factor that mainly expresses the degree of unevenness of particles, whereas the aspect ratio is a shape factor that mainly expresses the acicularity of particles.

The inventors have evaluated the relationship between toner shape and cleaning properties, and found that the shape, particularly the aspect ratio, has a close correlation with the cleaning characteristics. The toner having a small aspect ratio has a large interaction force between the toner particles under the compacting condition, and is clogged by the blade in the process of clogging (cleaning) the transfer residual toner on the photoreceptor with a cleaning blade or the like. The toner tends to aggregate and form a toner layer. Accordingly, the transfer residual toner is blocked not only by the blade but also by the toner layer blocked by the blade, and the amount of toner passing through the cleaning blade is reduced, so that a good cleaning property can be obtained.
When the toner has an aspect ratio of greater than 0.90, the cleaning property is deteriorated. On the other hand, when the aspect ratio is less than 0.80, a trouble caused by low fluidity in a process other than cleaning, specifically, in a pipe Problems such as toner clogging become significant. For this reason, the aspect ratio has an optimum range, and its value is 0.80 to 0.90.

As a problem that has not been found so far, in the process of charging and developing the toner, it has been found that the following tendencies (1) to (4) exist between the shape of the toner and the charging characteristics.
(1) The closer the toner shape is to a sphere, the more likely the toner and the carrier are in point contact, or the toner contacts while rotating on the carrier, so that the toner easily rolls on the surface of the carrier, paraffin wax, low molecular weight A toner component such as a resin component is easily fixed on the carrier. As a result, the charging ability of the carrier is easily lowered. This corresponds to a small contact area between the toner and the carrier (two-component development method) and a small contact area between the toner and the developing sleeve (one-component development method).
(2) On the other hand, when the surface shape of the toner is rough and there are many irregularities, the toner and the carrier are in surface contact, so that the toner is difficult to roll on the surface of the carrier, but the contact area between the toner and the carrier is large, and the paraffin wax In addition, toner components such as low molecular weight resin components are easily fixed on the carrier. As a result, the charging ability of the carrier is easily lowered. This corresponds to a large contact area between the toner and the carrier (two-component development method) and a large contact area between the toner and the developing sleeve (one-component development method).
(3) When the toner and the carrier are stirred for a long time, the influence of the shape appears more strongly than the unevenness. In other words, when the toner and the carrier are stirred in the developing machine for a long time in durability evaluation under actual use conditions, the unevenness on the toner is scraped or deformed, so that the unevenness does not remain. The effect of 1) appears.
(4) For this reason, it is preferable to look at the toner shape related to the chargeability of the toner, especially the decrease in the charging ability of the carrier due to long-term agitation. The lower the aspect ratio, the more difficult it is to roll on the carrier. The higher the value, the closer to the spherical shape, so it is easier to roll on the carrier. Therefore, it is preferable that the aspect ratio of the range in which the toner component is not fixed on the carrier while maintaining a proper contact between the toner and the carrier is in the range of 0.80 to 0.90.

  From the above points, the toner aspect ratio has an optimum range, and its value is 0.80 to 0.90. However, when looking at transfer performance as a new issue, the greater the torque evaluated by this torque evaluation method, the more likely the worm-eating phenomenon occurs during transfer, so the surface properties of the photoconductor and intermediate transfer belt, specifically It was necessary to optimize the surface friction coefficient, and it was found that good results can be obtained in any of the cleanability, developability, and transferability that are tradeoffs.

(SF-1, SF-2)
It is preferable that the shape factor SF-1 of the toner is in the range of 130 to 160, and the shape factor SF-2 is in the range of 110 to 140.
FIGS. 1 and 2 are diagrams schematically showing the shape of the toner for explaining the shape factor SF-1 and the shape factor SF-2. The shape factor SF-1 indicates the ratio of the roundness of the toner shape and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases.

The shape factor SF-2 indicates the ratio of the unevenness of the toner shape, and is represented by the following formula (2). A value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-2 = {(PERI) ² / AREA} × (100π / 4) Expression (2)
When the value of SF-2 is 100, there is no unevenness on the toner surface, and as the value of SF-2 increases, the unevenness of the toner surface becomes more prominent.

Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.) and introducing it into an image analyzer (LUSEX3: manufactured by Nireco). 100 pieces were analyzed and calculated.
When a toner having D / S of 15 to 40% and (L / M)> 2 is expressed by SF-1 and SF-2, SF-1 is in the range of 130 to 160, and the shape factor SF-2 is 110 to 110. In the range of 140

(Toner density)
In a full-color image forming apparatus, the toner concentration in the developer is often used in a toner concentration range of 3 to 12 wt%. The image density is controlled in consideration of the particle size of the toner and the carrier in the developer, that is, the surface area, and the occupied area of the toner to be tightened to the carrier surface area is controlled to be 100% or less. This is a measure for maintaining contact and preventing insufficient charging of the toner due to poor contact between the toner and the carrier. Here, in the developer having a high toner concentration, there is a problem that a low melting point wax, a resin or the like in the toner is fixed on the carrier surface and the charging ability of the carrier is lowered.

(Endothermic peak endotherm derived from release agent by DSC)
In the present invention, the glass transition point (Tg) of the toner is usually 40 to 70 ° C., preferably 40 to 60 ° C. If it is less than 40 ° C., the heat resistance of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of a modified polyester such as a urea-modified polyester resin, the toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.
Further, in order to obtain hot offset resistance among the fixing performance, it is preferable that the release material is large. On the other hand, since the release agent is easily fixed to the carrier, in order to maintain the charging ability of the developer carrier for a long period of time. Less is preferred. From this point of view, the content of the release agent in the toner is excellent in hot offset resistance in that the endothermic amount of the endothermic peak derived from the release agent in DSC is in the range of 3.5 to 5.5 J / g. This is desirable in terms of maintaining the charging ability of the carrier.

Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
・ Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. In the analysis method, the DrDSC curve, which is the DSC differential curve of the second temperature rise, specifies two locations on the low-temperature side and high-temperature side of the endothermic peak corresponding to the endotherm when the release agent melts. The peak endotherm is obtained using the peak analysis function. The endothermic peak corresponding to the endotherm at the time of melting of the release agent is an endothermic peak obtained by performing DSC measurement of the release agent alone by the above procedure.
In addition, the toner Tg is designated with a range of ± 5 ° C. around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature increase, and is peaked using the peak analysis function of the analysis software. Find the temperature. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.

Other toner constituent materials will be described.
-Modified polyester-
The toner of the present invention contains a modified polyester (i) as a binder resin. The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin through a covalent bond or an ionic bond. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

  Examples of the modified polyester (i) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

The urea-modified polyester is produced as follows.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. As trihydric or higher polyhydric alcohol (TO), trihydric or higher polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) and a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; phenol derivatives, oximes, polyisocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

  The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass. %. If it is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acids (B5), and (B6) in which the amino group of (B1) to (B5) is blocked.
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.).
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), And oxazolidine compounds.
Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).
The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

-Unmodified polyester-
In the present invention, not only the modified polyester (i) is used alone, but also the unmodified polyester (ii) can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to single use. Examples of (ii) include polycondensates of polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) similar to the polyester component of (i) above, and preferred ones are also the same as (i). . (Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000 to 10,000, preferably 2000 to 8000, and more preferably 2000 to 5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is preferably 1 to 5, more preferably 2 to 4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.

  The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C., preferably 40 to 65 ° C., more preferably 40 to 60 ° C. when toner particles containing other toner materials are used. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

-Colorant-
As the colorant, known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Vulcan fast yellow (5G, R) ), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, parachlor ortho nitroa Phosphorus Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Po Azo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalo Anine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded together with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salt or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSYVP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (manufactured by Nippon Carlit) ), Copper phthalocyanine, perylene, quinacridone, azo face And other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of the charge control agent used is determined based on the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite.

―Inorganic filler―
As the inorganic filler for controlling the toner shape, montmorillonite or an organic modified product thereof (Clayton APA) is used. The function of the inorganic filler is to form irregularities on the toner surface, and the mechanism is as follows.
In a toner manufacturing method in which a toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles, the inorganic filler in the toner material liquid moves to the interface between the organic solvent and the aqueous solvent during emulsification, and the emulsion dispersion Collect on the surface shape of the (reactant). Next, in the step of removing the organic solvent from the emulsified dispersion (reactant), washing and drying, the inorganic filler present on the surface forms irregularities on the surface of the reaction product. Therefore, in obtaining the shape of the present invention, the amount of the inorganic filler can be controlled within the range of 0.1 to 10 parts by weight to change the shape, and the larger the amount of the inorganic filler, the more SF-1 and SF-2. The value of becomes larger and deforms.

-External additive-
Inorganic fine particles are preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles. The primary particle diameter of the inorganic fine particles is preferably 5 × 10 ^{−3 to} 0.3 μm. Moreover, it is preferable that the specific surface area by BET method is 100-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass.

  Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester, acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Examples thereof include polymer particles made of a resin.

Such external additives can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
In particular, it is preferable to use hydrophobic silica and hydrophobic titanium oxide obtained by subjecting silica and titanium oxide to the above surface treatment.

Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
(Production method of toner binder)
The toner binder can be manufactured by the following method. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with a polyvalent isocyanate compound (PIC), and the prepolymer (A) which has an isocyanate group is obtained. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond.
When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers Inactive to polyvalent isocyanate compounds (PIC) such as benzene (such as tetrahydrofuran).
When the unmodified polyester (ii) is used in combination, (ii) is produced by the same method as that for the polyester having a hydroxyl group, and this is dissolved and mixed in the solution after completion of the reaction (i).

(Toner production method)
1) A toner material liquid is prepared by dispersing a colorant, unmodified polyester (i), a polyester prepolymer (A) having an isocyanate group, and a release agent in an organic solvent. The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. The usage-amount of an organic solvent is 0-300 mass parts normally with respect to 100 mass parts of polyester prepolymers, Preferably it is 0-100 mass parts, More preferably, it is 25-70 mass parts.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by mass of the toner material liquid is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by mass, it is not economical.

The glass transition point (Tg) of the resin fine particles dispersed in the aqueous medium is preferably 50 to 110 ° C., more preferably 50 to 90 ° C. When the glass transition point (Tg) is less than 50 ° C., toner storage stability is obtained. Or the probability of fixing and aggregation in the toner recovery path during recycling increases. When the glass transition point (Tg) is higher than 110 ° C., the resin fine particles hinder the adhesion to the fixing paper, and the fixing minimum temperature is increased. A more preferred range is a range of 50 to 70 ° C.
The weight average molecular weight is desirably 100,000 or less. Preferably it is 50,000 or less. The lower limit is usually 4000. When the weight average molecular weight exceeds 100,000, the resin fine particles inhibit the adhesiveness with the fixing paper, and the minimum fixing temperature increases.

  As the resin fine particles, known resins can be used as long as they can form an aqueous dispersion, and thermoplastic resins or thermosetting resins may be used. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, and polyester resins. It is done. As the resin fine particles, two or more of the above resins may be used in combination. Among these, those made of a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, or a combination resin thereof are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.

Vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene-acrylic acid ester resins, styrene-methacrylic acid ester resins, styrene-butadiene copolymers, acrylic acid-acrylic acid ester polymers. Methacrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and the like.
In the resin fine particles, the volume average particle diameter is a value measured with a light scattering photometer (manufactured by Otsuka Electronics), and is 10 to 200 nm, preferably 20 to 80 nm.
Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium or to prevent the wax from being exposed to the outermost surface of the toner. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%.
In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl , 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Nitrogen-containing compounds such as ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, polyoxypro Len, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene Polyoxyethylenes such as nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

3) At the same time as the preparation of the emulsion, the amines (B) are added to react with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent-based toner base particles can be produced by removing the solvent. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to

(Transfer device)
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 3 is a schematic diagram illustrating an example of a color image forming apparatus. In the image forming section of the image forming apparatus shown here, an intermediate transfer belt (1) as an image carrier is disposed, and the intermediate transfer belt (1) is composed of rollers (2), (3), (4), (5 ) And one of the rollers (2) and (3) is driven to rotate in the direction of arrow A by being driven to rotate clockwise as a driving roller. The image forming unit is provided with first to fourth image forming units (6a), (6b), (6c), and (6d) facing the upper running side of the intermediate transfer belt (1). The first to fourth image forming units (6a), (6b), (6c), (6d) are drum-shaped photoconductors (7a), (7b), (7c), (7d) as image carriers. And a magenta toner image, a cyan toner image, a yellow toner image, and a black toner image are formed on the respective photoreceptors.

The first to fourth image forming units (6a), (6b), (6c), and (6d) are substantially the same in structure and operation as to form a toner image on the image carrier. Only the configuration for forming a toner image on the photoreceptor (7a) of the first image forming unit (6a) will be described with reference to FIG.
The photoconductor (7) is rotated counterclockwise in FIG. 4, and at this time, the surface of the image carrier is uniformly charged to a predetermined polarity by the charging roller (8). Then, the charged surface is irradiated with a light-modulated laser beam (L) emitted from the laser writing unit (9) shown in FIG. As a result, an electrostatic latent image is formed on the photoreceptor (7), and the electrostatic latent image is visualized by the developing device (10) as, for example, a magenta toner image.
The magenta toner image formed in this way is applied with a voltage having a polarity opposite to that of the toner to the transfer roller (11) disposed with the photoconductor (7) and the intermediate transfer belt (1) interposed therebetween. (7) The upper magenta toner image is transferred onto the intermediate transfer belt (1). Untransferred toner that is not transferred to the intermediate transfer belt (1) and remains on the photoreceptor (7) is removed by the cleaning device (12).
In exactly the same manner, a cyan toner image, a yellow toner image, and a black toner are formed on the photoreceptors (7b), (7c), and (7d) of the second to fourth image forming units (6b), (6c), and (6d). Each toner image is formed, and these toner images are sequentially superimposed and transferred onto the intermediate transfer belt (1) on which the magenta toner image is transferred. Thus, the four color toner images formed on the intermediate transfer belt (1) move to the secondary transfer portion provided with the secondary transfer roller (13) at the right end of FIG. 3 as the belt travels.
On the other hand, a paper feeding unit (not shown) is provided at the lower part of the apparatus main body, and a recording material (P) made of transfer paper, for example, is fed from the paper feeding unit. The fed recording material (P) is abutted against the registration roller (14) shown in FIG. 3, and then the secondary transfer portion of the intermediate transfer belt (1) at the timing when the toner image is correctly transferred to the recording material. It is sent to. A voltage having a polarity opposite to that of the toner on the intermediate transfer belt (1) is applied to the secondary transfer roller (13), whereby the toner image superimposed and transferred on the intermediate transfer belt (1) is recorded on the recording material (P ) Is transferred to the top. The recording material (P) onto which the toner image has been transferred is transported to the fixing device (16) via the transport belt (15), where the toner image is fixed and then discharged to a paper discharge section (not shown). .
Further, after the secondary transfer, the transfer residual toner that has not been transferred to the recording material (P) is removed by the belt cleaning device (20). The belt cleaning device (20) includes a cleaning blade (21) that is in sliding contact with the intermediate transfer belt (1). Reference numeral (22) denotes a backup roller for obtaining a reliable sliding contact of the blade (21) with the intermediate transfer belt (1).

  By the way, in the intermediate transfer type image forming apparatus as described above, a so-called worm-eating phenomenon in which the toner image is locally lost may occur in the primary transfer portion. It has been found from the experiment results of the present inventor that the worm-eaten is less likely to occur when the surface friction coefficient of the photoreceptor (7) is lower than the surface friction coefficient of the intermediate transfer belt (1).

  On the other hand, there is a case where a pattern is created between images for toner adhesion amount control and positional deviation correction. Since these patterns are not transferred to the paper, they come into contact with the secondary transfer roller (13), and all or part of the patterns are transferred to the roller surface, and a cleaning means is required to remove them. A cleaning blade is generally used as the cleaning means. However, there is a case where the blade is turned over to inhibit or stop the rotation of the roller.

(apparatus)
In the apparatus used in the examples and comparative examples, a lubricant applying device (30) as a lubricant supplying means is provided on the photoreceptor (7), the intermediate transfer belt (1), and the secondary transfer roller (13).
The intermediate transfer belt (1) uses polyimide as a material thereof, disperses carbon black in a solution of polyamic acid, flows the dispersion into a metal drum and dries it, and then peels it from the metal drum. The film was stretched at a high temperature to form a polyimide film, cut into an appropriate size, and an endless belt made of polyimide resin was produced. According to a general method, film formation was performed by injecting a polymer solution in which carbon black was dispersed into a cylindrical mold, rotating the cylindrical mold while heating at 100 to 200 ° C., and forming a film by centrifugal molding. The film thus obtained was demolded in a semi-cured state and covered with an iron core, and the polyimide transfer reaction was allowed to proceed at 300 to 450 ° C. to cure the intermediate transfer belt (1). At this time, the resistance of the belt can be adjusted by changing the carbon amount, the firing temperature, the curing speed, and the like. The surface friction coefficient of the belt made in this way was 0.45. For measurement of the surface friction coefficient, HEIDON TRIBOGEAR μs 94i manufactured by Shinto Kagaku was used.

Here, a specific configuration of the lubricant application device will be described with reference to FIG. The lubricant application device (30) shown in FIG. 4 supplies the lubricant to the photoconductor (7), but the lubricant application device attached to the intermediate transfer belt (1) and the secondary transfer roller (13). Is also applicable.
In FIG. 4, the lubricant application device (30) is provided in the cleaning device (12), and the device includes an application brush (31) and a lubricant unit (32). As shown in FIG. 6, the lubricant unit (32) includes a solid lubricant (33) and a spring (34) as a pressurizing unit that presses the lubricant against the application brush (31). The application amount of the lubricant (33) can be varied by selecting the pressing force of 34). Further, as the pressurizing means, a weight (35) as shown in FIG. 5 can be used instead of the spring (34). Also in this case, the application amount of the lubricant (33) can be varied by selecting the weight of the weight (35).

The lubricant application device (30) configured as described above is provided for the photosensitive member (7), the intermediate transfer belt (1), and the secondary transfer roller (13), respectively, so that the photosensitive member (7), the intermediate transfer device (30) is provided. The surface friction coefficients of the transfer belt (1) and the secondary transfer roller (13) can be set as appropriate, and the intermediate transfer belt (1) is determined from the surface friction coefficients of the photoreceptor (7) and the secondary transfer roller (13). ) To increase the surface friction coefficient.
Each of the photoreceptor (7), the intermediate transfer belt (1), and the secondary transfer roller (13) is provided with a lubricant application device (30). The lubricant application device (30) is connected to the photoreceptor (7). Provided for the secondary transfer roller (13), the intermediate transfer belt is not provided with the lubricant applying device (30), and the lubricant for the intermediate transfer belt (1) is the photoreceptor (7) and the secondary transfer roller. You may comprise so that what apply | coated to (13) may be apply | coated indirectly. Also in this case, since the lubricant is indirectly applied to the intermediate transfer belt (1), the application amount is smaller than that of the photoreceptor (7) and the secondary transfer roller (13), and the photoreceptor (7) and the secondary transfer belt (1). It is easy to increase the surface friction coefficient of the intermediate transfer belt (1) from each surface friction coefficient of the next transfer roller (13).
Furthermore, in order to satisfy the relationship of the friction coefficient that the surface friction coefficient of the intermediate transfer belt (1) is made larger than the surface friction coefficients of the photosensitive member (7) and the secondary transfer roller (13), the surface of the photosensitive member (7). A surface layer for reducing the friction coefficient may be provided on the surface of the photoreceptor.

Materials used for the surface layer of the photoreceptor (7) include styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, olefin-vinyl monomer copolymer, chlorinated poly Ether, aryl, phenol, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethyne, polyethylene terephthalate, polyimide, acrylic, polymethylpentene, polypropylene, polyphenylene oxide, Examples thereof include resins such as polysulfone, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy.
A lubricant such as fluororesin particles, polyolefin resin particles, and silicone resin particles is added to these resins for the purpose of reducing the friction coefficient.
Specific examples of the fluororesin particles include polymers such as tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride and perfluoroalkyl vinyl ether, and copolymers thereof. Used.
Specific examples of polyolefin resin particles include homopolymers of olefins such as ethylene, propylene, and butene, copolymers with different olefins, or particles of heat-modified products thereof. Specifically, polyethylene, polypropylene, polybutene , Polyhexene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-hexene copolymer, and the like.
Specific examples of the silicone resin particles include a siloxane bond in a three-dimensional structure, a network structure, and a silicon atom substituted with an alkyl group, an aryl group, an amino-substituted alkyl group, a dialkyl silicone, or the like and insoluble in an organic solvent. Things.
The surface friction coefficient of the photoreceptor (7) provided with such a surface layer is generally about 0.1 to 0.3.
The surface friction coefficient of the intermediate transfer belt (1) varies depending on the roughness of the surface, but is generally about 0.35 to 0.7 from the material.
When such a photosensitive member and an intermediate transfer belt were used, the surface friction coefficient of the photosensitive member was lower than the surface friction coefficient of the intermediate transfer belt, so that worm erosion was prevented and good transfer efficiency could be obtained.
Furthermore, the secondary transfer roller (13) can be provided with a lubricant application device (30) to prevent the cleaning blade (27) from turning up.
As a result of investigating to what extent the difference in surface friction coefficient between the photoreceptor (7) and the intermediate transfer belt (1) has an effect on insect worms and transferability (transfer efficiency), the surface friction of the photoreceptor (7) Whatever the coefficient value, when the surface friction coefficient of the photoconductor (7) is lower than the surface friction coefficient of the intermediate transfer belt (1), it was found that the worm-eaten was within an allowable range. . The surface friction coefficient of the photoreceptor (7) and the intermediate transfer belt (1) was adjusted by adjusting the lubricant supply amount. The supply amount was adjusted by changing the pressure of the solid lubricant applied to the object, but there are other methods such as changing the contact time of the application mechanism to the object and changing the contact area. .

Next, the influence on the transfer efficiency was examined. As a result, the primary transfer efficiency is greatly affected by the difference in surface friction coefficient between the photoconductor (7) and the intermediate transfer belt (1), and the surface friction of the photoconductor (7) as compared with the intermediate transfer belt (1). It was found that the lower the coefficient, the higher the transfer efficiency. Therefore, by making the surface friction coefficient of the photoconductor (7) lower than the surface friction coefficient of the intermediate transfer belt (1), it was possible to prevent worm erosion and to obtain good transfer efficiency. The relationship between the surface friction coefficients can be achieved by making the amount of lubricant supplied to the intermediate transfer belt (1) smaller than the amount of lubricant supplied to the photoreceptor (7).
Further, the relationship between the surface friction coefficient of the intermediate transfer belt (1) and the secondary transfer roller (13) and the blade turning was investigated. By adjusting the amount of lubricant applied to the intermediate transfer belt and the secondary transfer roller, the respective surface friction coefficients were adjusted to the same value, and the ease of occurrence of blade turning was compared by continuously passing paper. As a result, the blade that is in contact with the secondary transfer roller is more likely to be turned over than the blade that is in contact with the intermediate transfer belt, and both blades are more likely to be turned up as the surface friction coefficient of the contacted object is higher. It turns out that it is easy to occur. Further, it can be seen that the secondary transfer roller blades are turned faster than the intermediate transfer belt blades. This indicates that the secondary transfer roller blade is more likely to be turned than the belt blade. Therefore, in order to prevent the secondary transfer roller from turning over, it is necessary that the friction coefficient of the roller be at least equal to or less than the friction coefficient of the belt. This indicates that when the friction coefficient of the intermediate transfer belt is set to a value that does not cause the intermediate transfer belt to be turned over, the secondary transfer roller is very effective in preventing the blade from turning up. .

Next, an example of toner production is shown below.
<Production Example 1>
(Synthesis of organic fine particle emulsion)
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and then an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The volume average particle size of the [fine particle dispersion 1] measured with a laser diffraction / scattering particle size distribution analyzer (LA-920: manufactured by Horiba, Ltd.) was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

(Adjustment of aqueous phase)
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white liquid. Got. This is designated as [Aqueous Phase 1].

(Synthesis of low molecular weight polyester 1)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were placed, polycondensed at 230 ° C. for 7 hours under normal pressure, and further 10-15 mmHg Was reacted for 5 hours under reduced pressure to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2300, a weight average molecular weight of 6700, a peak molecular weight of 3800, a Tg of 43 ° C., and an acid value of 4.

(Synthesis of intermediate polyester)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 7 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, a peak molecular weight of 3000, a Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53%.

(Synthesis of ketimine)
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 hours and half to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

(Synthesis of master batch)
1200 parts of water, 540 parts of carbon black (Printex35: manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

(Production of oil phase)
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 100 parts of paraffin wax (melting point 70 ° C.), and 947 parts of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring, and remains at 80 ° C. After holding for 5 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1], 30 parts of organically modified montmorillonite and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80 vol% Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to two passes by the bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] was 50%.

(Emulsification to solvent removal)
[Pigment / Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 7 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

(Washing-drying)
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(I): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(Ii): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (i), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered under reduced pressure.
(Iii): 100 parts of 10% hydrochloric acid was added to the filter cake of (ii), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(Iv): Add 300 parts of ion-exchanged water to the filter cake of (iii), mix with a TK homomixer (10 minutes at 12,000 rpm), and then filter twice. Obtained.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain [Toner Base Particles 1]. Thereafter, 100 parts of [Toner Base Particles 1] were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain the toner of Production Example 1.

<Production Example 2>
A toner of Production Example 2 was obtained in the same manner as Production Example 1 except that 30 parts of organically modified montmorillonite was changed to 0 part.

<Production Example 3>
A toner of Production Example 3 was obtained in the same manner as in Production Example 1 except that 30 parts of the organically modified montmorillonite was changed to 55 parts.

<Examples of developer production>
The toner of the above production example and the carrier of the following production method were mixed for 10 minutes with a tumbler mixer at a maximum stirring intensity of 1 kg, a toner concentration of 3 wt%, and a toner concentration of 12 wt%. Used for.
<Carrier manufacturing method>
Acrylic resin solution (solid content 50 wt%) 21.0 parts Guanamin solution (solid content 70 wt%) 6.4 parts Alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts Silicon resin solution [ Solid content 23wt%
(SR2410: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 65.0 parts aminosilane [solid content: 100 wt%
(SH6020: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 0.3 parts Toluene 60 parts Butyl cellosolve 60 parts are dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of acrylic resin and silicon resin containing alumina particles. It was. A fired ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 35 μm] was used as the core material, and the coating film forming solution was applied to the surface of the core material. It was applied by a Spira coater (Okada Seiko Co., Ltd.) so as to have a thickness of 0.15 μm and dried. The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain [Carrier 1]. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. The properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.

The evaluation methods / conditions listed in Table 2 are as follows.
(Decreased carrier charging ability)
Using a digital full-color copier (imageColor 2800 manufactured by Ricoh), running 30,000 image charts with a 50% image area in a monochrome mode in an environment of temperature 25 ° C and humidity 50%, and then partially sampling the developer Then, the amount of charge was measured by the blow-off method, and the amount of decrease in the charging ability of the carrier was evaluated. When the amount of change in the charge amount before and after running 30,000 sheets was less than 5 μc / g, it was evaluated as ◯, when 5-10 μc /, Δ when it exceeded 5-10 μc /. Further, in this test, the test was performed under two conditions when the toner concentration was 3 wt% and when the toner concentration was 12 wt%.

(Fixability evaluation)
Ricoh Co., Ltd. Copier with Teflon (registered trademark) roller as the fixing roller MF2200 A modified version of the fixing unit was used to create an unfixed image on Ricoh type 6200 paper (toner adhesion) An amount of 1.0 mg / cm ² , a rectangular solid image of ² cm × 7 cm) was passed through and a fixing test was performed.
The fixing temperature was changed by 5 ° C., and the cold offset generation temperature and the hot offset generation temperature were obtained. The evaluation conditions for low-temperature fixing are a paper feed linear velocity of 120 mm / sec, a surface pressure of 1.2 kgf / cm ² , a nip width of 3 mm, and the high temperature offset is an evaluation condition of a paper feed linear velocity of 50 mm / sec and a surface pressure. It was set to 2.0 kgf / cm ² and a nip width of 4.5 mm.
Table 3 shows the evaluation results of Examples and Comparative Examples performed by combining the above apparatus and toner.

注）中間転写ベルトの表面摩擦係数−感光体の表面摩擦係数

Note) Surface friction coefficient of intermediate transfer belt-Surface friction coefficient of photoconductor

The evaluation method is as follows.
In order to investigate how much the difference in surface friction coefficient between the photoconductor (7) and the intermediate transfer belt (1) has an effect on insect worms and transferability (transfer efficiency), the photoconductor (7) and intermediate transfer The surface friction coefficient of the belt (1) was determined by adjusting the lubricant supply amount. The supply amount was adjusted by changing the pressure of the solid lubricant applied to the object.
The worm-eating rank in Table 3 was classified based on the evaluation of the worm-eating occurrence level rank of the image after transfer.

Moreover, the cleaning property evaluation was performed as follows.
(1) The obtained toner and device are all left in an environmental room at 25 ° C. and 50% for one day.
(2) Remove all toner from Imagio neo C600 commercial product PCU, leaving only the carrier in the developing device.
(3) 28 g of black toner serving as a sample is put into a developing device including only a carrier, and 400 g of a developer having a toner concentration of 7% is prepared.
(4) A developing device is mounted on the Imagio neo C600 main body, and only the developing device is spun for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
(5) Both the developing sleeve and the photoconductor were rotated at 300 mm / s trailing, and the charging potential and the developing bias were adjusted so that the toner on the photoconductor was 0.6 ± 0.05 mg / cm ² .
(6) The cleaning blade was only one cleaning blade mounted on the Imagio neo C600 commercial product PCU, the elastic modulus was 70%, the thickness was 2 mm, and the contact angle with the image carrier at the counter was 20 °.
(7) Under the above development conditions, the transfer current is adjusted so that the transfer rate is 96 ± 2%.
(8) Using the above set values, 1000 charts (FIG. 8) with a band of 4 cm in the paper passing direction and 25 cm in the paper passing width direction were output.
(9) With respect to the last output image, the image quality of the white paper portion in the printing paper feeding direction center portion and the width direction center portion was evaluated, and the presence or absence of occurrence of an abnormal image due to defective cleaning was evaluated.
(10) For evaluation of the output image, an image ID (X-RITE 938, v-value manufactured by X-RITE) was measured.
(11) When the image ID after passing paper is 0.01 or less compared to the image ID of paper that has not passed, the cleaning performance is OK (◯), and when the image ID is higher than that, the cleaning performance NG (×) Rank evaluation. Next, the photosensitive member and the intermediate transfer belt were observed, and the cleaning properties of the photosensitive member and the intermediate transfer belt were ranked based on the toner adhesion state after the visual cleaning.

It is SF-1 measurement conceptual diagram. It is SF-2 measurement conceptual diagram. 1 is a schematic view of a main part of an image forming apparatus showing an embodiment of the present invention. It is sectional drawing of the image formation unit which shows one Embodiment of this invention. It is explanatory drawing which shows an example of a lubricant supply means. It is explanatory drawing which shows the other example of a lubricant supply means. It is explanatory drawing which shows the other example of a lubricant supply means. It is the chart used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transfer belt 2 Roller 3 Roller 4 Roller 5 Roller 6a 1st image formation unit 6b 2nd image formation unit 6c 3rd image formation unit 6d 4th image formation unit 7 Photoconductor 7a Photoconductor 7b Photoconductor 7c Photoconductor 7d Photoconductor 8 Charging roller 9 Laser writing unit 10 Developing device 11 Transfer roller 12 Cleaning device 13 Secondary transfer roller 14 Registration roller 15 Conveying belt 16 Fixing device 20 Belt cleaning device 21 Cleaning blade 22 Backup roller 27 Cleaning blade 30 Lubricant coating device 31 Application Brush 32 Lubricant unit 33 Lubricant 34 Spring 35 Weight L Laser beam P Recording material

Claims (7)

An image carrier on which a toner image corresponding to image information is formed, an intermediate transfer member in contact with the image carrier, a primary transfer means for transferring the toner image on the image carrier to the intermediate transfer member, In an image forming apparatus having a secondary transfer unit that collectively presses a toner image that is pressed against the intermediate transfer member and transferred and held on the intermediate transfer member to a recording medium, the surface friction coefficient of the image carrier is the intermediate transfer member below the surface friction coefficient of, and, as a toner, an aspect ratio of 0.80 to 0.90, an image forming apparatus which is characterized by using a toner containing a paraffin wax base particles . The toner has base particles containing a paraffin wax having a melting point of 60 ° C. or higher and 90 ° C. or lower and a binder resin, and the base particles have an endothermic amount derived from the paraffin wax of an endothermic peak in DSC measurement. 2. The image forming apparatus according to claim 1, wherein the image forming apparatus has an average circularity of 0.950 or more and 0.980 or less and 5 J / g or more and 5.5 J / g or less. The toner base particles are dispersed in an aqueous medium, at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a dispersion in which the paraffin wax and an inorganic filler are dispersed in an organic solvent. The polyester prepolymer is obtained by crosslinking reaction and / or elongation reaction, and the base particle has a shape factor SF1 of 130 or more and 160 or less, and a shape factor SF2 of 110 or more and 140 or less. The image forming apparatus according to claim 1. 4. The toner according to claim 1, wherein the toner has a weight average particle diameter of 3 μm or more and 8 μm or less, and a ratio of the weight average particle diameter to the number average particle diameter of 1.00 or more and 1.30 or less. An image forming apparatus according to claim 1. The image forming apparatus according to claim 1, wherein the inorganic filler in the toner is montmorillonite or a modified product of montmorillonite. The image forming apparatus according to claim 1, wherein the toner has a glass transition point of 40 ° C. or more and 60 ° C. or less. The image forming apparatus according to claim 1, wherein the toner contains 1 to 10% by weight of the base particles having a particle diameter of 2 μm or less.

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