JP4181960B2 - Silica fine powder - Google Patents

Description

  The present invention relates to silica fine particles, a toner, a two-component developer, which can be suitably used when forming and developing an electric latent image in electrophotography, electrostatic printing, toner jet method, and the like. Further, the present invention relates to an image forming method using the toner.

  Conventionally, many methods are known as electrophotographic methods. In general, a photoconductive substance is used, and an electrostatic charge latent image is formed on the photoconductor by various means, and then the latent image is developed with toner to form a toner image. After the toner image is transferred to the transfer material, the toner image is fixed on the transfer material by heat, pressure, heat and pressure, etc. to obtain a copy or printed matter. Toner particles that are not transferred onto the transfer material but remain on the photoconductor are removed from the photoconductor by a cleaning process.

  Conventionally, means such as blade cleaning, fur brush cleaning, and roller cleaning have been used for the cleaning process of the photoreceptor. The means mechanically scrapes off the transfer residual toner on the photoconductor or stops it to collect the transfer residual toner in a waste toner container. However, a problem that the surface of the photoreceptor is worn due to the member constituting such means being pressed against the surface of the photoreceptor tends to occur.

  In addition, since the cleaning device is provided, the entire apparatus inevitably becomes large, which has become a bottleneck when aiming to make the apparatus compact.

  Furthermore, from the viewpoint of ecology, a system without waste toner has been awaited.

  For example, Patent Document 1 proposes an image forming apparatus that employs a technique called development / cleaning or cleaner-less. In the image forming apparatus, one image is formed per one rotation of the photoreceptor so that the influence of the transfer residual toner does not appear on the same image. In Patent Documents 2 to 5, a method in which a transfer residual toner is scattered on a photosensitive member by a scattering member and is made non-patterned, so that even when the same surface of the photosensitive member is used a plurality of times for one image, it is difficult to reveal on the image. Has proposed.

  However, in order to achieve a cleaner-less system by making the residual toner non-patterned, it is necessary to arrange a device for applying a voltage to the member for making the non-pattern, and it is difficult to make the whole device compact. It is.

  Patent Document 6 proposes to obtain stable charging characteristics by using a spherical toner and a spherical carrier in a cleanerless electrophotographic printing method. No mention is made of toner physical properties, particularly external additives present on the surface.

  Further, Patent Document 7 proposes to obtain stable charging characteristics by making the toner resistance value and charge amount appropriate in the cleanerless electrophotographic printing method. However, the toner physical properties, particularly on the surface, are proposed. There is no mention of existing external additives.

  In addition, various cleaner-less electrophotographic printing systems have been proposed in Patent Documents 8 to 11 and the like, but there is no mention of a preferable form that matches the cleaner-less system with respect to external additives.

  Furthermore, the user's demand for high image quality is strong, and from this point of view, the physical properties of the toner, particularly the form of the external additive present on the surface, is important. Patent Document 12 and others specify the particle size and shape of the external additive. Toners having excellent development stability have been proposed. However, this document does not mention the coarse particles of the silica fine powder used. When many coarse particles are present, in an image forming apparatus using a charging roller as a charging member, there is a problem that the roller, the latent image carrier, and the like are easily stained, and further improvement is required.

  In recent years, various organic photoconductive materials have been developed as photoconductive materials for electrophotographic photoreceptors. In particular, functionally separated types in which a charge generation layer and a charge transport layer are laminated have been put to practical use. Installed in facsimile machines. As a charging means in such an electrophotographic apparatus, means using corona discharge has been used, but ozone is generated when corona discharge is used.

  As a technique for solving such a problem, a charging member such as a roller or a blade is brought into contact with the surface of the photoconductor to form a narrow space near the contact portion, which can be interpreted by the so-called Paschen's law. A charging method has been developed that suppresses ozone generation as much as possible by forming a discharge. Among these, a roller charging method using a charging roller as a charging member is particularly preferably used from the viewpoint of charging stability.

  Since this charging is performed by discharging from the charging member to the member to be charged, charging is started by applying a voltage higher than a certain threshold voltage. For example, when a charging roller is brought into contact with a photoreceptor containing an organic photoconductive material having a thickness of about 25 μm, the surface potential of the photoreceptor increases when a voltage of about 640 V or more is applied. Thereafter, the photosensitive member surface potential increases linearly with a slope of 1 with respect to the applied voltage. Hereinafter, this threshold voltage is defined as the charging start voltage Vth. That is, in order to obtain the photoreceptor surface potential Vd, the charging roller needs a DC voltage higher than that required, that is, Vd + Vth. Furthermore, since the resistance value of the charging roller fluctuates due to environmental fluctuations or the like, it is difficult to set the potential of the photosensitive member to a desired value.

  For this reason, as disclosed in Patent Document 13 in order to achieve uniform charging, a voltage obtained by superimposing an AC voltage having a peak-to-peak voltage of 2 × Vth or more on a DC voltage corresponding to a desired Vd is set as a contact charging roller. A DC + AC charging method applied to is used. This is for the purpose of leveling the potential due to AC, and the potential of the charged object converges to Vd, which is the center of the peak of the AC voltage, and is not easily affected by disturbances such as environmental fluctuations.

  However, even in such a charging method, the essential charging mechanism uses a discharge phenomenon from the charging member to the photoconductor, so that the voltage required for charging is the surface of the photoconductor as described above. A value greater than the potential is required. Furthermore, the occurrence of vibration and noise between the charging member and the photosensitive member (hereinafter referred to as AC charging sound) due to the electric field of the AC voltage, and the deterioration of the photosensitive member surface due to discharge, become a new problem. It was.

  Patent Document 14 proposes to use secondary particles obtained by fusing primary polymer particles as a toner, and Patent Document 15 proposes to use a polymerized toner that transmits photoconductor exposure light. Patent Document 16 proposes to use a toner that defines volume average particle diameter, number average particle diameter, toner charge amount, toner projected image area ratio, toner BET specific surface area, and the like. An excellent image forming method using a developing and collecting system is desired.

  When a technique called development / collection system or cleaner-less is used, the transfer residual toner blocks exposure and prevents formation of an electrostatic latent image, and the desired potential cannot be controlled. Is likely to occur. Furthermore, if there is a large amount of toner remaining after transfer, the toner cannot be completely collected in the development process, and a positive memory tends to be generated on the image. Using a non-patterned member, the image quality tends to deteriorate.

  On the other hand, in the toner, small particles of inorganic fine particles are externally added to colored particles (toner particles) for the purpose of obtaining good developability, cleaning properties, and transferability by adjusting the chargeability and fluidity of the toner. Is generally known.

  However, the toner to which such small particle size inorganic fine particles are externally added is, for example, stress with a carrier when used as a two-component developer, developer coating blade when used as a one-component developer When using for a long time due to stress from the developer supply roller, or the inner wall of the developing unit, the stirring blade, and the collision between toners, it is confirmed that small-sized inorganic fine particles are embedded in the surface. Has been.

  In order to reduce the burying of the small particle size inorganic fine particles, a method using large particle size inorganic fine particles in combination is effective as disclosed in Patent Documents 17 to 21.

  The addition of large-sized inorganic fine particles produces a so-called spacer effect, and the toner surface to which the small-sized inorganic fine particles adhere is the carrier, developer coating blade, developer supply roller, developing device inner wall, stirring blade, other toner, etc. Prevent direct contact and reduce stress. Thereby, the embedding of the small particle size inorganic fine particles is suppressed, and the life of the toner is extended.

  Furthermore, in order to continue this spacer effect, it is preferable to use silica as the large particle size inorganic fine particles. This is due to the following reasons. Large particle size inorganic fine particles have relatively weak electrostatic adhesion to the toner surface compared to small particle size inorganic fine particles. For this reason, the large particle size inorganic fine particles are easily released from the toner surface, and are consumed and reduced by development or the like, and the spacer effect tends not to last for a long time. Here, silica has a large charge amount among inorganic powders and also has a large adhesion to the toner surface. Therefore, when silica is used as the large particle size inorganic fine particles, liberation is suppressed and the spacer effect is continued. Can do.

  However, as described above, a toner obtained by externally adding a small particle size inorganic fine particle and a large particle size silica to the toner becomes too charged in a low-humidity environment, and is likely to cause so-called charge-up. Inferior aspects are seen.

  On the other hand, Patent Document 22 proposes a toner using hydrophobic silica of 15 to 20 nm, hydrophobic silica of 13 nm or less, and alumina as external additives. However, although this toner can provide excellent environmental characteristics in a two-component developer using a carrier, in a non-magnetic one-component developer, 15 to 20 nm of hydrophobic silica is released from the toner surface and the spacer effect. As a result, it was found that sufficient performance was not obtained, silica was buried in the toner surface, fogging was increased, cleaning was poor, and transfer efficiency was decreased. In addition, sufficient performance was not obtained with respect to environmental characteristics, and a decrease in image density and image unevenness due to charge-up were observed. This is presumably because, in non-magnetic one-component development, mechanical stress from the blade as a charging member is larger than that in two-component development.

  Further, with respect to the cleaning and fusion of the photosensitive member, the physical properties of the external additive have been improved, but conventionally, a specific surface area by the BET method has been widely used as an index of the particle size of the inorganic fine particles. However, this method shows the approximate size of the particles. For example, even if the specific surface area is the same, it is difficult to determine the size of the primary particles and the size of the higher-order particles in which they aggregate and solidify. is there.

  In addition, Patent Documents 23 and 24 propose a technique in which the toner 2 transfers silica having a prescribed particle size distribution. However, in these documents, the particle size distribution of inorganic fine particles is measured by an aperture type particle size distribution meter. In this measurement method, particles larger than the aperture diameter cannot be measured, and particles having a small particle size of about 1 μm or less. However, the measurement range is very narrow because it cannot be measured at the detection limit, and it is difficult to determine the particle size, and there is still room for improvement in terms of controlling the particle size distribution. In these documents, the main purpose is to suppress the abundance of coarse particles.

  In view of such a demand, development of new inorganic fine particles based on a method for measuring the size and degree of aggregation of particles and the measurement method is eagerly desired.

Further, in Patent Document 25, silica having a specific surface area is proposed and the particle size distribution of silica is also described, but there is no description regarding the particle size distribution of fine particles of less than 1 μm.
Japanese Patent Publication No. 5-69427 JP-A 64-20587 JP-A-2-259784 JP-A-4-50886 JP-A-5-165378 JP-A-2-511168 JP-A-5-2287 JP-A-6-250566 JP-A-8-292640 Japanese Patent Laid-Open No. 11-38730 JP 11-311890 A Japanese Patent Laid-Open No. 11-147331 JP-A 63-149669 Japanese Patent Laid-Open No. 5-19662 JP-A-4-296766 Japanese Patent Laid-Open No. 5-188737 JP-A-4-204751 JP-A-5-346682 JP-A-6-313980 JP-A-6-332235 JP-A-7-92724 JP-A-7-104501 JP 7-319201 A JP-A-11-167250 Japanese Patent Laid-Open No. 10-67510

  An object of the present invention is to provide a silica fine powder, a toner, a two-component developer, and an image forming method that have solved the above-described problems.

  An object of the present invention is to provide a toner and an image forming method that are excellent in transferability, suppressed in occurrence of fog, and excellent in durability and stability even when a large number of continuous prints are performed.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and an image forming method that have clear image characteristics and excellent durability stability even when a large number of continuous prints are made. is there.

  An object of the present invention is to provide a toner and an image forming method with less image wear and good image density stability.

The present invention is a hydrophobic treatment by silicone oil, a 3 to 35 parts by weight amount of the silicone oil with respect to the original body 100 parts by mass of the silica fine powder, and volume by a laser diffraction type particle size distribution meter In the standard particle size distribution, there are peaks in the ranges of at least 0.04 μm or more and less than 1 μm and 1 μm or more and less than 100 μm, the frequency ratio of 0.04 μm or more and less than 1 μm to all peaks is 10 to 80%, and 20 μm for all peaks The present invention relates to a silica fine powder characterized in that the frequency ratio of less than 2000 μm is less than 16%.

  In the toner of the present invention, the particle size of the external additive for performing external addition treatment on the toner surface is set to a predetermined distribution, and the external additive is subjected to hydrophobic treatment to contaminate or damage the member and the photosensitive drum. Therefore, even when a large number of sheets are continuously printed, an image forming method with stable image density and excellent durability and stability without fogging can be obtained.

  When there is a member that is in pressure contact with the drum, such as a charging roller, contamination or wear of the member or drum may occur as the durability progresses, and toner may adhere to or fuse to the drum surface or roller surface. .

  On the other hand, as a result of intensive studies, the present inventors have determined that the particle size of the external additive to be externally applied to the toner surface has a predetermined distribution, and further hydrophobizes the external additive, so It was found that the drum is less likely to be contaminated or damaged.

  Furthermore, the surface hardness of the charging roller is set within a predetermined range, and the structure and molecular weight of the surface layer of the photoconductor are regulated to prevent the transfer residual toner from adhering (adhering) to the surface of the charging roller and the drum surface. Furthermore, by reducing the toner damage at the nip portion between the charging roller and the photosensitive drum, the present inventors succeeded in suppressing image defects due to contamination of the charging roller and accompanying transfer failure images.

  First, the silica fine powder (silica fine powder (A)) of the present invention, the toner containing the silica fine powder, and the two-component developer will be described.

  The silica fine powder of the present invention (silica fine powder (A)) is hydrophobized, and has a volume-based particle size distribution of at least 0.04 μm and less than 1 μm, and between 1 μm and less than 100 μm in a laser diffraction particle size distribution meter. Each range has a peak, the frequency ratio of 0.04 μm or more and less than 1 μm to all peaks is 10% to 80%, and the frequency ratio of 20 μm or more to less than 2000 μm to all peaks is less than 16%. When such a silica fine powder is contained in the toner, contamination of the charging member and the image carrier (photoconductor) is suppressed, and stable developability can be provided.

  More preferably, if the frequency ratio of 0.04 μm or more and less than 1 μm with respect to all peaks is 20% to 70%, and the frequency ratio of 20 μm or more and less than 2000 μm with respect to all peaks is less than 12%, the above-described effects are further improved.

  Here, a method for measuring the volume-based particle size distribution using the laser diffraction type particle size distribution meter in the present invention will be described.

  The particle size of the silica fine powder (silica fine powder (A)) is measured using a Coulter LS-230 particle size distribution meter (manufactured by Coulter, Inc.) of a laser diffraction type particle size distribution meter. Ethanol is used as a measurement solvent. Wash and replace the measurement system of the particle size distribution analyzer several times with ethanol and execute the background function.

  Next, a sample solution is obtained as described below, and the sample solution is gradually added into the measurement system of the measurement device so that the PIDS (concentration) on the screen of the device is 45 to 55%. The sample concentration is adjusted and measured, and the frequency ratio is obtained from the distribution calculated from the volume distribution.

  The measurement was performed with the refractive index of ethanol as 1.36 as the device coefficient and 1.08 (real part) -0.00i (imaginary part) as the optical model. The particle size measurement range of the Coulter LS-230 type particle size distribution meter of the laser diffraction type particle size distribution meter in the present invention is 0.04 to 2000 μm. The measurement temperature was 20 ° C to 25 ° C.

  As a method for preparing a sample in the present invention, 0.4 g of a fine powder to be measured is weighed, put into a beaker containing 100 ml of ethyl alcohol, and stirred for 1 minute by stirring with a stirrer. Transfer the beaker to the ultrasonic vibration layer and treat for 3 minutes. Immediately after completion of the treatment, the dispersion solution is added to the measurement part filled with ethanol until the measurement allowable concentration is reached, and measurement is started.

  In addition, as the ultrasonic vibration layer in the present invention, ULTRASONIC CLEANER VS-150 type (frequency 50 kHz, maximum output 150 W) manufactured by Inoue Seieido Co., Ltd. was used.

  The sample concentration in this measurement is suitable for observing the agglomeration and dispersion of the fine powder and is a concentration at which the particle size distribution of the fine powder can be accurately observed. In the case of measuring a sample having a small particle size or low cohesion, the sample amount may be 0.2 g and the amount of ethyl alcohol may be 50 ml.

  In the Coulter LS-230 type particle size distribution analyzer, the particle size of each particle is first determined and distributed to the following channels. Then, assuming that the center diameter of each channel is the representative value of the channel and the sphere having the representative value as the diameter is assumed, the volume-based particle size distribution is obtained based on the volume of the sphere.

  First, in the present invention, the frequency ratio of 0.04 μm or more and less than 1 μm with respect to all peaks needs to be 10 to 80%. This particle size range of 0.04 μm or more and less than 1 μm is slightly smaller than the toner base particles, and is necessary for preventing durability deterioration due to embedding external additives on the toner surface and improving toner transfer efficiency. The particle size distribution.

  If the frequency ratio of 0.04 μm or more and less than 1 μm with respect to all peaks is less than 10%, the transferability of the toner is lowered and a satisfactory image cannot be obtained. In addition, the inorganic fine particles to be used together are embedded in the toner particle surfaces, and image deterioration occurs due to a decrease in fluidity.

  When the frequency ratio of 0.04 μm or more and less than 1 μm with respect to the entire peak exceeds 80%, the silica fine powder released from the toner surface increases and adheres to the charging member, developing member, photosensitive drum, etc., leading to image defects.

  When the frequency ratio of 0.04 μm or more and less than 1 μm with respect to all peaks is 20 to 70%, the above-described effect is further improved.

  Furthermore, in the present invention, the frequency ratio of 20 μm or more and less than 2000 μm with respect to all peaks needs to be less than 16%. The particle size range of 20 μm or more and less than 2000 μm is larger than the toner base particles and is equal to or smaller than the opening of the sieve that removes coarse particles after the external addition treatment.

  If the frequency ratio of 20 μm or more and less than 2000 μm with respect to the entire peak is 16% or more, it tends to adhere to the charging member, the developing member, the photosensitive drum, etc., leading to image defects.

  If the frequency ratio of 20 μm or more and less than 2000 μm with respect to all the peaks is less than 12%, the above-described effect is further improved.

  The silica fine powder (silica fine powder (A)) of the present invention needs to have a peak in the range of 0.04 μm or more and less than 1 μm. By having a peak in this range, the effect of improving transferability and preventing embedding on the toner surface can be obtained. Conversely, if there is no peak in this range, the external additive on the toner surface Are likely to be embedded, and roughness due to transfer defects is likely to occur in the second half of the durability.

  Further, the silica fine powder (silica fine powder (A)) of the present invention needs to have a peak in the range of 1 μm or more and less than 100 μm. The particle size in this range is close to the particle size of the toner, and packing between the toners can be prevented. When there is no peak in this range, the toner and the developer are easily packed densely, and the developer is likely to be deteriorated earlier.

  In the present invention, it is preferable that the full width at half maximum of the maximum peak in the range of 1 μm or more and less than 100 μm is 5 to 25 μm. Even when the half-value width is less than 5 μm, the toner and the developer are likely to be densely packed, and the developer tends to be deteriorated earlier.

  When the full width at half maximum of the maximum peak in the range of 1 μm or more and less than 100 μm exceeds 25 μm, coarse particles increase, and the toner adheres to the charging member, the developing member, the photosensitive drum, and the like, and easily causes image defects.

  More preferably, the full width at half maximum of the maximum peak in the range of 1 μm or more and less than 100 μm is 8 to 20 μm.

  In the silica fine powder (silica fine powder (A)) of the present invention, the volume average particle size determined by a laser diffraction type particle size distribution meter is preferably 0.1 to 20 μm, and more preferably the volume average particle size is 0.00. The thickness is preferably 3 μm to 12 μm.

  When the volume average particle size is less than 0.1 μm, the number of particles having a spacer effect is reduced, transferability is lowered, toner and developer are easily packed densely, and developer deterioration is likely to be accelerated.

  The silica fine powder (silica fine powder (A)) according to the present invention preferably has a primary number average major axis of 18 to 200 nm, more preferably 20 to 100 nm. The measuring method of the primary number average major axis will be described later.

  The silica fine powder (silica fine powder (A)) of the present invention has a peak in two different particle size ranges as described above, and a composite in which a plurality of primary particles having the above primary particle sizes are combined. It is preferred that the particle size distribution of the present invention be achieved by forming particles. By the presence of the composite particles, the effect as the spacer particles can be obtained, and the transferability can be improved and the toner deterioration can be satisfactorily achieved.

  In addition, it is difficult to determine the size of the particles based on the specific surface area of the fine silica powder (silica fine powder (A)) by nitrogen adsorption according to the BET method. Since this changes, it is necessary to control this.

When the specific surface area of the fine silica powder (silica fine powder (A)) by nitrogen adsorption by the BET method is 30 to 100 m ² / g, the development characteristics are good.

When the specific surface area of the fine silica powder (silica fine powder (A)) by nitrogen adsorption by the BET method is less than 30 m ² / g, it is considered that the cohesiveness is too high and the composite particles are too large. It will be released and easily contaminate the parts.

When the specific surface area of the fine silica powder (silica fine powder (A)) by nitrogen adsorption by the BET method is larger than 100 m ² / g, it is considered that the composite particles in the present invention are difficult to form, and the effect of the invention is achieved. It is difficult to obtain.

  When the fine silica powder (silica fine powder (A)) of the present invention is added to the toner, the amount of addition is 0.05 to 1.0 part by mass with respect to 100 parts by mass of the toner particles. Even if the image forming apparatus has a transfer process twice, good transfer is possible and good image formation is performed.

  When the addition amount of silica fine powder (silica fine powder (A)) is less than 0.05 parts by mass, the transferability is deteriorated and the effect as a spacer is difficult to be exhibited. However, developability deteriorates.

  When the addition amount of the silica fine powder exceeds 1.0 part by mass, the silica fine powder is easily released from the toner, and the member is easily contaminated.

  In the present invention, the measurement of the BET specific surface area of the powder is performed as follows using a specific surface area meter autosorb 1 manufactured by QUANTACHROME.

About 0.1 g of a measurement sample is weighed in a cell, and degassed for 12 hours or more at a temperature of 40 ° C. and a degree of vacuum of 1.0 × 10 ⁻³ mmHg. Thereafter, nitrogen gas is adsorbed while being cooled with liquid nitrogen, and a value is obtained by a multipoint method.

  In the present invention, as described above, in addition to the silica fine powder (silica fine powder (A)), there are at least one fine powder (B) having a number average major axis of primary particles smaller than that of the silica fine powder (A). It is preferably contained. Particles finer than the silica fine powder (A) make the charge on the toner surface uniform, sharpen the charge amount distribution of the toner, and further improve the fluidity of the toner.

  The number average major axis of the primary particles of the fine powder (B) is preferably 1 to 50 nm. The primary particle size in this range is optimal for the fine particles to make the charge on the toner surface uniform, to sharpen the charge distribution of the toner, and to improve the fluidity of the toner.

  Here, the average major axis of the primary particles of the silica fine powder (A) and the fine powder (B) is measured by the surface of the toner particles magnified 500,000 times by a scanning electron microscope FE-SEM (S-4700, manufactured by Hitachi, Ltd.). The photograph of this is taken, and the enlarged photograph is performed as a measurement object.

  The average major axis of primary particles is measured over 10 fields in an enlarged photograph, and the average is taken as the average major axis. Of the parallel lines drawn so as to be in contact with the contours of the primary particles of the fine powder, the one having the maximum distance between the parallel lines is defined as the major axis.

  When the number average major axis of the primary particles of the fine powder (B) is less than 1 nm, the fine powder (B) is buried in the toner surface, and the toner deteriorates with long-term use.

  When the number average major axis of the primary particles of the fine powder (B) exceeds 50 nm, the charge on the toner surface is inferior, the toner charge amount distribution becomes broad, and problems such as toner scattering and fogging are likely to occur. In addition, since the particle size is large, it is difficult to uniformly cover the toner surface, and it is difficult to obtain the effects of the present invention.

When the specific surface area (BET specific surface area) due to nitrogen adsorption of the fine powder (B) by the BET method is 100 to 200 m ² / g, the development characteristics in the image forming apparatus of the present invention are good.

When the BET specific surface area of the fine powder (B) is less than 100 m ² / g, the powder is too cohesive and it is difficult to obtain uniform charging characteristics.

When the BET specific surface area of the fine powder (B) is larger than 200 m ² / g, the moisture adsorbed on the fine powder increases, and the tribo difference between high and low humidity tends to increase.

  Further, if the addition amount of the fine powder (B) is 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the toner particles, the developer fluidity is improved and the transfer property is improved and the charge is increased under low humidity. Effects such as prevention can be obtained.

  When the addition amount of the fine powder (B) is less than 0.1 parts by mass, the fluidity of the toner is inferior, the developability and transferability are deteriorated, and the fogging is performed to make the dispersion of other external additives non-uniform. Will also get worse. When the amount of the fine powder (B) added exceeds 2.0 parts by mass, the amount of the fine powder present on the toner surface increases, and the member is contaminated or fixing is inhibited.

  Unlike the corona charging method and the magnetic brush charging method, in the roller charging type image forming apparatus, the charging roller and the image carrier rotate while contacting with a certain pressure. The toner and external additives are likely to be fused to the image carrier. In particular, in a cleanerless system without a cleaning blade, the toner remaining after transfer passes through the nip between the charging roller and the image carrier, so that the toner and the external additive are more easily fused. Even in such a case, it is possible to prevent the toner and the external additive itself from being contaminated by being hydrophobized as silica fine powder (silica fine powder (A)). As the hydrophobization treatment for the silica fine powder (A) of the present invention, treatment with a silane coupling agent or silicone oil is preferred, but treatment with both is more preferred.

  Hydrophobic treatment can be performed using fluorine oil or various modified oils instead of silicone oil, but silicone oil is preferred in the present invention.

  Examples of the silicone oil include those represented by the following formula.

[Wherein, R represents a C1-3 alkyl group, and R ′ represents a C1-3 alkyl group, a halogen-modified alkyl group, a phenyl group, a C1-3 alkyl group phenyl group, or a halogen-modified phenyl group. , R ″ represents a C 1-3 alkyl group or an alkoxy group.]
Examples thereof include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. The silicone oil having a viscosity of 50 to 100 mm ² / s at 25 ° C. is preferably used.

  When the silica fine powder (silica fine powder (A)) of the present invention is treated with oil in an amount of 3 to 35 parts by mass with respect to 100 parts by mass of the fine powder matrix, the adhesion of the developer to the member is suppressed and charging is performed. Image defects such as defects can be suppressed, and an effect of improving transferability can be obtained.

  When the amount of oil treated to the silica fine powder (silica fine powder (A)) is less than 3 parts by mass, the effect of preventing contamination of the member is hardly exhibited.

  When the amount of oil processed to silica fine powder (silica fine powder (A)) exceeds 35 parts by mass, the treated fine powder (A) tends to aggregate and toner chargeability and developability are non-uniform. End up.

  In the case of this invention, the effect mentioned above further increases that it is 5-25 mass parts.

  Further, the silica fine powder (silica fine powder (A)) is classified in order to control the amount of the composite particles in the range of 0.1 μm or more and less than 1 μm and the composite particles in the range of 20 μm or more and less than 100 μm necessary for the present invention. And / or a crushing process may be performed.

  Examples of the method include a method of performing particle size selection using an air classifier, a method of rotating a rotor to loosen composite particles by impact (for example, a hybridizer, a cosmomizer, etc.), a method of a pin mill, a jet mill, or the like used for pulverization. However, it is important to control to the particle size distribution of the present invention, and the apparatus is not particularly limited as long as it can be controlled.

  As the fine powder (B) used in the present invention, conventionally known fine powders can be used. Silica fine particles, alumina fine particles, titanium oxide fine particles, zirconium oxide fine particles, magnesium oxide fine particles are used for improving developability, fluidity and storage stability. Or a group consisting of these composite fine particles.

  As the silica, both a so-called dry process produced by vapor phase oxidation of silicon halides and alkoxides or a dry process silica called fumed silica, and wet silica produced from alkoxide and water glass can be used. However, dry silica having less silanol groups on the surface and inside the fine powder and less production residue is preferred.

  Further, in the present invention, the fine powder (B) may be subjected to a surface treatment for forming a silane coupling treatment, a silicone oil treatment or an alumina coating for the purpose of enhancing hydrophobicity and improving the operability of particle size and shape control. . In the present invention, as the fine powder (B), silica fine particles treated with silicone oil or titanium oxide fine particles treated with a silane coupling agent are particularly preferred, and in some cases, these may be used in combination.

Specific examples of the silane coupling agent include hexamethyldisilazane and those represented by the following formula (1).
RmSiYn (1)
R: an alkoxy group or a chlorine atom m: an integer of 1 to 3 Y: an alkyl group or a hydrocarbon group containing a vinyl group, a glycidoxy group or a methacryl group n: an integer of 1 to 3 As the compound represented by the above (1), For example, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, isobutyltrimethoxysilane, n-butyltrimethoxy Examples include silane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

  The silane coupling agent treatment method is a dry method in which a vaporized silane coupling agent is reacted with a fine powder made into a cloud by stirring, or a wet method in which fine powder is dispersed in a solvent and the silane coupling agent is dropped. Either of these can be processed.

  For the treatment with the silicone oil, a silicone oil as described as the treating agent for the fine silica powder (A) can be used.

  As the method for forming the alumina coating, aluminum chloride, aluminum nitrate, aluminum sulfate or the like is added in an aqueous solution or solvent, and the fine particles are immersed and dried, or hydrous alumina, hydrous alumina-silica, hydrous alumina-titanium oxide. The method can be carried out by adding water-containing alumina-titanium oxide-silica or water-containing alumina-titanium oxide-silica-zinc oxide, and immersing and drying the fine particles in the aqueous solution.

  In addition to the silica fine powder (silica fine powder (A)) and fine powder (B) used in the present invention, a fine powder may be further added to adjust the charge amount and assist fluidity.

  For example, examples of the fluidity-imparting agent include metal oxides (silica, alumina, titanium oxide, etc.), carbon black, silica, and the like, and those that have been subjected to hydrophobic treatment are more preferable. Abrasives include metal oxides (strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, Calcium carbonate). Examples of the charge controllable particles include metal oxides (tin oxide, titanium oxide, zinc oxide, silica, alumina, etc.), carbon black, and the like.

  In the present invention, the average circularity is preferably 0.950 to 0.995 in the particle size distribution measured by a flow particle image analyzer of toner particles.

  Here, the flow type particle image measuring apparatus is an apparatus that statistically performs image analysis of particle imaging, and the average circularity is calculated by the arithmetic average of the circularity obtained by the following equation using the apparatus.

  In the above equation, the perimeter of the particle projection image is the length of the contour line obtained by connecting the edge points of the binarized particle image, and the perimeter of the equivalent circle is the binarized particle image Is the length of the outer circumference of a circle having the same area.

  FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.) is used as a flow type particle image measuring apparatus.

  As a measuring method, 0.02 g of a measurement sample is added to 10 ml (20 ° C.) of a solution prepared by adding 0.1 to 0.5 mass% of a surfactant (preferably Wako Pure Chemicals Contaminone) to ion-exchanged water. A sample dispersion was prepared by uniformly dispersing. As a means for dispersion, an ultrasonic disperser UM-50 manufactured by SMT Co., Ltd. (vibrator is a titanium alloy chip having a diameter of 5 mm) is used, and the dispersion time is 5 minutes. At this time, the temperature of the dispersion medium does not exceed 40 ° C. To cool. In the measurement, the range of 0.60 to 400 μm was divided into 226 channels. In actual measurement, the equivalent circle diameter was measured in the range of 0.60 μm or more and less than 159.21 μm.

  When the average circularity is 0.950 to 0.995, the toner shape is almost spherical, so that there is little toner remaining after transfer, and a good result can be obtained with less load in charging in the roller and recovery in the developing device. When the ratio is preferably 0.960 to 0.995, the above-described effect is improved.

  On the other hand, when the average circularity is less than 0.950, there is a large amount of toner remaining after transfer, and the toner tends to be fused to the charging roller.

  Examples of the low softening point substance that can be contained in the toner of the present invention include paraffin wax, polyolefin wax, modified products thereof (for example, oxides and grafted products), higher fatty acids and metal salts thereof, amides, and the like. Waxes, ketone waxes, ester waxes and the like can be mentioned. When used in color toners, amide waxes and ester waxes are preferred because high crystallinity hinders OHP permeability.

  The low softening point substance is blended in an amount of 1 to 35 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the binder resin.

  As the binder resin used in the toner of the present invention, the following binder resins can be used.

  For example, styrene and its substituted homopolymers such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrene copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride; phenol Resin; natural modification Enol resin; Naturally modified maleic acid resin; Acrylic resin; Methacrylic resin; Polyvinyl acetate; Silicone resin; Polyester resin; Polyurethane; Polyamide resin; Furan resin; Petroleum resin can be used. Preferred binder materials include styrene copolymers or polyester resins.

  Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. Acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, monocarboxylic acid having a double bond such as acrylamide or a substituted product thereof; for example, maleic acid, butyl maleate, Dicarboxylic acids having a double bond such as methyl maleate and dimethyl maleate and substituted products thereof; for example, vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; for example, ethylene, propylene, Ethylene monomers such as ethylene; vinyl monomers such as vinyl methyl ketone, vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Are used alone or in combination of two or more.

  The styrenic polymer or styrenic copolymer may be cross-linked, or may be a mixed resin of a cross-linked resin and a non-cross-linked resin.

  As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; , Divinyl aniline, divinyl ether, divinyl sulfide, divinyl sulfone and the like; and compounds having three or more vinyl groups are used alone or as a mixture.

  As addition amount of a crosslinking agent, 0.001-10 mass parts is preferable with respect to 100 mass parts of polymerizable monomers.

  The toner of the present invention may contain a charge control agent.

  The following substances are used for controlling the toner to be negatively charged.

  For example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Also, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene- An acrylic-sulfonic acid copolymer, a nonmetal carboxylic acid compound, etc. are mentioned. Further, a resin into which the charge control compound is introduced may be internally added to the toner.

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

  For example, modified products by nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; Over DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; can be used in combination singly, or two or more kinds. Among these, a charge control agent such as a nigrosine-type quaternary ammonium salt is particularly preferably used. Further, a resin into which the charge control compound is introduced may be internally added to the toner.

  These charge control agents may be used in an amount of 0.01 to 20 parts by mass (more preferably 0.5 to 10 parts by mass) with respect to 100 parts by mass of the resin component.

  As the colorant used in the present invention, as the black colorant, a carbon black, a grafted carbon, or a color toned in black using a yellow / magenta / cyan colorant shown below is used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, and the like are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191, 192, 170, 199, etc. Used.

  In addition, C.I. I. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 and the like.

  If necessary, yellow pigments and dyes may be used alone, or several kinds of pigments and dyes may be used in combination.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202 206, 220, 221, 238, 254 and C.I. I. Pigment Violet 19 and the like are particularly preferable.

  If necessary, magenta pigments and dyes may be used alone, or several kinds of pigments and dyes may be used in combination.

  As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.

  If necessary, cyan pigments and dyes may be used alone, or several kinds of pigments and dyes may be used in combination.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  Next, a method for producing the toner used in the present invention will be described. The toner used in the present invention can be manufactured using a pulverized toner manufacturing method and a polymerized toner manufacturing method.

  In the present invention, the method for producing a pulverized toner includes a binder resin, a low softening point substance, a pigment as a colorant, a dye or a magnetic substance, and, if necessary, a charge control agent and other additives such as a Henschel mixer and a ball mill. Mix thoroughly with a mixer; the resulting mixture is melt-kneaded using a heat kneader such as a heating roll, kneader, extruder, etc., while the resin components are mutually compatible, a low softening point substance, a pigment, a dye, The magnetic material is dispersed or dissolved; the obtained kneaded product is cooled and solidified, and then pulverized and classified to obtain a toner.

  Furthermore, if necessary, desired additives can be sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner used in the present invention.

  In the present invention, a polymerized toner is produced by a method described in Japanese Examined Patent Publication No. 56-13945 or the like using a disk or a multi-fluid nozzle to atomize the molten mixture into the air to obtain a spherical toner, or Japanese Examined Patent Publication No. 36-10231. JP-A-59-53856, JP-A-59-61842, a method of directly producing toner using a suspension polymerization method, An emulsion polymerization method typified by a dispersion polymerization method in which a toner is directly produced using an aqueous organic solvent in which the coalescence is insoluble, or a soap-free polymerization method in which a toner is produced by direct polymerization in the presence of a water-soluble polar polymerization initiator, After making the polar emulsion polymer particles, it is possible to produce a toner using a hetero-aggregation method in which polar particles having opposite charges are added and associated.

  However, in the dispersion polymerization method, the obtained toner shows a very sharp particle size distribution, but the manufacturing apparatus is used from the viewpoint of the processing of the waste solvent and the flammability of the solvent due to the narrow selection of materials to be used and the use of organic solvents. Complicated and complicated. An emulsion polymerization method typified by soap-free polymerization is effective because the particle size distribution of the toner is relatively uniform. However, when the used emulsifier and initiator terminal are present on the toner particle surface, the environmental characteristics are easily deteriorated.

  Therefore, in the present invention, a suspension polymerization method under normal pressure or under pressure, which can obtain a fine particle toner having a sharp particle size distribution relatively easily, is particularly preferable. A so-called seed polymerization method in which a monomer is further adsorbed to the polymer particles once obtained and then polymerized using a polymerization initiator can be suitably used in the present invention.

  When the direct polymerization method is used in the toner manufacturing method of the present invention, the toner can be specifically manufactured by the following manufacturing method. Dispersion stabilizer is a monomer system in which a low softening point substance, a colorant, a charge control agent, a polymerization initiator and other additives are added to the monomer, and the monomer system is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, etc. Is dispersed in a water phase containing water by an ordinary stirrer, homomixer, homogenizer or the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers and by-products that cause odor during toner fixing, the latter half of the reaction, or the completion of the reaction. A part of the aqueous medium may be distilled off later. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer system.

  A more preferable toner used in the present invention is manufactured by a direct polymerization method in which a low softening point substance is encapsulated in an outer shell resin layer in a tomographic measurement method of a toner using a transmission electron microscope (TEM). Is. From the viewpoint of fixing properties, it is necessary to include a large amount of a low softening point substance in the toner. Therefore, it is necessary to encapsulate the necessary low softening point substance in the outer shell resin. If the toner cannot be encapsulated, it will not be finely pulverized unless special freeze pulverization is used in the pulverization process, resulting in only a wide particle size distribution, and toner fusion to the device will also occur. That's bad. Further, in freeze pulverization, the apparatus becomes complicated to prevent dew condensation on the apparatus, and when the toner absorbs moisture, the workability of the toner is lowered, and it is necessary to add a drying process, which becomes a problem. As a specific method for encapsulating the low softening point substance, the polarity of the material in the aqueous medium is set to be smaller than that of the main monomer, and a small amount of a large polar resin or simple substance is used. By adding a monomer, a toner having a so-called core-shell structure in which a low softening point substance is coated with an outer shell resin can be obtained. Toner particle size distribution control and particle size control can be done by changing the type and amount of a poorly water-soluble inorganic salt or protective colloid dispersant and mechanical device conditions such as rotor peripheral speed, number of passes, and stirring blades. The predetermined toner of the present invention can be obtained by controlling the stirring conditions such as the shape, the container shape, or the solid content concentration in the aqueous solution.

  In the present invention, as a specific method for measuring the tomographic plane of the toner, there are four cured products obtained by sufficiently dispersing the toner in a room temperature curable epoxy resin and curing it in an atmosphere at a temperature of 40 ° C. for two days. After staining with ruthenium trioxide and, if necessary, osmium tetroxide, a flaky sample was cut out using a microtome equipped with diamond teeth, and the tomographic morphology of the toner was measured using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to provide a contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell.

  A monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used as the vinyl polymerizable monomer capable of radical polymerization used when a toner is produced by a polymerization method.

  Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene polymerizable monomers such as phenyl styrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n -Hexyl acrylate, 2-ethylhexyl acrylate Acrylic polymerizable monomers such as relate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl Methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, Examples thereof include vinyl polymerizable monomers such as vinyl ethers such as vinyl isobutyl ether and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis [4- (acryloxy-diethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis [4- (methacryloxy-diethoxy) phenyl] propane, Examples include 2,2′-bis [4- (methacryloxy / polyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  The monofunctional polymerizable monomers can be used alone or in combination of two or more, or a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer can be used in combination. Moreover, it is also possible to use the said polyfunctional polymerizable monomer as a crosslinking agent.

  In the present invention, it is preferable to use a polar resin together in order to form a core-shell structure in the toner. Examples of polar resins such as polar polymers and polar copolymers that can be used in the present invention are given below.

  Polar resins include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or copolymers of nitrogen-containing monomers and styrene-unsaturated carboxylic acid esters; nitriles such as acrylonitrile Monomer; Halogen-containing monomer such as vinyl chloride; Unsaturated carboxylic acid such as acrylic acid and methacrylic acid; Unsaturated dibasic acid; Unsaturated dibasic acid anhydride; Polymer of nitro monomer or Examples thereof include copolymers of styrene monomers and polyesters; epoxy resins. More preferred are styrene and (meth) acrylic acid copolymers, maleic acid copolymers, saturated or unsaturated polyester resins, and epoxy resins.

  Examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile). ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or isoazo polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydro Peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis (4,4-t-butylperoxycyclohexyl) propane, tris- (T-butyl peroxy ) Polymeric initiator having a side chain a peroxide-based initiator or a peroxide such as triazine, potassium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide, etc. are used.

  The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by mass per 100 parts by mass of the polymerizable monomer, and may be used alone or in combination.

  Moreover, in order to control molecular weight in this invention, you may add a well-known crosslinking agent and a chain transfer agent, As a preferable addition amount, it is 0.001-15 mass parts.

  In the present invention, any suitable stabilizer is used for the dispersion medium used in the production of the polymerization toner by emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization, polymerization method using hetero-aggregation method, or the like. To do. For example, as an inorganic compound, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. Organic compounds include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch, polyacrylamide, polyethylene oxide, nonionic or ionic surfactants, etc. used.

  In the case of using the emulsion polymerization method and the heteroaggregation method, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and a nonionic surfactant are used. These stabilizers are preferably used in an amount of 0.2 to 30 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Among these stabilizers, when an inorganic compound is used, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be produced in a dispersion medium.

  Moreover, you may use 0.001-0.1 mass part surfactant for fine dispersion | distribution of these stabilizers. This is to promote the desired action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, lauric acid. Examples thereof include sodium, potassium stearate, calcium oleate and the like.

  The toner of the present invention can usually be used for one-component and two-component developers. When using a non-magnetic toner that does not contain a magnetic material as a one-component developer, there is a method in which a blade or roller is used to forcibly frictionally charge with a developing sleeve, and the toner is deposited on the sleeve and conveyed. is there.

  Next, carriers that can be used in the two-component developer of the present invention will be described.

  The method for measuring the volume-based 50% particle size and particle size distribution of the carrier particles of the present invention is a laser diffraction particle size distribution measuring device (manufactured by SYNPATEC) equipped with a dry disperser (Rodos <RODOS>). Loss <HELOS>) and measured under conditions of a feed air pressure of 3 bar and a suction pressure of 0.1 bar.

  The carrier particle diameter is preferably 50% particle diameter (D) on a volume basis, preferably 15 to 60 μm, more preferably 25 to 50 μm. Further, the content of particles having a particle size of 2/3 or less of the 50% particle size (2D / 3 ≧) is preferably 5% by volume or less, more preferably 0.1 to 5% by volume. good.

  When the 50% particle size of the carrier is less than 15 μm, carrier adhesion to the non-image area due to particles on the fine particle side of the carrier particle size distribution may not be satisfactorily prevented. When the 50% particle diameter of the carrier is larger than 60 μm, the sweep due to the rigidity of the magnetic brush does not occur, but the image may be uneven due to its size.

  As the shape of the carrier, the value of the shape factor SF-1 is preferably 100 to 130.

  In the present invention, SF-1 indicating a shape factor is, for example, 100 images that have been magnified to 500 times magnification using, for example, an FE-SEM (S-800) manufactured by Hitachi, Ltd. For example, the image is introduced into an image analysis apparatus (Luzex III) manufactured by Nireco Corporation and analyzed, and the value obtained from the following equation is defined as a shape factor SF-1.

(Where MXLNG indicates the absolute maximum length of the particle, and AREA indicates the projected area of the particle.)
The shape factor SF-1 indicates the degree of roundness of the particles.

  When SF-1 of the carrier is larger than 130, the added fine powder is excessively accumulated in the concave portion of the carrier, so that the charge imparting property of the carrier becomes nonuniform and the drum surface is easily damaged.

In the present invention, the specific resistance of the carrier is preferably 1 × 10 ⁸ to 1 × 10 ¹⁶ Ω · cm, and more preferably 1 × 10 ⁹ to 1 × 10 ¹⁵ Ω · cm.

If the specific resistance of the carrier is less than 1 × 10 ⁸ , the carrier tends to adhere to the surface of the photoconductor, and the photoconductor is easily scratched or directly transferred onto paper to cause image defects. Further, the developing bias may leak through the carrier and disturb the electrostatic latent image drawn on the photosensitive drum.

If the specific resistance of the carrier exceeds 1 × 10 ¹⁶ Ω · cm, an edge-enhanced image is likely to be formed, and further, the charge on the carrier surface is difficult to leak. In some cases, fogging and scattering may occur due to the inability to charge the toner supplied to the toner. Further, the toner is charged with a substance such as an inner wall of the developing device, and the charge amount of the toner to be originally applied may become non-uniform. In addition, it tends to cause image defects such as electrostatic external additives.

The specific resistance of the carrier was measured using a powder insulation resistance measuring instrument manufactured by Vacuum Riko Co., Ltd. Measurement conditions are as follows: a carrier left at 23 ° C. and 60% for 24 hours or more is placed in a measurement cell having a diameter of 20 mm (0.283 cm ² ), sandwiched between 120 g / cm ² load electrodes, and the thickness is set to 2 mm. The voltage was measured at 500V.

The magnetic property of the carrier is such a low magnetic force that the magnetization strength at 1000 / 4π (kA / m) is preferably 20 to 100 Am ² / kg, more preferably 30 to 65 Am ² / kg. Is good.

If the magnetization intensity of the carrier exceeds 100 Am ² / kg, it is also related to the carrier particle diameter, but the density of the magnetic brush formed on the developing sleeve at the developing pole decreases, the head length becomes longer, and the rigidity is increased. Therefore, the unevenness of the sweep is likely to occur on the copy image, and particularly, the durability of the toner is likely to deteriorate due to the copying or printing of a large number of sheets.

If the magnetization strength of the carrier is less than 20 Am ² / kg, even if the carrier fine powder is removed, the magnetic force of the carrier is lowered, carrier adhesion is likely to occur, and toner transportability is liable to be lowered.

The measurement of the magnetic properties of the carrier was performed using an oscillating magnetic field type magnetic property automatic recording apparatus BHV-35 manufactured by Riken Denshi Co., Ltd. As measurement conditions, an external magnetic field of 1000 / 4π (kA / m) was created as the magnetic characteristics of the carrier powder, and the strength of magnetization at that time was determined. Make the carrier packed in a cylindrical plastic container so that the carrier particles do not move sufficiently, measure the magnetization moment in this state, measure the actual weight when the sample is put in The magnetization intensity (Am ² / kg) was determined.

  The carrier according to the present invention may be a resin-coated carrier having ferrite or the like as a core, but has a core in which a metal compound is dispersed in a binder resin and the core surface is coated with a resin. It is preferable that In the case of a magnetic material dispersion type coated carrier, the ratio of the metal oxide in the core is preferably 80 to 99% by mass.

Examples of the metal compound used for the carrier core include magnetite or ferrite having ferromagnetism represented by the following formula (1) or (2).
MO · Fe ₂ O ₃ (1)
M · Fe ₂ O ₄ (2)
(In the formula, M represents a trivalent, divalent or monovalent metal ion.)
M includes Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Nb, Mo, Cd, Sn, Ba, Pb and Li can be mentioned, and these can be used alone or in plural.

  Specific examples of the metal compound particles (ferromagnet) having ferromagnetism include, for example, magnetite, Zn—Fe based ferrite, Mn—Zn—Fe based ferrite, Ni—Zn—Fe ferrite, Mn—Mg—. Examples thereof include iron-based oxides such as Fe-based ferrite, Ca-Mn-Fe-based ferrite, Ca-Mg-Fe-based ferrite, Li-Fe-based ferrite, and Cu-Zn-Fe-based ferrite.

  Furthermore, in the present invention, the metal compound particles used for the carrier core may be a mixture of the above-described ferromagnetic metal compound and the following nonmagnetic metal compound. In this case, as the nonmagnetic metal compound, it is preferable to use a compound having a higher resistance than the metal compound particles having ferromagnetism. Moreover, it is preferable to use so that the ratio of the metal compound which has ferromagnetism may be 50-95 mass% with respect to the total amount of metal oxide.

Nonmagnetic metal compounds include, for example, Al ₂ O ₃ , SiO ₂ , CaO, TiO ₂ , V ₂ O ₅ , CrO, MnO ₂ , α-Fe ₂ O ₃ , CoO, NiO, CuO, ZnO, SrO, Y ₂ O ₃ and ZrO ₂ are mentioned. In this case, one kind of metal compound can be used, but it is particularly preferable to use a mixture of at least two kinds of metal compounds. In that case, it is more preferable to use particles having similar specific gravity and shape in order to increase the adhesion to the binder resin and the strength of the carrier core particles.

Specific examples of combinations include, for example, magnetite and hematite, magnetite and r-Fe ₂ O ₃ , magnetite and SiO ₂ , magnetite and Al ₂ O ₃ , magnetite and TiO ₂ , magnetite and Ca—Mn—Fe based ferrite, magnetite And Ca—MgFe ferrite can be preferably used. Among these, a combination of magnetite and hematite can be particularly preferably used.

  The binder resin for the carrier core particles used in the present invention is a thermosetting resin and is preferably a resin partially or wholly crosslinked three-dimensionally. As a result, the dispersed metal compound particles can be tightly bound, so that the strength of the carrier core can be increased, the metal compound is hardly detached even in a large number of copies, and the coating resin is better. As a result, it becomes easy to control the amount of adsorbed moisture within the scope of the present invention.

  The method for obtaining the magnetic material-dispersed carrier core is not particularly limited to the method described below, but in the present invention, from a solution in which the monomer and the solvent are uniformly dispersed or dissolved, Production method of polymerization method in which particles are produced by polymerizing monomers, in particular, a magnetic substance with a sharp particle size distribution and a small amount of fine powder by applying a lipophilic treatment to the metal oxide dispersed in the carrier core particles A method of obtaining a dispersed resin carrier core is preferably used.

  In the present invention, in the case of a carrier used in combination with a small particle size toner having a weight average particle size of 1 to 10 μm in order to achieve high image quality, the carrier particle size is also reduced according to the particle size of the toner. The above-described manufacturing method is particularly preferable because a carrier with less fine powder can be manufactured regardless of the average particle diameter even if the carrier particle diameter is reduced.

  As the monomer used for the binder resin of the carrier core particle, a radical polymerizable monomer can be used. For example, styrene; styrene derivatives such as o-methyl styrene, m-methyl styrene, p-methoxy styrene, p-ethyl styrene, p-tertiary butyl styrene; acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate Acrylates such as n-propyl acrylate, isobutyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; methacrylic acid, methyl methacrylate , Ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, meta Methacrylic acid esters such as phenyl laurate, dimethylaminomethyl methacrylate, diethylaminoethyl methacrylate, benzyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate; acrylonitrile, methacrylonitrile, acrylamide; methyl vinyl ether, ethyl vinyl ether , Propyl vinyl ether, n-butyl ether, isobutyl ether, β-chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl ether, p-chlorophenyl ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p-methoxyphenyl vinyl ether And vinyl ethers; and diene compounds such as butadiene.

  These monomers can be used alone or in combination, and a suitable polymer composition can be selected so that preferable characteristics can be obtained.

  As described above, the binder resin of the carrier core particles is preferably three-dimensionally crosslinked. However, as a crosslinking agent for three-dimensionally crosslinking the binder resin, a polymerizable double bond is used. It is preferable to use a crosslinking agent having two or more per molecule. Examples of such a crosslinking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and 1,3-butylene glycol. Dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, penta Erythritol dimethacrylate, pentaerythritol tetramethacrylate, glycerol Alkoxy dimethacrylate, N, N-divinyl aniline, divinyl ether, and a divinyl sulfide and divinyl sulfone. These may be used by mixing two or more kinds as appropriate. The cross-linking agent can be mixed in advance with the polymerizable mixture, or can be appropriately added during the polymerization as necessary.

  Other binder resin monomers for carrier core particles include bisphenols and epichlorohydrin as starting materials for epoxy resins; phenols and aldehydes of phenolic resins; urea and aldehydes of urea resins; melamine and aldehydes.

  The most preferred binder resin is a phenolic resin. Examples of the starting material include phenol compounds such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcil, and p-tert-butylphenol, and aldehyde compounds such as formalin, paraformaldehyde, and furfural. A combination of phenol and formalin is particularly preferable.

  When these phenol resins or melamine resins are used, a basic catalyst can be used as a curing catalyst. As the basic catalyst, various catalysts used in the production of ordinary resole resins can be used. Specific examples include amines such as aqueous ammonia, hexamethylenetetramine, diethyltriamine, and polyethyleneimine.

  In the present invention, the metal compound contained in the carrier core is preferably oleophilic in order to sharpen the particle size distribution of the magnetic carrier particles and to prevent the metal compound particles from being detached from the carrier. . When forming carrier core particles in which a metal compound subjected to lipophilic treatment is dispersed, particles insolubilized in the solution are generated at the same time as the polymerization reaction proceeds from a liquid in which the monomer and solvent are uniformly dispersed or dissolved. At that time, it is considered that the metal oxide is taken in uniformly and at a high density inside the particles and has an effect of preventing aggregation of the particles and sharpening the particle size distribution. Furthermore, when a metal compound subjected to oleophilic treatment is used, it is not necessary to use a suspension stabilizer such as calcium fluoride, charging stability is inhibited due to the suspension stabilizer remaining on the carrier surface, and during coating Inhomogeneity of the coating resin and reaction inhibition when a reactive resin such as a silicone resin is coated can be prevented.

  The oleophilic treatment is treated with an oleophilic agent which is an organic compound having one or more functional groups selected from epoxy groups, amino groups and mercapto groups, and a mixture thereof. Is preferred.

  The magnetic metal oxide particles are preferably treated with a lipophilic treatment agent in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 6 parts by weight per 100 parts by weight of the magnetic metal oxide particles. It is preferable for enhancing the lipophilicity and hydrophobicity of the metal oxide particles.

  Examples of the lipophilic agent having an epoxy group include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) trimethoxysilane, epichlorohydrin, and glycidol. And styrene- (meth) acrylic acid glycidyl copolymer.

  Examples of the lipophilic agent having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropylmethoxydiethoxysilane, γ-aminopropyltriethoxysilane, and N-β (aminoethyl) -γ-amino. Propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, ethylenediamine, ethylenetriamine, styrene- (meth) acrylic acid dimethylaminoethyl copolymer Combined and isopropyl tri (N-aminoethyl) titanate are used.

  Examples of the lipophilic agent having a mercapto group include mercaptoethanol, mercaptopropionic acid, and γ-mercaptopropyltrimethoxysilane.

  The resin that coats the surface of the carrier core is not particularly limited. Specifically, for example, acrylic resin such as polystyrene and styrene-acrylic copolymer, vinyl chloride, vinyl acetate, polyvinylidene fluoride resin, fluorocarbon resin, perfluorocarbon resin, solvent-soluble perfluorocarbon resin, polyvinyl alcohol, polyvinyl acetal, Polyvinyl pyrrolidone, petroleum resin, cellulose, cellulose derivative, novolak resin, low molecular weight polyethylene, saturated alkyl polyester resin, aromatic polyester resin, polyamide resin, polyacetal resin, polycarbonate resin, polyethersulfone resin, polysulfone resin, polyphenylene sulfide resin, poly Ether ketone resin, phenol resin, modified phenol resin, maleic resin, alkyd resin, epoxy resin, acrylic resin, anhydrous male Unsaturated polyester, urea resin, melamine resin, urea-melamine resin, xylene resin, toluene resin, guanamine resin, melamine-guanamine resin, acetoguanamine resin, gliptal resin obtained by polycondensation of styrene, terephthalic acid and polyhydric alcohol , Furan resin, silicone resin, polyimide resin, polyamideimide resin, polyetherimide resin and polyurethane resin.

  Of these, silicone resins are preferably used from the viewpoint of adhesion to the core and prevention of spent. The silicone resin can be used alone, but is preferably used in combination with a coupling agent in order to increase the strength of the coating layer and control the charge to a preferable level. Furthermore, the coupling agent described above is preferably used as a so-called primer agent in which a part of the coupling agent is treated on the surface of the carrier core before coating the resin, and the subsequent coating layer is accompanied by a covalent bond. , It can be formed in a more adhesive state.

  Aminosilane is preferably used as the coupling agent. As a result, an amino group having positive chargeability can be introduced on the surface of the carrier, and the toner can be favorably imparted with negative charge characteristics. Furthermore, the presence of amino groups activates both the lipophilic treatment agent that is preferably treated with the metal compound and the silicone resin, thereby further improving the adhesion between the silicone resin carrier core and simultaneously curing the resin. By promoting the above, a stronger coating layer can be formed.

  Hereinafter, an image forming method (image forming apparatus) will be described.

  FIG. 1 is a schematic configuration model diagram of an example of an image forming apparatus according to the present invention. The image forming apparatus of this example is a laser beam printer using a transfer type electrophotographic process, a contact charging method, a reversal development method, cleaner-less, and a maximum sheet passing size of A3 size.

(1) Overall schematic configuration of printer a) Image carrier (photosensitive drum)
Reference numeral 1 denotes a rotating drum type image carrier (hereinafter referred to as a photosensitive drum). As shown in the layer configuration model diagram of FIG. 2, the photosensitive drum 1 includes an undercoat layer 1 b that suppresses light interference and improves the adhesion of the upper layer on the surface of an aluminum cylinder (conductive drum base) 1 a. The photocharge generation layer 1c and the charge transport layer 1d are coated in order from the bottom.

  The photosensitive drum of the present invention is not limited to the above. Hereinafter, typical configurations of other image carriers will be described with reference to FIGS. 3, 4, and 5.

  The photosensitive layer is composed mainly of an organic photoconductor. As the organic photoconductor, an organic photoconductive polymer such as polyvinyl carbazole or a low molecular weight organic photoconductive substance is used in a binder resin. There are things contained in.

  In the electrophotographic photosensitive member of FIG. 3, a photosensitive layer 17 is provided on a conductive support 16, and this photosensitive layer 17 includes a charge generation layer 19 in which a charge generation material 18 is dispersedly contained in a binder resin, and charge transport. It is a laminated structure of the layer 20. In this case, the charge transport layer 20 is laminated on the charge generation layer 19.

  In the electrophotographic photosensitive member of FIG. 4, unlike the case of FIG. 3, the charge transport layer 20 is laminated under the charge generation layer 19. In this case, the charge generation layer 19 may contain a charge transport material.

  In the electrophotographic photosensitive member of FIG. 5, a photosensitive layer 17 is provided on a conductive support 16, and the photosensitive layer 17 contains a charge generation material 18 and a charge transport material (not shown) in a binder resin. Has been.

  Among these, as shown in FIG. 3, a photoreceptor having a structure in which the charge generation layer 19 and then the charge transport layer 20 are laminated in this order from the conductive support 16 side is preferable in the present invention.

  As the conductive support 16, a metal such as aluminum or stainless steel, a cylindrical cylinder such as paper or plastic, a sheet or a film is used. In addition, these cylindrical cylinders, sheets, or films may have a conductive polymer layer or a resin layer containing conductive particles such as tin oxide, titanium oxide, and silver particles as necessary.

  An undercoat layer (adhesive layer) having a barrier function and an undercoat function can be provided between the conductive support 16 and the photosensitive layer 17.

  The undercoat layer is formed to improve the adhesion of the photosensitive layer, improve coating properties, protect the support, cover defects on the support, improve charge injection from the support, and protect against electrical breakdown of the photosensitive layer. Is done. The film thickness is about 0.2 to 2 μm.

  Examples of the charge generation material include bililium, thiopiorilium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzbilenequinone pigments, pyratron pigments, azo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanines, and quinocyanines.

  As the charge transport material, hydrazone compounds, pyrazoline compounds, styryl compounds, oxazole compounds, thiazole compounds, triarylmethane compounds, polyarylalkane compounds, and the like can be used.

  In the charge generation layer 19, the charge generation material is well dispersed by a method such as a homogenizer, an ultrasonic wave, a ball mill, a vibration ball mill, a sand mill, an attritor, and a roll mill together with a binder resin and a solvent in an amount of 0.5 to 4 times. Then, it is formed by coating and drying. The thickness is preferably 5 μm or less, particularly preferably in the range of 0.01 to 1 μm.

  The charge transport layer 20 is generally formed by dissolving the charge transport material and the binder resin in a solvent and applying them. The mixing ratio of the charge transport material and the binder resin is about 2: 1 to 1: 2. Solvents include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and chlorinated hydrocarbons such as chlorobenzene, chloroform, and carbon tetrachloride. Is used. When this solution is applied, for example, a coating method such as a dip coating method, a spray coating method, or a spinner coating method can be used, and drying is performed at a temperature in the range of 10 ° C to 200 ° C, preferably 20 ° C to 150 ° C. 5 minutes to 5 hours, preferably 10 minutes to 2 hours, and the drying can be carried out under blast drying or static drying. The thickness of the generated charge transport layer is preferably 5 to 30 μm, particularly preferably 10 to 25 μm.

  Examples of the binder resin used to form the charge generation layer 19 and the charge transport layer 20 include acrylic resin, styrene resin, polyester, polycarbonate resin, polyarylate, polysulfone, polyphenylene oxide, epoxy resin, polyurethane resin, and alkyd resin. And a resin selected from unsaturated resins and the like are preferable. Particularly preferred resins include polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, polycarbonate resin or diallyl phthalate resin.

  In addition, the charge generation layer or the charge transport layer can contain various additives such as an antioxidant, an ultraviolet absorber, and a lubricant.

b) Charging means 2 is a contact charging device (contact charger) as a charging means for uniformly charging the peripheral surface of the photosensitive drum 1, and in this example, a charging roller (roller charger).

  The charging roller 2 rotatably holds both ends of the cored bar 2a by bearing members (not shown), and is urged in the direction of the photosensitive drum by a pressing pressure spring 2e so that a predetermined amount is applied to the surface of the photosensitive drum 1. It is brought into pressure contact with a pressing force, and rotates following the rotation of the photosensitive drum 1. A pressure contact portion between the photosensitive drum 1 and the charging roller 2 is a charging portion (charging nip portion) a.

  A charging bias voltage of a predetermined condition is applied to the core metal 2a of the charging roller 2 from the power source S1, whereby the peripheral surface of the rotating photosensitive drum 1 is contact-charged to a predetermined polarity and potential. In this example, as the charging bias voltage for the charging roller 2, an oscillating voltage obtained by superimposing a DC voltage (Vdc) and an AC voltage (Vac) is applied.

  Specifically, a vibration voltage in which a DC voltage: −500 V, a frequency f: 1000 Hz, a peak-to-peak voltage Vpp: 1400 V, and an alternating voltage whose waveform is a sine wave is superimposed is applied, and the peripheral surface of the photosensitive drum 1 is applied. Is uniformly charged to −500 V (dark potential Vd).

  The longitudinal length of the charging roller 2 is 320 mm, and the elastic layer 2b, the resistance control layer 2c, and the surface layer 2d are disposed below the cored bar (supporting member) 2a as shown in the layer configuration model diagram of FIG. It is a three-layer structure laminated sequentially. The elastic layer 2b is a foamed sponge layer for reducing charging noise, the resistance control layer 2c is a conductive layer for obtaining a uniform resistance as the entire charging roller, and the surface layer 2d is provided with a pinhole or the like on the photosensitive drum 1. This is a protective layer provided to prevent leakage even if there is a defect.

  Further details will be described.

  In FIG. 2, 2 is a charging member, 2a is a conductive support, 2b is an elastic layer, 2c is a resistance control layer, and 2d is a surface layer. The charging roller may have a configuration of the elastic layer 2b and the surface layer 2d without the resistance control layer 2c.

  For the conductive support 2a used in the present invention, metals such as iron, copper, stainless steel, aluminum and nickel can be used. Furthermore, these metal surfaces may be plated for the purpose of providing rust prevention and scratch resistance, but it is necessary not to impair the conductivity.

  In the charging roller 2, the elastic layer 2 b has appropriate elasticity to ensure good uniform adhesion of the charging roller 2 to the photoreceptor 1.

  The conductivity of the elastic layer 2b is adjusted by adding conductive particles such as carbon black or a conductive agent such as alkali metal salt and ammonium salt to an elastic material such as rubber. Elasticity is adjusted by the addition of process oil and plasticizer. Specific elastic materials for the elastic layer 2b include, for example, natural rubber, ethylene propylene diene methylene rubber (EPDM), styrene-butadiene rubber (SBR), silicone rubber, urethane rubber, epichlorohydrin rubber, isoprene rubber (IR), butadiene rubber. Examples include synthetic rubbers such as (BR), nitrile-butadiene rubber (NBR), and chloroprene rubber (CR), and resins such as polyamide resin, polyurethane resin, silicone resin, and fluororesin. Moreover, you may use the foam of the above-mentioned elastic material for the elastic layer 2b.

The elastic layer preferably has electrical conductivity in the range of 1 × 10 ³ to 1 × 10 ¹⁰ (Ω · cm). Further, since the film thickness depends on the diameter of the conductive support, it is not particularly limited.

  The surface layer 2d is often provided in order to prevent bleed-out of the plasticizer or the like in the elastic layer 2b to the surface of the charging roller, or to maintain the slidability and smoothness of the surface of the charging roller. The surface layer 2d is provided by coating or coating a tube.

  When the surface layer 2d is provided by coating, specific materials include polyamide resins, polyurethane resins, acrylic resins, fluororesins, silicone resins, and the like, as well as epichlorohydrin rubber, urethane rubber, chloroprene rubber, acrylonitrile rubber, etc. Is mentioned. As a coating method, a dip coating method, a roll coating method, a spray coating method, or the like is preferable.

  When the surface layer 2d is provided by covering a tube, specific materials include nylon 12, PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin), PVDF (polyvinylidene fluoride), FEP ( And a thermoplastic elastomer such as polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, and polyamide.

  The tube may be a heat-shrinkable tube or a non-heat-shrinkable tube. In order to impart appropriate conductivity to the surface layer 2d, conductive particles such as carbon black and carbon graphite, conductive metal oxides such as conductive titanium oxide, conductive zinc oxide, and conductive tin oxide are used. A conductive agent is used.

The electric resistance of the surface layer is preferably in the range of 1 × 10 ⁶ to 1 × 10 ¹⁴ (Ω · cm).

  The film thickness is preferably 2 to 500 μm. More preferably, it is 2 to 250 μm.

  The resistance control layer 2c is often provided to control the resistance of the charging member. Specific materials for the resistance control layer 2c include resins such as polyamide resin, polyurethane resin, fluororesin, and silicone resin, as well as epichlorohydrin rubber, urethane rubber, chloroprene rubber, and acrylonitrile rubber. For the purpose of adjusting the resistance of the resistance control layer 2c, conductive particles such as carbon black and carbon graphite, conductive metal oxides such as conductive titanium oxide, conductive zinc oxide and conductive tin oxide, or alkali metal salts In addition, a conductive agent such as an ammonium salt can be dispersed.

  The resistance control layer 2c is also provided by coating or coating a tube.

The electrical resistance of the resistance control layer is preferably in the range of 1 × 10 ⁶ to 1 × 10 ¹⁰ (Ω · cm).

  The film thickness is preferably 10 to 1000 μm. More preferably, it is 10 to 750 μm.

  The volume resistivity in the present invention is measured according to JIS K 6911.

  In FIG. 2, reference numeral 2f denotes a charging roller cleaning member, which is a flexible cleaning film in this example. The cleaning film 2f is arranged in parallel to the longitudinal direction of the charging roller 2 and fixed at one end to a support member 2g that reciprocates a certain amount in the longitudinal direction. It is arranged to form a contact nip. The support member 2g is driven to reciprocate by a certain amount in the longitudinal direction via a gear train by a drive motor of the printer, and the charging roller surface layer 2d is rubbed with the cleaning film 2f. As a result, the adhered contaminants (fine toner, external additives, etc.) on the charging roller surface layer 2d are removed.

c) Information writing means 3 is exposure as information writing means for forming an electrostatic latent image on the surface of the charged photosensitive drum 1. There are a method using an LED array, a method using a semiconductor laser, a method using a liquid crystal shutter array, and the like.

  This example is a laser beam scanner using a semiconductor laser. A laser beam modulated in response to an image signal sent from the host device such as an image reading device to the printer side is output, and the uniformly charged surface of the rotary photosensitive drum 1 is scanned at the exposure position b by laser scanning exposure L (image). Exposure). The laser scanning exposure L lowers the potential of the photosensitive drum 1 surface irradiated with the laser light, so that electrostatic latent images corresponding to the image information scanned and exposed are sequentially formed on the rotating photosensitive drum 1 surface. To go.

d) Developing means 4 is a developing device (developer) as a developing means for supplying a developer (toner) to the electrostatic latent image on the photosensitive drum 1 to visualize the electrostatic latent image. This is a brush developing type reversal developing device.

  4a is a developing container, 4b is a non-magnetic developing sleeve, and this developing sleeve 4b is rotatably arranged in the developing container 4a with a part of its outer peripheral surface exposed to the outside. 4c is a non-rotating fixed magnet roller inserted into the developing sleeve 4b, 4d is a developer coating blade, 4e is a two-component developer contained in the developing container, and 4f is disposed on the bottom side in the developing container. A developer agitating member, 4g is a toner hopper, which contains replenishing toner.

  Accordingly, the toner in the developer coated as a thin layer on the surface of the rotating developing sleeve 4b and conveyed to the developing section c is subjected to the photosensitive drum by the electric field generated by the developing bias under a predetermined condition applied by the power source S2. The electrostatic latent image is developed as a toner image by selectively adhering to one surface corresponding to the electrostatic latent image. In the case of this example, the toner adheres to the exposed bright portion of the surface of the photosensitive drum 1 and the electrostatic latent image is reversely developed.

  The developer thin layer on the developing sleeve 4b that has passed through the developing section c is returned to the developer reservoir in the developing container 4a with the subsequent rotation of the developing sleeve.

  In order to maintain the toner concentration of the two-component developer 4e in the developing container 4a within a predetermined substantially constant range, the toner concentration of the two-component developer 4e in the developing container 4a is adjusted by, for example, an optical toner concentration sensor (not shown). The toner hopper 4g is driven and controlled according to the detected information, and the toner in the toner hopper is supplied to the two-component developer 4e in the developing container 4a. The toner supplied to the two-component developer 4e is stirred by the stirring member 4f.

e) Transfer means / fixing means 5 is a transfer device, and this example is a transfer roller. The transfer roller 5 is brought into pressure contact with the photosensitive drum 1 with a predetermined pressing force, and the pressure nip portion is a transfer portion d. A transfer material (a member to be transferred, a recording material) P is fed to the transfer portion d from a paper feeding mechanism portion (not shown) at a predetermined control timing.

  The transfer material P fed to the transfer portion d is nipped and conveyed between the rotating photosensitive drum 1 and the transfer roller 5, and during that time, the transfer roller 5 has a negative polarity that is the normal charging polarity of the toner from the power source S 3. Is applied with a positive polarity transfer bias of reverse polarity, in this example +2 kV, so that the toner image on the surface of the photosensitive drum 1 side is electrostatically electrostatically applied to the surface of the transfer material P that is nipped and conveyed by the transfer portion d. It will be transcribed.

  The transfer material P which has received the transfer of the toner image through the transfer portion d is sequentially separated from the surface of the rotary photosensitive drum 1 and is conveyed to the fixing device 6 (for example, a heat roller fixing device) to receive the toner image fixing process. Output as an image formed product (print, copy).

(2) Cleanerless system and toner charge amount control The printer of this example is cleanerless, and a dedicated cleaning device that removes a small amount of transfer residual toner remaining on the surface of the photosensitive drum 1 after the transfer of the toner image to the transfer material P is used. Not equipped. The transfer residual toner on the surface of the photosensitive drum 1 after the transfer is carried to the developing portion c through the charging portion a and the exposure portion b as the photosensitive drum 1 continues to rotate, and is developed and cleaned (collected) by the developing device 4. (Cleanerless system)

  In this embodiment, as described above, the developing sleeve 4b of the developing device 4 is rotated in the developing portion c in a direction opposite to the traveling direction of the surface of the photosensitive drum 1, which is the transfer plate toner on the photosensitive drum 1. It is advantageous for recovery.

  Since the untransferred toner on the surface of the photosensitive drum 1 passes through the exposure portion b, the exposure process is performed from the untransferred toner.

  However, as described above, the transfer residual toner includes a mixture of normal polarity, reverse polarity (reversal toner), and low charge amount, among which reverse toner and toner with low charge amount. Adhering to the charging roller 2 when passing through the charging portion a causes the charging roller to contaminate the toner more than permissible, resulting in a charging failure.

  Further, in order to effectively develop and collect the transfer residual toner on the surface of the photosensitive drum 1 by the developing device 3, the charging polarity of the transfer residual toner on the photosensitive drum carried to the developing unit c is a normal polarity. In addition, the charge amount needs to be a charge amount of toner that can develop the electrostatic latent image on the photosensitive drum by the developing device. Reversal toner and toner with an inappropriate charge amount cannot be removed and collected from the photosensitive drum to the developing device, causing a defective image.

  Therefore, in the present embodiment, the charging polarity of the residual toner after transfer is aligned with the negative polarity that is the normal polarity at the position downstream of the transfer portion d in the photosensitive drum rotation direction and upstream of the charging portion a. Toner charge amount control means 7 is provided.

  By aligning the charge polarity of the transfer residual toner to the negative polarity that is the normal polarity, the photosensitive drum 1 is charged when the surface of the photosensitive drum 1 is charged from above the transfer residual toner in the charging unit a located further downstream. Therefore, the transfer residual toner is prevented from adhering to the charging roller 2.

  Next, recovery of transfer residual toner in the development process will be described.

  The developing device 4 is as described above, and is a cleanerless system that cleans the transfer residual toner when performing development.

  The toner charge amount for collecting the transfer residual toner on the photosensitive drum 1 to the developing device 4 is an absolute charge amount smaller than the absolute value of the charge amount when the developer charge amount control means is charged. It is necessary to make it. This is so-called neutralization, and if the charge amount of the transfer residual toner is high, the affinity with the drum is superior, and the toner is not collected by the developing device 4 and causes an image defect.

  However, as described above, in order to prevent the toner remaining on the charging roller 2 from being negatively charged by the toner charge amount control means 7, in order to collect the transfer residual toner in the developing device 4, the charge removal is performed. There is a need to do. The charge removal is performed by the charging unit a. That is, as described above, the AC voltage of 1000 Hz and 1400 V is applied to the charging roller 2, whereby the transfer residual toner is subjected to AC neutralization. Further, by adjusting the AC voltage applied to the charging roller 2, the toner charge amount after passing through the charging portion a can be adjusted by AC neutralization. In the developing step, the transfer residual toner on the photosensitive drum 1 where the toner should not be developed is collected by the developing device 4 for the above reason.

  Thus, the tribo of the transfer residual toner on the photosensitive drum 1 carried from the transfer part d to the charging part a is charged by the toner charge amount control means 7 connected to the power source S4 so as to have the normal polarity and the negative polarity. In this way, the photosensitive drum 1 is charged to a predetermined potential by the charging roller 2 while preventing the transfer residual toner from adhering to the charging roller 2, and at the same time, charged to the negative polarity having the normal polarity by the toner charge amount control means 7. By controlling the charge amount of the processed transfer residual toner to an appropriate charge amount by which the electrostatic latent image on the photosensitive drum can be developed by the developing device 4, the transfer residual toner can be efficiently collected by the developing device. Thus, it is possible to provide an image forming apparatus that is free from charging defects and defective images and that takes advantage of the cleanerless system.

(Example)
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the examples.

  A method for manufacturing the carrier will be described below.

(Magnetic carrier production example 1)
After mixing and dispersing a phenol / formaldehyde monomer (50:50) in an aqueous medium, 600 parts by mass of 0.25 μm magnetite particles and 0.6 μm hematite surface-treated with a titanium coupling agent with respect to 100 parts by mass of the monomer. 400 parts by mass of particles were uniformly dispersed, and the monomer was polymerized while appropriately adding ammonia to obtain a magnetic material-dispersed coated carrier core material 1 (volume-based 50% diameter 33 μm, saturation magnetization 38 Am ² / kg).

On the other hand, 20 parts by mass of toluene, 20 parts by mass of butanol, 20 parts by mass of water, and 40 parts by mass of ice are placed in a four-necked flask, and a mixture of 15 mol of CH ₃ SiCl _{3 and} 10 mol of (CH ₃ ) ₂ SiCl ₂ is stirred. After adding 40 parts by mass and further stirring for 30 minutes, a condensation reaction was performed at 60 ° C. for 1 hour. Thereafter, the siloxane was thoroughly washed with water and dissolved in a toluene-methyl ethyl ketone-butanol mixed solvent to prepare a silicone varnish having a solid content of 10%.

  In this silicone varnish, 2.0 parts by mass of ion-exchange water and 2.0 parts by mass of the following curing agent (1) and 1.0 part by mass of the following aminosilane coupling agent (2) with respect to 100 parts by mass of siloxane solids. And 5.0 mass parts lower silane coupling agent (3) was added simultaneously, and carrier coating solution I was produced. The solution I was applied to 100 parts by mass of the carrier core material with a coating machine (Okada Seiko Co., Ltd .: Spiracoater) so that the resin coating amount was 1 part by mass to obtain a coated carrier 1.

This carrier has a volume-based 50% diameter of 33 μm, a content of particles having a particle size of 2/3 or less of the 50% diameter (2D / 3 ≧) is 3.2% by volume, and has a value of SF-1. Was 113. Furthermore, the specific resistance was 7 × 10 ¹³ Ω · cm, and the saturation magnetization was 41 Am ² / kg.

(Magnetic carrier production example 2)
A carrier core was produced in the same manner as in Production Example 1 except that the ratio of the phenol / formaldehyde monomer was changed to (45:55) to produce a carrier core material, and the obtained carrier core material was classified. Coated carrier 2 having a 50% diameter of 13 μm on a volume basis was obtained.

(Magnetic carrier production example 3)
A carrier core was produced in the same manner as in Production Example 1 except that the ratio of phenol / formaldehyde monomer was changed to (55:45) to produce a carrier core material, and the obtained carrier core material was classified. Coated carrier 3 having a 50% diameter of 70 μm on a volume basis was obtained.

(Magnetic carrier production example 4)
After being atomized using 15 parts by mass of MgO, 10 parts by mass of MnO, and 75 parts by mass of Fe ₂ O _3, granulated by adding water, fired at 1200 ° C., and 50% diameter on a volume basis is 33 μm. A ferrite carrier core material in which the content of particles having a particle size of 2/3 or less of the 50% diameter (2D / 3 ≧) was 9.4% by volume was obtained.

The core material was coated with a resin in the same manner as in Production Example 1 to obtain a coated carrier 4. The SF-1 value of this carrier was 126. Furthermore, the specific resistance was 3 × 10 ¹² Ω · cm, and the saturation magnetization was 57 Am ² / kg.

(Magnetic carrier production example 5)
The ferrite carrier core material obtained in Production Example 4 is classified, and the content of particles having a 50% diameter on a volume basis of 38 μm and a particle diameter of 2/3 or less of the 50% diameter (2D / 3 ≧) is 4. A 1% by volume ferrite carrier core material was obtained. The core was coated with a resin in the same manner as in Production Example 1 to obtain a coated carrier 5.

(Manufacture example 6 of a magnetic carrier)
The ferrite carrier core material obtained in Production Example 4 was pulverized and classified, and the content of particles having a 50% diameter on a volume basis of 36 μm and a particle diameter of 2/3 or less of the 50% particle diameter (2D / 3 ≧) Of 4.2% by volume of ferrite carrier core material was obtained.

  The core material was coated with a resin in the same manner as in Production Example 1 to obtain a coated carrier 6. The SF-1 value of this carrier was 139.

(Manufacture example 7 of a magnetic carrier)
Coated carrier 7 was obtained in the same manner as in Production Example 1 except that the mass was changed to 200 parts by mass of magnetite and 800 parts by mass of hematite.

This carrier has a 50% diameter by volume of 36 μm, a content of particles having a particle size of 2/3 or less of the 50% diameter (2D / 3 ≧) is 4.4% by volume, and has a value of SF-1. Was 115. Furthermore, the specific resistance was 2 × 10 ¹⁶ Ω · cm, and the saturation magnetization was 18 Am ² / kg.

(Manufacture example 8 of a magnetic carrier)
A coated carrier 8 was obtained in the same manner as in Production Example 1 except that 1% of carbon black was contained in Solution I.

This carrier has a 50% diameter on a volume basis of 34 μm, a content of particles having a particle size of 2/3 or less (2D / 3 ≧) of the 50% diameter is 3.9% by volume, and the value of SF-1 Was 118. Furthermore, the specific resistance was 8 × 10 ⁶ Ω · cm, and the saturation magnetization was 47 Am ² / kg.

(Magnetic carrier production example 9)
Coated carrier 9 was obtained in the same manner as in Production Example 1 except that the magnetite was changed to 1000 parts by mass and hematite was not used.

This carrier has a 50% diameter on a volume basis of 38 μm, a content of particles having a particle size of 2/3 or less of the 50% diameter (2D / 3 ≧) is 4.4% by volume, and has a value of SF-1. Was 116. Furthermore, the specific resistance was 5 × 10 ¹⁴ Ω · cm, and the saturation magnetization was 102 Am ² / kg.

  The physical properties of the obtained coated carriers 1 to 9 are shown in Table 2.

  Below, the manufacturing method of a charging roller is demonstrated.

(Production example 1 of charging roller)
Conductive compound 1 was produced by adding and kneading 40 parts by mass of conductive carbon black, 50 parts by mass of paraffin oil, a foaming agent, a crosslinking agent and other compounding agents with respect to 100 parts by mass of EPDM. Next, the compound was vulcanized and formed on a stainless steel core having a diameter of 6 mm, and then the outer diameter was polished to produce an elastic layer 1 which is a foam having a thickness of 3 mm.

  Next, 14.5 parts by mass of conductive carbon black was blended with 10 parts by mass of an ether-based thermoplastic urethane elastomer (Asker C hardness: 62), and melt kneaded at 180 ° C. for 10 minutes using a pressure kneader. Further, after cooling, the mixture was pulverized by a pulverizer and then pelletized using a single screw extruder.

  This pellet was used to obtain a seamless tube having an inner diameter of 10.5 mm and a wall thickness of 500 μm using an extruder. This tube is hereinafter referred to as tube A.

Further, using the same pellet, a disk-like sheet having a diameter of 5 mm and a thickness of 3 mm was produced by hot pressing, and immersed in paraffin oil which is a softening agent for the elastic layer 1 for 7 days. When the weight change rate and the volume resistivity before and after leaving the sheet were measured, the weight change rate was 0.03%, the volume resistivity was 1.9 × 10 ⁶ Ω · cm before being left, and 2 after being left to stand. 0.0 × 10 ⁶ Ω · cm was almost unchanged.

  Separately, 100 parts by mass of conductive carbon black of 14 parts by mass of a thermoplastic elastomer (Asker C hardness: 62) in which a polystyrene molecular chain is bonded to one end of an ethylene butylene rubber molecular chain and an olefin crystal to the other end is covalently bonded. And kneaded at 200 ° C. for 10 minutes using a pressure kneader. Further, after cooling, the mixture was pulverized by a pulverizer and then pelletized using a single screw extruder. Further, a seamless tube having an inner diameter of 11.5 mm and a wall thickness of 200 μm was obtained from the pellets using an extruder. This tube is hereinafter referred to as tube B.

  Subsequently, air was blown into the tube A to expand the outer diameter, the elastic layer 1 was inserted to cover the tube, and then the tube B was coated on the outside in the same manner to obtain the charging roller 1.

Each characteristic of the obtained charging roller 1 was as follows.
Electrical resistance value:
L / L environment (temperature 15 ° C., humidity 10%) 1.2 × 10 ⁶ Ω
H / H environment (temperature 32.5 ° C, humidity 80%) 1.0 × 10 ⁶ Ω
Surface hardness (Asker C): 62 degrees The electrical resistance value was measured by applying a DC voltage of 250 V between the cored bar and the aluminum foil, with an aluminum foil having a width of 10 mm around the outer periphery of the charging roller, and applying an ohmmeter HIOKI3119 DIGITAL MΩ This is a value measured using Hioki Electric).

  The surface hardness (Asker C) is measured using an Asker C rubber hardness meter (manufactured by Kobunshi Keiki Co., Ltd.), and a numerical value is obtained with an average of 5 points. In addition, the measurement is performed with a 500 g load on one side.

(Production example 2 of charging roller)
A charging roller 2 was obtained in the same manner as in Production Example 1 except that the Asker C hardness of the thermoplastic elastomer used for the tube A was 25 degrees and the Asker C hardness of the thermoplastic elastomer used for the tube B was 25 degrees.

(Production example 3 of charging roller)
The charging roller 3 was obtained in the same manner as in Production Example 1 except that the Asker C hardness of the thermoplastic elastomer used for the tube A was 86 degrees and the Asker C hardness of the thermoplastic elastomer used for the tube B was 86 degrees.

(Production example 4 of charging roller)
The charging roller 4 was obtained in the same manner as in Production Example 1 except that the Asker C hardness of the thermoplastic elastomer used for the tube A was 35 degrees and the Asker C hardness of the thermoplastic elastomer used for the tube B was 35 degrees.

(Production example 5 of charging roller)
A charging roller 5 was obtained in the same manner as in Production Example 1 except that the Asker C hardness of the thermoplastic elastomer used for the tube A was 77 degrees and the Asker C hardness of the thermoplastic elastomer used for the tube B was 77 degrees.

  Below, the manufacturing method of the inorganic fine powder used for this invention is demonstrated.

(Inorganic fine powder production example 1)
Commercially available silica obtained by vapor-phase oxidation and high-temperature firing in a hexane solution containing 10 parts by mass of hexamethyldisilazane and 15 parts by mass of polydimethylsiloxane (trade name: KF-96-50cs, manufactured by Shin-Etsu Chemical Co., Ltd.) Add 100 parts by mass of fine particle Aerosil # 90 (manufactured by Nippon Aerosil Co., Ltd.), hydrophobize it at 250 ° C, use a pin mill after the treatment, crush it at a peripheral speed of 50m / sec, and use the Coanda effect Then, the particle size was adjusted to obtain silica fine powder (1) (number average major axis of primary particles 40 nm, measured BET specific surface area 64 m ² / g). FIG. 8 shows a chart of volume-based particle size distribution measured with a laser diffraction particle size distribution meter for the obtained silica fine powder (1).

(Inorganic fine powder production example 2)
Sintered at a slightly lower temperature than in Production Example 1 to produce the active silica, then subjected to the same hydrophobizing treatment as in Production Example 1, further crushed and classified to adjust the particle size, and fine silica powder (3) (number average major axis of primary particles 40 nm, measured BET specific surface area 72 m ² / g) was obtained.

(Inorganic fine powder production example 3)
A raw silica is produced by baking at a slightly higher temperature than Production Example 1, followed by hydrophobization treatment similar to Production Example 1, further pulverization treatment and classification treatment, particle size adjustment, and silica fine powder. (4) (Primary particle number average major axis 40 nm, measured BET specific surface area 68 m ² / g) was obtained.

(Inorganic fine powder production example 4)
The base silica is produced in the same manner as in Production Example 1, and then the hydrophobization treatment is conducted in the same manner as in Production Example 1. Further, only the pulverization treatment is performed, and silica fine powder (5) (number average major axis of primary particles 40 nm, actual measurement) BET specific surface area of 78 m ² / g) was obtained.

(Inorganic fine powder production example 5)
The base silica is produced in the same manner as in Production Example 1, and then the hydrophobization treatment is carried out in the same manner as in Production Example 1, and only the classification treatment is performed. Fine silica powder (6) (number average major axis of primary particles 40 nm, measured BET Specific surface area of 59 m ² / g) was obtained.

(Inorganic fine powder production example 6)
The base silica was produced in the same manner as in Production Example 1 and was not subjected to a hydrophobization treatment, and was made into silica fine powder (7) (number average major axis of primary particles 55 nm, measured BET specific surface area 65 m ² / g).

(Inorganic fine powder production example 7)
Sintered at a slightly lower temperature than in Production Example 2 to produce the base silica, then subjected to the same hydrophobizing treatment as in Production Example 1, and further subjected to only the classification treatment to adjust the particle size to obtain silica fine powder (8) (Number average major axis of primary particles 40 nm, measured BET specific surface area 72 m ² / g) was obtained.

(Inorganic fine powder production example 8)
A raw silica is produced by baking at a slightly higher temperature than in Production Example 3, followed by hydrophobizing treatment similar to that in Production Example 1, further performing only a classification treatment to adjust the particle size, and silica fine powder (9) (Number average major axis of primary particles 40 nm, measured BET specific surface area 76 m ² / g) was obtained.

(Inorganic fine powder production example 9)
The base silica is produced in the same manner as in Production Example 3, and then the same hydrophobization treatment as in Production Example 1 is performed, and the fine silica powder (10) (number average major axis of primary particles 40 nm, (Measured BET specific surface area 51 m ² / g) was obtained.

(Inorganic fine powder production example 10)
Raw material silica having a slightly larger primary particle size than that of Production Example 1 was produced, and then 100 parts of the obtained raw silica fine particles were mixed with dimethylpolysiloxane (trade name: KF-96-50cs, Shin-Etsu Chemical Co., Ltd.). The product is hydrophobized with only 15 parts, and after the treatment, the particle size is adjusted by crushing and classification, and the silica fine powder (11) (number average major axis of primary particles 60 nm, measured BET specific surface area 35 m ² / g). )

(Inorganic fine powder production example 11)
The base silica is produced by firing at a higher temperature (350 ° C. or higher) than in Production Example 3, and thereafter the same hydrophobization treatment, pulverization treatment and classification treatment as in Production Example 1 are carried out. ) (Number average major axis of primary particles 40 nm, measured BET specific surface area 25 m ² / g).

(Inorganic Fine Powder Production Example 12)
The raw silica is produced by firing at a lower temperature (less than 200 ° C.) compared to Production Example 2, and then the same hydrophobization treatment, pulverization treatment and classification treatment as in Production Example 1 are carried out to obtain fine silica powder (13) (Number average major axis of primary particles 40 nm, measured BET specific surface area 130 m ² / g) was obtained.

(Inorganic fine powder production example 13)
A raw silica is produced in the same manner as in Production Example 1, and then 10 parts of hexamethyldisilazane and dimethylpolysiloxane (trade name: KF-96-50cs, Shin-Etsu Chemical Co., Ltd.) are obtained with respect to 100 parts of the resulting fine silica particles. Hydrophobic treatment is performed with 2 parts, and after the treatment, pulverization treatment and classification treatment are performed to adjust the particle size, and silica fine powder (14) (number average major axis of primary particles 40 nm, measured BET specific surface area 84 m ² / g). )

(Inorganic fine powder production example 14)
A raw silica is produced in the same manner as in Production Example 1, and then 10 parts of hexamethyldisilazane and dimethylpolysiloxane (trade name: KF-96-50cs, Shin-Etsu Chemical Co., Ltd.) are obtained with respect to 100 parts of the resulting fine silica particles. Hydrophobic treatment was performed with 38 parts by the company, and after the treatment, pulverization treatment and classification treatment were performed to adjust the particle size, and silica fine powder (15) (number average major axis of primary particles 40 nm, measured BET specific surface area 57 m ² / g). )

  Hereinafter, a toner manufacturing method will be described.

(Toner Production Example 1)
910 parts by mass of ion-exchanged water and 1 part by mass of polyvinyl alcohol are added to a 2 liter four-necked flask equipped with a high-speed agitator TK-homomixer, the number of revolutions is adjusted to 12,000 revolutions, and the mixture is heated to 60 ° C. Dispersant system.

On the other hand, the following were used as the dispersoid system.
Styrene monomer 165 parts by mass n-butyl acrylate monomer 35 parts by mass phthalocyanine pigment (CI Pigment Blue 15: 3) 10 parts by mass saturated polyester resin (condensation product of bisphenol A propylene oxide and terephthalic acid, Mw 10,000 , Mn 6000, acid value 10 mg KOH / g, glass transition point 70 ° C.) 10 parts by mass di-tert-butylsalicylic acid aluminum compound 3 parts by mass divinylbenzene 0.2 parts by mass Low softening point substance (paraffin wax Mw = 1200, Mn = 750) , Mw / Mn = 1.6) 30 parts by mass After the above mixture was dispersed for 3 hours using an attritor, 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added. The added dispersion is put into the dispersion medium and the rotation speed is maintained. Granulated for 12 minutes. Thereafter, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, the internal temperature was raised to 65 ° C., and the polymerization was continued for 10 hours at 50 revolutions.

  After completion of the polymerization, the slurry was cooled, washed with water and dried to obtain cyan toner particles (1). When the particle size distribution of the obtained cyan toner particles (1) was measured with a Coulter counter, the weight average particle size was 6.8 μm.

For 100 parts by mass of the obtained cyan toner particles (1),
Silica fine powder (1) [average primary particle size 40 nm, BET specific surface area 64 m ² / g] 0.6 parts by mass Silica fine particles hydrophobized with polydimethylsiloxane (2) [average primary particle size 13 nm, BET specific surface area 135 m ² / g] 0.3 parts by mass. Titanium oxide fine particles hydrophobized with hexamethyldisilazane (1) [average primary particle size 30 nm, BET specific surface area 110 m ² / g] 0.3 mass The toner was diffused using a Henschel mixer (Mitsui Mining Co., Ltd.) to obtain cyan toner (1). Tables 3 and 4 show the formulation and physical properties of the obtained cyan toner (1).

(Toner Production Examples 2 to 17)
In the cyan toner (1) in Production Example 1, as shown in Tables 3 and 4, respectively, the type and / or addition amount of the silica fine powder to be used was changed to obtain cyan toners (2) to (17). Tables 3 and 4 show the formulations and physical properties of the obtained cyan toners (2) to (17).

(Toner Production Example 18)
Styrene-2-ethylhexyl acrylate-divinylbenzene copolymer (glass transition point 65 ° C.) 100 parts by mass phthalocyanine pigment (CI Pigment Blue 15: 3) 7 parts by mass saturated polyester resin (bisphenol A propylene oxide and terephthalic acid Polycondensation product, Mw 10,000, Mn 6000, acid value 10 mg KOH / g, glass transition point 65 ° C.) 5 parts by mass di-tert-butylsalicylic acid aluminum compound 1 part by mass low softening point substance (paraffin wax, Mw = 1200, Mn = 750, Mw / Mn = 1.6) 8 parts by mass The above mixture is premixed with a Henschel mixer, melt kneaded at a temperature of 130 ° C. with a twin screw extruder kneader, cooled, coarsely pulverized with a hammer mill, and then air It was pulverized with a fine pulverizer using a jet method. . This was classified to obtain cyan toner particles (2). The average circularity of the obtained cyan toner particles (2) was 0.937.

  The cyan toner particles (2) were externally added in the same manner as in Production Example 1 to obtain cyan toner (18). Tables 3 and 4 show the formulation and physical properties of the obtained cyan toner (18).

(Toner Production Example 19)
The cyan toner particles (2) in Production Example 18 were subjected to spheronization treatment using a surface treatment device of a type in which the blades rotate and mechanically processed to obtain cyan toner particles (3). The resulting cyan toner particles (3) had an average circularity of 0.955.

  The cyan toner particles (3) were externally added in the same manner as in Production Example 1 to obtain cyan toner (19). Tables 3 and 4 show the formulation and physical properties of the obtained cyan toner (19).

(Toner Production Example 20)
Except for using magenta colorant (CI Pigment Red 122), yellow colorant (CI Pigment Yellow 93), or black colorant (grafted carbon black) as a colorant in place of the phthalocyanine pigment. In the same manner as in Production Example 1, magenta toner (1), yellow toner (1) and black toner (1) were prepared.

(Toner Production Example 21)
For 100 parts by mass of the cyan toner particles (1) obtained in Production Example 1,
Commercially available silica fine powder R972 [manufactured by Nippon Aerosil Co., Ltd .; average primary particle size 15 nm, BET specific surface area 130 m ² / g] 0.6 parts by mass • Titanium oxide fine particles hydrophobized with hexamethyldisilazane (1) [Average primary particle size 30 nm, BET specific surface area 110 m ² / g] 0.6 parts by mass was added and diffused using a Henschel mixer (Mitsui Mining Co., Ltd.) to obtain cyan toner (20). Tables 3 and 4 show the formulation and physical properties of the obtained cyan toner (20).

  In addition, FIG. 9 shows a volume-based particle size distribution of the silica fine powder used by a laser diffraction type particle size distribution meter.

(Toner Production Example 22)
For 100 parts by mass of the cyan toner particles (1) obtained in Production Example 1,
Commercially available silica fine powder RX200 [manufactured by Nippon Aerosil Co., Ltd .; average primary particle size 12 nm, BET specific surface area 145 m ² / g] 0.6 parts by mass • Titanium oxide fine particles hydrophobized with hexamethyldisilazane (1) [Average primary particle size 30 nm, BET specific surface area 110 m ² / g] 0.6 parts by mass was added and diffused using a Henschel mixer (Mitsui Mining Co., Ltd.) to obtain cyan toner (21). Tables 3 and 4 show the formulation and physical properties of the obtained cyan toner (21).

  Further, FIG. 10 shows a volume-based particle size distribution of the silica fine powder used by a laser diffraction particle size distribution meter.

(Example 1)
Cyan two-component developer 1 was prepared by mixing cyan toner 1 and coat carrier 1 at a toner concentration of 8%.

  Next, a developing device of a commercially available copying machine GP55 (manufactured by Canon) was modified as shown in FIG. 1, and a SUS sleeve having a diameter of 16 mm was developed as a developing sleeve by a sandblasting process, and the surface shape was 10-point average roughness (Rz) = 9. The one adjusted to 0.0 was used.

  In this example, the toner charging control means 7 is provided, and the applied voltage is -800V. A charging roller 31 is used as the charging member. The charging roller is urged in the direction of the image carrier (photosensitive drum) 36 and is brought into pressure contact with the surface of the photosensitive drum with a predetermined pressing force, and is rotated by the rotation of the photosensitive drum. A pressure contact portion between the photosensitive drum and the charging roller is a charging portion (charging nip portion).

  Further, in this example, the charging bias voltage 44 for the charging roller is an oscillating voltage obtained by superimposing a DC voltage (Vdc) and an AC voltage (Vac).

  More specifically, it is a vibration voltage obtained by superimposing a DC voltage of −500 V, a frequency f1000 Hz, a peak-to-peak voltage Vpp 1400 V, and an AC voltage whose waveform is a sine wave, and the circumferential surface of the photosensitive drum 36 is −500 V ( The contact charging process is uniformly applied to the dark portion potential Vd).

  The cleaning unit is removed, the development contrast is set to 250 V, the reversal contrast with fog is set to −150 V, the development bias having a discontinuous AC electric field is applied, the above-described cyan binary developer 1 is used, and high temperature and high humidity ( H / H: 30 ° C./80%), low temperature and low humidity (L / L: 15 ° C./10%), an image was printed using an original document with an image area ratio of 10%, and an initial evaluation was performed. Tables 5 and 6 show the results of continuous copying of 10,000 sheets.

  As shown in Tables 5 and 6, the image quality was good, image change and member contamination due to continuous copying were small, and very good image formation was performed without any problem of toner scattering.

[Developability evaluation method]
(Image density change)
The image density is measured with a Macbeth densitometer or a color reflection densitometer (for example, Color reflection densitometer X-RITE 404 Amanufactured by X-Rite Co.).
Evaluation is based on the difference between the initial density and the density after the endurance of 10,000 sheets.
A: 0.1% or less.
B: More than 0.1% and 0.2% or less.
C: More than 0.2% and 0.3% or less.
D: More than 0.3%.

(Measurement of fog)
For the measurement of fog, the reflectance was measured using a REFECTOMETER MODEL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.), and calculated according to the following formula. A smaller fog value is better. As a sample, an image after 10,000 sheets was used.
Fog (%) = (Reflectance of standard paper;%) − (Reflectance of white solid part of sample;%)
A: 1.2% or less.
B: More than 1.2% and 1.6% or less.
C: More than 1.6% and 2.0% or less.
D: It exceeds 2.0%.

(Charge amount change)
The change in charge amount was evaluated based on the following evaluation criteria for the amount of change in the charge amount value after the end of durability of the developer in the developer container and after 10,000 sheets were passed.
A: The amount of change is 10% or less based on the initial durability.
B: The amount of change exceeds 10% and 15% or less with reference to the initial durability.
C: The amount of change exceeds 15% and 20% or less with reference to the initial durability.
D: The amount of change exceeds 20% based on the initial durability.

  Here, the charge amount of the toner is obtained by mixing 98 parts by mass of a resin-coated ferrite carrier with 2 parts by mass of the toner, leaving it at room temperature and normal pressure for 24 hours, and then shaking for 2 minutes with a good shaker. Measured in the following manner. As the ferrite carrier used at this time, a ternary ferrite core of Cu—Zn—Fe (Fe: about 50%, Cu: about 10%, Zn: about 10%), polyvinylidene fluoride and styrene— A mixture prepared by coating about 1% by mass of a mixture of methyl methacrylate copolymer in a ratio of 50:50 was used so that 250 mesh pass and 350 mesh on would be 70% by mass or more.

FIG. 6 is an explanatory diagram of a charge amount measuring apparatus that measures the tribo charge amount of the toner. First, in a metal measuring vessel 112 having a 500 mesh screen 113 at the bottom, a mixture of toner and carrier to be measured for triboelectric charge is put into a 50-100 ml polyethylene bottle, and hand is taken for 5-10 minutes. And about 0.5 to 1.5 g of the mixture (developer) is added and a metal lid 114 is placed. The total weight of the measurement container 112 at this time is weighed, and the value is defined as W ₁ (g). Next, in the suction device 111 (at least the insulator is in contact with the measurement container 112), suction is performed from the suction port 117, and the air volume control valve 116 is adjusted so that the pressure of the vacuum gauge 115 is 250 mmAq. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 119 at this time is set to V (volt). Here, 118 is a capacitor, and the capacity is C (μF). Next, the weight of the entire measurement container after suction is weighed and is defined as W ₂ (g). The triboelectric charge amount (mC / kg) of the toner is calculated by the following equation using the value measured above.
Toner triboelectric charge amount (mC / kg) = (C × V) / (W ₁ −W ₂ )

(Charging roller dirty)
The charging roller contamination was evaluated based on the following evaluation criteria by visually observing the roller surface and the halftone image.
A: Defects are not recognized at all on the roller surface and the image.
B: Stain is slightly observed on the roller surface in the latter half of durability, but does not appear in the image.
C: In the latter half of the durability, some contamination is observed on the roller surface, and some density unevenness is also generated in the image.
D: In the latter half of the durability, the roller surface is very dirty, and the image has uneven density.

(Transfer efficiency)
As for transfer efficiency, the toner basis weight of the developer developed on the photoconductor under normal temperature and humidity conditions (N / N: 23.5 ° C./50%) using the image forming apparatus shown in FIG. The ratio of the toner basis weight transferred on the paper to the amount was evaluated based on the following evaluation criteria.
A: 90% or more.
B: More than 80% and less than 90%.
C: More than 70% and less than 80%.
D: Less than 70%.

(Solid uniformity)
The obtained solid image on the transfer paper was evaluated as A, B, C, and D with a density difference of 5 points. As a sample, an image after 10,000 sheets was used.
A: 0.1% or less.
B: More than 0.1% and 0.2% or less.
C: More than 0.2% and 0.3% or less.
D: More than 0.3%.

(Drum scraping)
The drum scraping was evaluated based on the following evaluation criteria by visually observing the drum surface and image after enduring 10,000 sheets.
A: Defects are not recognized at all on the drum surface and the image.
B: In the latter half of the durability, a slight decrease in drum surface gloss is observed, but it does not appear in the image.
C: Some scratches are observed on the drum surface in the latter half of the durability, and some streaks are generated in the image.
D: Deep scratches are observed on the drum surface in the latter half of the durability, and streaks are also generated in the image.

(Drum fusion)
The drum fusion was evaluated based on the following evaluation criteria by visually observing the drum surface and solid white image after enduring 10,000 sheets.
A: Defects are not recognized at all on the drum surface and the image.
B: In the latter half of the durability, the drum surface is slightly stained but does not appear in the image.
C: In the latter half of the durability, some stains are observed on the drum surface, and some black spots appear in the image.
D: In the latter half of durability, the drum surface is very dirty, and black spots appear in the image.

(Examples 2 to 19 and Comparative Examples 1 to 7)
In Example 1, the evaluation was performed in the same manner except that the toner, the coat carrier, and the charging roller having the numbers shown in Tables 5 and 6 were used. The evaluation results are shown in Tables 5 and 6.

(Example 20)
Evaluation was performed in the same manner as in Example 1 except that the toner charge control means was removed in place of Example 1. The results are shown in Tables 5 and 6.

(Example 21)
Evaluation was performed in the same manner as in Example 1 except that the toner charge control means was removed instead of Example 1 and a cleaning blade was attached. The results are shown in Tables 5 and 6.

(Examples 22 and 23)
Evaluation was performed in the same manner as in Example 1 except that the outermost surface layer resin of the photosensitive drum was changed from the polyarylate resin to the polyester resin having the molecular weight shown in Tables 5 and 6 instead of Example 1. The results are shown in Tables 5 and 6.

(Example 24)
In Example 1, in the same manner as the cyan two-component developer used, a yellow two-component developer using yellow toner 1, a magenta two-component developer using magenta toner 1, and a black toner 1 are used. Each black two-component developer was obtained. When the image forming apparatus having the configuration shown in FIG. 7 was put into the four-color two-component developer, and 20,000 full-color images were produced, the same good results as in Example 1 were obtained.

  In the image forming apparatus shown in FIG. 7, the development unit of the Canon full-color copying machine CP2100 is changed to a roller charging type development unit similar to that in FIG. 1 (Example 1), and the paper transport belt is an intermediate transfer made of polyimide. The belt 8 is changed. 8a and 8b are tension rollers, 9 is a primary transfer blade, 10 is a secondary transfer roller, 11 is an intermediate transfer belt cleaner, and 12 is a paper transport roller.

1 is a schematic explanatory diagram illustrating an example of an image forming apparatus that can be applied to the present invention. It is a schematic explanatory drawing which shows an example of the charging roller which can be applied to this invention. 1 is a schematic explanatory diagram illustrating an example of an electrophotographic photosensitive member that can be applied to the present invention. It is a schematic explanatory drawing which shows another example of the electrophotographic photoreceptor which can be applied to the present invention. It is a schematic explanatory drawing which shows another example of the electrophotographic photoreceptor which can be applied to the present invention. It is a schematic explanatory drawing of the apparatus which measures a triboelectric charge amount. 1 is a schematic explanatory view showing a full-color image forming apparatus capable of performing an image forming method applicable to the present invention. 2 is a chart showing a volume distribution of silica fine powder 1. 10 is a chart showing a volume distribution of silica fine powder used in Toner Production Example 21. 14 is a chart showing a volume distribution of silica fine powder used in Toner Production Example 22.

Claims (11)

A silicone oil are subjected to hydrophobic treatment, the addition amount of the silicone oil is 3 to 35 parts by weight with respect to the original body 100 parts by mass of the silica fine powder, in and laser diffraction type particle size distribution meter volume-based particle size distribution by Each having a peak in a range of at least 0.04 μm or more and less than 1 μm and 1 μm or more and less than 100 μm, the frequency ratio of 0.04 μm or more and less than 1 μm with respect to all the peaks is 10 to 80%, Silica fine powder characterized by having a frequency ratio of less than 16%.   In the volume-based particle size distribution by a laser diffraction particle size distribution meter, the frequency ratio of 0.04 μm or more and less than 1 μm to all peaks is 20 to 70%, and the frequency ratio of 20 μm or more to less than 2000 μm to all peaks is less than 12%. The silica fine powder according to claim 1, wherein:   3. The fine silica powder according to claim 1, wherein a half-width of a maximum peak in a range of 1 μm or more and less than 100 μm is 5 to 25 μm in a volume-based particle size distribution by a laser diffraction type particle size distribution meter.   3. The fine silica powder according to claim 1, wherein a half-width of a maximum peak in a range of 1 μm or more and less than 100 μm is 8 to 20 μm in a volume reference particle size distribution by a laser diffraction type particle size distribution meter.   The silica fine powder according to any one of 1 to 4, wherein the volume average particle size distribution is 0.1 to 20 μm in a volume-based particle size distribution measured by a laser diffraction particle size distribution meter.   The silica fine powder according to any one of 1 to 4, wherein a volume average particle size is 0.3 to 12 μm in a volume-based particle size distribution by a laser diffraction type particle size distribution meter. Silica fine powder according to any one of 1 to 6, wherein the BET specific surface area of not more than ^{30 m} 2 / g or more 100 m ² / g.   The silica fine powder according to any one of 1 to 7, wherein the silica fine powder includes a part of composite particles formed by combining a plurality of primary particles. The silica fine powder, silica fine powder according to any one of 1 to 8, characterized in that the hydrophobized with a silane coupling Zai及beauty shea recone oil. The silica fine powder after being treated with a silane coupling agent and silicone oil, the classification step and / or silica fine powder according to 9, characterized in that it is produced by performing the crushing step. The silica fine powder according to any one of 1 to 8, wherein the addition amount of the silicone oil is 5 to 25 parts by mass with respect to 100 parts by mass of the silica fine powder base.

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