JP4227538B2 - Color toner - Google Patents

Description

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

  In recent years, copiers and printers have been sought to be smaller, lighter, faster, and more reliable due to demands for space and energy savings. Machines are composed of simpler elements in various ways. It is becoming. As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, a superior machine cannot be realized.

  For example, various methods and apparatuses have been developed for fixing a toner image on a sheet such as paper. Conventionally, for the purpose of preventing the toner from adhering to the surface of the fixing member, the toner is formed of a material having excellent releasability, and the surface of the releasable material such as silicone oil is used to prevent offset and roller surface fatigue on the surface. The roller surface is coated with a good liquid film.

  However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device is complicated because an apparatus for supplying the liquid for preventing offset is necessary. This is opposite to the reduction in size and weight, and silicone oil may evaporate due to heat and contaminate the interior of the machine. Therefore, instead of using a silicone oil supply device, instead of trying to supply an anti-offset liquid from the toner during heating, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner was proposed. Has been.

  The effect of including a release agent in the toner is not so much pressure at the time of fixing, and appears prominently in the fixing configuration in which the release agent is deposited on the toner surface by melting and fixed, but in the vicinity of the toner surface. If no release agent is present, the releasability with the fixing member cannot be sufficiently exhibited and the fixability is poor. Especially in today's colorization, in order to express colors by mixing colors, a large amount of toner is inevitably fixed at one time, so the use of a release agent having a low melting point effective for fixing becomes a problem.

  Furthermore, for toners containing a release agent by the pulverization method, the release agent present in the vicinity of the toner surface is significantly different in charging performance from resin, so no matter how highly charged material can be put in the resin, charging is necessary. It was difficult to make it uniform. In addition, if a large amount of release agent is present in the vicinity of the toner surface, the release agent will contaminate the charging member, such as the developing sleeve and carrier, that the toner will rub against strongly during long-term printing of a plurality of sheets, thereby reducing developability. There was something to do. As described above, since the amount of the release agent in the vicinity of the toner surface affects the overall electrophotographic characteristics, it is important that the release agent exists in the vicinity of the toner surface in a balanced manner.

  In an apparatus using an intermediate transfer member, the toner shape has a great influence on the transfer. In particular, the effect of residual toner due to repeated transfer multiple times is large. If there is a large amount of residual toner, the load on the main body, such as the collection system, will increase, and the amount of toner used per sheet will increase. . Therefore, a method for increasing the transfer efficiency by making the shape as spherical as possible is effective.

  On the other hand, as a full-color transfer material, in addition to ordinary paper and overhead projector film (OHP), there is an increasing need for various materials to be used on cardboard, card, postcard and other small-size paper. The transfer method using is becoming effective. In a system that normally uses an intermediate transfer member, it is necessary to transfer the developed color image of the toner from the photosensitive member to the intermediate transfer member, and then transfer it again from the intermediate transfer member onto the transfer material, which is compared with the conventional method. Therefore, it is necessary to increase the toner transfer efficiency more than before. In particular, in the case of using a full-color copying machine that transfers a plurality of toner images after development, the amount of toner on the photoconductor increases as compared with the case of one-color black toner used in a black-and-white copying machine. It is difficult to improve the transfer efficiency only with use.

  Therefore, in recent years, as one of the techniques for increasing the transfer efficiency, the toner shape has been made closer to a spherical shape. For example, a polymerization toner such as suspension polymerization or emulsion polymerization, a method of spheroidizing a pulverized toner in a solvent (for example, see Patent Document 1), a method of spheronizing with hot air (for example, see Patent Document 2), mechanical impact A method of making a sphere by force (for example, see Patent Document 3) is known. These techniques are very effective techniques for improving transfer efficiency.

  However, in the case of polymerized toner, the release agent is inevitably included, so that when the pressure is not so much applied during fixing (for example, in the case of surf fixing), the release agent is difficult to come out on the toner surface and the fixability is poor. become. In addition, when the pulverized toner is made spherical, the release agent is likely to be eluted on the toner surface by a solvent or heat, and the amount of the release agent present on the surface is increased more than necessary. Nara Machinery's hybrid system, Hosokawa Micron's mechano-fusion system, Kawasaki Heavy Industries' kryptron system, Nisshin Engineering's super rotor, etc. The device that gives a mechanical impact force, as it appears, does not seem to have a large amount of heat at first glance. However, when trying to obtain particles that are nearly spherical, in fact, a considerable amount of heat is given to the particles to be processed, and the resulting toner particles Actually, it adversely affects the electrophotographic characteristics. Furthermore, the fine powder generated during the pulverization process adheres to or is driven into the toner surface, which is a harmful effect of promoting spheroidization, and if the heat is not increased, particles close to a sphere cannot be obtained. There were also challenges. If these fine powders are not processed, such fine powders are difficult to classify, and thus cannot be avoided as they are mixed in the product as toners, which also have an adverse effect on electrophotographic characteristics.

From the above, further improvement for the toner containing the release agent in the pulverization method, particularly the toner containing the release agent having a low melting point has a great influence on the electrophotographic characteristics, and therefore further improvement of the toner is required. It was.
Japanese Patent Laid-Open No. 11-44969 JP 2000-029241 A Japanese Patent Laid-Open No. 7-181732

  The present invention has been proposed to solve the above problems.

  Another object of the present invention is to provide a color toner which is excellent in contamination of the developing sleeve and has a sufficient fixable region.

  Another object of the present invention is to provide a color toner capable of obtaining sufficient developability even in continuous durability.

  Another object of the present invention is to provide a color toner that has high transfer efficiency, suppresses scattering, can be easily easily cleaned, and can easily form a beautiful pictorial full-color image. is there.

That is, the present invention is a color toner containing at least a binder resin, a colorant, and a release agent,
The color toner is a toner that has been surface-treated using a batch-type surface treatment device,
The surface treatment device continuously discharges and removes fine powder having a predetermined particle diameter or less to the outside of the device, surface treatment means for performing surface treatment of toner particles using a mechanical impact force, the classification device, and the classification device An apparatus having a guide means for partitioning a space between the surface treatment means into a first space and a second space,
The particles to be treated are introduced into the first space and classified by the classification means, the classified particles are introduced into the surface treatment means via the second space and subjected to the surface treatment, and further the surface treatment The toner obtained by performing the surface treatment by repeating the surface modification treatment using classification and mechanical impact force for a certain period of time by circulating the particles again to the first space,
The color toner is
(I) the binder resin includes at least a polyester unit;
(Ii) The color toner has a weight average particle diameter of more than 6.5 μm and not more than 11 μm,
(Iii) The color toner has an average circularity A of 0.915 ≦ A ≦ 0.960 in particles having an equivalent circle diameter of 3 μm or more,
(Iv) The color toner has a transmittance B (%) in a 45 volume% methanol aqueous solution of 10 ≦ B ≦ 70,
(V) The color toner has one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C. in the endothermic curve in differential scanning calorimetry (DSC) measurement, and the temperature of the maximum endothermic peak in the endothermic peak. The present invention relates to a color toner, wherein Tsc is 65 ° C. <Tsc <105 ° C.

  According to the present invention, it is possible to obtain a color toner that has a high transfer efficiency and suppresses scattering, can be easily cleaned easily, and can easily form a beautiful pictorial full-color image.

  As a result of intensive studies, the present inventors have found that a color toner that solves the aforementioned problems can be obtained by balancing the shape of the color toner and the amount of various materials present on the surface of the color toner. The present invention has been completed.

  In the present invention, the desired color toner shape means that the average circularity A is 0.915 ≦ A ≦ 0.960, preferably 0.920 ≦ A ≦ 0, in particles having an equivalent circle diameter of 3 μm or more of the color toner. .945, more preferably 0.923 ≦ A ≦ 0.943. If the value of A is less than 0.915, the transferability, particularly the transfer efficiency, is inferior. On the other hand, if the value of A is greater than 0.960, the cleaning blade slips through the photosensitive drum to cause image defects due to poor cleaning. It tends to occur.

  In the present invention, the amount of the release agent on the surface of the color toner is controlled.

  The amount of the release agent in the vicinity of the color toner surface can be easily and accurately grasped with respect to the entire color toner particles by measuring the transmittance in a 45 volume% methanol aqueous solution. In this measurement method, color toner is forcibly dispersed once in a mixed solvent to easily influence the surface abundance of the release agent for each color toner particle, and the transmittance after a certain time is measured. By doing so, it is possible to accurately grasp the surface existing amount of the release agent in the entire color toner. In other words, when a large amount of hydrophobic release agent is present on the toner surface, it becomes difficult to disperse in the solvent and agglomerates, resulting in a high transmittance. On the contrary, if the release agent is not present on the toner surface, the polyester unit of the binder resin that is hydrophilic occupies the surface, so that it is uniformly dispersed and the transmittance becomes a small value.

  In the present invention, the desired transmittance is such that the transmittance B (%) in an aqueous solution of 45% by volume of methanol is 10 ≦ B ≦ 70, preferably 15 ≦ B ≦ 50. If the value of B is less than 10, the release agent on the toner surface is small and the releasing effect is difficult to appear at the time of fixing, so that it is difficult to perform low-temperature fixing, which is desired from the viewpoint of energy saving. Requires the required load. On the other hand, if it is larger than 70, there are many release agents on the toner surface, which contaminates the member in contact with the toner and, for example, fuses it onto the developing sleeve to increase the resistance, reducing the effectiveness of the actual development bias for development. The image density may decrease.

  Here, in comparison with the physical properties of conventional color toners, in color toners and polymerized toners that do not use a release agent, since the hydrophobic release agent does not exist on the toner surface, the transmittance becomes small, and the transmittance B is less than 10. Even if a release agent is used, if the amount is small or if the toner has a melting point or maximum endothermic peak of 105 ° C. or higher, the transmittance decreases and the transmittance B becomes less than 10%. It becomes insufficient for sex.

  In addition, as described above, the present invention also defines other performances of the color toner, specifically, the endothermic peak temperature of the color toner.

And the temperature of the desired endothermic peak in the present invention, in the endothermic curve in the color differential scanning thermal weight analysis of toner (DSC) measurement of the present invention, has one or more endothermic peaks in a temperature range of 30 to 200 ° C. The peak temperature Tsc of the maximum endothermic peak in the endothermic peak is in the range of 65 ° C. <Tsc <105 ° C., more preferably in the range of 70 ° C. <Tsc <90 ° C. This is because if Tsc is 65 ° C. or lower, the blocking property is inferior, and if it is 105 ° C. or higher, low-temperature fixing desired from the viewpoint of energy saving becomes difficult, and a considerable pressure is required also in the fixing device configuration.

  The primary factor that determines the value of the peak temperature Tsc of the maximum endothermic peak of this color toner is the release agent, and the endothermic peak value is appropriately adjusted by considering the type of the release agent. Can do.

  In the present invention, in order to obtain a color toner having the desired shape and performance as described above, in the process of producing the color toner, a step of applying a mechanical impact force while discharging the generated fine powder out of the system (this The present inventors have confirmed that it is effective to apply the details of the process described below. In other words, in the pulverization step and the spheronization step, even if each step is performed alone or both steps are performed simultaneously, if the generated fine powder is not discharged while being discharged out of the system, Since a very small fine powder generated during the spheronization process aggregates and causes irregularities in the particle shape, a mechanical impact force is required more than necessary to achieve the desired sphericity, resulting in an excess amount of heat and resulting in a toner surface. As a result, the amount of the mold release agent increases, causing a harmful effect. In addition, the small fine powder is one of the major factors that worsen the spent on the carrier used in the two-component developer. When the particles pulverized by the mechanical impact force are put on an air stream as they are and introduced into the classifying section without stopping the air stream, the fine powder is efficiently discharged out of the system without re-aggregation. From the above, when a mechanical impact force is applied while discharging the generated fine powder out of the system, the toner shape, the fine powder amount, and the amount of the release agent can be controlled as desired. Thus, the color toner of the present invention that satisfies the above requirements obtained by considering the balance between the degree of the sphere and the amount of the release agent etc. on the surface of the color toner is not simply formed into a sphere. The problems of the conventional color toner described above can be solved.

  When color toner is manufactured by a method different from the above manufacturing method, the average circularity A and transmittance B defined in the present invention are as follows, for example.

  When a color toner using a release agent is manufactured by an air jet method, the average circularity A is less than 0.915 although the desired transmittance B can be in the range of 10 ≦ B ≦ 70. Therefore, the desired value cannot be obtained.

  When color toners are manufactured using a spheroidization method such as a hybridization system manufactured by Nara Machinery Co., Ltd., it is impossible to remove the fairly small fine powder generated during pulverization, so the rotational speed is increased more than necessary, or the residence time is increased. As a result, too much heat is applied as a result, the amount of wax on the toner surface increases, and the value of the transmittance B exceeds 70.

  Also, when color toners are manufactured using a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nissin Engineering Co., Ltd. Too much is given, and the value of the transmittance B exceeds 70.

  Further, when a color toner is manufactured using a surfing system manufactured by Nippon Pneumatic Co., Ltd., which is heated by applying heat to make it spherical, of course, since the amount of heat is considerable, the value of the transmittance B is 70. It will exceed.

  In the color toner of the present invention, a more preferable color toner can be obtained by satisfying the requirement defining the relationship between the toner particle size and the ratio of the toner having a high sphericity in addition to the above-described requirements.

  The color toner of the present invention has a weight average particle size of more than 6.5 μm and 11 μm or less. When the weight average particle diameter is 6.5 μm or less, toner aggregation or fog tends to occur, and when the weight average particle diameter exceeds 11 μm, it is difficult to obtain a high-definition image. turn into. The color toner of the present invention preferably has a weight average particle diameter of 6.7 to 9.5 μm.

  In the color toner of the present invention, the effect of the present invention can be further enhanced by controlling the relationship between the color toner particle size and the ratio of the color toner having a high sphericity. Specifically, as shown in FIG. 1, for example, the weight average particle diameter X (μm) of the color toner and the number-based cumulative value Y (%) of particles having a circularity of 0.960 or more are −X + 20 ≦ Y ≦ −. It is preferable to satisfy X + 70. Furthermore, it is preferable that −X + 20 ≦ Y ≦ −X + 50 is satisfied. The meaning of this formula is to define the size of the color toner and the ratio of the color toner with high sphericity in the color toner, and shows a suitable region for achieving both developability and transferability. Is. In order to improve developability, it is important to reduce contamination on the developing sleeve. To that end, it is preferable that the toner packing property is low, and the color toner particle size is large or the color toner has a low sphericity. Is good. On the other hand, in order to improve transfer efficiency such as transfer efficiency and scattering, a higher color toner sphericity is preferable. A smaller color toner particle size is better in terms of image quality such as dot reproducibility. Specifically, when the number-based cumulative value of particles having a circularity of 0.960 or more is larger than 60%, the color toner packing property tends to increase and the release agent contamination to the developing sleeve tends to increase. If the number-based cumulative value of particles having a circularity of 0.960 or more is less than 9%, the transfer efficiency tends to decrease or the scattering tends to be significant.

  In the present invention, the average circularity A, the transmittance B, the weight average particle diameter X, the number-based cumulative value Y of the circularity of 0.960 or more, and the maximum endothermic peak temperature Tsc are measured as follows. Do. In addition, it measured similarly also in the below-mentioned Example.

<Measurement of Average Circularity A and Number-Based Cumulative Value Y of Particles Above 0.960>
The equivalent circle diameter, circularity, and frequency distribution of the color toner are used as a simple method for quantitatively expressing the shape of the color toner particles. In the present invention, the flow type particle image measuring device “FPIA-2100” is used. Measurement is performed using “type” (manufactured by Sysmex Corporation), and calculation is performed using the following formula.

  Here, the “particle projected area” is the area of the binarized color toner particle image, and the “perimeter of the particle projected image” is the contour line obtained by connecting the edge points of the color toner particle image. Define length. The circularity in the present invention is an index indicating the degree of unevenness of the color toner particles, and is 1.000 when the color toner particles are perfectly spherical, and the circularity becomes smaller as the surface shape becomes more complicated. .

  In the present invention, the average circularity C, which means the average value of the circularity distribution, is calculated from the following equation, where the circularity (center value) at the dividing point i of the particle size distribution is ci and the frequency is fci.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  The shape of the color toner particles is measured using the flow type particle image measuring device, and the concentration of the dispersion is readjusted so that the color toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. 1000 or more are measured. After the measurement, using this data, data of 3 μm or less is cut, and the number reference cumulative value Y of 0.960 or more is obtained from the average circularity A or circularity frequency distribution of the color toner particles.

<Transmittance B in methanol 45 volume% aqueous solution>
(I) Preparation of Color Toner Dispersion An aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), 20 mg of color toner is infiltrated on the liquid surface and the bottle is covered. Then, shake for 5 seconds at 150 reciprocations / minute with a Yayoi-type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. And it is shaken once forward and backward once, and when returning to just above, it counts as one reciprocation. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after standing for 30 seconds is used as a measurement dispersion.

(Ii) Transmittance measurement The dispersion obtained in (i) is placed in a 1 cm square quartz cell, and the transmittance at a wavelength of 600 nm of the dispersion after 10 minutes using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation) ( %) (See next formula).
Transmittance B (%) = I / I ₀ × 100
(I ₀ is the incident light beam, and I is the transmitted light beam.)

<Measurement of particle size of color toner>
In the present invention, Coulter Multisizer (manufactured by Coulter, Inc.) can be used for the average particle size and particle size distribution of the color toner. As the electrolytic solution, a 1% NaCl aqueous solution prepared using primary sodium chloride may be used. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) may be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles of 2.00 μm or more are measured by using the 100 μm aperture as the aperture by the measuring device. The distribution and the number distribution are calculated to determine the weight average particle diameter (D4) (the median value of each channel is the representative value for each channel).

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

<Measurement of maximum endothermic peak Tsc of color toner>
The maximum endothermic peak Tsc of the color toner is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DCS-7 (manufactured by PerkinElmer) or DSC2920 (manufactured by TA Instruments Japan). .

The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. It is put in an aluminum pan, an empty aluminum pan is used as a reference, and the temperature is raised and lowered as follows within a measurement range of 30 to 200 ° C.
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)

  The maximum endothermic peak of the color toner is the one having the highest height from the baseline in the region above the Tg endothermic peak of the color toner in the process of temperature increase II, or the endothermic peak of Tg of the color toner is different. When it is difficult to discriminate overlapping with the endothermic peak, the maximum peak of the overlapping peak is the highest endothermic peak of the color toner of the present invention.

  Next, the binder resin contained in the color toner of the present invention will be described.

The binder resin contained in the color toner of the present invention includes the following groups (a) to (f):
(A) polyester resin,
(B) a hybrid resin having a polyester unit and a vinyl polymer unit;
(C) a mixture of a hybrid resin and a vinyl polymer;
(D) a mixture of a polyester resin and a vinyl polymer;
(E) a mixture of a hybrid resin and a polyester resin;
(F) a mixture of a polyester resin, a hybrid resin and a vinyl polymer;
Is preferably selected from. In particular, it is preferable to use a binder resin containing a hybrid resin.

  In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl monomer constituting the vinyl polymer unit is a monomer component having a vinyl group. A monomer having a polyvalent carboxylic acid component and a vinyl group or a monomer having a polyhydric alcohol component and a vinyl group is defined as a “polyester monomer”.

  The binder resin preferably has a main peak (MP) at a molecular weight of 3,500 to 30,000 in a molecular weight distribution measured by gel permeation chromatography (GPC), and a molecular weight of 5,000 to 20 It is more preferable to have it at 1,000. Moreover, it is preferable that ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 5.0 or more.

  When the main peak is in a region having a molecular weight of less than 3,500, the hot offset resistance of the toner tends to be poor. On the other hand, when the main peak is in a region having a molecular weight exceeding 30,000, the low temperature of the toner is low. It tends to be inferior in terms of fixability, making it difficult to apply to high speed fixing. Moreover, when Mw / Mn is less than 5.0, it becomes difficult to obtain good offset resistance.

  In the present invention, the molecular weight distribution is measured by GPC measurement as follows. In addition, it measured similarly also in the below-mentioned Example.

<Molecular weight distribution by GPC measurement>
The molecular weight distribution by GPC in the resin component is measured by GPC using a THF-soluble component obtained by dissolving a sample in a THF (tetrahydrofuran) solvent as described below.

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

The GPC measurement of the sample prepared by the above method was performed by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min. Is measured by injecting about 50 to 200 μl. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. The molecular weights made are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ⁴ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8 It is suitable to use a standard polystyrene sample of at least about 10 points, using .6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ . An RI (refractive index) detector is used as the detector.

As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to use a combination of a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802 manufactured by Showa Denko KK , 803, 804, 805, 806, and 807, and combinations of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters.

  Next, the material of the binder resin will be described.

  As a polyester monomer for producing a polyester resin or a polyester unit, alcohol and carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester can be used as raw material monomers.

  Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

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

  Examples of the carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;

  Among the above, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component (for example, a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof) Polyester resins obtained by condensation polymerization of fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and the like as acid components are preferable because they have good charging characteristics.

  Furthermore, in the present invention, when a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved release agent dispersibility, low-temperature fixability, and offset resistance can be expected. .

  In the binder resin, the “hybrid resin component” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.

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

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

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  The vinyl resin or vinyl polymer unit of the binder resin referred to in the present invention may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.

  Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. Examples of diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 , Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing methacrylates with acrylates; diacrylate compounds linked by a chain containing an aromatic group and an ether bond For example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the above compounds The thing which replaced the acrylate with the methacrylate is mentioned.

  As polyfunctional cross-linking agents, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and acrylates of the above compounds are replaced by methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

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

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

  Examples of the polymerization initiator used for producing the vinyl polymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvalero). Nitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1, 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl- 4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexane Ketone peroxides such as Sanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl Peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, -N-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t -Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy Benzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhexa Idro terephthalate, di -t- butyl peroxy azelate and the like.

  Next, the manufacturing method of the hybrid resin used for the binder resin of this invention is demonstrated. The hybrid resin of the present invention can be produced by the production methods shown in the following (1) to (5).

  (1) A vinyl polymer and a polyester resin are separately produced, then dissolved and swollen in a small amount of an organic solvent, an esterification catalyst and an alcohol are added, and the mixture is heated to perform a transesterification reaction and synthesized.

  (2) A method for producing a polyester resin and a hybrid resin component in the presence of a vinyl polymer after the production of the vinyl polymer. The hybrid resin component is produced by a reaction between a vinyl polymer (a vinyl monomer can be added if necessary), a polyester monomer (alcohol, carboxylic acid), a polyester resin, or both. . Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer and a hybrid resin component in the presence of the polyester resin after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer.

  (4) After the vinyl polymer and the polyester resin are produced, the hybrid resin component is produced by adding one or both of the vinyl monomer and the polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. The Also in this case, an organic solvent can be appropriately used.

  (5) A vinyl polymer unit, a polyester resin, and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate.

  Further, after producing the hybrid resin component by the production method of (1) to (4) above, either one or both of a vinyl monomer and a polyester monomer (alcohol, carboxylic acid) are added to perform addition polymerization and condensation polymerization reaction. The vinyl polymer and the polyester resin may be added by performing at least one of the above.

  In the above production methods (1) to (5), a polymer unit having a plurality of different molecular weights and crosslinking degrees can be used for the vinyl polymer and the polyester unit.

  The glass transition temperature of the binder resin contained in the color toner of the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the binder resin is preferably 1 to 40 mgKOH / g.

  In the present invention, the proportion of the polyester unit in the binder resin is preferably in the range of 50 to 100% by mass.

  Next, the following are mentioned as a mold release agent used for this invention.

  Low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; block of aliphatic hydrocarbon wax Copolymers; waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.

  Examples thereof include a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  Particularly preferred waxes are aliphatic hydrocarbon waxes such as paraffin wax, polyethylene, and Fischer-Tropsch wax, which have a short molecular chain and little steric hindrance and excellent mobility.

  In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 350-2400, more preferably in the region of 400-2000. By giving such a molecular weight distribution, favorable thermal characteristics can be imparted to the color toner. The maximum endothermic peak temperature of the wax is preferably 63 ° C. or higher and lower than 105 ° C., more preferably 70 ° C. or higher and lower than 90 ° C.

  The addition amount of the release agent used in the present invention is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the binder resin. This is because if the amount is less than 1 part by mass, a sufficient amount of heat and pressure are required because the amount is small in order to come out on the surface of the color toner and exhibit the releasability when melted. On the other hand, when the amount exceeds 10 parts by mass, the amount of the release agent in the color toner is too large, and the transparency and charging characteristics tend to be inferior.

  Next, the colorant contained in the color toner of the present invention will be described.

  As the colorant used in the present invention, pigments and / or dyes can be used.

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

  Such a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

  Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. are mentioned.

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

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

  In addition, the usage-amount of a coloring agent is 0.1-60 mass parts with respect to 100 mass parts of binder resin, Preferably it is good to make it contain 0.5-50 mass parts.

  Further, the color toner of the present invention may contain a known charge control agent.

  Examples of the charge control agent include organometallic complexes, metal salts, and chelate compounds such as monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. In addition, carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic acid anhydrides and esters, and condensates of aromatic compounds are also included. In addition, phenol derivatives such as bisphenols and calixarene are also used. Preferably, a metal compound of an aromatic carboxylic acid is used from the viewpoint of rising of charge.

  The addition amount of the charge control agent used in the present invention is 0.3 to 10 parts by mass, preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the binder resin.

  If the amount is less than 0.3 parts by mass, the effect of charging rise cannot be obtained. Conversely, if the amount is more than 10 parts by mass, environmental fluctuation increases.

  The color toner of the present invention may contain a fluidizing agent.

  For example, after passing through a pulverization / classification step, a color toner having excellent fluidity can be obtained by mixing a fluidizing agent or the like with a mixer such as a Henschel mixer.

  Any fluidizing agent can be used as long as it can be added to the colorant-containing binder resin particles to increase the fluidity before and after the addition. For example, fluorinated resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine process silica such as dry process silica, silane compound, and organic Examples include treated silica that has been surface-treated with a silicon compound, a titanium coupling agent, silicone oil, and the like.

  The dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is called so-called dry process silica or fumed silica, and is manufactured by a conventionally known technique. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. . The average particle size is preferably in the range of 0.001 to 2 μm, particularly preferably silica fine powder in the range of 0.002 to 0.2 μm.

  As the titanium oxide fine powder, fine particles of titanium oxide obtained by a low-temperature oxidation method (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate are used. It is done. As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  In addition, the alumina fine powder includes the buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride Alumina fine powder obtained by flame decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type, amorphous type, α, δ, γ, θ, mixed crystal can be used. A mold or an amorphous material is preferably used.

  Further, as the silica subjected to the above surface treatment, those obtained by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with inorganic fine powders are used. Specifically, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchloro. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisilo Xan, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit It is done. These are used alone or in a mixture of two or more.

  Further, as the fluidizing agent used in the present invention, the above-described dry process silica may be used after being treated with a coupling agent having an amino group or silicone oil.

The fluidizing agent used in the present invention has good results when the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more, preferably 50 m ² / g or more. The fluidizing agent is added in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the color toner.

  As described above, the color toner of the present invention configured as described above uses a binder resin containing a polyester unit having good charge rise characteristics, and the transmittance B is set to a desired range. As a result, the contamination of the sleeve can be reduced and the developability can be improved synergistically. Further, by setting the value of the average circularity A within a desired range, the transfer efficiency can be increased and the running cost can be reduced. Moreover, by setting the value of Tsc in the DSC measurement within a desired range, it is excellent in low-temperature fixability and can contribute to energy saving.

  Furthermore, the color toner of the present invention that satisfies the requirement defining the relationship between the weight average particle diameter X and the Y representing the ratio of the circularity has reduced packing property, reduced sleeve contamination, and improved developability. It will be.

  The color toner described above can be suitably used for non-magnetic one-component development.

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

  The coated carrier obtained by coating the surfaces of the magnetic carrier particles with a resin can be particularly preferably used in a developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particle, and a method in which the magnetic carrier core particle and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particle include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural.

  The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. These carriers have an average particle diameter of 10 to 100 μm, preferably 20 to 70 μm.

  When the two-component developer is prepared by mixing the color toner of the present invention and the magnetic carrier, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the color toner concentration in the developer. Then usually good results are obtained. If the color toner density is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  Even when the color toner of the present invention is used for one-component development, good results can be obtained because it is resistant to sleeve contamination.

<About the production method of the color toner of the present invention>
Next, a procedure for producing the color toner of the present invention will be described.

  First, in the raw material mixing step, as a toner internal additive, at least a binder resin, a colorant, and a release agent are weighed and mixed and mixed. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the binder resin, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd. or the like. After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal class turbo plex (manufactured by Hosokawa Micron Co., Ltd.), and the weight average particle size A classified product of 4 to 11 μm is obtained.

  If necessary, surface modification (= spheroidizing treatment) can be performed in the surface modification process, for example, a hybridization system manufactured by Nara Machinery Co., Ltd., a mechano-fusion system manufactured by Hosokawa Micron Co., Ltd. is used as a classified product You can also.

  However, as a preferable production process of the color toner of the present invention, mechanical pulverization is not used in the pulverization process, but after pulverization with an air jet pulverizer, classification and mechanical impact force shown in FIGS. 2 and 3 are used. It is to obtain a classified product having a weight average particle diameter of 4 to 11 μm using the apparatus A that simultaneously performs the surface modification treatment.

  In addition, you may use sieving machines, such as a high volta of a wind-type sieve (made by Shin Tokyo Machine Co., Ltd.) as needed. Furthermore, when processing with an external additive, a high-speed stirrer that gives a shearing force to powder such as a Henschel mixer or a super mixer is blended with a predetermined amount of classified toner and various known external additives. Can be used as The color toner of the present invention can be obtained by stirring and mixing.

  Here, the apparatus A used in the present invention will be described in detail below.

  As shown in FIG. 2, in the surface reforming apparatus, a casing 30, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, a casing 30, which is attached to the central rotating shaft, and has a square disk on the upper surface. Alternatively, a plurality of cylindrical pins 40 are provided, and a dispersion rotor 36 (surface modification means, see also FIG. 3), which is a disk-like rotating body that rotates at high speed, is held at a constant interval on the outer periphery of the dispersion rotor 36. Liner 34 provided with a number of grooves on the surface on which it is disposed (note that there may be no grooves on the liner surface), and means for classifying the surface-modified raw material into a predetermined particle size The classifying rotor 31, the cold air inlet 35 for introducing cold air, the raw material supply port 33 for introducing the raw material to be treated, and the surface modification time can be freely opened and closed. What An installed discharge valve 38, a powder discharge port 37 for discharging processed powder, a fine powder discharge port 32 for discharging fine powder, a classification rotor 31 as classification means, and a dispersion rotor as surface modification means The space between the 36-liner 34 is a first space 41 before being introduced into the classifying means, and a second space 42 for introducing the particles from which fine powder has been removed by the classifying means into the surface treatment means. It is comprised from the cylindrical guide ring 39 which is a guide means to partition into. A gap portion between the dispersion rotor 36 and the liner 34 is a surface modification zone, and a classification rotor 31 and a rotor peripheral portion are classification zones.

  As described above, the batch type surface reforming apparatus includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the apparatus, a surface treatment means using a mechanical impact force, and the classifying means and the surface. Guide for partitioning the space between the processing means into a first space before being introduced into the classification means and a second space for introducing the particles from which fine powder has been removed by the classification means into the surface treatment means Means.

  Then, using this surface modification device, the finely pulverized product is introduced into the first space, and the fine particles having a predetermined particle diameter or less are continuously discharged and removed from the device by the classifying means, while passing through the second space. Then, it is introduced into the surface treatment means using mechanical impact force, surface modification treatment is performed, and the surface modification treatment using mechanical impact force is repeated for a certain period of time by circulating again to the first space. When the step is performed, a surface-modified color toner having a desired shape and performance from which fine powder having a predetermined particle diameter or less is removed can be obtained.

  The process will be described more specifically with reference to FIGS.

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

As a result of investigations by the present inventors, it has been found that the time until the discharge valve is opened (cycle time) and the rotational speed of the dispersion rotor are important in controlling the sphericity and the amount of the surface release agent. To increase the sphericity, it is effective to increase the cycle time or increase the peripheral speed of the dispersion rotor. In order to keep the amount of the surface release agent low, it is effective to shorten the cycle time or lower the peripheral speed. In particular, it is necessary to lengthen the cycle time because the spherical shape cannot be efficiently spheroidized unless the peripheral speed of the dispersed rotor exceeds a certain level. In this case, considering the relationship with the amount of surface release agent, the peripheral speed And cycle time need to be set. In the present invention, the peripheral speed is 1.2 × 10 ⁵ mm / sec or more, and the cycle time is effectively 5 to 60 seconds.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example of hybrid resin production)
As a monomer for forming a vinyl polymer unit, 2.0 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.14 mol of fumaric acid, 0.03 mol of a dimer of α-methylstyrene, and dicumyl peroxide as a polymerization initiator 0.05 mol is put into the dropping funnel. Moreover, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4) are used as monomers for forming the polyester unit. -Hydroxyphenyl) propane 3.0 mol, terephthalic acid 3.0 mol, trimellitic anhydride 1.9 mol, fumaric acid 5.0 mol and 0.2 g of dibutyltin oxide as a catalyst are placed in a 4-liter 4-neck flask made of glass. A thermometer, a stirring bar, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the vinyl monomer and the polymerization initiator were dropped from the previous dropping funnel over 4 hours while stirring at a temperature of 145 ° C. Next, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin. The results of molecular weight measurement by GPC are shown in Table 1.

(Example of polyester resin production)
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 1.4 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.12 g of dibutyltin oxide are placed in a 4-liter glass four-necked flask, a thermometer, a stirring rod, a condenser and a nitrogen inlet tube And placed in the mantle heater. Under a nitrogen atmosphere, reaction was performed at 215 ° C. for 5 hours to obtain a polyester resin. The results of molecular weight measurement by GPC are shown in Table 1.

(Example of styrene-acrylic resin production)
-Styrene 70 parts by mass-N-butyl acrylate 24 parts by mass-Monobutyl maleate 6 parts by mass-Di-t-butyl peroxide 1 part by mass

  While stirring 200 parts by mass of xylene in a four-necked flask, the above components were sufficiently replaced with nitrogen and heated to 120 ° C., and then dropped over 3.5 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a styrene-acrylic resin. The results of molecular weight measurement by GPC are shown in Table 1.

  Next, Table 2 shows the wax used in this example.

<Example 1>
Toner 1 was prepared by the following method.
Hybrid resin 100 parts by weight Wax A 3 parts by weight 1,4-di-t-butylsalicylic acid aluminum compound 2 parts by weight Cyan pigment (Pigment Blue 15: 3) 5 parts by weight

  Preliminarily mixed with a Henschel mixer with the above formulation, melt-kneaded with a twin-screw extruder kneader, cooled and roughly crushed to about 1 to 2 mm using a hammer mill, and then finely pulverized by an air jet method. Finely pulverized to a particle size of 20 μm or less. As shown in Table 3, the obtained finely pulverized product was further pulverized by the apparatus A that simultaneously performs the classification shown in FIGS. 2 and 3 and the surface modification treatment using mechanical impact force. To obtain cyan particles 1 (classified product).

1.0 part by mass of acicular titanium oxide fine powder (MT-100T: manufactured by Teica, BET = 62 m ² / g, treatment with 10% by mass of isobutylsilane coupling agent) is added to 100 parts by mass of the cyan particles. To add cyan toner 1. The cyan toner 1 had a weight average particle diameter of 7.0 μm, an average circularity A of 0.925, and a number-based cumulative value Y of particles having a circularity of 0.960 or more was 24.0%. At this time, the transmittance B in a 45% by volume aqueous methanol solution was 30%.

  Further, cyan toner 1 and magnetic ferrite carrier particles (volume average particle diameter 45 μm: Mn—Mg ferrite) surface-coated with a silicone resin are mixed so that the toner concentration becomes 7.0% by mass. Cyan developer 1 was obtained. Table 4 shows the measurement results of the developer.

  Using this two-component cyan developer 1 and a modified machine from which the oil application mechanism of the fixing unit of the color copying machine CLC-1000 (manufactured by Canon) is removed, in a single color mode at room temperature and low humidity (23 ° C / 5 %), An evaluation of 10,000 printing durability tests was performed using an original document with an image area ratio of 5%. Even after the endurance of 10,000 sheets, the initial charge fluctuation was small, there was no problem in terms of cleaning properties and sleeve contamination, and a cyan image that faithfully reproduced the original without fogging was obtained. Separately, the transfer efficiency, scattering, fixable area, and anti-blocking property were evaluated. As shown in Table 4, good results were obtained in all cases.

  FIG. 1 shows the relationship between the weight average particle diameter X and the number-based cumulative value Y of particles having a circularity of 0.960 or more in the toner manufactured in this embodiment.

  The measurement method of the triboelectric charge amount used in this example and the evaluation criteria for each evaluation are as follows.

<Method for measuring triboelectric charge amount of color toner>
A schematic view of an apparatus for measuring the triboelectric charge amount is shown in FIG. About 0.5 to 1.5 g of a two-component developer collected from the developing sleeve is placed in a metal measuring container 52 having a 500-mesh screen 53 at the bottom, and a metal lid 54 is placed. The total weight of the measurement container 52 at this time is weighed and is defined as W1 (kg). Next, in the suction device 51 (at least the insulator is in contact with the measurement container 52), the suction is performed through the suction port 57 and the air volume control valve 56 is adjusted so that the pressure of the vacuum gauge 55 is 250 mmAq. In this state, suction is sufficiently performed, preferably for 2 minutes, and the toner is removed by suction. The potential of the electrometer 59 at this time is set to V (volt). Here, 58 is a capacitor, and the capacity is C (mF). Further, the weight of the entire measurement container after the suction is weighed and is defined as W2 (kg). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)

The following is the change in charging with a durability of 10,000 sheets from the start.
A: Less than 2 mC / kg.
B: 2 mC / kg or more and less than 4 mC / kg.
C: 4 mC / kg or more and less than 6 mC / kg.
D: 6 mC / kg or more and less than 8 mC / kg.
E: 8 mC / kg or more.

<Transfer efficiency>
Using a color copier CLC-1000 (manufactured by Canon Inc.), using a chart that can form a plurality of circle or band images, transfer the remaining density on the drum and tap the density on the paper. The concentration taped on the top is set as D2 and calculated as the following equation.
Transfer efficiency (%) = D2 / (D1 + D2) × 100
A: 96% or more.
B: 93% or more and less than 96%.
C: 90% or more and less than 93%.
D: 87% or more and less than 90%.
E: Less than 87%.

<Fixable area>
The fixing unit is subjected to a fixing test using a laser jet 4100 (manufactured by Hewlett-Packard Co.) fixing machine and the fixing unit is modified so that the fixing temperature can be manually set. The fixing temperature is increased by 10 ° C. in order from 120 ° C., and a temperature range in which no offset or wrapping occurs is set as a fixable region. The unfixed image was prepared by adjusting the development contrast so that the applied amount of toner on paper was 1.2 mg / cm ² in a single color mode using CLC1000 in a normal temperature and normal humidity environment (23 ° C./60%). . The image was an image with an area ratio of 25%, and TKCLA4 (manufactured by Canon) was used as the transfer paper.
A: Fixable temperature range is 40 ° C. or more.
B: Fixable temperature range is 30 ° C. or higher and lower than 40 ° C.
C: Fixable temperature range is 20 ° C. or higher and lower than 30 ° C.
D: Fixable temperature range is less than 20 ° C.
E: No fixable temperature range.

<Spattering>
Evaluation of image splatter is performed by evaluating the image splatter of a horizontal line pattern in which 4-dot horizontal lines are printed every 176 dot spaces, using the above-described image testing machine.
A: Almost no image splattered even by magnified observation.
B: Image scattering is small even by magnified observation.
C: Characters blur slightly due to scattering.
D: Unevenness appears in the line thickness due to scattering.
E: Some characters are crushed due to scattering.

<Cleanability>
In a printing durability test for 10,000 sheets, when a vertical streak or a spot due to the residual toner is seen on the image, a cleaning failure occurs.
A: There are no image defects.
B: 1 to 3 spotted patterns are generated.
C: Some spots or streaks appear.
D: Spots, streaks, and uneven density occur.
E: The influence of dirt is large, density unevenness and charging unevenness are also generated, and the image is disturbed.

<Blocking resistance>
About 10 g of toner is put in a 100 ml polycup, left at 50 ° C. for 3 days, and then visually evaluated.
A: Aggregates are not seen.
B: Aggregates are slightly seen but easily collapse.
C: Aggregates are seen but easily collapse.
D: Agglomerates are seen, but collapse if shaken.
E: Aggregates can be grasped and do not collapse easily.

<Fog measurement>
After the endurance test, fog was evaluated. The fog was measured as follows.

In the case of a cyan image, the average reflectance Dr (%) of plain paper before image printing is measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.). On the other hand, a solid white image is drawn on plain paper, and then the reflectance Ds (%) of the solid white image is measured. The fog (Fog (%)) is calculated by the following formula.
Fog (%) = Dr (%) − Ds (%)

In the case of a magenta image, the above measurement is performed using a green filter, and in the case of a yellow image, the above measurement is performed for calculation.
A: Less than 0.7%.
B: 0.7 or more and less than 1.2%.
C: 1.2 or more and less than 1.5%.
D: 1.5 or more and less than 2.0%.
E: 2.0% or more.

<Stained sleeve>
Tap on the developing sleeve before the developer is added, and the reflection density of the tape affixed on the paper is defined as Dini.

  After the developer is put in and the printing durability test for 10,000 sheets is completed, the developer is recovered from the bottom of the toner tank of the developing device while the developing sleeve is idling. Then, the toner remaining on the developing sleeve is taped, and the reflection density pasted on the paper is defined as Dlast. The reflection density is measured using a reflection densitometer X-RITE 500 series (X-RITE, Inc.).

The difference in taping density on the developing sleeve before and after the endurance as shown in the following equation is calculated and defined as S1 contamination.
Sleeve contamination = Dini-Dlast

<Example 2>
In Example 1, cyan toner 2 was obtained in substantially the same manner except that wax B was used as shown in Table 3 and the production conditions were changed. Using the obtained cyan toner 2, a two-component cyan developer 2 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, cleaning, fixable area and sleeve contamination, and charge change Although it was slightly inferior, it was a favorable result.

<Example 3>
In Example 1, cyan toner 3 was obtained in substantially the same manner except that wax C was used as shown in Table 3 and the production conditions were changed. Using the obtained cyan toner 3, a two-component cyan developer 3 was prepared, and various evaluations were made in the same manner as in Example 1. As shown in Table 4, transfer efficiency, fixable area, blocking and charge change were observed. Although it was slightly inferior, it was a favorable result.

<Example 4>
In Example 3, cyan toner 4 was obtained in substantially the same manner except that the manufacturing conditions were changed. Using the obtained cyan toner 4, a two-component cyan developer 4 was prepared and variously evaluated in the same manner as in Example 1. As shown in Table 4, the cleaning property, sleeve contamination, blocking and charge change were inferior. The other items were good results and showed good overall results.

<Example 5>
In Example 2, cyan toner 5 was obtained in substantially the same manner except that the manufacturing conditions were changed. Using the obtained cyan toner 5, a two-component cyan developer 5 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, the transfer efficiency, the fixable area, and the scattering were inferior. The other items were good results, and overall, good results were shown.

<Example 6>
In Example 1, cyan toner 6 was obtained in substantially the same manner except that wax D was used as shown in Table 3 and production conditions were changed. Using the obtained cyan toner 6, a two-component cyan developer 6 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, transfer efficiency, fixable area, blocking, charge change, Although the fog is inferior, the overall evaluation showed good results.

<Example 7>
In Example 1, cyan toner 7 was obtained in substantially the same manner except that the production conditions were changed using wax E. Using the obtained cyan toner 7, a two-component cyan developer 7 was prepared, and various evaluations were made in the same manner as in Example 1. As shown in Table 4, cleaning, fixable area, sleeve contamination, charge change, Although the fog is inferior, the overall evaluation showed good results.

<Example 8>
In Example 2, as shown in Table 3, cyan toner 8 was obtained in substantially the same manner except that 50 parts of each of polyester resin and hybrid resin were used and the production conditions were changed. Using the obtained cyan toner 8, a two-component cyan developer 8 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, the transfer efficiency, the fixable region and the scattering were inferior. Overall evaluation showed good results.

<Example 9>
In Example 2, cyan toner 9 was obtained in substantially the same manner except that the production conditions were changed using a polyester resin as shown in Table 3. Using the obtained cyan toner 9, a two-component cyan developer 9 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, cleaning, fixable area, sleeve contamination, charge change, Although the fog is inferior, the overall evaluation showed good results.

<Example 10>
In Example 1, yellow toner 1 was obtained in substantially the same manner except that Pigment Yellow 180 was used as shown in Table 3. Using the obtained yellow toner 1, a two-component yellow developer 1 was prepared, and various evaluations were made in the same manner as in Example 1. As a result, as shown in Table 4, good results were obtained.

<Example 11>
In Example 1, magenta toner 1 was obtained in substantially the same manner except that Pigment Red 122 was used as shown in Table 3. Using the obtained magenta toner 1, a two-component magenta developer 1 was prepared and variously evaluated in the same manner as in Example 1. As a result, good results were obtained as shown in Table 4.

<Comparative Example 1>
In Example 9, the spheroidizing treatment is not performed by the apparatus A, but a super rotor manufactured by Nissin Engineering Co., Ltd. and a classifying apparatus (elbow jet classifier) that does not spheroidize are used. Toner 10 was obtained. Using the obtained cyan toner 10, a two-component cyan developer 10 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, the results were inferior in terms of sleeve contamination, charge change, and fogging. Met.

<Comparative example 2>
In Example 9, after performing the spheroidizing treatment not by the device A but by the classifying device (elbow jet classifier) that does not spheroidize, except that the hybridization system manufactured by Nara Machinery Co., Ltd. is used, Cyan toner 11 was obtained in substantially the same manner. Using the obtained cyan toner 11, a two-component cyan developer 11 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, the results were inferior in terms of sleeve contamination, charge change, and fogging. Met.

<Comparative Example 3>
In Example 9, after performing the spheroidizing treatment not by the device A but by the classifying device (elbow jet classifier) that does not spheroidize, except for using a surfing system manufactured by Nippon Pneumatic Co., Ltd., the rest Cyan toner 12 was obtained in substantially the same manner. Using the obtained cyan toner 12, a two-component cyan developer 12 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, regarding cleaning, sleeve contamination, blocking and charge change, and fogging Was inferior.

<Comparative example 4>
In Example 9, cyan toner 13 was obtained in substantially the same manner except that the production conditions were changed using styrene-acrylic resin. Using the obtained cyan toner 13, a two-component cyan developer 13 was prepared and variously evaluated in the same manner as in Example 1. As a result, as shown in Table 4, the charge change and fog were inferior.

<Comparative Example 5>
In Example 9, cyan toner 14 was obtained in substantially the same manner except that the manufacturing conditions were changed using wax F. Using the cyan toner 14 thus obtained, a two-component cyan developer 14 was prepared and subjected to various evaluations in the same manner as in Example 1. As a result, as shown in Table 4, the fixable area became very narrow.

<Comparative Example 6>
A cyan toner 15 was obtained in substantially the same manner as in Example 9 except that the wax G was used. Using the obtained cyan toner 15, a two-component cyan developer 15 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, regarding sleeve contamination, blocking, charge change, and fogging, The result was inferior.

<Comparative Example 7>
In Example 9, cyan toner 16 was obtained in substantially the same manner except that the spheroidizing treatment was not performed by apparatus A, but a classification apparatus (elbow jet classifier) that did not perform spheronization was performed. Using the obtained cyan toner 16, a two-component cyan developer 16 was prepared and evaluated in the same manner as in Example 1. As shown in Table 4, the transfer efficiency was low.

<Example 12>
Using the two-component cyan developer 1, the two-component yellow developer 1, and the two-component magenta developer 1, YMC color evaluation was performed. The transfer efficiency, cleaning, sleeve contamination, blocking, and charge change of each developer were as good as those in Examples 1, 10, and 11. In the fixable area test, the image area on which about 50% of cyan toner 1 and yellow toner 1 were placed was as good as that in Example 1. Similarly, in a test using a combination of cyan toner 1 and magenta toner 1, a combination of yellow toner 1 and magenta toner 1, and about 1/3 each of cyan toner 1, yellow toner 1 and magenta toner 1. It was as good as Example 1. With respect to the image, scattering using cyan toner 1, yellow toner 1 and magenta toner 1 was B, and fog was about 1.2.

<Example 13>
Using cyan toner 1, yellow toner 1 and magenta toner 1, YMC color one-component development evaluation was performed. The apparatus used was a modified machine with a cleaner unit attached to LBP-2040 (manufactured by Canon Inc.). The transfer efficiency, cleaning, sleeve contamination, and blocking of each developer were all good at “A”, and the charge change was good at B. Further, in the fixable area test, all the combinations as in Example 12 were good. For the image, the scattering using cyan toner 1, yellow toner 1 and magenta toner 1 was about B and the fog was about 1.8.

  As described above, as is clear from the results of the above embodiments, the amount of the release agent present on the surface of the color toner particles and the conditions contributing to the color toner shape are controlled, for reducing the contamination of the charging member and low-temperature fixing for high-speed copying. It is possible to obtain a color toner that is excellent in blocking resistance and charge stability by continuous copying.

It is a figure which shows the relationship between the weight average particle diameter X and the number reference | standard accumulation value Y of the particle | grains of circularity 0.960 or more. It is the schematic which shows an example of the surface modification apparatus used in order to manufacture the color toner of this invention. It is the schematic which shows an example of the top view of the dispersion | distribution rotor shown in FIG. FIG. 3 is a schematic diagram illustrating an example of an apparatus for measuring the triboelectric charge amount of toner.

Claims (10)

A color toner containing at least a binder resin, a colorant, and a release agent,
The color toner is a toner that has been surface-treated using a batch-type surface treatment device,
The surface treatment device continuously discharges and removes fine powder having a predetermined particle diameter or less to the outside of the device, surface treatment means for performing surface treatment of toner particles using a mechanical impact force, the classification device, and the classification device An apparatus having a guide means for partitioning a space between the surface treatment means into a first space and a second space,
The particles to be treated are introduced into the first space and classified by the classification means, the classified particles are introduced into the surface treatment means via the second space and subjected to the surface treatment, and further the surface treatment The toner obtained by performing the surface treatment by repeating the surface modification treatment using classification and mechanical impact force for a certain period of time by circulating the particles again to the first space,
The color toner is
(I) the binder resin includes at least a polyester unit;
(Ii) The color toner has a weight average particle diameter of more than 6.5 μm and not more than 11 μm,
(Iii) The color toner has an average circularity A of 0.915 ≦ A ≦ 0.960 in particles having an equivalent circle diameter of 3 μm or more,
(Iv) The color toner has a transmittance B (%) in a 45 volume% methanol aqueous solution of 10 ≦ B ≦ 70,
(V) The color toner has one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C. in the endothermic curve in differential scanning calorimetry (DSC) measurement, and the temperature of the maximum endothermic peak in the endothermic peak. A color toner, wherein Tsc is 65 ° C. <Tsc <105 ° C. In the color toner, the weight-average particle diameter X (μm) and the number-based cumulative value Y (%) of particles having a circularity of 0.960 or more have the following relational expression: −X + 20 ≦ Y ≦ −X + 70
The color toner according to claim 1, wherein: For the color toner, the following relational expression −X + 20 ≦ Y ≦ −X + 50 regarding the number-based cumulative value Y of particles having a weight average particle diameter X and a circularity of 0.960 or more.
The color toner according to claim 1, wherein: The releasing agent is, the color toner according to any one of claims 1 to 3, characterized in that a hydrocarbon wax. The color toner, the color toner according to any one of claims 1 to 4, characterized by containing a metal compound of an aromatic carboxylic acid. The color toner, the circle equivalent diameter 3μm or more particles, the color toner according to any one of claims 1 to 5 average circularity A is characterized by a 0.920 ≦ A ≦ 0.945. The color toner, the color toner according to the transmittance B in methanol 45 vol% aqueous solution, any one of claims 1 to 6, characterized in that it is 15 ≦ B ≦ 50. The color toner according to any one of claims 1 to 7 temperature Tsc of the highest endothermic peak of endothermic in peak, characterized in that it is a 70 ℃ <Tsc <90 ℃. The color toner according to the color toner, yellow toner, magenta toner, any one of claims 1 to 8, characterized in that either a cyan toner. The color toner according to any one of claims 1 to 9 , wherein the color toner is mixed with a carrier and used as a two-component developer.

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