JP5458836B2 - Toner production method - Google Patents

Description

  The present invention relates to a toner manufacturing method.

  The developer used to develop the electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, etc., for example, is once attached to the electrostatic latent image carrier on which the electrostatic latent image is formed. Thereafter, the electrostatic latent image carrier is transferred to a transfer medium and fixed. As such a developer, a two-component developer composed of a carrier and a toner, and a one-component developer (magnetic toner, non-magnetic toner) that does not require a carrier are known.

  Conventionally, a pulverization method is known as a method for producing such a toner. However, the pulverization method has a problem that the variation in the shape of the toner is large and the particle size distribution is wide.

  Recently, polymerization methods such as a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, and an ester extension polymerization method are known as toner production methods. However, since the polymerization method removes the organic solvent from the system containing water, there is a problem that the efficiency of removing the organic solvent is low. Further, since the organic solvent is removed and then the water is removed for washing, a large amount of washing water is required.

  Therefore, Patent Document 1 discloses a droplet forming unit that forms a droplet by discharging a solution or dispersion of a toner material containing a resin and a colorant from a nozzle that is vibrated at a constant frequency. There is disclosed a toner production apparatus having toner particle forming means for drying the droplets by removing the solvent contained in the droplets to form toner particles.

  However, when a toner is produced using a toner material liquid containing a release agent, there is a problem that the discharge port is easily clogged.

  SUMMARY OF THE INVENTION In view of the above-described problems of the prior art, the present invention provides a toner manufacturing method capable of suppressing clogging of discharge ports even when toner is manufactured using a toner material liquid containing a release agent. For the purpose.

According to a first aspect of the present invention, in the method for producing a toner, a step of filtering a toner material solution in which a toner material containing a resin and a release agent is dissolved or dispersed in an organic solvent is filtered with the filter, Supplying the toner material liquid to a storage member having a film in which a plurality of discharge ports are formed; discharging the toner material liquid from the plurality of discharge ports; and discharging the toner material liquid from the plurality of discharge ports droplets are dried, and forming a base particle, wherein the ratio of the pore size of the filter with respect to the opening diameter of the discharge ports Ri der 1/20 or more and 1 or less, wherein the filter is downstream from the upstream side It is characterized in that a hole whose hole diameter is reduced toward is formed .

The invention described in claim 2 is the method for producing a toner according to claim 1, in filtering the toner material liquid in the filter, characterized in that vibrating the filter.

According to a third aspect of the present invention, in the toner manufacturing method according to the second aspect, the vibrator having a surface substantially parallel to the filter is periodically vibrated in a direction substantially perpendicular to the filter. The vibrator that vibrates the filter and has a plane substantially parallel to the filter is formed in an annular shape around the hole of the filter.

According to a fourth aspect of the present invention, in the toner manufacturing method according to the third aspect, the vibrator having a surface substantially parallel to the filter is an electrostrictive vibrator.

According to a fifth aspect of the present invention, in the toner production method according to any one of the first to fourth aspects, the filter is heated to a temperature not lower than the melting point of the release agent and not higher than the boiling point of the organic solvent. It further has the process to maintain.

According to a sixth aspect of the present invention, in the toner manufacturing method according to any one of the first to fifth aspects, the opening diameter of the discharge port is 5 μm or more and 15 μm or less.

According to a seventh aspect of the present invention, in the toner manufacturing method according to any one of the first to sixth aspects, the toner material liquid is ejected from the plurality of ejection ports by vibrating the film. It is characterized by.

According to an eighth aspect of the present invention, in the toner manufacturing method according to the seventh aspect, the vibrator having a surface substantially parallel to the film is periodically vibrated in a direction substantially perpendicular to the film. The film is vibrated.

According to a ninth aspect of the invention, in the toner manufacturing method according to the eighth aspect of the invention, the amplitude of vibration of a vibrator having a surface substantially parallel to the film is amplified using a horn.

According to a tenth aspect of the present invention, in the toner manufacturing method according to the ninth aspect , the horn also serves as a part of the storage member.

According to an eleventh aspect of the present invention, in the toner manufacturing method according to the eighth aspect, the vibrator having a surface substantially parallel to the film is formed in an annular shape around the plurality of ejection openings of the film. It is characterized by.

According to a twelfth aspect of the present invention, in the toner manufacturing method according to any one of the eighth to eleventh aspects, the vibrator having a surface substantially parallel to the film is an electrostrictive vibrator. And

The invention described in claim 13 further includes a step of adjusting the speed of the droplets discharged from the plurality of discharge ports in the toner manufacturing method according to any one of claims 1 to 12 , The droplet having the adjusted speed is dried to form base particles.

According to a fourteenth aspect of the present invention, in the toner production method according to any one of the first to thirteenth aspects, the base particles have a ratio of a weight average particle diameter to a number average particle diameter of 1.00 or more and .15 or less.

According to a fifteenth aspect of the present invention, in the toner manufacturing method according to any one of the first to fourteenth aspects, the base particles have a weight average particle diameter of 3 μm or more and 10 μm or less.

  According to the present invention, it is possible to provide a toner manufacturing method capable of suppressing clogging of discharge ports even when toner is manufactured using a toner material liquid containing a release agent.

It is a schematic diagram showing an example of a toner manufacturing apparatus used in the present invention. It is a figure which shows the droplet discharge unit of FIG. It is a figure which shows the manufacturing method of the modification of the thin film of FIG. It is sectional drawing which shows the modification of the horn of FIG. It is side surface sectional drawing which shows the droplet discharge unit of FIG. It is sectional drawing which shows the structure by which the several droplet discharge unit is hold | maintained at the drying tower. It is sectional drawing which shows a part of filter of FIG. It is sectional drawing which shows the modification of the filter of FIG. It is a figure which shows the filter and filter chamber of FIG. It is a schematic sectional drawing which shows the modification of the droplet discharge unit of FIG. It is a schematic sectional drawing which shows the modification of the droplet discharge unit of FIG. FIG. 6 is a schematic diagram illustrating a modified example of the toner manufacturing apparatus in FIG. 1. It is a figure which shows the droplet discharge unit of FIG. It is a figure which shows the fundamental vibration of a flexural vibration at the time of fixing the circumference | surroundings of a circular film | membrane. It is a figure which shows the high-order vibration mode of a bending vibration at the time of fixing the circumference | surroundings of a circular film | membrane. It is a figure which shows the bending vibration at the time of fixing the circumference | surroundings of the circular film | membrane whose center part is convex shape.

  Next, the form for implementing this invention is demonstrated with drawing.

  FIG. 1 shows an example of a toner production apparatus used in the present invention. The toner manufacturing apparatus 100 is disposed below the droplet discharge unit 110, a droplet discharge unit 110 that discharges a toner material liquid L in which a toner material containing a resin and a release agent is dissolved or dispersed in an organic solvent, The droplet L ′ discharged from the droplet discharge unit 110 is dried using the dry gas G to form the base particle T, the collection unit 130 for collecting the base particle T, and the collection The storage unit 140 stores the base particles T collected by the unit 130, and the supply unit 150 supplies the toner material liquid L to the droplet discharge unit 110. In addition, the dry gas G means the gas whose dew point temperature under atmospheric pressure is -10 degrees C or less.

  FIG. 2 shows the droplet discharge unit 110. The droplet discharge unit 110 includes a storage member 111 that stores the toner material liquid L and a vibration member 112. 2A and 2B are a schematic cross-sectional view and a bottom view, respectively.

  The storage member 111 includes a thin film 111a in which a plurality of discharge ports N are formed, a storage member main body 111b, and a storage portion 111c that stores the toner material liquid L.

  The thin film 111a is joined to the storage member main body 111b using a resin or solder having resistance to the organic solvent contained in the toner material liquid L.

  The material constituting the thin film 111a is not particularly limited as long as it is a material having a large elastic modulus, and examples thereof include nickel, nickel alloy, SUS, silicon, silicon oxide, and the like, but a discharge port having a large aspect ratio can be accurately formed. In view of the capability, nickel, nickel alloy, silicon, and silicon oxide are preferable.

  Examples of the method for manufacturing the thin film 111a include an electroforming method and a silicon process. Further, the thin film 111a may be manufactured by forming the discharge port N using a punch.

  The thin film 111a usually has a thickness of 5 to 500 μm and an opening diameter of the discharge port N of 5 to 15 μm. If the thickness is less than 5 μm, the rigidity of the thin film 111a may be reduced, and if it exceeds 500 μm, it may be difficult to discharge the toner material liquid L. Further, if the opening diameter of the discharge port N is less than 1 μm, the discharge port N may be easily clogged, and if it exceeds 40 μm, it may be difficult to form the base particles T having a narrow particle size distribution. is there. The opening diameter of the discharge port N means the diameter if the shape of the discharge port N is a perfect circle, and means the short diameter if the shape is an ellipse.

  In addition, 2 to 3000 discharge ports N are formed in the thin film 111a. If the number of discharge ports N is less than 2, the productivity may be lowered, and if it exceeds 3000, it may be difficult to form base particles having a narrow particle size distribution.

  FIG. 3 shows a manufacturing method of a modification of the thin film 111a. First, a resist D is applied to both surfaces of an SOI (Silicon on Insulator) substrate in which a dielectric layer B and an active layer C are stacked on a support layer A (see FIG. 3A). Next, after covering with a photomask having a discharge port pattern formed thereon, ultraviolet rays are exposed to form a discharge port pattern (see FIG. 3B). Further, dry etching using ICP discharge is performed from the support layer A side to form an opening N1 ′, and then dry etching is similarly performed from the active layer C side to form an opening N2 ′. (See FIG. 3C). Finally, the dielectric layer B is removed using a hydrofluoric acid-based etchant to form a discharge port N ′ whose opening diameter changes in two steps, thereby obtaining a thin film 111a ′ (see FIG. 3D). . This makes it possible to uniformly form the deep discharge port N ′.

  The thin film 111a ′ usually has a thickness of 30 μm to 1 mm and an opening diameter of the discharge port N ′ of 5 to 15 μm.

  In addition, even if a silicon substrate is used instead of the SOI substrate, the thin film 111a ′ having a plurality of discharge ports N ′ can be manufactured in the same manner. In this case, the depth of the opening can be adjusted by adjusting the etching time.

  The storage member 111 is provided with a support member (not shown), whereby the droplet discharge unit 110 is held on the top surface of the drying tower 120. At this time, the droplet discharge unit 110 may be held on the side surface of the drying tower 120.

  The vibrating member 112 includes an electrostrictive vibrator 112a having a plane parallel to the thin film 111a, a horn 112b that amplifies the amplitude of flexural vibration generated by the electrostrictive vibrator 112a, electrodes 112c and 112d that sandwich the electrostrictive vibrator 112a, A power source 112e for applying an AC voltage is provided between the electrodes 112c and 112d. At this time, when an AC voltage is applied between the electrodes 112c and 112d, the plane parallel to the thin film 111a of the electrostrictive vibrator 112a is flexibly vibrated in a direction perpendicular to the thin film 111a. Further, the amplitude of the flexural vibration generated by the electrostrictive vibrator 112a is amplified by the horn 112b, and the plane P parallel to the thin film 111a of the horn 112b periodically flexes and vibrates in a direction perpendicular to the thin film 111a. . As a result, the thin film 111 a flexes and vibrates periodically, and the toner material liquid L is discharged from the plurality of discharge ports N.

  The frequency at which the thin film 111a flexes and vibrates is usually 20 kHz to 2 MHz, and preferably 50 to 500 kHz. If the frequency is less than 20 kHz, the discharge port N may be easily clogged, and if it is 2 MHz or more, it may be difficult to form the base particles T having a narrow particle size distribution. At this time, the vibration waveform in which the electrostrictive vibrator 112a flexes and vibrates is not particularly limited, and examples thereof include a sin waveform and a rectangular waveform.

The electrostrictive vibrator 112a is not particularly limited, and examples thereof include piezoelectric ceramics such as lead zirconate titanate (PZT). Piezoelectric ceramics are generally used as laminates because of their small vibration displacement. Other electrostrictive vibrators 112a include piezoelectric polymers such as polyvinylidene fluoride (PVDF), piezoelectric single crystal materials such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ .

  Further, as the electrostrictive vibrator 112a, a bolt-clamped Langevin vibrator is preferable because piezoelectric ceramic is mechanically coupled and has high strength. Thereby, damage can be suppressed when exciting with a high amplitude.

  Note that an alternating current may be applied between the electrodes 112c and 112d using a magnetostrictive vibrator instead of the electrostrictive vibrator 112a. The magnetostrictive vibrator is not particularly limited, and examples thereof include ferromagnetic materials such as nickel, iron, and ferrite.

  Since the horn 112b can amplify the amplitude of the flexural vibration generated in the electrostrictive vibrator 112a, the amplitude of the flexural vibration generated in the electrostrictive vibrator 112a may be small, and the mechanical load is reduced. The life of the vibration member 112 can be extended. At this time, the plane P parallel to the thin film 111a of the horn 112b is designed to be the maximum vibration surface.

  The horn 112b may have other shapes, for example, a step type (see FIG. 4A), an exponential type (see FIG. 4B), a conical type (see FIG. 4C), etc. Is mentioned.

  If the amplitude of the flexural vibration generated by the electrostrictive vibrator 112a is large, the horn 112b may be omitted.

As shown in FIG. 5, the droplet discharge unit 110 has a flow path 113 for supplying the dry gas G ′ in a direction substantially the same as the direction in which the toner material liquid L is discharged. The velocity V ₁ of the dry gas G ′ only needs to be larger than the initial velocity of the ejected droplets, and is preferably larger than the initial velocity V ₀ of the droplet L ′ ejected from the ejection port N. Since the dry gas G ′ adjusts the speed of the droplets L ′ ejected from the plurality of ejection ports N, the coalescence of the droplets L ′ can be suppressed. The dry gas G ′ preferably forms a uniform laminar flow in the circumferential direction of the flow path 113. When the dry gas G ′ forms a turbulent flow, the droplet L ′ may coalesce. Although it does not specifically limit as dry gas G ', Air, nitrogen, etc. are mentioned.

  In the flow path 113, a throttle 111 d that restricts the flow of the dry gas G ′ is provided in the vicinity of the plurality of discharge ports N, and openings 111 e that face the plurality of discharge ports N are formed. At this time, since the clearance C between the thin film 111a and the diaphragm 111d is smaller than the width D of the opening 111e, the clearance C is a main factor for determining the speed of the dry gas G ′. In addition, since the opening 111e has a tapered shape that expands from the upstream side toward the downstream side, it is possible to suppress the droplet L ′ from adhering to the diaphragm 111d.

A drying gas G is supplied into the drying tower 120 from a drying gas supply port 121. The dry gas G forms a uniform laminar flow in the circumferential direction of the drying tower 120, and transports and dries the droplet L ′ discharged from the opening 111 e. Thereby, coalescence of the droplets L ′ released from the opening 111e can be suppressed. At this time, the speed V ₂ of the drying gas G is preferably rate or more dry gas G '. When V ₂ is less than V _1, it is possible to form a turbulent flow. The pressure _{P 1} in the pressure gauge PG1 is preferably a pressure _{P 2} less at the pressure gauge PG2. If P ₁ exceeds P ₂ or less, a negative pressure may act on the droplet L ′ to cause a reverse flow.

  At this time, instead of supplying the dry gas G from the dry gas supply port 121, suction may be performed from the lower portion of the drying tower 120.

  In FIG. 1, one droplet discharge unit 110 is held in the drying tower 120, but in order to further improve productivity, a plurality of droplet discharge units 110 are connected to the drying tower as shown in FIG. 6. 120 may be held. At this time, the number of droplet discharge units 110 held in the drying tower 120 is preferably 100 to 1000. When the number of droplet discharge units 110 is less than 100, the toner productivity may be reduced. When the number of droplet discharge units 110 is more than 1000, it may be difficult to control the droplet discharge units 110. At this time, the toner material liquid L may be supplied to the plurality of droplet discharge units 110 from a single supply unit.

  In the drying tower 120, the droplet L ′ discharged from the droplet discharge unit 110 is transported by using the dry gas G flowing in the substantially same direction as the direction in which the toner material liquid L is discharged. Is dried and the base particles T are formed.

  The collection unit 130 is provided downstream from the drying direction of the base particle T in the conveying direction, and has a tapered surface 131 whose opening diameter decreases from the upstream side toward the downstream side. Furthermore, by using a suction pump (not shown) for suction, a vortex S is generated in the collection unit 130 from the upstream side to the downstream side. As a result, the base particles T are collected, transferred to the storage unit 140 via the pipe 132, and stored. At this time, the base particle T may be pumped from the collection unit 130 to the storage unit 140, or the base particle T may be sucked from the storage unit 140 side.

  The supply unit 150 includes a tank 151 that stores the toner material liquid L, a pump 152 that pumps and supplies the toner material liquid L, a pipe 153 that supplies the toner material liquid L to the droplet discharge unit 110, and the toner material liquid L. A circulation system is constructed by including a pipe 154 for discharging from the droplet discharge unit 110. Further, the pipe 153 is provided with a filter 155 for filtering the toner material liquid L. At this time, when the toner material liquid L is discharged from the droplet discharge unit 110, the toner material liquid L supplied from the tank 151 using the pump 152 is filtered by the filter 155, and then the droplet discharge unit 110. To be supplied. The filter 155 also discharges bubbles in the toner material liquid L.

  FIG. 7 shows a part of the filter 155. Since the filter 155 has a tapered hole whose diameter decreases from the upstream side toward the downstream side, the filtering efficiency is excellent. At this time, the taper angle θ of the tapered hole is usually 30 to 80 °, and preferably 45 to 70 °.

  The ratio of the hole diameter of the filter 155 to the opening diameter of the discharge port N is usually 1/20 to 1, and preferably 1/6 to 1/2. When this ratio is less than 1/20, the particle size of the release agent in the base particle T becomes small and the offset resistance decreases. When it exceeds 1, the discharge port N is likely to be clogged.

  Note that the hole diameter of the filter 155 when the hole diameter changes from the upstream side toward the downstream side means the minimum value of the hole diameter of the filter 155.

  The material constituting the filter 155 is not particularly limited as long as it has resistance to the organic solvent contained in the toner material liquid L, and includes metals, and stainless steel and nickel are preferable from the viewpoint of processing accuracy and strength. .

  A method for manufacturing the filter 155 is not particularly limited, and examples thereof include a photoetching method and an electroforming method. Examples of metals to which the photoetching method can be applied include stainless steel, copper, copper alloys, brass, aluminum, phosphor bronze, beryllium copper, nickel, permalloy, and the like. Moreover, nickel, copper, etc. are mentioned as a metal which can apply an electroforming method.

  Instead of the filter 155, a filter having a curved hole whose diameter decreases from the upstream side toward the downstream side when viewed in cross section (see FIG. 8), the cross section when viewed from the upstream side toward the downstream side. For example, a filter in which curved holes are formed, which are enlarged after the hole diameter is reduced, or a filter in which holes having a constant hole diameter are formed may be used.

  As shown in FIG. 9A, the filter 155 is provided with a vibrating member 156 that vibrates the filter 155. Therefore, even if the pressure of the pump 152 is reduced, the filtration efficiency is excellent, and the toner material Since the liquid L can be redispersed, clogging of the filter 155 can be suppressed. The vibration member 156 includes an electrostrictive vibrator 156a having a plane parallel to the filter 155, electrodes 156b and 156c that sandwich the electrostrictive vibrator 156a, and a power source 156d that applies an AC voltage between the electrodes 156b and 156c. Note that the laminate in which the electrostrictive vibrator 156a is sandwiched between the electrodes 156b and 156c is provided in an annular shape around the hole of the filter 155. At this time, when an AC voltage is applied between the electrodes 156b and 156c, the plane parallel to the filter 155 of the electrostrictive vibrator 156a periodically flexes and vibrates in a direction perpendicular to the filter 155. As a result, the filter 155 flexes and vibrates periodically, and the toner material liquid L is filtered.

  The frequency at which the filter 155 flexes and vibrates is usually the resonance frequency of the filter 155. At this time, the vibration waveform in which the electrostrictive vibrator 156a flexibly vibrates is not particularly limited, and examples thereof include a sin waveform and a rectangular waveform. Thereby, since the filter 155 vibrates efficiently, the filtration efficiency can be improved. The resonance frequency of the filter 155 is obtained by measuring the impedance characteristics of the electrostrictive vibrator 156a using 4294A (manufactured by Agilent Technologies) under the same conditions as when the toner material liquid L is filtered.

The electrostrictive vibrator 156a is not particularly limited, and examples thereof include piezoelectric ceramics such as lead zirconate titanate (PZT). Piezoelectric ceramics are generally used as laminates because of their small vibration displacement. Other electrostrictive vibrators 156a include piezoelectric polymers such as polyvinylidene fluoride (PVDF), piezoelectric single crystal materials such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ .

  Further, as the electrostrictive vibrator 156a, piezoelectric ceramic is mechanically bonded, and lead zirconate titanate (PZT) is preferable.

  Note that an alternating current may be applied between the electrodes 156b and 156c using a magnetostrictive vibrator instead of the electrostrictive vibrator 156a. The magnetostrictive vibrator is not particularly limited, and examples thereof include ferromagnetic materials such as nickel, iron, and ferrite.

  As shown in FIG. 9A, the filter 155 is provided with a heating member 157 for heating the filter 155 and a sensor 158 for detecting the temperature of the filter 155. The heating member 157 is provided in an annular shape around the hole of the filter 155.

  When maintaining the filter 155, it is preferable to heat the filter 155 to a temperature not lower than the melting point of the release agent and not higher than the boiling point of the organic solvent contained in the toner material liquid L. When the filter 155 is heated to a temperature lower than the melting point of the release agent, it may be difficult to remove the clogging when the filter 155 is clogged due to the release agent. On the other hand, when the filter 155 is heated to a temperature exceeding the boiling point of the organic solvent, the organic solvent may boil.

  The heating member 157 is not particularly limited as long as the vibration of the filter 155 is not hindered, and examples thereof include a sheet heater.

  The sensor 158 is not particularly limited as long as the vibration of the filter 155 is not hindered, and examples thereof include a thermocouple.

  The filter 155 is installed in the pipe 153 with the upstream outer peripheral portion fixed to the fixing member 159. The fixing member 159 is not particularly limited as long as the filter 155 can be fixed, and examples thereof include metals.

  As shown in FIG. 9B, a filter chamber 153 ′ in which a plurality of filters 155 are installed may be provided via a fixing member 159. In FIG. 9B, the power supply 156d is not shown for simplification.

  Next, a method for producing a transparent toner using the toner production apparatus 100 will be described. First, in a state where the toner material liquid L is supplied to the storage member 111 of the droplet discharge unit 110, an AC voltage is applied to the electrostrictive vibrator 112a of the vibration member 112, so that flexural vibration is generated in the electrostrictive vibrator 112a. To do. Further, the amplitude of the flexural vibration is amplified by the horn 112b, and the plane P parallel to the thin film 111a of the horn 112b periodically vibrates in a direction perpendicular to the thin film 111a. That is, the flexural vibration of the surface P parallel to the thin film 111a of the vibration member 112 is propagated to the toner material liquid L in the storage member 111, and the pressure changes periodically. As a result, the thin film 111 a is periodically bent and vibrated, and the toner material liquid L is discharged into the drying tower 120.

  Then, the droplet L ′ discharged into the drying tower 120 is transported using the dry gas G flowing in the substantially same direction as the direction in which the toner material liquid L is discharged, thereby removing the organic solvent, Base particles T are formed. Further, the base particles T are collected using the vortex S in the collection unit 130 on the downstream side of the drying tower 120, transferred to the storage unit 140, and stored. As a result, base particles T having a weight average particle size to number average particle size ratio of 1.00 to 1.15 can be produced. Moreover, the base particle T whose weight average particle diameter is 3-10 micrometers can be manufactured.

  FIG. 10 shows a modification of the droplet discharge unit 110. The droplet discharge unit 110 ′ has the same configuration as the droplet discharge unit 110 except that a horn 112b ′ having a storage portion 111c ′ for storing the toner material liquid is provided instead of the storage member 111 and the horn 112b. It is. At this time, the horn 112b ′ is joined to the thin film 111a using a resin or solder having resistance to the organic solvent contained in the toner material liquid L, and also serves as a part of the storage member. The reservoir 111c ′ is connected to the pipes 153 and 154, and the droplet discharge unit 110 ′ is held in the drying tower 120 using an elastic body as necessary.

  FIG. 11 shows a modified example of the droplet discharge unit 110. In the droplet discharge unit 110 '', a stacked body in which two layers of the electrostrictive vibrator 112a are stacked instead of the storage member 111, the electrostrictive vibrator 112a, and the horn 112b stores the horn 112b and the toner material liquid. The configuration is the same as that of the droplet discharge unit 110 except that a bolt-clamped Langevin type vibrator sandwiched by a horn 112b ′ having a portion 111c ′ is used.

  FIG. 12 shows a modification of the toner manufacturing apparatus 100. The toner manufacturing apparatus 200 has the same configuration as the toner manufacturing apparatus 100 except that a droplet discharge unit 210 is provided instead of the droplet discharge unit 110.

  FIG. 13 shows the droplet discharge unit 210. The droplet discharge unit 210 includes a storage member 211 that stores the toner material liquid L and a vibration member 212. FIGS. 13A and 13B are a cross-sectional view and a bottom view, respectively. At this time, similarly to the droplet discharge unit 110, the droplet discharge unit 210 is also provided with a flow path 113 for supplying the dry gas in the same direction as the direction in which the toner material liquid L is discharged.

  The storage member 211 has the same configuration as the storage member 111 except that a storage member main body 211b and a storage part 211c having different shapes are provided instead of the storage member main body 111b and the storage part 111c.

  The thin film 111a is joined to the storage member main body 211b using a resin or solder having resistance to the organic solvent contained in the toner material liquid L.

  The storage member 211 is provided with a support member (not shown), whereby the droplet discharge unit 210 is held on the top surface portion of the drying tower 120. At this time, the droplet discharge unit 110 may be held on the side surface of the drying tower 120.

  The vibrating member 212 is not provided with the horn 112b, and instead of the laminated body in which the electrostrictive vibrator 112a is sandwiched between the electrodes 112c and 112d, the electrostrictive vibrator 212a having a plane parallel to the thin film 111a is provided with the electrodes 212c and 212d. The structure is the same as that of the vibrating member 112 except that the laminated body sandwiched between is provided in an annular shape around the plurality of discharge ports N of the thin film 111a. At this time, when an AC voltage is applied between the electrodes 212c and 212d, the plane parallel to the thin film 111a of the electrostrictive vibrator 212a is flexibly vibrated in a direction perpendicular to the thin film 111a. As a result, the thin film 111 a flexes and vibrates periodically, and the toner material liquid L is discharged from the plurality of discharge ports N.

  The frequency at which the thin film 111a flexes and vibrates is usually 20 kHz to 2 MHz, and preferably 50 to 500 kHz. If the frequency is less than 20 kHz, the discharge port N may be easily clogged, and if it is 2 MHz or more, it may be difficult to form the base particles T having a narrow particle size distribution. At this time, the vibration waveform in which the electrostrictive vibrator 212a flexes and vibrates is not particularly limited, and examples thereof include a sin waveform and a rectangular waveform.

  Moreover, since the laminated body is provided in the area | region which is not joined with the storage member main body 211b of the thin film 111a, the displacement of the flexural vibration of the thin film 111a can be enlarged.

  In FIG. 12, one droplet discharge unit 210 is held in the drying tower 120. However, in order to further improve productivity, a plurality of droplet discharge units 210 may be held in the drying tower 120. Good. At this time, the number of droplet discharge units 210 held in the drying tower 120 is preferably 100 to 1000. When the number of droplet discharge units 210 is less than 100, the toner productivity may be reduced. When the number of droplet discharge units 210 is more than 1000, it may be difficult to control the droplet discharge units 210. At this time, the toner material liquid L may be supplied to a plurality of droplet discharge units 210 from a single supply unit.

Next, a mechanism for ejecting droplets using the droplet ejection unit 210 will be described. Here, a case where the periphery of a circular film having a radius r ₀ is fixed will be described. A plurality of discharge ports are formed in a concentric circle having a radius r ₁ . In this case, fundamental vibration of the bending vibration, as shown in FIG. 14, the periphery _(r = r ₀₎ is the section center O (r = 0) in the displacement ΔL of the vibration maximum (ΔLmax), and the periodic It bends and vibrates. 14 (a) and 14 (b) show the relationship between the displacement of the vibration with respect to the radial coordinate at the time t of the circular film and the sectional view in the radial direction of the circular film, respectively.

Further, when the periphery of a circular film having a radius r ₀ is fixed, it is known that a high-order vibration mode as shown in FIG. 15 exists in the flexural vibration. Higher order vibration modes have one or more concentric nodes. Furthermore, as shown in FIG. 16, by making the central portion of the circular film convex, it is possible to control the droplet ejection direction and adjust the amplitude of the flexural vibration.

On the other hand, when the toner material liquid is present in the vicinity of the discharge port provided in the circular film due to the flexural vibration of the circular film, a sound pressure Pac proportional to the speed Vm of the flexural vibration of the circular film is generated. Further, it is known that the sound pressure Pac is generated as a reaction of the radiation impedance Zr of the toner material liquid. The sound pressure Pac is a product of the radiation impedance Zr and the flexural vibration velocity Vm of the circular film. (R, t) = Zr · Vm (r, t)
It is represented by At this time, since the flexural vibration speed Vm of the circular film periodically changes, the sound pressure Pac proportional to the flexural vibration speed Vm of the circular film also periodically changes. As a result, the toner material liquid L in the vicinity of the discharge port is discharged into the gas phase. Since the discharged toner material liquid becomes a sphere due to the difference in surface tension from the gas phase, droplets are periodically generated.

  At this time, the displacement of the sound pressure Pac is normally 10 to 500 kPa, and preferably 10 to 100 kPa. If the displacement of the sound pressure Pac is less than 10 kPa, the discharge port may be easily clogged, and if it exceeds 500 kPa, cavitation of the toner material liquid may be likely to occur.

The diameter of the droplet tends to increase as the displacement of the flexural vibration in the vicinity of the ejection port increases. If the displacement of the flexural vibration at r = r ₁ is ΔLmin (see FIGS. 14 and 15), the particle size distribution of the base particles can be narrowed when ΔLmax / ΔLmin is 2.0 or less.

  Next, the toner material liquid L will be described. The toner material liquid L includes a resin and a release agent, and can be obtained by dissolving or dispersing a toner material further containing a colorant, a charge control agent, and a magnetic material in an organic solvent as necessary. At this time, the toner material may be mixed and kneaded using a high shearing dispersion device such as a three-roll mill.

The organic solvent is not particularly limited as long as it can dissolve or disperse the toner material, but toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane. , Trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. Among these, because of excellent solubility of the polyester, SP value of organic solvent is preferably ^{8~9.8cal 1/2 / cm 3/2, 8.5~9.5cal 1/2} / cm 3 ^{/ 2} is more preferable. Furthermore, since the crystal growth of the release agent can be effectively suppressed, ester solvents and ketone solvents are preferable, and ethyl acetate and methyl ethyl ketone are particularly preferable because they can be easily removed.

  The resin is not particularly limited, but a styrene polymer, a (meth) acrylic resin, a vinyl resin such as a styrene- (meth) acrylic resin, a polyester, a polyol resin, a phenol resin, a silicone resin, a polyurethane, a polyamide, A furan resin, an epoxy resin, a xylene resin, a terpene resin, a coumarone indene resin, a polycarbonate, a petroleum resin, and the like may be used, and two or more kinds may be used in combination.

  The monomer used when synthesizing the vinyl resin is not particularly limited, but styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, pn-amylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p- Styrene monomers such as n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; acrylic acid, methyl acrylate , Ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-acrylate Acrylic monomers such as chill, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Methacrylic monomers such as: Monoolefins such as ethylene, propylene, butylene and isobutylene; Polyenes such as butadiene and isoprene; Halogenation such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride Nyls; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; Vinylnaphthalenes; (Meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; maleic acid Unsaturated dibasic acids such as citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid or the anhydrides thereof; monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl citraconic acid, Monoesters of unsaturated dibasic acids such as monoethyl citraconic acid, monobutyl citraconic acid, monomethyl itaconate, monomethyl alkenyl succinate, monomethyl fumarate and monomethyl mesaconic acid; of unsaturated dibasic acids such as dimethyl maleate and dimethyl fumarate Diesters; α, β-unsaturated acids such as crotonic acid and cinnamic acid, their anhydrides or anhydrides with lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their anhydrides or monoesters thereof; Hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl ) Monomers having a hydroxy group such as styrene may be mentioned, and two or more kinds may be used in combination.

  When synthesizing vinyl resins such as styrene copolymers and styrene- (meth) acrylic copolymers, if a crosslinking agent having two or more vinyl groups is used, the vinyl resin may be crosslinked. it can.

  The bifunctional crosslinking agent is not particularly limited, but is an aromatic divinyl compound such as divinylbenzene or divinylnaphthalene; ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butane Di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like bonded with an alkylene group ( Meth) acrylate compound; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (# 400) di (meth) acrylate, polyethylene glycol (# 6) 0) di (meth) acrylate, di (meth) acrylate compound bonded by an alkylene group containing an ether bond, such as dipropylene glycol di (meth) acrylate and the like, may be used in combination. Examples of other bifunctional crosslinking agents include di (meth) acrylate compounds and polyester-type diacrylate compounds bonded with an arylene group or an arylene group containing an ether bond. Examples of commercially available polyester diacrylate compounds include MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  The polyfunctional crosslinking agent is not particularly limited, but pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, oligoester (Meth) acrylate, triallyl cyanurate, triallyl trimellitate and the like may be mentioned, and two or more kinds may be used in combination.

  The cross-linking agent is preferably an aromatic divinyl compound (particularly divinylbenzene), a di (meth) acrylate compound bonded with an arylene group or an arylene group containing one ether bond from the viewpoint of toner fixing properties and offset resistance.

  These crosslinking agents are preferably used in an amount of 0.01 to 10% by weight, more preferably 0.03 to 5% by weight, based on the monomer.

  The polymerization initiator used in synthesizing the vinyl resin is not particularly limited, but 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvalero) Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1 '-Azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2', 4 ' -Dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide Ketone peroxides such as oxide; 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3 , 5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, diisopropyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate Di-n-propyl peroxydicarbonate, bis (2-ethoxyethyl) peroxycarbonate, bis (ethoxyisopropyl) peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyloxybenzoate, tert -Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert Butylperoxy to hexa hydro terephthalate, tert- butylperoxy azelate, and the like, may be used in combination.

The styrene- (meth) acrylic resin has a molecular weight of 3 × 10 ^{3 to} 5 × 10 ⁴ on the GPC chart of a component soluble in tetrahydrofuran (THF) in terms of toner fixing property, offset property, and storage property. It is preferable that at least one peak exists in a certain region, and at least one peak exists in a region having a molecular weight of 1 × 10 ⁵ or more. In the gel permeation chromatography (GPC) chart of components soluble in tetrahydrofuran (THF), the content of components having a molecular weight of 1 × 10 ⁵ or less is preferably 50 to 90%, The molecular weight is more preferably 5 × 10 ^{3 to} 3 × 10 ⁴ , and the molecular weight of the main peak is particularly preferably 5 × 10 ³ to 2 × 10 ⁴ .

  In the present invention, the molecular weight in the GPC chart is a molecular weight in terms of polystyrene, and THF is used as a developing solvent for GPC.

  The vinyl resin preferably has an acid value of 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and particularly preferably 0.1 to 50 mgKOH / g.

  The polyester can be synthesized by condensing a divalent or higher alcohol and a divalent or higher carboxylic acid. In addition, when synthesizing the polyester, the polyester can be crosslinked by using a trivalent or higher alcohol and / or a trivalent or higher carboxylic acid.

  The divalent alcohol is not particularly limited, but ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentane. Obtained by ring-opening addition of cyclic ethers such as ethylene oxide and propylene oxide to diol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A or bisphenol A The diol etc. which are mentioned are mentioned, You may use 2 or more types together.

  Although it does not specifically limit as trihydric or more alcohol, Although sorbitol, 1,2,3,6-hexane tetrol, 1, 4- sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene Etc., and two or more of them may be used in combination.

  The divalent carboxylic acid is not particularly limited, but benzene dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid or the anhydride; alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or the like Anhydrous anhydrides: unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid, or anhydrides thereof, and two or more of them may be used in combination.

  Although it does not specifically limit as carboxylic acid more than trivalence, Trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid, anhydrides thereof, partial lower alkyl esters and the like may be mentioned, and two or more kinds may be used in combination.

Polyester may have at least one peak in a region having a molecular weight of 3 × 10 ^{3 to} 5 × 10 ⁴ in a GPC chart of a component soluble in THF from the viewpoint of toner fixing property and offset resistance. preferable. Moreover, in the GPC chart of the component soluble in THF, the content of the component having a molecular weight of 1 × 10 ⁵ or less is preferably 60 to 100%, and the molecular weight is 5 × 10 ³ to 2 × 10 ⁴ . More preferably, at least one peak is present in the region.

  The polyester preferably has an acid value of 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and particularly preferably 0.1 to 50 mgKOH / g.

  In addition, when using together other resin with vinyl-type resin and / or polyester, it is preferable that content of resin whose acid value in all the resins is 0.1-50 mgKOH / g is 60-100 mass%. .

  In the present invention, the acid value can be measured using a method described in JIS K0070.

  The release agent is not particularly limited, but aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and sazol wax, and oxidized hydrocarbon wax. Wax oxides or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, waxy wax, jojoba wax; animal waxes such as beeswax, lanolin, whale wax; ozokerite, ceresin, petrolatum, etc. Mineral waxes; waxes mainly composed of fatty acid esters such as montanic acid ester wax and castor wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax; palmitic acid, stearic acid, Mon Saturated linear fatty acids such as acids; Unsaturated fatty acids such as prandidic acid, eleostearic acid and valinalic acid; Saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, and mesyl alcohol Polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, olefinic acid amide, lauric acid amide; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; Unsaturated fatty acid amides such as oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepacic acid amide; m-xylene bis stearic acid amide, N, N-di Aromatic bisamides such as stearylisophthalamide; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; Aliphatic hydrocarbon wax grafted with vinyl monomers such as styrene and acrylic acid A partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl esterified product having a hydroxyl group obtained by hydrogenating vegetable oils and fats, and two or more of them may be used in combination. Among them, polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, polyolefins polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressure, radiation, electromagnetic waves Or synthesized using light-polymerized polyolefin, low-molecular-weight polyolefin obtained by pyrolyzing high-molecular-weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. A hydrocarbon wax, a synthetic wax having a compound having 1 carbon atom as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, a hydrocarbon wax and a hydrocarbon wax having a functional group Mixed Things, styrene these waxes, maleic acid esters, acrylic acid, methacrylic acid, those obtained by grafting vinyl monomers such as maleic acid.

  In addition, the mold release agent can be narrowed in molecular weight distribution, low molecular weight solid fatty acid, low molecular weight using press sweating method, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or solution liquid crystal deposition method. It is preferable to remove impurities such as solid alcohol and low molecular weight solid compounds.

  The mold release agent preferably has a melting point of 60 to 140 ° C, and more preferably 60 to 120 ° C. When the melting point is less than 60 ° C., the blocking resistance may be lowered, and when it exceeds 140 ° C., the offset resistance may be insufficient.

  In the present invention, the melting point can be measured by using a highly accurate internal heat input compensation type differential scanning calorimeter, and is the temperature at the peak top of the maximum endothermic peak of the DSC curve. The melting point can be measured according to ASTM D3418-82, and after taking a previous history by raising and lowering the temperature once, a DSC curve is obtained by raising the temperature at a rate of temperature rise of 10 ° C./min. It is done.

  Moreover, by using together the mold release agent whose melting | fusing point difference is 10-100 degreeC, the plasticizing effect | action and the mold release action which a mold release agent have can be expressed simultaneously. Examples of the release agent having a relatively low melting point that exhibits a plasticizing action include those having a branched structure, those having a polar group, and the like. Includes those having a linear structure and nonpolar ones having no polar group. At this time, the melting point of at least one of the waxes is preferably 60 to 120 ° C, more preferably 60 to 100 ° C.

  Such combinations of release agents include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes , Fatty acid wax or ester wax and hydrocarbon wax combination, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, carnauba wax , Candelilla wax, rice wax or montan wax and carbonized water Combinations of system wax.

  The content of the release agent in the toner material is preferably 0.2 to 20% by mass and more preferably 0.5 to 10% by mass with respect to the resin. When the content is less than 0.2% by mass, the releasability of the toner may be insufficient. When the content exceeds 20% by mass, filming on the photoreceptor may occur or the developer may deteriorate. It may be easy to do.

  Although it does not specifically limit as a coloring agent, Carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Rake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, Parachloro Ortho Nitroaniline Red, Risorf Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B , Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B , Thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome bar Lion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC ), Indigo, Ultramarine Blue, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraki Non-green, titanium oxide, zinc white, lithobon and the like can be mentioned, and two or more kinds may be used in combination.

  The content of the colorant is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass with respect to the toner material.

  When a pigment is used as the colorant, the toner material preferably contains a pigment dispersant having high compatibility with the resin. Examples of commercially available pigment dispersants include Addisper PB821, Addisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk-2001 (manufactured by Big Chemie), EFKA-4010 (manufactured by EFKA), and the like.

  The content of the pigment dispersant in the toner material is preferably 0.1 to 10% by mass with respect to the pigment. When the content is less than 0.1% by mass, the dispersibility of the pigment may be insufficient. When the content exceeds 10% by mass, the chargeability of the toner under high humidity may be reduced.

Pigment dispersant, the GPC chart, preferably has a molecular weight of the maximum value of the main peak is 500 to 1 × 10 ^5, more preferably ^{3 × 10 3 ~1 × 10 5} , 5 × 10 3 ~5 × 10 ⁴ is particularly preferable, and 5 × 10 ^{3 to} 3 × 10 ⁴ is most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the pigment may decrease. When it exceeds 1 × 10 ⁵ , the affinity with the solvent increases and the dispersibility of the pigment decreases. Sometimes.

  In addition, as a coloring agent, the masterbatch by which the pigment and resin were compounded can also be used. Although it does not specifically limit as resin for masterbatch, Styrenic homopolymers, such as a polystyrene, poly p-chlorostyrene, polyvinyltoluene, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl Ketone copolymer, styrene Styrene copolymers such as diene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic ester copolymer; polymethyl methacrylate, Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid, rosin, modified rosin, terpene resin, aliphatic or alicyclic Aromatic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like may be mentioned, and two or more of them may be used in combination.

  The resin for the master batch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100 mgKOH / g, an acid value of 20 mgKOH / g or less, and an amine value of 10 to 50 mgKOH / g. preferable. When the acid value exceeds 30 mgKOH / g, the chargeability of the toner under high humidity may be lowered, and the dispersibility of the pigment may be insufficient. Further, when the amine value is less than 1 mgKOH / g or more than 100 mgKOH / g, the dispersibility of the pigment may be insufficient.

  In the present invention, the amine value can be measured using the method described in JIS K7237.

  The master batch is obtained by applying high shear force to the resin and the colorant and mixing and kneading. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin.

  Moreover, you may manufacture a masterbatch using the flushing method. Specifically, the colorant is transferred to the resin side by mixing and kneading an aqueous paste of the colorant with the resin and the organic solvent, and then the water and the organic solvent are removed. In this case, since the wet cake of the colorant can be used as it is, there is no need to dry it.

  When mixing and kneading, a high shear dispersion device such as a three-roll mill can be used.

  The content of the master batch in the toner material is preferably 0.1 to 20% by mass with respect to the resin.

  The charge control agent is not particularly limited, but nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine-modified quaternary ammonium salt) Salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorosurfactants, salicylic acid metal salts, metal salts of salicylic acid derivatives, copper phthalocyanines, perylenes, quinacridones, azo pigments, etc. . Examples of the charge control agent other than these include polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium base.

  Commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal Complex E-84, phenol-based condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), 4 Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (from Hoechst), LRA-901, boron complex LR- 147 (made by Nippon Carlit Co., Ltd.).

  The usage-amount of a charge control agent is 0.1-10 mass% normally with respect to resin, and 0.2-5 mass% is preferable.

  Further, the magnetic material is not particularly limited, but magnetic iron oxide such as magnetite, maghemite, and ferrite, or iron oxide containing other metal oxides; metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, Examples thereof include alloys with metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and two or more of them may be used in combination.

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , PbFe ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, nickel powder and the like can be mentioned, among which Fe ₃ O ₄ Γ-Fe ₂ O ₃ is preferred.

  In addition, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements can also be used as the magnetic material. The heterogeneous element is not particularly limited, but lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, Examples include zinc, gallium, etc. Among them, magnesium, aluminum, silicon, phosphorus, and zirconium are preferable. Heterogeneous elements may be incorporated into the crystal lattice of iron oxide or may exist as an oxide or hydroxide on the surface of iron oxide, but are incorporated into iron oxide as an oxide. Preferably it is.

  The foreign element can be incorporated into the magnetic body by mixing a salt of the different element and adjusting the pH when the magnetic body is produced. Further, after the production of the magnetic substance, the pH can be adjusted, or by adding a salt of a different element to adjust the pH, the magnetic substance can be present on the surface of the magnetic substance.

  The magnetic material preferably has a number average particle diameter of 0.1 to 2 μm, more preferably 0.1 to 0.5 μm. The number average particle diameter can be measured by measuring a photograph taken with a transmission electron microscope with a digitizer.

  The magnetic material preferably has a coercive force of 20 to 150 Oe, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g when a magnetic field of 10 kOe is applied.

  The content of the magnetic substance in the toner material is preferably 10 to 200 parts by mass, and more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the resin.

  The magnetic material can also be used as a colorant.

  In the present invention, the base particle T may be used as the toner, or a toner obtained by adding an external additive such as a fluidity improving agent or a cleaning property improving agent to the base particle T may be used.

  The fluidity improver is not particularly limited, but fluorine resin particles such as vinylidene fluoride and polytetrafluoroethylene; silica particles such as wet process silica and dry process silica, titanium oxide particles, alumina particles or these particles. The thing hydrophobized with the silane compound etc. is mentioned, You may use 2 or more types together. Among these, silica particles, titanium oxide particles, and alumina particles are preferable, and silica particles that have been hydrophobized with a silane compound are more preferable.

  Dry process silica is produced by vapor phase oxidation of silicon halides. Commercially available products of dry process silica include AEROSIL-130, 300, 380, TT600, MOX170, MOX80, COK84 (above, Nippon Aerosil Co., Ltd.), Ca-O-SiL-M-5, MS-7, MS-75. , HS-5, EH-5 (above, manufactured by CABOT), Wacker HDK-N20 V15, N20E, T30, T40 (above, made by WACKER-CHEMIE), D-CFineSilica (produced by Dow Corning), Fransol (Fransil) Etc.).

  The number average particle size of the fluidity improver is usually 5 to 100 nm, preferably 5 to 50 nm.

Flow improver is preferably specific surface area measured by the BET method is ^{30 m} 2 / g or more, further preferably 60~400m ² / g. Also, flow improvers which are hydrophobized is preferably specific surface area measured by the BET method is ^{20 m} 2 / g or more, more preferably 40 to 300 m ² / g.

  Silica hydrophobized with a silane compound is chemically or physically adsorbed on the silica, but the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%.

  Silane compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, divinyl. Chlorosilane, γ-methacryloyloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α- Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and the like, and two or more of them may be used in combination. Among them, dimethylpolysiloxane having 2 to 12 siloxane units and having 0 to 1 silanol group at each end is preferable. Examples of silane compounds other than these include silicone oils such as dimethyl silicone oil.

  The addition amount of the fluidity improver is preferably 0.03 to 8% by mass with respect to the base particle T.

  Although it does not specifically limit as a cleaning property improvement agent, Fatty acid or its metal salt particle | grains, such as a zinc stearate particle | grain, a calcium stearate particle | grain, and a stearic acid particle | grain; Resin particles and the like.

  The resin particles preferably have a volume average particle diameter of 0.01 to 1 μm.

  When the external additive is added, a mixer such as a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, a hybridizer, a mechanofusion, and a Q mixer can be used.

  In the present invention, the toner may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer. At this time, the two-component developer is preferably mixed with 1 to 200 parts by mass of toner, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the carrier.

  The one-component developer or the two-component developer can be used when developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, or the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to an Example at all. In addition, a part means a mass part.

[Preparation of Toner Material Liquid L]
First, 17 parts of carbon black Regal 400 (manufactured by Cabot), 3 parts of dispersant Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and 80 parts of ethyl acetate were first dispersed using a mixer having stirring blades, It was used and secondarily dispersed to obtain a pigment dispersion.

  18 parts of carnauba wax, 2 parts of dispersant and 80 parts of ethyl acetate were primarily dispersed using a mixer having stirring blades. Next, it heated up to 80 degreeC, stirring, after dissolving carnauba wax, it cooled to room temperature and deposited carnauba wax. Furthermore, secondary dispersion was performed using a dyno mill to obtain a wax dispersion. The dispersant used was a polyethylene wax grafted with a styrene-butyl acrylate copolymer.

100 parts of polyester, 30 parts of pigment dispersion, 30 parts of wax dispersion and 840 parts of ethyl acetate are stirred for 10 minutes using a mixer having a stirring blade, and a toner material liquid having a specific gravity of 1.19 g / cm ^3. L was obtained.

[Example 1]
The toner manufacturing apparatus 200 (see FIG. 12) in which the toner material liquid L is provided with a filter chamber 153 ′ (see FIG. 9B) in which 50 filters 155 are arranged in parallel through a vibration buffer member 159. The toner material liquid L was discharged from the tank 151 to the droplet discharge unit 210 using the pump 152. The filter 155 is manufactured using an electroforming method, has a diameter of 20 mm, and has a tapered hole whose diameter decreases from 10 μm to 3 μm from the upstream side toward the downstream side (see FIG. 7). ). The electrostrictive vibrator 156a is lead zirconate titanate (PZT) having an outer diameter of 15 mm, an inner diameter of 5.0 mm, and a thickness of 0.5 mm. At this time, a sin wave having a peak voltage of 20 V and a frequency of 60 kHz was applied to the electrostrictive vibrator 156a to cause the filter 155 to bend and vibrate at a frequency of 60 kHz. The heating member 157 is a seat heater, and the sensor 158 is a thermocouple. At this time, the temperature of the filter 155 was not controlled and set to room temperature. The thin film 111a of the storage member 211 is manufactured using an electroforming method, and a perfectly circular discharge port N having an opening diameter of 10 μm is formed on a nickel plate having an outer diameter of 15 mm and a thickness of 50 μm. (See FIG. 13). At this time, the discharge ports N are formed in a staggered pattern at a pitch of 100 μm in a region 4 mm in diameter from the center of the thin film 111a. The electrostrictive vibrator 212a is lead zirconate titanate (PZT) having an outer diameter of 15 mm, an inner diameter of 5.0 mm, and a thickness of 1 mm. At this time, a sin wave having a peak voltage of 10.5 V and a frequency of 98 kHz was applied to the electrostrictive vibrator 212a to cause the thin film 111a to flexurally vibrate at a frequency of 98 kHz. Nitrogen gas was flowed through the flow path 113 at 50 L / min, and nitrogen gas was flowed through the drying tower 120 at 30 L / min. At this time, the dew point temperature of nitrogen gas was −20 ° C., and the temperature of the drying tower 120 was 27 to 28 ° C.

  Under the above conditions (see Table 1), the toner material liquid L is discharged at 0.51 g / min and then dried in the drying tower 120, whereby the base particles T can be produced at 0.05 g / min. did it. In addition, after neutralizing by irradiating soft X-rays in the collection part 130, it collected using the filter with a hole diameter of 1 micrometer, and stored in the storage part 140. FIG. At this time, the base particles T stored in the storage unit 140 had a weight average particle diameter of 5.2 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.06. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.50 g / min. Next, when the thin film 111a was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, clogging was not confirmed. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, the four holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated for 10 minutes by using a pump 152 through a pipe (not shown) that bypasses the droplet discharge unit 210. At this time, the temperature of the filter 155 was controlled to 60 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, clogging was not confirmed. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

(Measurement method of particle size distribution of base particles)
First, nonionic surface activity in 10 ml of water obtained by removing fine dust through a filter and having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is 20/10 ⁻³ cm ³ or less. A few drops of the agent Contaminone N (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 mg of base particles were added. Next, using an ultrasonic disperser UH-50 (manufactured by STM), the dispersion treatment is performed for 1 minute under the conditions of 20 kHz and 50 W / 10 cm ³ , and then the dispersion treatment is performed for a total of 5 minutes. A dispersion having a concentration of particles of 0.60 μm or more and less than 159.21 μm in a range of 4000 to 8000/10 ⁻³ cm ³ was prepared, and the particle size distribution was measured.

  Specifically, the dispersion liquid is passed through a flow path extending along the flow direction of a flat and flat transparent flow cell having a thickness of about 200 μm. At this time, in order to form an optical path that passes through the flow cell in the thickness direction, the strobe and the CCD camera are mounted so as to be opposite to each other with respect to the thickness direction of the flow cell. Furthermore, strobe light is irradiated at 1/30 second intervals to obtain an image of particles flowing through the flow cell while the dispersion is flowing. As a result, the base particle is photographed as a two-dimensional image parallel to the flow cell, and the diameter of a circle having the same area as the area of the two-dimensional image is calculated as the equivalent circle diameter. At this time, the range of 0.06 to 400 μm is divided into 226 channels, and the equivalent circle diameter of 1200 or more base particles is calculated in about 1 minute.

[Example 2]
The hole of the filter 155 is tapered so that the hole diameter is reduced from 13 μm to 5 μm from the upstream side to the downstream side, the opening diameter of the thin film 111a is 15 μm, and the peak voltage of the sin wave applied to the electrostrictive vibrator 212a is 9. Base particles T were obtained in the same manner as in Example 1 except that the voltage was 5V.

  Under the above conditions (see Table 1), the toner material liquid L was discharged at 0.82 g / min and then dried in the drying tower 120. As a result, the base particles T stored in the storage unit 140 were weight average. The particle diameter was 8.9 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.12. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.80 g / min. Next, when the thin film 111a was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, clogging was not confirmed. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, 6 holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated for 10 minutes by using a pump 152 through a pipe (not shown) that bypasses the droplet discharge unit 210. At this time, the temperature of the filter 155 was controlled to 60 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, clogging was not confirmed. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

[Example 3]
6. The hole of the filter 155 is tapered so that the hole diameter decreases from 4 μm to 2 μm from the upstream side to the downstream side, the opening diameter of the thin film 111a is 5 μm, and the peak voltage of the sine wave applied to the electrostrictive vibrator 212a is 7. Base particles T were obtained in the same manner as in Example 1 except that the voltage was 2V.

  Under the above conditions (see Table 1), the toner material liquid L was discharged at 0.21 g / min and then dried in the drying tower 120. As a result, the base particles T stored in the storage unit 140 were weight average. The particle diameter was 3.2 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.10. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.19 g / min. Next, when the thin film 111a was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, clogging was not confirmed. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, 8 holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated for 10 minutes by using a pump 152 through a pipe (not shown) that bypasses the droplet discharge unit 210. At this time, the temperature of the filter 155 was controlled to 60 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, clogging was not confirmed. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

[Example 4]
Example 1 except that the hole of the filter 155 is tapered so that the hole diameter is reduced from 18 μm to 10 μm from the upstream side to the downstream side, and the peak voltage of the sin wave applied to the electrostrictive vibrator 212a is 7.5V. In the same manner, base particles T were obtained.

  Under the above conditions (see Table 1), the toner material liquid L was discharged at 0.52 g / min and then dried in the drying tower 120. As a result, the base particles T stored in the storage unit 140 were weight average. The particle diameter was 5.3 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.12. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.48 g / min. Next, when the thin film 111a was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, the 6 discharge ports N were clogged. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, 6 holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated for 10 minutes by using a pump 152 through a pipe (not shown) that bypasses the droplet discharge unit 210. At this time, the temperature of the filter 155 was controlled to 60 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, clogging was not confirmed. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

[Example 5]
Base particles T were obtained in the same manner as in Example 1 except that the pores of the filter 155 were tapered so that the pore diameter was reduced from 12 μm to 5 μm from the upstream side toward the downstream side.

  Under the conditions described above (see Table 1), the toner material liquid L was discharged at 0.51 g / min and then dried in the drying tower 120. As a result, the base particles T stored in the storage unit 140 were weight average. The particle diameter was 5.2 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.07. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.50 g / min. Next, when the thin film 111a was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, the four discharge ports N were clogged. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, the four holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated for 10 minutes by using a pump 152 through a pipe (not shown) that bypasses the droplet discharge unit 210. At this time, the temperature of the filter 155 was controlled to 60 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, clogging was not confirmed. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

[Example 6]
Except for using the droplet discharge unit 110 (see FIG. 2) instead of the droplet discharge unit 210 and using the thin film 111a ′ (see FIG. 3) instead of the thin film 111a, Base particles T were obtained. The thin film 111a ′ is formed on an SOI substrate having a thickness of 500 μm, and an ejection port N ′ in which the diameter of the opening N1 ′ is 100 μm and the diameter of the opening N2 ′ is 8.5 μm. At this time, the discharge ports N ′ are formed in a staggered pattern at a pitch of 100 μm in a region having a diameter of 4 mm from the center of the thin film 111a ′. The electrostrictive vibrator 112a is lead zirconate titanate (PZT) having an outer diameter of 20 mm, an inner diameter of 5.0 mm, and a thickness of 2 mm. At this time, a sin wave having a peak voltage of 10.5 V and a frequency of 52 kHz was applied to the electrostrictive vibrator 212a to cause the thin film 111a ′ to flexurally vibrate at a frequency of 52 kHz.

  Under the above conditions (see Table 1), after the toner material liquid L was discharged at 0.43 g / min and then dried in the drying tower 120, the base particles T stored in the storage unit 140 were weight average. The particle diameter was 5.0 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.12. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.40 g / min. Next, when the thin film 111a ′ was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, clogging was not confirmed. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, 16 holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated through the pipe 152 (not shown) bypassing the droplet discharge unit 110 while the toner material liquid L was backflowed for 10 minutes. At this time, the temperature of the filter 155 was controlled to 60 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, clogging was not confirmed. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

[Example 7]
The toner material liquid L was discharged at 0.42 g / min under the conditions of Example 6, and then dried in the drying tower 120. As a result, the base particles T stored in the storage unit 140 had a weight average particle size of 4. The ratio of the weight average particle diameter to the number average particle diameter was 1.10. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.40 g / min. Next, when the thin film 111a ′ was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, clogging was not confirmed. Similarly, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, 16 holes were clogged (see Table 2).

  Further, after the filter 155 was attached, the toner material liquid L was circulated for 10 minutes by using a pump 152 through a pipe (not shown) that bypasses the droplet discharge unit 210. At this time, the temperature of the filter 155 was controlled to 40 ° C. Next, when the filter 155 was removed and 200 holes were arbitrarily observed using an optical microscope, 6 holes were clogged. From this, it can be seen that the base particles T can be produced stably over a long period of time by performing maintenance once every 20 hours.

[Comparative Example 1]
Base particles T were obtained in the same manner as in Example 1 except that the filter chamber 153 ′ was not provided and the pipes 153 at both ends of the filter chamber 153 ′ were connected.

  Under the above conditions (see Table 1), the toner material liquid L was discharged at 0.50 g / min and then dried in the drying tower 120. As a result, the base particles T stored in the storage unit 140 were weight average. The particle diameter was 5.3 μm, and the ratio of the weight average particle diameter to the number average particle diameter was 1.19. When the base particles T were produced for 20 hours, the discharge amount of the toner material liquid L was 0.20 g / min. Next, when the thin film 111a was removed and 200 discharge ports N were arbitrarily observed using an optical microscope, 100 discharge ports N were clogged (see Table 2).

なお、Ｄ４及びＤｎは、それぞれ重量平均粒径及び個数平均粒径である。

D4 and Dn are a weight average particle diameter and a number average particle diameter, respectively.

[Production of toner]
Using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), 1.0% by mass of hydrophobic silica H2000 (manufactured by Clariant Japan) was mixed with the base particles T to obtain a toner.

[Production of developer]
In a heated state, a dispersion in which silicone resin is dispersed in toluene is spray-coated onto spherical ferrite particles having an average particle diameter of 50 μm, and then fired and cooled, whereby a coating layer having a thickness of 0.2 μm is obtained. Formed a career.

  Next, 4 parts of toner and 96 parts of carrier were mixed to obtain a developer.

100, 200 Toner manufacturing apparatus 110, 110 ′, 110 ″, 210 Droplet discharge unit 111, 211 Storage member 111a, 111a ′ Thin film 111b, 211b Storage member body 111c, 111c ′, 211c Storage unit 111d Restriction 111e Opening 112, 212 Vibration member 112a, 212a Electrostrictive vibrator 112b, 112b 'Horn 112c, 112d, 212c, 212d Electrode 112e Power source 113 Channel 120 Drying tower 130 Collection unit 131 Tapered surface 132 Pipe 140 Storage unit 150 Supply unit 151 Tank 152 Pump 153, 154 Piping 153 'Filter chamber 155 Filter 156 Vibrating member 156a Electrostrictive vibrator 156b, 156c Electrode 156d Power source 157 Heating member 158 Sensor 159 Fixing member L Toner material liquid L 'droplet G, G' dry gas T base particle N, N 'discharge port S vortex

JP 2006-293320 A

Claims (15)

Filtering a toner material solution in which a toner material containing a resin and a release agent is dissolved or dispersed in an organic solvent with a filter;
Supplying the toner material liquid filtered by the filter to a storage member having a film in which a plurality of discharge ports are formed;
A step of discharging the toner material liquid from the plurality of discharge ports;
And drying the droplets discharged from the plurality of discharge ports to form base particles,
Wherein the ratio of the pore size of the filter with respect to the opening diameter of the discharge ports Ri der 1/20 or more and 1 or less,
The method for producing toner according to claim 1, wherein the filter is formed with holes whose diameter decreases from the upstream side toward the downstream side . The toner material liquid in filtering with a filter, method for producing a toner according to claim 1, characterized in that vibrating the filter. By periodically vibrating a vibrator having a surface substantially parallel to the filter in a direction substantially perpendicular to the filter, the filter is vibrated,
The toner manufacturing method according to claim 2 , wherein the vibrator having a surface substantially parallel to the filter is formed in an annular shape around the hole of the filter. The toner manufacturing method according to claim 3 , wherein the vibrator having a surface substantially parallel to the filter is an electrostrictive vibrator. Method for producing a toner according to any one of claims 1 to 4, further comprising the step of maintaining by heating the filter to the releasing agent temperature below the boiling point of the organic solvent above the melting point of the . Method for producing a toner according to any one of claims 1 to 5, wherein the opening diameter of the discharge port is 5μm or more 15μm or less. By vibrating the membrane, method for producing a toner according to any one of claims 1 to 6, characterized in that discharging the toner material liquid from said plurality of discharge ports. The toner manufacturing method according to claim 7 , wherein the film is vibrated by periodically vibrating a vibrator having a surface substantially parallel to the film in a direction substantially perpendicular to the film. . The toner manufacturing method according to claim 8 , wherein the amplitude of vibration of a vibrator having a surface substantially parallel to the film is amplified using a horn. The toner manufacturing method according to claim 9 , wherein the horn also serves as a part of the storage member. The toner manufacturing method according to claim 8 , wherein the vibrator having a surface substantially parallel to the film is formed in an annular shape around the plurality of ejection openings of the film. Vibrator having a surface approximately parallel to said membrane, method for producing a toner according to any one of claims 8 to 11, characterized in that the electrostrictive vibrator. A step of adjusting the speed of droplets discharged from the plurality of discharge ports;
The speed was the dried the adjusted drop method for producing a toner according to any one of claims 1 to 12, characterized in that to form the base particles. The base particles, method for producing a toner according to any one of claims 1 to 13 ratio of the weight average particle diameter to number average particle diameter, characterized in that 1.00 to 1.15. The base particles, method for producing a toner according to any one of claims 1 to 14, wherein the weight average particle diameter of 3μm or more 10μm or less.

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