JP5586844B2 - Toner cartridge - Google Patents

Description

  The present invention relates to a toner (developer) used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, or the like, and a container for storing the toner.

  More specifically, the present invention relates to a toner used in an image forming apparatus such as a copying machine, a printer, or a fax machine that forms a toner image on a photosensitive member in advance and then transfers the toner image onto a transfer material to form an image.

  Furthermore, the present invention relates to a toner cartridge which is composed of at least the toner and a toner container and replenishes the image forming apparatus with toner as necessary.

  Conventionally, many methods are known as electrophotographic methods.

  In general electrophotography, a photoconductive substance is used to form an electrical latent image on an image carrier (hereinafter also referred to as a photoreceptor) by various means, and then the latent image is developed. A method is known in which a toner image is obtained by transferring an agent (hereinafter, also referred to as toner) to a visible image.

  Further, after transferring the toner image to a transfer material such as paper as necessary, the toner image is fixed on the transfer material by heat / pressure to obtain a copy.

  These image forming apparatuses using electrophotography are applied as printers and facsimiles in addition to copying machines.

  In recent years, as image forming devices have become smaller and cheaper, they are not only installed in a stable environment with air conditioning, but also spread to various places such as small offices and factory production sites. However, it has been used in various environments around the world and in various situations.

  Under such circumstances, the image forming device has stability that can obtain good image quality in any environment, such as high humidity / high temperature, low humidity / low temperature, which exceeds conventional assumptions, and a switch on the main body of the device. There is a demand for stability of image quality immediately after putting in, and stability of image quality before and after toner replenishment.

  Various ideas have been made and improved for the purpose of improving the stability with respect to such environments and usage conditions. For example, as an approach from the toner side, a method (Patent Documents 1 and 2) in which two or more kinds of toners per color are appropriately replenished depending on the environment has been proposed.

  However, according to these proposals, although it is possible to replenish toner optimally designed according to the environment, two or more replenishment units per color are installed in the image forming apparatus, and the number of types of toner cartridges increases. This leads to an increase in the size of the device and a complicated handling.

  Furthermore, a method using two or more kinds of externally treated external additives (Patent Documents 3 to 4), a method of making the aggregation state of external additives released from the toner surface constant (Patent Document 5), a charge control agent There is a proposal such as a method of mixing the toner with a toner base and fixing it to the toner surface (Patent Document 6).

  According to these methods, there is an effect as long as it is within the range of the apparatus that is regularly used in the conventional standard number of durable developing devices, or within the range of the conventional use environment.

  However, especially in a high-temperature and high-humidity environment that has been left for a long time beyond the conventional assumptions, the method of mutual effect of the two types of external additives changes the adhesion state of the external additives and the balance is lost. In some cases, the effect may not be sufficient.

  In addition, in the method based on the aggregation state of the liberated external additive, the aggregation state may change. In the method of fixing the charge control agent to the toner surface, the charge control agent is selectively applied to the charge control agent portion by another external additive. These effects may not be sufficient, such as contamination.

  Further, in recent years, even in places where the image forming apparatus is not used regularly, for example, in the first place in the morning in a non-air-conditioned manufacturing factory, or where the manufacturing data for the day is simply printed out by a printer at the end of the day. Image forming apparatuses are widely used.

  Under such circumstances, the conventional assumption range such as when restarting after being left for a long time in a cold place with low air conditioning or in a high-temperature and high-humidity environment, and when toner is consumed rapidly after restarting There is a demand for stability in usage forms exceeding.

  On the other hand, as for the toner storage container, a process cartridge (Patent Document 7) that is used and replaced integrally with a consumable part such as a photoconductor, and a toner cartridge (separate from the photoconductor etc.) that can replace only the toner storage container ( Patent Document 8) is known.

  In recent years, from the viewpoint of reducing running costs and ecology, it is required to extend the life of consumable members such as a photoconductor. For example, a photoconductor has a long life by providing a hard surface layer (Patent Documents 9 to 11). Proposed and realized.

  Regarding the above-described toner container, in the case of the process cartridge type, if the toner capacity is increased in accordance with the life of the photosensitive member having a long life, the process cartridge becomes large and the entire image forming apparatus becomes large.

  To achieve both reduction in running cost and downsizing and cost reduction of the device, a type of toner cartridge that can replace the toner container and replenish the toner even if it has a long life. Is more preferable.

  As a method for manufacturing a toner container in a toner cartridge, for example, a method in which two or more members are joined by injection molding (Patent Document 12), a method by biaxial stretch blow molding (Patent Document 13), and the like are known.

  According to these, as a matter to be considered in selecting the material of the toner container, there are limitations due to the manufacturing method, or strength, flame retardancy, light shielding properties, etc., but materials that have some function with respect to image quality Consideration from such a viewpoint is not made.

  As a member having a function of contacting with toner and triboelectrically charging, for example, a toner carrier for one-component development and a carrier for two-component development have been proposed, and many improvements have been made so far. Has been added.

  However, from the viewpoint of serving as a functional member for environmental stability and image stability, the material and shape of the toner container that contacts and rubs with the toner have been improved with many proposals regarding toner discharge properties. This is not enough.

Japanese Patent Laid-Open No. 08-082950 JP 2004-354788 A JP 2003-050477 A JP 2004-126240 A Japanese Patent Application Laid-Open No. 08-202073 JP 2004-271818 A JP 2002-139914 A JP 2003-177597 A JP 05-035156 A JP 05-088397 A Japanese Patent Laid-Open No. 06-083091 JP 2004-004792 A Japanese Patent Laid-Open No. 2002-221858

  An object of the present invention is to provide a toner cartridge that solves the problems of the prior art.

  That is, an object of the present invention is to provide a toner cartridge capable of obtaining stable image quality regardless of diversified use environments and use forms.

  The invention according to the present application for achieving the above-described object is as follows.

(1) Consists of at least a toner container for storing toner and can be attached to and detached from the image forming apparatus. When the toner cartridge is attached to the image forming apparatus, toner is supplied to the image forming apparatus by rotation of the toner cartridge. In the toner cartridge,
The toner container is obtained by molding a resin by a blow molding method with stretching,
The resin is mainly composed of a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol, and contains either one or both of titanium oxide and zinc oxide,
The toner has toner particles containing at least a binder resin and a colorant, and inorganic fine powder particles having a number average particle diameter of 80 nm to 400 nm, and the free rate of the inorganic fine powder particles from the toner particles is 5 A toner cartridge having a content of 0.0 mass% or more and 35.0 mass% or less.
(2) The shape of the inorganic fine powder particles is an octahedron that is a convex polyhedron surrounded by eight triangles and / or a hexahedron that is a convex polyhedron surrounded by six squares. The toner cartridge according to (1).
(3) The toner cartridge according to (1) or (2), wherein the inorganic fine powder particles are hydrophobized with a coupling agent or a fatty acid metal salt.

  As a result of studying the constituent material of the toner, the constituent material of the toner container, and the manufacturing method, the present inventors can obtain a stable image quality regardless of diversified use environments and use forms in a specific combination. It has been found that a toner cartridge can be provided.

  According to the present invention, appropriate preliminary charging can be given to the toner replenished to the image forming apparatus.

  As a result, when the image forming apparatus that has been left for a long time is restarted, not only the toner charge rise is stable regardless of the environment, but also stable image quality can be obtained even when the toner is consumed rapidly. Can do.

  The present invention relates to a toner cartridge including at least a toner that can be attached to and detached from an image forming apparatus and a toner container that stores the toner.

  Although the present invention can be used for a process cartridge that uses up toner, only a part of the effects of the present invention can be obtained because fresh toner is not replenished to the image forming apparatus from the replenishing container.

  The toner container in the present invention is formed by molding a molding resin containing a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol and containing at least one of titanium oxide and zinc oxide by a stretch blow method. It is characterized by that.

  By using polyester obtained by polymerizing aromatic dicarboxylic acid and alkylene glycol as a main component, it is possible to obtain a toner container with low moisture permeability, and it is possible to suppress changes in humidity inside the container even when the external environment fluctuates. A container is obtained.

  Since the humidity change inside the container can be suppressed, not only the influence of humidity on the toner can be prevented, but also the rubbing state between the toner and the container inner surface does not change depending on the environment. It can be obtained stably.

  In addition, by containing at least one of titanium oxide and zinc oxide in the molding resin, the toner is appropriately charged when the toner and the container are rubbed due to rotational movement for discharging the toner or internal stirring. effective.

  This is presumably because the fine particles of titanium oxide or zinc oxide contained in the resin of the container material act as a resin-coated carrier used for charging the toner with the two-component toner.

  The main component is a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol, and the titanium oxide or zinc oxide contained is suitably dispersed in the resin by molding by a stretch blow method.

  In a toner container that does not preliminarily charge toner, toner without charge is supplied to the image forming apparatus. However, when the toner is consumed rapidly, the charge amount distribution of the toner particles in the image forming apparatus shows the charge amount. Spread to the lower side of the image, leading to a decrease in image density.

  However, by containing at least one of titanium oxide and zinc oxide in the molding resin, the toner to be replenished to the image forming apparatus is preliminarily charged, and even if the toner is consumed rapidly, the charging in the image forming apparatus can be performed. Distribution can be stabilized.

  It is estimated that the same effect can be obtained with the inorganic substance contained in other substances having a difference between the toner and the charge train, but it does not cause problems such as toner adhesion to the container or aggregation due to excessive charging, and in production. Titanium oxide or zinc oxide, which has no problem and is suitable in terms of cost, is preferable.

  In addition, in a molding method such as injection molding that does not involve stretch blow, the distribution state of fine particles of titanium oxide or zinc oxide contained in the resin is not suitable, and the effects of the present invention may not be obtained.

  The toner of the present invention has toner particles and inorganic fine powder particles having a number average particle diameter of 80 nm or more and 400 nm or less, and the free rate of the inorganic fine powder particles from the toner particles is 5.0 mass% or more and 35.35%. It is 0 mass% or less.

  Due to the spacer effect of the inorganic fine powder particles having a number average particle diameter of 80 nm or more and 400 nm or less released from the toner, adhesion of the toner charged in the container to the container can be prevented.

  On the other hand, the inorganic fine powder that is not released from the toner can maintain the fluidity regardless of the environment, and prevent image density fluctuations.

  If the number average particle diameter is smaller than 80 nm, the spacer effect is thin, so that the toner adheres to the inner surface of the container and the charging effect by the container cannot be obtained. If the number average particle diameter is larger than 400 nm, the fluidity is deteriorated and the toner discharge from the container is hindered. There is.

  The effect of the present invention can be exhibited when the liberation rate of the inorganic fine powder particles from the toner particles is 5.0% by mass or more and 35.0% by mass or less.

  The liberation rate in the present invention is the ratio of the inorganic fine powder that is detached from the toner base when the toner particles to which the inorganic fine powder is added are dispersed in the aqueous surfactant solution and the external additive is peeled off at a specific dispersion strength ( Mass%). By using the liberation rate of the present invention, a correlation with the external additive desorbed from the toner base in the toner container can be obtained.

  If the liberation rate is less than 5.0% by mass, the spacer effect is thin, and toner adhesion may occur in the container. If it is greater than 35.0% by mass, the free inorganic fine powder covers the inner surface of the container. The toner charging by the container is hindered.

  In order to control the inorganic fine powder particles to a predetermined release rate, different mixing conditions may be used, such as changing the mixing time with other external additives in the external addition step.

  The particle shape of the inorganic fine powder is based on at least one of an octahedron that is a convex polyhedron surrounded by eight triangles and a hexahedron that is a convex polyhedron surrounded by six quadrilaterals. preferable.

  Since the inorganic fine powder particles have a shape having apexes and ridges, the inorganic fine particles have an effect of preventing the inorganic fine particles adhering to the toner from dropping off. In particular, the inorganic fine powder particles are effective in preventing an increase in release rate due to durability in a high temperature and high humidity environment. is there.

  More preferably, the inorganic fine powder particles are further subjected to a hydrophobic treatment. By performing the hydrophobization treatment, the stability in a high temperature and high humidity environment can be further enhanced.

  The toner cartridge according to the present invention includes at least a toner that can be attached to and detached from the image forming apparatus and a toner container that stores the toner.

  The toner container of the present invention is a blow molding method that involves stretching a molding resin containing, as a main component, a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol, and containing at least one of titanium oxide and zinc oxide. It is obtained by molding by (stretch blow method).

  Specifically, the polyester of the present invention is obtained by polycondensation of an aromatic dicarboxylic acid and an alkylene glycol such as ethylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, or polyalkylene glycol.

  Also, other types of diol components (for example, cyclohexanedimethanol) or other types of dicarboxylic acid components (for example, isophthalic acid, phthalic acid naphthalenedicarboxylic acid, adipic acid, sebacic acid, etc.) may be copolymerized.

  Specific examples of the polyester of the present invention include polyethylene terephthalate (PET), polytetramethylene terephthalate (PBT), polyethylene-2.6-naphthalenedicarboxylate (PEN), and the like.

  By molding these polyesters by the stretch blow method, a toner container having low moisture permeability can be obtained.

  Even if the external environment fluctuates, the humidity change inside the container can be suppressed, and not only the influence of humidity on the toner can be prevented, but also the rubbing state between the toner and the container inner surface does not change depending on the environment.

  The content of titanium oxide and zinc oxide added to the toner container of the present invention is preferably 0.01% by mass or more and 50% by mass or less based on the resin mass.

  If the content is less than 0.01% by mass, the action on the toner may be insufficient, and if it is more than 50% by mass, the resin becomes brittle and the processability deteriorates.

  The particle diameter of titanium oxide and zinc oxide added to the toner container of the present invention is preferably 0.08 μm or more and 300 μm or less.

  When the particle size is smaller than 0.08 μm, it becomes easy to form a container having excellent transparency, but the charging effect on the toner is reduced. On the other hand, if it is larger than 300 μm, it may fall off from the container or a resin defect may occur during stretching.

  Further, when the surfaces of titanium oxide and zinc oxide added to the toner container are coated with an oxide such as alumina or silica, the dispersibility in the resin can be improved. In addition, a known surface treatment or the like may be applied as necessary as long as the effects of the present invention are not impaired.

  The method for dispersing titanium oxide or zinc oxide in the resin is not particularly limited as long as it can be uniformly dispersed.

  Titanium oxide or zinc oxide may be added during the synthesis of the resin, or pellets obtained by adding titanium oxide or zinc oxide to the synthesized resin may be prepared and melt-kneaded.

  In addition to containing at least one of titanium oxide and zinc oxide based on the polyester as a main component, various known additives such as antioxidants, antistatic agents, inorganic particle fillers, organic particle fillers, and colorants Etc. may be added.

  If necessary, for example, a known dispersant may be added to help disperse titanium oxide or zinc oxide. For example, a resin having a softening point lower than that of a main component resin for improving blow moldability. May be added as a minor component.

  If necessary, for example, a polycarbonate or other auxiliary component may be blended to increase the strength. When other functional resins are used, such as for blocking light, gas, or ultraviolet rays, the inner surface of the container is used. If the molding resin of the invention is used, the resin layer may have a structure of two or more layers.

  In addition, a known surface treatment such as DLC vapor deposition, CVD coating, plating other than the inner surface of the container, or decorative printing may be performed as necessary as long as the effects of the present invention are not impaired.

  The toner container may be molded by any method as long as it is blow molding that involves stretching, such as extrusion blow molding or injection blow molding. Of these, the most preferable method is, for example, a biaxial stretch blow molding of an injection molded test tubular preform or parison.

  By molding a resin containing titanium oxide or zinc oxide by a method that involves stretching, for example, the same effect as when the rice-containing rice cake is stretched is produced. That is, the titanium oxide or zinc oxide in the resin is dispersed by stretching, and the titanium oxide or zinc oxide is disposed on the inner surface of the container at a position close to the resin surface. When titanium oxide or zinc oxide is disposed at a position sufficiently close to the inner surface of the container in the container resin, an effect of imparting a charge to the toner stored in the container can be obtained. For example, in molding without stretching such as injection molding, it is difficult to suitably dispose titanium oxide or zinc oxide near the inner surface of the container.

  As an example of a specific method for molding a toner container, first, titanium oxide or zinc oxide is added to polyester obtained by polymerizing aromatic dicarboxylic acid and alkylene glycol to form granular pellets, for example, a twin screw extrusion kneader. Is melt kneaded.

  It is preferable to pass the molten resin through a wire mesh filter or a sintered metal filter at this time because dispersibility of titanium oxide or zinc oxide is improved.

  The melt-kneaded resin is formed into a test tubular preform or parison by, for example, an injection molding machine. The preform or parison can be heated and, for example, biaxially stretched and blown to mold the toner container body.

  Further, a toner sealing member such as a cap or a shutter, or a member such as a rib or a blade for stirring the toner may be attached to the toner container body as necessary.

  The shape of the toner container body is not particularly limited. For example, if a cylindrical container having a rib on the outer periphery rotates and agitates and discharges toner, the inner surface of the container often rubs against the toner. It is preferable because it is easily charged.

  At this time, a structure capable of stirring without toner discharge is more preferable because it enables control to give sufficient preliminary charging as required before discharging.

  In addition, as the structure of the toner container, a structure in which toner is discharged while the container arranged in a rotary shape revolves, a structure in which a stirring shaft is provided in the container and toner is discharged by rotation of the stirring shaft, and the like are known. .

  Of these structures, any shape may be used as long as the inner surface of the container slides on the toner as the toner is discharged.

  The toner of the present invention has toner particles containing at least a binder resin and a colorant, and inorganic fine powder particles having a number average particle diameter of 80 nm or more and 400 nm or less, and the liberation rate of the inorganic fine powder particles from the toner particles is low. It is 5.0 mass% or more and 35.0 mass% or less.

  The method for producing the toner particles is not particularly limited, and the toner particles may be produced by any known method such as suspension polymerization method, emulsion polymerization method, associative polymerization method, kneading and pulverizing method.

  As an example, a method for producing the toner of the present invention in the kneading and pulverizing method will be described.

  In the toner of the present invention, a binder resin, a colorant, other additives and the like are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then a heat kneader such as a heating roll, a kneader, or an extruder is used. Melt-knead, cool and solidify, then pulverize and classify.

  In particular, it is preferable to use a mechanical pulverizer as the pulverizing means used in the toner production method in which the shape of coarse particles is controlled. Examples of the mechanical pulverizer include a pulverizer inomizer manufactured by Hosokawa Micron Corporation, a pulverizer KTM manufactured by Kawasaki Heavy Industries, Ltd., and a turbo mill manufactured by Turbo Industry Co., Ltd. It is preferable to use these apparatuses as they are or after being appropriately modified.

  Furthermore, the inorganic fine powder having a number average particle diameter of 80 nm or more and 400 nm or less and, if necessary, a desired additive are sufficiently mixed by a mixer such as a Henschel mixer to prepare.

  Alternatively, mixing can be externally added at any time after the production of the toner particles. For example, it can be externally added to the toner in the step of classifying or spheroidizing the toner particles.

  As another example, a method for producing the toner of the present invention in the suspension polymerization method will be described.

  First, a low softening point substance, a polar resin, a colorant, a charge control agent, a polymerization initiator, and other additives are added to the polymerizable monomer and uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like. The dispersed monomer is added to an aqueous phase containing a dispersion stabilizer, and dispersed with a normal stirrer, homogenizer, homomixer or the like.

  At this time, granulation is preferably 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 by the action of the dispersion stabilizer and precipitation of the particles is prevented.

  The polymerization temperature is preferably set to 40 ° C. or higher, and generally 50 ° C. or higher and 90 ° C. or lower. In addition, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers, by-products and the like that cause odors during toner fixing, the temperature may be increased in the latter half of the reaction or at the end of the reaction. The partial aqueous medium may be distilled off.

  After completion of the reaction, the produced toner particles are washed, collected by 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.

  The particle size distribution control and particle size control of the toner particles can be carried out by adjusting the pH of the system during granulation, and changing the kind and amount of a hardly water-soluble inorganic salt or a dispersant that acts as a protective colloid.

  Alternatively, it is carried out by controlling mechanical apparatus conditions, for example, the circumferential speed of the rotor, the number of passes, the stirring conditions such as the shape of the stirring blades, the container shape or the solid content concentration in the aqueous solution.

  The toner particles prepared by the above method are classified as necessary. Hereinafter, similarly to the kneading and pulverization method, inorganic fine powder having a number average particle diameter of 80 nm or more and 400 nm or less and, if necessary, desired additives are added to Henschel. It is prepared by mixing thoroughly with a mixer such as a mixer.

  The toner of the present invention may be produced by any method regardless of the method described above, but has at least inorganic fine powder.

  Examples of the inorganic fine powder include metal oxides such as zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, and antimony, and composite metals such as calcium titanate, magnesium titanate, and strontium titanate. Metal salts such as oxides, barium sulfate, calcium carbonate, magnesium carbonate, aluminum carbonate, viscosity minerals such as kaolin, phosphate compounds such as apatite, silica compounds such as silica, silicon carbide, and silicon nitride, carbon black, graphite, etc. Of carbon powder.

  The method for selecting and adjusting the inorganic fine powder is not particularly limited as long as it is within the scope of the present invention.

  Two or more different substances may be selected together, or the same substances with different particle sizes may be selected together. The same substances with different shapes may be mixed, or those with different adjustment methods may be mixed.

  For example, in the case where the base material is a negatively charged toner, inorganic fine powder having a weakly positively charged characteristic is preferable because it is difficult to transfer to a transfer material and cause image problems.

  Further, for example, strontium titanate is more preferable because the release rate from the toner base can be easily controlled and a preferable particle diameter can be obtained.

  The number average particle diameter of the inorganic fine powder is preferably 80 nm or more and 400 nm or less, and more preferably 80 nm or more and 200 nm or less.

  Further, the preferable release rate of the inorganic fine powder from the toner particles is 5.0% by mass or more and 35.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less.

  Due to the spacer effect of the inorganic fine powder particles having a number average particle diameter of 80 nm or more and 400 nm or less released from the toner, adhesion of the toner charged in the container to the container can be prevented.

  On the other hand, the inorganic fine powder that is not released from the toner can maintain the fluidity regardless of the environment, and prevent image density fluctuations.

  If the number average particle diameter is smaller than 80 nm, the spacer effect is thin, so that the toner adheres to the inner surface of the container and the charging effect by the container cannot be obtained. If the number average particle diameter is larger than 400 nm, the fluidity is deteriorated and the toner discharge from the container is hindered. There is.

  When the liberation rate is less than 5.0% by mass, the spacer effect is thin, and toner adhesion to the container may occur. On the other hand, if it is larger than 35.0% by mass, the free inorganic fine powder covers the inner surface of the container, and the toner charging by the container is hindered.

  The number average particle size of the inorganic fine powder in the present invention is obtained by randomly taking 100 samples from a photograph taken with an electron microscope at a magnification of 50,000 times.

  For spherical particles, the diameter, elliptical spherical shape, or rectangular parallelepiped particles, the average value of the minor axis and the major axis is taken as the particle size of the particles, the average value thereof is obtained, and the average is obtained as the number average particle size. It was.

The measurement of the liberation rate of the present invention is performed by the following method when the toner base contains a magnetic substance and the inorganic fine particles do not contain a magnetic substance.
1-1) 50 ml polyethylene sample bottle capable of sealing a solution prepared by adding 2% by mass of nonionic surfactant, preferably Contaminone N (manufactured by Wako Pure Chemical Industries, Ltd .: trade name) to ion-exchanged water 40 g (20 ° C.) is added, 1.5 g of a measurement sample is added, and the mixture is allowed to stand on the magnet sheet for 1 hour.
1-2) The sample that has been allowed to stand for 1 hour is shaken at 1.67S ^-1 for 1 minute using a Yayoi shaker YS-LD (manufactured by Yayoi Co., Ltd .: trade name). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. Place the shaken sample bottle on the magnet and let stand for 1 minute.
1-3) Collect the supernatant of the sample left on the magnet for 1 minute in a separate sample bottle. Remove any toner clumps.
1-4) The sample bottle containing the toner, excluding the supernatant, is dried for 10 hours or more in a vacuum dryer (40 ° C.) without a lid, and then pelletized into an inorganic fine powder by fluorescent X-rays. Measure the X-ray intensity of the corresponding element.
1-5) The X-ray intensity of the same element is also measured for the sample not subjected to the above separation treatment and the toner base sample to which the inorganic fine powder is not added. Ask.

Further, the measurement of the liberation rate when the toner base material does not contain a magnetic material is performed as follows.
2-1) 50 ml polyethylene sample bottle capable of sealing a solution prepared by adding 2% by mass of nonionic surfactant, preferably Contaminone N (manufactured by Wako Pure Chemical Industries, Ltd .: trade name) to ion-exchanged water 40 g (20 ° C.) is added, 1.5 g of a measurement sample is added, and the sealed container is shaken lightly and left to stand for 1 hour.
2-2) The sample that has been allowed to stand for 1 hour is shaken at 1.67S ^-1 for 1 minute using a Yayoi shaker YS-LD (manufactured by Yayoi Co., Ltd .: trade name). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. Immediately transfer the shaken sample to a centrifuge container.
2-3) Using a R26A rotor with a high-speed cooling centrifuge, himac CR20E (trade name, manufactured by Hitachi Koki Co., Ltd.), the set temperature is 20 ° C, and acceleration / deceleration is the shortest time. After centrifuging at a rotation speed of 5.00 S ⁻¹ and a rotation time of 3 minutes, the supernatant is immediately collected in another sample bottle. Remove any toner clumps.
2-4) The sample bottle containing the toner, excluding the supernatant, is dried in a vacuum dryer (40 ° C.) for 10 hours or more without a lid, and then pelletized to form an inorganic fine powder by fluorescent X-rays. Measure the X-ray intensity of the corresponding element.
2-5) For the sample not subjected to the above separation treatment and the toner base sample to which the inorganic fine powder is not added, the X-ray intensity measurement of the same element is performed, and the calculation is performed in the same manner as in the case of the magnetic toner described above. Then, the liberation rate of the inorganic fine powder is obtained.

  For example, in the case of a Henschel mixer, the liberation rate of the inorganic fine powder in the present invention is to change the strength of mixing, such as the rotational speed and time during mixing, the shape of the mixing blade and baffle plate, and the amount of raw materials to be charged. It can be adjusted with.

  When the classified toner base and the inorganic fine powder and, if necessary, the desired additive are added at the same time and mixed, the release rate of the inorganic fine powder of the present invention from the toner base and the most of the other additives The external additive strength that exhibits the effect may not be obtained at the same time.

  In that case, each mixing condition may be adjusted to a suitable one, and the mixing method and mixing conditions are not limited as long as the liberation rate falls within the above range.

  For example, the input timing of the inorganic fine powder and other external additives may be changed during the entire mixing time, or the inorganic fine powder may be premixed. Further, after removing the inorganic fine powder and mixing, other external additives may be additionally mixed under different conditions and different apparatuses.

  Specifically, for example, if the release rate of the inorganic fine powder becomes low when they are simultaneously added, for example, the entire mixing time is determined so that the effects of other additives are optimized.

  Furthermore, mixing the toner base and other additives, excluding the inorganic fine powder, started mixing, stopped at the time after subtracting the mixing time at which the release rate of the inorganic fine powder was optimal, and charged the inorganic fine powder And mix the remaining time.

  A preferable content of the inorganic fine powder contained in the toner of the present invention is 0.01 part by mass or more and 5.0 part by mass or less, more preferably 0.05 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the toner particles. 0.0 parts by mass or less.

  By setting the content of the inorganic fine powder within the above range, the liberated amount released from the toner of the inorganic fine powder at the liberation rate in the present invention is a preferable range for expressing the effects of the present invention. .

  The particle shape of the inorganic fine powder may be any of spherical shape, grape shape, needle shape, polyhedron, etc., but it is surrounded by octahedron, which is a convex polyhedron surrounded by 8 triangles, and 6 rectangles. It is preferable that at least one of hexahedrons which are convex polyhedrons is based.

  In the case of a shape such as a spherical shape that does not get caught, the release rate from the toner particles may increase, for example, at the start-up after being left for a long time in a high-temperature and high-humidity environment.

  A shape having apexes and ridges such as a cube is preferable because it catches on the toner surface and is prevented from falling off the toner. In a polyhedron that exceeds an octahedron, the behavior approaches that of a spherical particle, and therefore an octahedron or hexahedron particle shape is more preferred.

  More preferably, the inorganic fine powder particles are further hydrophobized.

  By subjecting the inorganic fine powder particles to a hydrophobization treatment, it is possible to further suppress fluctuations in the triboelectric charge amount due to the environment. Examples of the hydrophobic treatment agent include a treatment agent such as a coupling agent, silicone oil, and fatty acid metal salt.

  For example, in the case of a coupling agent that is a compound having a hydrophilic group and a hydrophobic group, the hydrophilic group side covers the surface of the inorganic fine powder, the hydrophobic group side becomes the outside, and the inorganic fine powder is hydrophobized.

  In addition, in the case of the hydrophobizing agent as described above, the shape of the inorganic fine powder is hardly changed due to the surface treatment at the molecular level, and the effect of the cubic or cuboid shape is maintained. More preferred.

  Examples of coupling agents include titanate, aluminum, and silane coupling agents. Examples of fatty acid metal salts include zinc stearate, sodium stearate, calcium stearate, zinc laurate, aluminum stearate, and magnesium stearate. The same effect can be obtained with stearic acid, which is a fatty acid.

  As a treatment method, a hydrophobization treatment agent or the like is dissolved and dispersed in a solvent, an inorganic fine powder is added therein, the solvent is removed while stirring, a wet treatment method, a coupling agent, a fatty acid metal salt And a dry method in which the inorganic fine powder is directly mixed and treated with stirring.

  Further, regarding the hydrophobization treatment, it is not necessary to completely treat and coat the inorganic fine powder, and the inorganic fine powder may be exposed as long as the effect is obtained. That is, the surface treatment may be formed discontinuously.

  In addition to the inorganic fine powder contained in the toner of the present invention, as other external additives, inorganic oxides such as silica, alumina and titanium oxide, inorganic fine powder having a fine particle size such as carbon black and carbon fluoride are used as toner particles. It may be added externally.

  These impart fluidity and chargeability to the toner.

  If the silica fine powder, alumina fine powder or titanium oxide fine powder dispersed on the surface of the toner particles are fine particles, these fine powders have a high fluidity-imparting effect. Therefore, these fine powders are preferably fine particles. .

  The number average particle diameter of these fine powders is preferably 5 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less.

  A preferable addition amount of these inorganic fine powders is 0.03 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the toner particles.

  When the added amount of the inorganic fine powder is less than 0.03 parts by mass, sufficient fluidity imparting effect cannot often be obtained. On the other hand, when the amount exceeds 5 parts by mass, the compression index of the toner becomes high, the toner is easily tightened, and an excessive external additive is liberated, which tends to have an adverse effect.

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

(Production Example 1 of Toner Container)
(1) Production of Titanium Oxide Particles After the metatitanic acid slurry was concentrated with an evaporator, it was dried in air at 200 ° C. to obtain raw material titanium oxide powder.

  The raw material titanium oxide powder was filled in an alumina container and then placed in a quartz furnace core tube.

  The atmospheric gas having a hydrogen chloride concentration of 100% by volume was heated from room temperature at 500 ° C./hour while being circulated at a linear flow rate of 22 mm / minute, baked at 1100 ° C. for 30 minutes, and then allowed to cool naturally. A titanium oxide powder was obtained.

(2) Molding of toner container After pulverizing a commercially available polyethylene terephthalate resin for blow molding (TR-8550T manufactured by Teijin Ltd.), 5% by mass of the titanium oxide was added and mixed at room temperature.

  After this mixture was melt-kneaded with a twin-screw extruder, the discharged molten strand was cooled with cold water to obtain a pellet cut to a length of about 5 mm.

  Using these pellets, a preform was molded by an injection molding machine at a cylinder temperature of 290 ° C.

  The molded preform is reheated to 110 ° C., biaxially stretch blow molded using a stretch blow molding machine, and then heat-set in a mold set at 140 ° C. for 10 seconds, with a resin part thickness of 0.6 mm. A hollow molded container having a capacity of 1000 cc was obtained.

  A toner sealing member is attached to this hollow molded container having a cylindrical shape and a spiral rib on the outer periphery, which is designated as a toner container Y1.

(Manufacturing Example 2 of Toner Container)
(1) Production of zinc oxide Zinc hydroxide was molded at a pressure of 120 kg / cm ² (11760 kPa) and sintered at a temperature of 500 ° C. for 5 hours. Thereafter, it was mechanically pulverized to obtain a zinc oxide powder.

(2) Molding of toner container Toner container Y2 was obtained in the same manner as in Toner Container Production Example 1 except that titanium oxide was replaced with zinc oxide.

(Manufacturing Example 3 of Toner Container)
A toner container Y3 was obtained in the same manner as in Toner Container Production Example 2 except that the amount of zinc oxide added was changed to 15% by mass.

(Toner Container Production Example 4)
After pulverizing commercially available polyethylene naphthalate resin for blow molding (TN-8065 manufactured by Teijin Limited), 15% by mass of the zinc oxide was added and mixed at room temperature.

  After this mixture was melt-kneaded with a twin-screw extruder, the discharged molten strand was cooled with cold water to obtain a pellet cut to a length of about 5 mm.

  Using this pellet, a toner container Y4 was obtained in the same manner as in Toner Container Production Example 1.

(Toner Container Production Example 5)
After pulverizing commercially available polyethylene terephthalate resin for blow molding (TR-8550T manufactured by Teijin Ltd.), 15% by mass of the zinc oxide and 2% by mass of pulverized commercially available polycarbonate resin (L1225Y manufactured by Teijin Ltd.) are added. And mixed at room temperature.

  After this mixture was melt-kneaded with a twin-screw extruder, the discharged molten strand was cooled with cold water to obtain a pellet cut to a length of about 5 mm.

  Using this pellet, a toner container Y5 was obtained in the same manner as in Toner Container Production Example 1.

(Manufacturing Example 6 of Toner Container)
A toner container Y6 was obtained in the same manner as in Toner Container Production Example 5 except that the amount of zinc oxide added was changed to 0.02% by mass.

(Toner Container Production Example 7)
After pulverizing commercially available polyethylene terephthalate resin for blow molding (TR-8550T manufactured by Teijin Ltd.), 2% by mass of pulverized commercially available polycarbonate resin (L1225Y manufactured by Teijin Ltd.) without adding titanium oxide or zinc oxide. In addition, a toner container Y7 was obtained in the same manner as in Toner Container Production Example 1 except that mixing was performed at room temperature.

(Manufacturing Example 8 of Toner Container)
A toner container Y8 was prepared in the same manner as in Toner Container Production Example 1 except that a commercially available polycarbonate resin (L1225Y manufactured by Teijin Ltd.) was pulverized and 0.02% by mass of the zinc oxide was added and mixed at room temperature. Obtained.

(Toner container production example 9)
After melt-kneading a commercially available polypropylene resin (J-2003GP, manufactured by Idemitsu Petrochemical Co., Ltd.) using a twin screw extruder, the molten preform is extruded at 220 ° C. and immediately melt blow molded in a mold. Thus, a hollow molded container Y9 having a resin part thickness of 1.8 mm and a capacity of 1000 cc was obtained.

(Inorganic fine powder production example 1)
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution.

  Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.65 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 4.5, and washing was repeated until the electrical conductivity of the supernatant reached 70 μS / cm.

A 0.97-fold molar amount of Sr (OH) 2.8H ₂ O was added to the hydrous titanium oxide, placed in a SUS reaction vessel, and purged with nitrogen gas.

Further, distilled water was added so as to be 0.5 mol / L in terms of SrTiO ₃ .

  The slurry was heated to 83 ° C. at 6.5 ° C./hour in a nitrogen atmosphere, and reacted for 5.5 hours after reaching 83 ° C. After the reaction, the mixture was cooled to room temperature, the supernatant was removed, and washing was repeated with pure water.

  Further, in a nitrogen atmosphere, the slurry is placed in an aqueous solution in which 6.5% by mass of sodium stearate is dissolved with respect to the solid content of the slurry, and while stirring, an aqueous zinc sulfate solution is added dropwise to the surface of the perovskite crystal. Zinc acid was precipitated.

  The slurry was washed repeatedly with pure water and then filtered with Nutsche, and the resulting cake was dried to obtain strontium titanate surface-treated with zinc stearate.

  The obtained strontium titanate had a hexahedral shape in which the particle shape was approximately cubic or cuboid.

  This hydrophobized number average particle diameter of 110 nm and hexahedral strontium titanate is designated as inorganic fine powder B1.

(Inorganic fine powder production example 2)
Magnetite particles of inorganic fine powder B6 described later were surface-treated with 0.5 part by mass of γ-glycidyltrimethoxysilane.

  The hydrophobized number average particle diameter of 180 nm and octahedral magnetite is designated as inorganic fine powder B2.

(Inorganic fine powder production example 3)
Using slaked lime powder obtained by dry slaked quicklime with a theoretical water ratio of 1.5, lime milk having a concentration of 450 g / L was prepared and processed with a high-speed impeller disperser.

Next, after adjusting the lime milk to a concentration of 120 g / L, a carbonation reaction was performed by blowing a CO ₂ -containing gas having a CO ₂ concentration of 29 vol% into the lime milk while stirring.

In the carbonation reaction, a CO ₂ -containing gas is blown until the carbonation rate becomes 6.2% at a feed rate of 18 m ³ / m ² · hr as a first stage, and then a feed rate of 1.5 m ³ / The gas was reduced to m ² · hr, and a CO ₂ -containing gas was blown until the carbonation rate reached 12.8%.

Further, as a third stage, the feed rate was increased to 18 m ³ / m ² · hr, and a CO ₂ -containing gas was blown into the reaction until the carbonation rate reached 44.5% to obtain a reaction product.

  1 mol of a calcium hydroxide aqueous suspension having a viscosity of 2500 cp at 25 ° C. and a concentration of 400 g / L was mixed with 1 mol of the obtained reaction product.

A carbon dioxide-containing gas having a carbon dioxide concentration of 30% by volume at a reaction start temperature of 25 ° C. was blown into the obtained mixture at a supply rate of 8.0 m ³ / m ² · hr to carbonate to a carbonation rate of 50.5%. On average, the product was coarsened to a major axis of 3.8 μm and a thickness of 0.4 μm to prepare an aqueous suspension A.

On the other hand, an aqueous calcium hydroxide suspension having a viscosity of 2500 cp at 25 ° C. and a concentration of 400 g / L is prepared to a concentration of 50 g / L, and a carbon dioxide-containing gas having a carbon dioxide concentration of 30 vol. Aqueous suspension B was prepared by blowing at a rate of 10.0 m ³ / m ² · hr until the carbonation rate was 32.3%.

Next, liquid A and liquid B were mixed so that the molar ratio of Ca-based compound in liquid A and Ca-based compound in liquid B was 100: 8, and the carbon dioxide concentration was 30% by volume at a reaction start temperature of 15 ° C. The carbon dioxide-containing gas was blown at a supply rate of 15 m ³ / m ² · hr and reacted to obtain uniform cubic calcium carbonate having a number average particle size of 150 nm.

  The suspension containing calcium carbonate was repeatedly washed with pure water, and then adjusted to a slurry with a solid content of 10% by mass.

  While stirring the slurry with a disperser at 65 ° C., a fatty acid mixture having a sodium oleate content of 60% by mass, a sodium stearate content of 20% by mass and a sodium palmitate content of 20% by mass was added, After stirring, the press was dehydrated.

  The obtained filter cake was dried with a box dryer and then crushed to obtain calcium carbonate particles treated with a fatty acid mixture.

  This hydrophobized number average particle diameter of 150 nm and hexahedral calcium carbonate is designated as inorganic fine powder B3.

(Inorganic fine powder production example 4)
A hydrous titanium oxide slurry obtained by thermal hydrolysis of an aqueous solution of titanyl sulfate was neutralized to pH 7 with ammonia water, filtered and washed with water. The cake obtained by washing with water was 5% by mass with respect to the titanium oxide of the cake (in terms of TiO ₂ ). Peptization with hydrochloric acid (converted to HCl) gave anatase titania sol having a concentration of 32% by mass converted to TiO ₂ .

  The average primary particle size of this sol was 7 nm.

Further, an illuminite ore containing 50% by mass of TiO ₂ equivalent as a starting material is used, and this raw material is dried at 150 ° C. for 2 hours, and then added with sulfuric acid to be dissolved, whereby an aqueous solution of TiOSO ₄ Got.

This was concentrated, and 3.5 parts by mass was added using the anatase titania sol as a seed, followed by hydrolysis at 120 ° C. to obtain a slurry of TiO (OH) ₂ containing impurities.

This slurry was repeatedly washed with water at pH 5 to 6 to sufficiently remove sulfuric acid, FeSO ₄ , and impurities. Then, a slurry of high purity metatitanic acid [TiO (OH) ₂ ] was obtained.

The metatitanic acid is heat-treated at 300 ° C. for 5 hours, and then sufficiently crushed to obtain a hydrophilic anatase crystal hydrophilic titanium oxide fine powder having a BET specific surface area of 120 m ² / g and a number average particle size of 100 nm. Obtained.

Next, while sufficiently dispersing 20 parts by mass of i-C ₄ H ₉ —Si— (OCH ₃ ) ₃ as a hydrophobizing agent with respect to 100 parts by mass of the hydrophilic titanium oxide in water, The mixture was added dropwise and subjected to a hydrophobic treatment.

  Then, after filtering and drying at 120 ° C. for 5 hours, heat treatment is performed at 170 ° C. for 5 hours, and pulverization is performed with a jet mill until aggregates of the hydrophobic titanium oxide fine particles disappear to obtain hydrophobic titanium oxide fine particles. It was.

  This hydrophobized number average particle diameter of 135 nm and spherical titanium oxide is used as inorganic fine powder B4.

(Inorganic fine powder production example 5)
After adding 148.7 ml of 1.6 mol / L ceric chloride CeCl ₃ aqueous solution and 19.7 g of 31 mass% hydrogen peroxide water in terms of CeO ₂ , pure water was added to make the total amount 200 ml. Hereinafter, this is referred to as raw material A.

On the other hand, a 28 wt% aqueous ammonia, NH ₃ and CeCl atomic ratio of Cl contained in the ₃ NH ₃ / Cl are weighed 65.6ml to be 1.5, to which the total amount by adding pure water 200ml It was. Hereinafter, this is referred to as raw material B.

  Next, both the raw material A and the raw material B were put into a beaker and dropped while stirring to precipitate cerium oxide-containing cerium gel. At this time, 50 ml of pure water was previously added to the beaker.

  Next, this precipitated gel was heat-treated at 150 ° C. for 24 hours in an autoclave to obtain 500 ml of slurry, which was filtered and washed 5 times with pure water, further washed with 200 ml of ethyl alcohol, stirred, filtered and dried under reduced pressure. Thus, cerium oxide powder was obtained.

  This number average particle diameter of 105 nm and hexahedral cerium oxide are designated as inorganic fine powder B5.

(Inorganic fine powder production example 6)
To a reaction vessel containing 20 L of 3.0 mol / L sodium hydroxide aqueous solution, 20 L of ferrous sulfate aqueous solution with Fe ²⁺ of 1.5 mol / L is added, and the temperature is set to 95 ° C. A ferrous salt suspension containing was produced.

  The mixture was stirred for 90 minutes while aeration of 100 L / min air was conducted to obtain a ferrous suspension containing magnetite. A 6.0 mol / L aqueous sodium hydroxide solution was added thereto to adjust the pH to 10.0.

  Furthermore, it stirred for 60 minutes, ventilating 100 L / min air, and the magnetite particle | grains were produced | generated. After stirring sufficiently, the magnetite was filtered off. The magnetite was washed with water; dried, and then crushed to obtain octahedral magnetite particles.

  This octahedral magnetite having a number average particle diameter of 180 nm is designated as inorganic fine powder B6.

(Inorganic fine powder production example 7)
A stirrer, a dropping funnel and a thermometer were set in a glass reactor, and ammonia water was added to ethanol and stirred, and kept at 25 ° C.

  Next, tetraethoxysilane was dropped into the solution for 60 minutes to react. After completion of the dropping, stirring was further continued at 25 ° C. for 3 hours to obtain a silica sol suspension. Next, this silica sol suspension was heated to remove ethanol, and then toluene was added and further heated to remove water.

  Thereafter, the suspension was heated to remove toluene, dried at 110 ° C. using a fluidized bed dryer, and then sufficiently crushed with a pin mill to obtain silica particles.

  This silica having an irregular shape with a number average particle diameter of 110 nm is designated as inorganic fine powder B7.

(Inorganic fine powder production example 8)
A ferrous sulfate solution containing 0.95 equivalents of sodium hydroxide aqueous solution was mixed with Fe ^{2+ in a} ferrous sulfate solution, and then a ferrous salt aqueous solution containing Fe (OH) ₂ was produced. Next, air was passed through the aqueous ferrous salt solution containing Fe (OH) ₂ at a temperature of 90 ° C. to cause an oxidation reaction under the condition of pH 7.

Further, 1.05 equivalent of an aqueous sodium hydroxide solution was added to this suspension with respect to the remaining Fe ²⁺ , and the mixture was further oxidized at a temperature of 8 to 11.5 while being heated at 90 ° C. To produce magnetite.

  The produced magnetite was washed, filtered and dried by a conventional method. Since the obtained primary particles of magnetite aggregate to form aggregates, the magnetite was crushed by applying a compressive force and a shearing force to the aggregates of magnetite using a mix muller.

  Spherical magnetite having a number average particle diameter of 210 nm is designated as inorganic fine powder B8.

(Inorganic fine powder production example 9)
Using aluminum hydroxide having a purity of 99.0% as a starting material, alumina fine particles having a number average particle diameter of 110 nm were synthesized by appropriately adjusting the sintering temperature condition and atmosphere using a production method by the Bayer method.

  This alumina having a number average particle diameter of 110 nm is designated as inorganic fine powder B9.

(Inorganic fine powder production example 10)
Cerium oxalate was molded at a pressure of 1200 kg / cm ² and sintered at a temperature of 1800 ° C. for 5 hours. Thereafter, it was mechanically pulverized to obtain cerium oxide having an average particle size of 90 nm.

  This cerium oxide having a number average particle diameter of 90 nm is designated as inorganic fine powder B10.

(Inorganic fine powder production example 11)
Trimethyl borate was synthesized from 1 mol of boron oxide and 7.5 mol of methanol. The obtained volatile trimethyl borate was introduced into a quartz tube attached to a tubular furnace using nitrogen gas, and heated to 700 ° C. in a stream of argon gas and ammonia gas.

  A 70 nm boron nitride powder adhered to the inner wall of the quartz tube was obtained. The obtained boron nitride was subsequently heated to 1100 ° C. in an ammonia gas stream and grown for about 8 hours until the particle diameter reached 350 nm.

  This boron nitride having a number average particle diameter of 350 nm is referred to as inorganic fine powder B11.

(Toner Production Example 1)
(1) Production of polyester resin / Aromatic dicarboxylic acid: 6.2 mol
-Dodecenyl succinic anhydride: 3.7 mol
-Trimellitic anhydride: 3.3 mol
・ PO-BPA: 7.4 mol
・ EO-BPA: 3.0 mol
The above polyester monomer is charged into an autoclave together with an esterification catalyst, and a condensation polymerization reaction is carried out while heating to 215 ° C. in a nitrogen gas atmosphere with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device A polyester resin was obtained.

(2) Production of Hybrid Resin Component 80 parts by mass of the polyester resin was dissolved and swollen in 100 parts by mass of xylene.

  Next, 15 parts by mass of styrene, 5 parts by mass of 2-ethylhexyl acrylate, and 0.15 parts by mass of dibutyltin oxide as an esterification catalyst were added and heated to the reflux temperature of xylene. The transesterification reaction with ethylhexyl was started.

  Further, a xylene solution in which 1 part by mass of t-butyl hydroperoxide was dissolved in 30 parts by mass of xylene as a radical polymerization initiator was dropped over about 1 hour. The radical polymerization reaction was completed by holding at that temperature for 6 hours.

  By removing the solvent by heating to 200 ° C. under reduced pressure, a transesterification reaction between the hydroxyl group of the polyester resin and 2-ethylhexyl acrylate, which is a copolymerization monomer of the vinyl polymer unit, is performed. A hybrid resin 1 produced by ester bonding of the polymer polymer and the polyester unit and the vinyl polymer unit was obtained.

  The obtained hybrid resin 1 has an acid value of 28.5 mgKOH / g, Tg of 58 ° C., peak molecular weight Mn of 7400, weight average molecular weight Mw of 45000, Mw / Mn of 8.3, THF About 12% by mass of insoluble matter was contained.

(3) Production of toner particles 100 parts by weight of the above hybrid resin 1 7 parts by weight of low molecular weight ethylene-propylene copolymer 2 parts by weight of charge control agent (azo-based iron complex compound) 90 parts by weight of magnetic iron oxide (average) (Particle size 0.19 μm, coercive force 11.2 KA / m, remanent magnetization 10.8 Am ² / kg, saturation magnetization 82.3 Am ² / kg)
The above mixture was melt-kneaded with a twin-screw kneader heated to 130 ° C., and the cooled mixture was coarsely pulverized with a hammer mill.

Further, the pulverization process uses a mechanical pulverizer (Turbo Kogyo Co., Ltd.) turbo mill T-250 type, the gap between the rotor and the stator is 1.5 mm, the tip peripheral speed of the rotor is 115 m / sec, and the conveying air flow rate Was operated at 30 m ³ / h and the supply of the coarsely crushed product was 24 kg / h.

  The obtained finely pulverized product was classified by an air classifier, and toner particles having a weight average particle diameter of 7.2 μm, 10.1 μm or more were 6.5% by volume.

With respect to 100 parts by mass of the toner particles, 1.0 part by mass of the inorganic fine powder B1, 1.0 part by mass of hydrophobic dry silica (BET specific surface area: 300 m ² / g), and stirring blade rotation speed of 26. The toner T1 of the present invention was obtained by rotating for 4 minutes with a 67S- ¹ Henschel mixer FM150 (Mitsui Miike).

  The release rate of the inorganic fine powder of the obtained toner was measured and shown in Table 1.

(Toner Production Examples 2 to 11)
Toners T2 to T11 were obtained in the same manner as in Toner Production Example 1 except that the inorganic fine powder to be added was changed to B2 to 11 as shown in Table 1, and the mixing conditions for external addition were changed as shown in Table 1. . The release rate of the inorganic fine powder of the obtained toner was measured and shown in Table 1.

(Toner Production Example 12)
630 parts of ion-exchanged water and 485 parts by mass of a 0.1 mol / L Na ₃ PO ₄ aqueous solution were added to a 2 L four-necked flask equipped with a high-speed stirrer CLEAMIX (M Technique Co., Ltd.). The number of revolutions of CLEARMIX was set to 233.3S- ¹ and heated to 65 ° C.

To this, 65 parts by mass of a 1.0 mol / L CaCl ₂ aqueous solution was gradually added, and 10% hydrochloric acid was added dropwise thereto, and pH = 5.8 containing a minute water-insoluble dispersant Ca ₃ (PO ₄ ) 2 was added. An aqueous dispersion medium was prepared.

-Styrene monomer 180 parts by mass-n-Butyl acrylate monomer 20 parts by mass-Carbon black 25 parts by mass-Aluminum compound of 3.5-di-tert-butylsalicylic acid 1.3 parts by mass A mixture was prepared by dispersing the mixture for 5 hours, and then the following components were added to the mixture and further dispersed for 2 hours to prepare a monomer mixture.

・ Saturated polyester resin (monomer composition: polycondensation product of propylene oxide modified bisphenol A and terephthalic acid)
(Acid value 8.8 mg KOH / g, peak molecular weight 12,500, weight average molecular weight 19500)
12 parts by mass / ester wax (composition: behenyl behenate, molecular weight 11500) 20 parts by mass

Next, a polymerization initiator composition is prepared by adding a polymerization initiator 2.2′-azobis (2.4-dimethylvaleronitrile) 5 (part by mass) to the monomer mixture, and then an aqueous dispersion medium. Then, the mixture was granulated at 250 S ⁻¹ for 15 minutes in a nitrogen atmosphere with an internal temperature of 70 ° C.

Thereafter, the stirrer was replaced with a propeller stirrer, and polymerization was performed for 5 hours while maintaining at 70 ° C. while stirring at 0.83 S ⁻¹ , and the internal temperature was raised to 80 ° C. for polymerization for 5 hours. After the polymerization was completed, the slurry was cooled and diluted hydrochloric acid was added to remove the dispersant.

  Further, it was washed with water, dried and classified to obtain toner particles having a weight average diameter of 6.8 μm.

With respect to 100 parts by mass of the toner particles, 1.0 part by mass of the inorganic fine powder B11, 1.0 part by mass of hydrophobic dry silica (BET specific surface area: 300 m ² / g), and a stirring blade rotation speed of 26. The toner T12 of the present invention was obtained by rotating for 4 minutes with a 67S- ¹ Henschel mixer FM150 (Mitsui Miike). The release rate of the inorganic fine powder of the obtained toner was measured and shown in Table 1.

(Toner Production Examples 13 to 14)
Toners T13 to T14 were obtained in the same manner as in Toner Production Example 12 except that the inorganic fine powder to be added was changed as shown in Table 1 and the external addition mixing conditions were changed as shown in Table 1. The release rate of the inorganic fine powder of the obtained toner was measured and shown in Table 1.

<Example 1>
The toner container Y1 was filled with 85% by volume of the toner T1 to obtain a toner cartridge A1.

  The Canon laser beam printer iR2270, which is a mechanism for replenishing toner by rotating a detachable toner cartridge, has been modified so that the toner cartridge of the present invention can be mounted in place of the toner cartridge for iR2270.

  Further, the sub hopper between the toner cartridge mounting portion and the developing machine is eliminated, and the toner discharged from the toner cartridge is remodeled to be directly supplied to the developing machine.

  Further, in order to make the image quality stability before and after toner replenishment appear well, the volume of the toner in the developing device is reduced to ½, and the toner flow in the developing device is changed. A stirring member was attached so that the toner amount was uniform in the longitudinal direction.

  Using this apparatus and the toner cartridge A1, a paper passing durability test was conducted.

  In an environmental test room where the temperature and humidity in the room can be adjusted, first, the solid image density and the fogging on the white background of the initial image were evaluated in an environment of 25 ° C./40% RH.

  Next, the temperature and humidity in the environmental test chamber were changed to 35 ° C./85% RH over 8 hours and left for 88 hours, and then the solid image density and white background fogging were evaluated.

  Next, the solid image density and the fogging on the white background were evaluated immediately after the continuous printing of 10,000 sheets using a document with a printing area of 30%.

  After confirming the initial image in an environment of 25 ° C./40% RH, the temperature and humidity in the environmental test chamber was changed to 5 ° C./15% RH over 8 hours and left for 88 hours. Image density and fogging on white background were evaluated.

  Next, the solid image density and the fogging on the white background were evaluated immediately after the continuous printing of 10,000 sheets using a document with a printing area of 30%.

  In addition, through the paper passing durability test, the presence or absence of other image defects and toner scattering in the machine was confirmed.

  The solid image density was averaged by measuring five solid portions of the original image with a color reflection densitometer (for example, X-RITE 404A: manufactured by X-Rite Co.).

  For the fog, the whiteness of the white background portion was measured with a reflectometer (densitometer TC6MC: Tokyo Denshoku Technical Center), and the fog amount (%) was calculated from the difference between the whiteness and the average whiteness of the transfer paper.

  From the above paper passing durability test results, it is possible to obtain an image at startup after being left in a high-temperature and high-humidity environment, and a good image with little fluctuation in image density even when a large amount of toner is consumed and replenished toner is sent. It was confirmed that

  The evaluation results were ranked in 5 stages, and were rated as pass 3 or higher. The evaluation results are shown in Table 2 together with confirmation of the presence of other image defects and toner scattering in the machine.

[Image density evaluation rank] Initial stage and after 10,000 sheets passed Rank 5: Reflection density 1.40 or higher Rank 4: Reflection density 1.35 to 1.39
Rank 3: Reflection density 1.30 to 1.34
Rank 2: Reflection density 1.25 to 1.29
Rank 1: Reflection density 1.24 or less

[Image density evaluation rank] After standing for 88 hours Rank 5: Reflection density 1.40 or higher Rank 4: Reflection density 1.30 to 1.39
Rank 3: reflection density 1.20 to 1.29
Rank 2: Reflection density 1.10 to 1.19
Rank 1: Reflection density 1.09 or less

[White background evaluation rank]
Rank 5: Cover 0.50% or less Rank 4: Cover 0.51 to 1.50%
Rank 3: Fog 1.51 to 3.00%
Rank 2: Cover 3.01 to 5.00%
Rank 1: Cover 5.01% or more

<Examples 2 to 12>
The toner containers Y2 to Y5 are filled with the toners T1 to T11 as shown in Table 1 to obtain toner cartridges A2 to A12. Evaluation was performed in the same manner as in Example 1 using the toner cartridges A2 to A12. The evaluation results are shown in Table 2.

<Example 13, Comparative Examples 1 to 4>
The toner containers Y5 to 9 are filled with the toners T12 to T14 as shown in Table 1 to obtain toner cartridges A13 to A17.

  For evaluation using a non-magnetic toner, a Canon color laser beam printer LBP2810, which is a process cartridge type, was modified to a toner cartridge type and used.

  First, the first to third stage process cartridges from the top were removed while leaving the process cartridge from which the toner had been removed in the cyan station at the bottom.

  The toner cartridge of the present invention and a member that rotates the toner cartridge and replenishes the toner are attached to the vacant space so that the toner is replenished from the toner cartridge to the process cartridge according to the remaining amount of toner in the process cartridge.

  Further, the volume was reduced so that the toner capacity in the lowermost process cartridge was halved, and a stirring member was attached so that the toner amount was uniform in the longitudinal direction of the developer carrier.

  Using this apparatus and toner cartridges A13 to A17, a paper passing durability test was conducted in the same manner as in Example 1. The evaluation results are shown in Table 2.

  From the above evaluation results, the effect of the present invention was confirmed.

  In Comparative Example 1 in which the liberation rate of the inorganic fine powder particles exceeded the preferable range, the inorganic fine powder particles adhered to the inner surface of the toner container to inhibit charging of the toner, and the toner was rapidly consumed under high temperature and high humidity. At this time, low-charge toner was supplied to the image forming apparatus, and the image density was lowered.

  In Comparative Example 2 in which the inorganic fine powder particles were not added, toner adhered to the inner surface of the toner container, and toner discharge failure occurred under low temperature and low humidity.

  In Comparative Examples 3 and 4 in which the main component of the toner container is not polyester, similar results to Comparative Example 1 were obtained because the toner was insufficiently precharged in the toner container.

  As the evaluation results of Examples 1 to 13 show, a molding resin containing, as a main component, a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol, and containing at least one of titanium oxide and zinc oxide, A toner container formed by a stretch blow method, toner particles containing at least a binder resin and a colorant, and inorganic fine powder particles having a number average particle diameter of 80 nm or more and 400 nm or less, from the toner particles of the inorganic fine powder particles If a toner cartridge composed of a toner having a liberation ratio of 5.0% by mass or more and 35.0% by mass or less is used, good image quality can be obtained regardless of the use environment or use form.

  Further, in Examples 1 to 5 in which the inorganic fine powder was subjected to a hydrophobic treatment, the decrease in image density when left for a long time under high temperature and high humidity was extremely small, and the particle shape of the inorganic fine powder particles was hexahedral or In Examples 1 to 4 and 6 to 7 which are octahedrons, even when used at a high temperature and high humidity for a long time, the image density is hardly lowered, which is a preferable result.

Claims (3)

In a toner cartridge that is composed of at least a toner container for storing toner and is detachable from the image forming apparatus, and when the toner cartridge is attached to the image forming apparatus, toner is supplied to the image forming apparatus by rotation of the toner cartridge. ,
The toner container is obtained by molding a resin by a blow molding method with stretching,
The resin is mainly composed of a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol, and contains either one or both of titanium oxide and zinc oxide,
The toner has toner particles containing at least a binder resin and a colorant, and inorganic fine powder particles having a number average particle diameter of 80 nm to 400 nm, and the free rate of the inorganic fine powder particles from the toner particles is 5 A toner cartridge having a content of 0.0 mass% or more and 35.0 mass% or less.   The shape of the inorganic fine powder particles is an octahedron that is a convex polyhedron surrounded by eight triangles and / or a hexahedron that is a convex polyhedron surrounded by six quadrilaterals. The toner cartridge according to 1.   The toner cartridge according to claim 1, wherein the inorganic fine powder particles are subjected to a hydrophobization treatment with a coupling agent or a fatty acid metal salt.