JP2011075660A - Device for producing toner, and the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a toner which gains a toner which is uniform for a long period and has a small variation range in particle size distribution in an injection granulation process, and to provide a device therefor and a toner. <P>SOLUTION: The method for producing a toner includes the steps, wherein a toner composition liquid in which a toner material containing a binding resin, a colorant and wax is dissolved or dispersed in a solvent, is introduced into a liquid chamber and then discharged to make the liquid droplets, and the solvent is removed, and then the droplets are hardened to produce toner particles. The liquid chamber discharges the toner composition liquid as the droplets by means of oscillation generated by a ring-shaped oscillation means which is arranged on the outer peripheral area, on one face side of a discharging plate having a plurality of nozzles which is provided on one face of the liquid chamber. The discharge plate is fixed firmly to the ring-shaped oscillation means in the area, in which the ring-shaped oscillation means is arranged, and is also fixed firmly to the frame of the liquid chamber on the opposite face side in the outer area. In this case, the elastic modulus of a connection member used for its firm fixation to the ring-shaped oscillation means is at least 1.0×10<SP>8</SP>. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic image in electrophotography, and the produced toner.

Conventionally, the only production method for electrophotographic toners used in copying machines, printers, fax machines, and composite machines based on the electrophotographic recording method has been the pulverization method, but in recent years, in an aqueous medium called a polymerization method. The method formed by (1) is widely performed, and the momentum surpasses the pulverization method (see, for example, Patent Document 1).
The toner by the polymerization method is called “polymerized toner” or “chemical toner” in some countries, but the polymerization method includes a manufacturing method that does not necessarily involve a polymerization process for convenience.
Currently used polymerization methods are suspension polymerization, emulsion aggregation, polymer suspension (polymer aggregation), and ester elongation.

Compared with the pulverization method, the polymerization method generally has advantages such as easy to obtain a small particle size toner, a sharp particle size distribution, and a shape close to a sphere. The solvent removal efficiency is poor, and a long time is required for the polymerization process.
Further, after the solidification is completed, it is necessary to separate the toner particles and water, and then repeat washing and drying, which requires a lot of time, a large amount of water, and a lot of energy.

As an alternative toner manufacturing method, a jet granulation method has been proposed in which a toner composition liquid is formed into droplets in a gas phase without using water and then solidified.
In Patent Document 2, a melted liquid or a liquid in which a toner composition liquid is dissolved is formed into fine particles using various atomizers and discharged, and dried to obtain particles.
However, since the particles obtained by the spray granulation method are relatively coarse and large, and the particle size distribution is wide, the characteristics of the toner itself are inferior to those of the conventional method.
On the other hand, in the toner manufacturing method disclosed in Patent Document 3, a piezoelectric pulse is applied to a fluid toner composition liquid containing a resin and a colorant, and the liquid droplets are ejected from a nozzle to a solidified portion. The toner particles are formed by drying and solidifying the fine droplets in the solidifying portion.
In addition, the manufacturing method disclosed in Patent Document 4 converges a piezoelectric pulse with an acoustic lens, and discharges a toner composition from a nozzle to a solidified portion by the converged acoustic pulse to form a fine droplet, which is dried and solidified. Thus, toner particles are formed.
In addition, the manufacturing method disclosed in Patent Document 5 forms a fine droplet by vibrating a fluid toner composition liquid containing a resin and a colorant at a certain frequency with a piezoelectric body and discharging the liquid from the nozzle. The fine droplets are dried and solidified to form toner particles.

However, in the toner manufacturing apparatuses described in Patent Document 3 and Patent Document 4, only a liquid droplet can be discharged from one nozzle using one piezoelectric body, and a liquid that can be discharged per unit time. There were the disadvantages of low drop count and poor productivity.
Further, as shown in Patent Document 5, when a plurality of nozzles are provided for one piezoelectric body, the speed at which the vibration of the piezoelectric body is transmitted to each nozzle differs depending on the distance from the piezoelectric body, so that the discharge from each nozzle is performed. There is a disadvantage in that a time lag occurs in the droplets to be discharged, and the discharge amount differs between nozzles. Furthermore, studies have been made to make the droplets discharged from each nozzle uniform and improve productivity.
In Patent Document 6, an improvement is attempted by fixing the end portion of the plate-like vibration means via an elastic adhesive. However, although an improvement in productivity is recognized, the controllability of the vibration portion is reduced. The effect was not sufficient.

  The present invention eliminates the conventional problems in the above-described spray granulation method, that is, in the spray granulation method, the toner composition liquid can be discharged as droplets having a uniform particle size distribution over a long period of time. It is an object of the present invention to provide a toner manufacturing method, a toner manufacturing apparatus, and a toner capable of obtaining a toner having a small range of variation in particle size distribution observed in the method.

The above-mentioned problems are solved by the present inventions (1) to (13) shown below.
(1) “Dropping into which a toner composition solution in which a toner material containing at least a binder resin, a colorant and wax is dissolved or dispersed in a solvent is introduced into a liquid chamber and discharged from the liquid chamber to form droplets; And a method for producing toner, comprising the step of removing the solvent from the liquid toner composition and solidifying the liquid droplets to produce toner particles, wherein the liquid chamber is provided on one surface thereof. The material toner composition liquid is ejected as droplets by vibration by an annular vibrating means disposed on the outer peripheral area on one surface side of the ejection plate having a plurality of nozzles, and the ejection plate The annular vibration means is fixed to the annular vibration means in the region where the annular vibration means is disposed, and is fixed to the liquid chamber frame on the outer region and the opposite surface side. Joining for use with the annular vibration means Method for producing a toner, wherein the elastic modulus of the wood is 1.0 × 10 ^ 8 or more ".
(2) “The method for producing a toner according to (1) above, wherein the melting temperature of the bonding agent is a metal material of 230 ° C. or lower”.
(3) “The method for producing a toner according to (1) or (2) above, wherein the bonding agent is mainly composed of tin, bismuth, and silver”.
(4) “The method for producing a toner according to (1) or (2) above, wherein the bonding agent is mainly composed of tin, copper, and silver”.
(5) The above-mentioned discharge plate is formed in a convex shape in a direction in which the droplets are discharged, and the plurality of nozzles are formed in a portion formed in the convex shape. (1) Item or (2) Item and (3) or (4) Method for Producing Toner ”
(6) The item (1), item (2), item (5), wherein the annular vibration means vibrates the discharge plate in a vibration mode having no nodes in the diameter direction. And a method for producing a toner according to any one of (3) or (4).
(7) “Nozzle diameter of the discharge plate is 5 to 15 μm, (1), (2), (5), (6) and (3) or (4) The method for producing a toner according to any one of Items).
(8) The item (1), (2), wherein the annular vibration means is a piezoelectric element, and a discharge condition of a droplet from the discharge plate to be controlled is a voltage applied to the element. Item, (5) Item, (6) Item, (7) Item, and (3) or (4) Toner Production Method ”.
(9) The item (1), wherein the annular vibration means is a piezoelectric element, and a discharge condition of a droplet from the discharge plate to be controlled is a frequency of a voltage applied to the element. Item 2), (5) to (8), and (3) or (4).
(10) The item (1), (2), (5), wherein after the material liquid is discharged as droplets from the discharge plate, the drop velocity of the droplets is increased or decreased by a conveying airflow. Item 9 to Item 9, and a method for producing a toner according to any one of Items (3) or (4).
(11) “Toner manufactured according to any one of items (1) to (10)”.
(12) “The toner according to item (11), wherein the particle size distribution (weight average particle diameter / number average particle diameter) is in the range of 1.00 to 1.15”.
(13) “The toner according to (11) or (12) above, wherein the weight average particle diameter is 3 to 10 μm”.

According to the present invention, it is possible to provide a toner manufacturing method capable of stably manufacturing a toner having a uniform particle size distribution for a long time.
As a result, it is possible to obtain a toner having a particle size distribution close to monodispersion that could not be achieved by conventional methods such as the pulverization method and the polymerization method. In many of the characteristic values required for this, the range of fluctuation due to particles is very small, and it can be used as a developer for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. Can be formed.

1 is a schematic configuration diagram illustrating an embodiment of a toner manufacturing apparatus according to the present invention. 4 is an enlarged explanatory view of a droplet jetting unit of the toner manufacturing apparatus of the present invention. FIG. FIG. 4 is a bottom explanatory view of a droplet ejecting unit of the toner manufacturing apparatus of the present invention as viewed from below. FIG. 5 is an enlarged cross-sectional explanatory view of a droplet forming unit of a droplet jetting unit of the toner manufacturing apparatus of the present invention. It is expansion sectional explanatory drawing of the droplet formation means which concerns on a comparative example structure. FIG. 3 is an explanatory diagram of a main part of a specific application of the toner manufacturing apparatus of the present invention. It is a typical explanatory view of a discharge plate used for explanation of an operation principle of droplet formation by a droplet jetting unit of the present invention. It is explanatory drawing with which it uses for description of the fundamental vibration mode of the droplet ejection unit of this invention. It is explanatory drawing with which it uses for description of the secondary vibration mode of the droplet ejection unit of this invention. It is explanatory drawing with which it uses for description of the tertiary vibration mode of the droplet ejection unit of this invention. It is explanatory drawing at the time of forming a convex part in the center part of the discharge plate of the droplet ejection unit of this invention. 5 is an embodiment of the film vibration type toner manufacturing apparatus according to the toner repair of the present invention;

As described in the background art, the present invention has been made in view of the problem that the ability is lowered in the conventional spray granulation method.
With regard to this problem, the vibration state of the nozzle part is unstable, so the particle size distribution of the discharged droplets becomes wide, and the discharge amount decreases due to the oozing out of the toner composition liquid around the nozzle with weak discharge force Can be prevented.

The present invention will be described in detail below according to the best mode for carrying out the invention.
The toner manufacturing method of the present invention has an annular vibration means around a discharge plate having a plurality of nozzles, the outer peripheral portion of the annular vibration means is fixed to a frame, and the toner composition liquid is vibrated by vibration by the annular vibration means. In a toner manufacturing apparatus obtained by drying and solidifying a liquid as a droplet, a metal bonding agent is used for joining the ejection plate and the annular vibration means and fixing the annular vibration means and the frame. Features.
By mechanically vibrating a discharge plate having a plurality of nozzles having the same opening diameter, a toner composition liquid is periodically discharged from the nozzles to generate droplets having a uniform particle diameter and dried to obtain toner particles. Is the method.

An example of the toner manufacturing apparatus will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus (1) uses a droplet as a droplet forming means in a periodic droplet forming process in which a toner composition liquid is periodically discharged from a plurality of nozzles having the same opening diameter to form droplets in a gas phase. The ejection unit (2) and the droplet ejection unit (2) are disposed above, and solidify the droplets of the toner composition liquid that has been formed into droplets, which are discharged from the droplet ejection unit (2). A particle forming unit (3) as a particle forming means in a particle forming step for forming (T), a toner collecting unit (4) for collecting toner particles (T) formed in the particle forming unit (3), and The toner particles (T) collected by the toner collecting unit (4) are transferred through the tube (5), and a toner storage unit (toner storage unit) that stores the transferred toner particles (T) ( 6), a raw material container (7) for accommodating the toner composition liquid (10), A pipe (liquid feed pipe) (8) for feeding the toner composition liquid (10) from the inside of the raw material container (7) to the droplet jetting unit (2), and a toner composition liquid (10) during operation, etc. And a pump (9).
Further, the toner composition liquid (10) from the raw material container (7) is supplied to the droplet ejection unit (2) in a self-sufficient manner due to droplet formation by the droplet ejection unit (2). In some cases, as described above, the liquid is supplied supplementarily using the pump (9).

The droplet jetting unit (2) using the annular mechanical vibration means will be described with reference to FIGS.
2 is a cross-sectional explanatory view of the liquid droplet ejecting unit (2), FIG. 3 is an explanatory bottom view of the main part when FIG. 2 is viewed from the lower side, and FIG. 4 is a schematic cross-sectional explanatory view of the droplet forming means.

The liquid droplet ejecting unit (2) supplies at least a liquid droplet forming means (16) that discharges the toner composition liquid (10) into liquid droplets, and supplies the liquid toner composition (10) to the liquid droplet forming means (16). And a frame (channel member) (15) in which a reservoir (liquid channel) (14) is formed.
The droplet forming means (16) includes an ejection plate (12) having a plurality of nozzles (ejection ports) (11) and an annular vibration generating means (electromechanical conversion) that vibrates the ejection plate (12). (Means) (17).
Here, the discharge plate (12) has the outermost peripheral portion (region shown by hatching in FIG. 4) joined and fixed to the flow path member, that is, the frame (15).
The vibration generating means (17) includes, for example, piezoelectric ceramics such as lead zirconate titanate (PZT), piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ . Examples thereof include crystals, but lead zirconate titanate (PZT) is most suitable in terms of vibration controllability.
The vibration generating means (17) is disposed on one surface side of the outer peripheral area provided with the nozzles in the deformable area (16A) of the discharge plate (12) (area not fixed to the flow path member (15)). It is arranged. The vibration generating means (17) is applied with a driving voltage (driving signal) having a required frequency from a driving circuit (driving signal generating source) through a lead wire, thereby generating, for example, flexural vibration.

  The droplet forming means (16) has an annular shape around the area where the nozzles in the deformable area (16A) of the discharge plate (12) having the plurality of nozzles (11) facing the storage section (14) are provided. The vibration generating means (17) is arranged, for example, as compared with the configuration in which the vibration generating means (17A) holds the periphery of the discharge plate (12) as in the comparative example configuration shown in FIG. The displacement amount of the discharge plate (12) becomes relatively large, and a plurality of nozzles (11) can be arranged in a region of a relatively large area (φ1 mm or more) from which this large displacement amount can be obtained. (11) More droplets can be stably formed and discharged at a time.

Although FIG. 1 shows an example in which one droplet ejecting unit (2) is arranged, preferably, as shown in FIG. 6, a plurality of, for example, 100 to 1,000 from the viewpoint of controllability. The droplet ejecting units (2) (only four are shown in FIG. 6) are arranged side by side on the top surface portion (3A) of the particle forming portion (3), and each droplet ejecting unit (2) has a pipe (8A). ) To the raw material container (7) (common liquid reservoir) to supply the toner composition liquid (10).
As a result, more droplets can be discharged at one time, and the production efficiency can be improved.

According to the present invention, the flow path member (15), that is, the joint (13a) between the part of the frame and the discharge plate (12), the other surface side, the discharge plate (12), and the vibration generating means (17) By using a joining member having an elastic modulus of 1 × 10 ^ 8 Pa or more for the joining portion (13b), a concentric uniform vibration state in the nozzle (11) is obtained, and the droplet discharge state is stabilized. A toner having a uniform particle size distribution can be obtained.
The reason why the bonding material having a high elastic modulus is used is to achieve the purpose of firmly fixing the bonding portion (13a) at the outermost peripheral portion of the discharge plate and the bonding portion (13b) between the vibration means and the discharge plate. This is because the vibration of the end-fixed circular film is established on the assumption that the outermost periphery is completely fixed, and the vibration from the vibration means is uniformly propagated to the discharge plate. If the joining member was 1 × 10 ^ 8 Pa or more, it was confirmed that the vibration state of the discharge plate was sufficiently uniform. Moreover, since the thing of the elasticity modulus of 10 ^ 12 or more was not obtained in experiment, it has not been confirmed.

The elastic modulus can be measured using a known method.
For example, there is a method of detecting a deflection generated when a load is applied to the center of a plate-like sample supported at both ends and calculating an elastic modulus, or a method of calculating from a propagation speed of acoustic vibration.

Although there is no restriction | limiting in particular as a joining member, In order to achieve a high elasticity modulus, it is desirable to use metal materials with melting | fusing point of 230 degrees C or less. When the melting point is 230 ° C. or less, when piezoelectric ceramics such as lead zirconate titanate (PZT) are used as the vibration means to be joined, deterioration of piezoelectric characteristics can be prevented.
When a metal is used for the joining member, an alloy of a predetermined component, that is, a so-called low melting point solder material can be used as the component. The solder material is not particularly limited as long as the melting point is 230 ° C. or less as described above, but from the viewpoint of durability and workability, solder mainly composed of tin and bismuth (melting point: about 150 ° C.), tin, A solder mainly composed of copper and silver (melting point: about 220 ° C.) is preferable.
Solder material may be paste-printed and applied by screen printing, and then the members may be joined and heated and cooled to join, or the material that has been processed in advance for the joint is sandwiched between the members Then, it may be joined by heating and cooling. In this case, the thickness of the bonding agent is estimated to be several μm to several tens of μm. It is necessary that the joining member uniformly spreads and joins the joining surface.

When a so-called adhesive is used for the bonding material, a type with a crosslinking reaction is preferable.
This is because the toner composition liquid to be discharged assumes an organic solvent.
Among them, the epoxy resin adhesive is excellent for achieving a high elastic modulus, adhesive force, workability, and solvent resistance in a balanced manner.
In order to increase the elastic modulus of the epoxy resin adhesive, it can be achieved by blending a high elastic modulus filler such as silicon oxide or silicon nitride. Since the thickness of the adhesive layer varies if the particle size of the filler is not uniform, it is desirable to use a filler having a uniform particle size distribution, and the average particle size is preferably about 1 μm to 15 μm. When the average particle size is 1 μm or less, the viscosity of the adhesive is increased and workability is lowered. When the average particle size is 15 μm or more, the filling efficiency of the filler is lowered and it becomes difficult to obtain high elasticity.
In addition to bisphenol A (diglycidyl ether of bisphenol A) as an epoxy resin, an epoxy resin having a cresol novolak-type moiety or a phenol novolac-type moiety can be used to increase the high elastic modulus and solvent resistance. it can.
The curing agent may be a general one such as tertiary amine, polyamine, acid anhydride, but it is desirable to use an acid anhydride curing agent from the viewpoint of solvent resistance.
The epoxy resin can be adhered to the member by heating and curing after screen printing or normal application to the parts to be joined. In this case, the thickness of the bonding agent depends on the maximum particle size of the inorganic filler in the epoxy resin, but is estimated to be several μm to several tens of μm. It is necessary that the joining member uniformly spreads and joins the joining surface.

In the prior art, it is common to use an adhesive typified by an epoxy resin from the viewpoint of adhesiveness and workability.
In addition, from the viewpoint of not disturbing the vibration of the discharge plate, there is also reported a technique of thickly applying and using a low elastic modulus and high strength adhesive such as silicone resin, nitrile rubber, and fluororubber, When such a material is used, the vibration state of the ejection plate becomes unstable, the particle size distribution of the ejected droplets becomes wider, and non-ejection nozzles are also generated. Since the toner composition liquid oozes around the non-ejection nozzles, and as a result, the nozzles existing around the non-ejection nozzles are clogged, so that productivity decreases with time.

(Droplet formation mechanism)
Next, the mechanism of droplet formation by the droplet ejecting unit (2) as the droplet forming means will be described.
As described above, the droplet ejecting unit (2) has vibration generated by the vibration means (13) which is mechanical vibration means on the discharge plate (12) having a plurality of nozzles (11) facing the storage section (14). , The discharge plate (12) is periodically vibrated, a plurality of nozzles (11) are disposed in a relatively large area (φ1 mm or more), and the droplets are periodically cycled from the plurality of nozzles (11). Therefore, it becomes possible to form and discharge stably.

When the peripheral portion (12A) of the discharge plate (12) as shown in FIG. 7 is fixed, the periphery of the basic vibration is a node, and the displacement ΔL is maximum at the center O of the discharge plate as shown in FIG. The cross-sectional shape becomes (ΔLmax), and it vibrates vertically in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 9 and 10 exist.
These modes have one or more concentric nodes in a circular membrane, and are substantially axisymmetric deformation shapes.
Further, as shown in FIG. 11, by making the central portion have a convex shape (12C), it is possible to control the traveling direction of the droplet and adjust the vibration amplitude.

Due to the vibration of the circular discharge plate, a sound pressure P _ac proportional to the vibration speed V _{m of the} film is generated in the liquid in the vicinity of the nozzles provided at various positions of the circular film.
Sound pressure, medium are known to occur as a reaction of the radiation impedance Z _r of (toner constituent liquid), sound pressure, using the following equation (1), the radiation impedance and film vibration velocity V _m Expressed as a product.
P _ac (r, t) = Z _r · V _m (r, t) (1)
Is a function of time (t) since the vibration speed V _m of the film fluctuates periodically with time, for example a sine wave, such as a rectangular waveform, it is possible to form various periodic variations.
Further, as described above, the vibration displacement in the vibration direction is different in each part of the film, and the vibration speed V _m is also a function of the position coordinates on the film.
The vibration mode of the film used in the present invention is an axial object as described above. Thus, it is essentially a function of the radius (r) coordinate.

As described above, a sound pressure proportional to the vibration displacement speed of the distributed film is generated, and the toner composition liquid is discharged into the gas phase in response to the periodic change of the sound pressure.
Since the toner composition liquid periodically discharged to the gas phase forms spheres due to the difference in surface tension between the liquid phase and the gas phase, droplet formation occurs periodically.

As the vibration frequency of the film that enables droplet formation, a region of 20 kHz to 2.0 MHz is used, and a range of 50 kHz to 500 kHz is more preferably used. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid.
Furthermore, when the displacement amount of the sound pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.

  Here, the diameter of the formed droplet tends to increase as the vibration displacement in the vicinity of the nozzle of the film increases. When the vibration displacement is small, a droplet is formed or does not become a droplet. In order to reduce such a variation in droplet size at each nozzle site, it is necessary to define the nozzle arrangement at an optimum position of the membrane vibration displacement.

In the present invention, as will be described with reference to FIGS. 8 to 10, the ratio R (= ΔLmax) of the maximum value ΔLmax and the minimum value ΔLmin of the vibration direction displacement ΔL of the film in the vicinity of the nozzle generated by the mechanical vibration means. / ΔLmin) is found to be within a necessary area as toner fine particles capable of providing a high-quality image by disposing the nozzle in a part where 2.0 is within 2.0. It was.
The conditions of the toner composition liquid were changed, and in the region where the viscosity was 20 mPa · s or less and the surface tension was 20 to 75 mN / m, the satellite generation start region was the same, so the displacement of the sound pressure was 500 kPa or less. More preferably, it must be 100 kPa or less.

(Discharge plate with multiple nozzles)
As described above, the discharge plate (12) having the nozzle is a member that discharges the dissolved or dispersed liquid of the toner composition to form droplets.
The material of the discharge plate (12) and the shape of the nozzle (11) are not particularly limited and may be appropriately selected. For example, the discharge plate (12) is a metal plate having a thickness of 5 to 500 μm. When the liquid droplets of the toner composition liquid (10) are ejected from the nozzle (11), the fine liquid is formed and the opening diameter of the nozzle (11) is 3 to 30 μm. This is preferable from the viewpoint of generating droplets.
The opening diameter of the nozzle (11) means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse. The number of the plurality of nozzles (11) is preferably 2 to 3000.

(Collection)
Although the toner production method by characteristic ejection has been described above, a mechanism relating to collection is omitted for the sake of simplicity. The explanation is given below.
FIG. 12 shows an embodiment of the toner production apparatus of the present invention.
In the present embodiment, the discharge unit has a shroud and has a transport airflow around the toner flow, and the transport airflow increases the group speed of the discharged toner group, and the initial discharge speed. If the value is high, decrease it. This effectively prevents coalescence due to collision between each other during the drying process until the discharged toner is solidified, and the resulting toner group has very little coalescence, improving productivity including yield. Can be made.

Also in this embodiment, a droplet ejecting unit is provided in the upper part of the apparatus, a chamber part (18) for ejecting and drying droplets, and a guide for sending the toner obtained in the chamber part (18) to the toner storing part. And a tube.
The droplet ejecting unit (2) is a droplet forming means (11) for dropletizing and discharging a toner composition liquid (10) in which a toner composition containing at least a resin and a colorant is dispersed or dissolved in an organic solvent. And a container (13) in which a reservoir (12) for supplying the toner composition liquid (10) to the droplet forming means (11) is formed.
The droplet forming means (11) is the same as the membrane vibration method.

A liquid supply hole (20) and a discharge hole (21) for supplying the toner composition liquid (10) to the reservoir (12) are connected to the toner container (13), respectively.
The droplet (23) is discharged from the nozzle (15) by the droplet forming means (11).
The outer side of the container (13) has an opening (30a) that opens at a portion facing the nozzle (15), and follows the discharge direction of the toner composition liquid (10) from the nozzle (15). A shroud portion (30) that forms an air flow path for the gas carrying the flowing droplet (23) is attached.
The shroud part (30) is composed of double pot-shaped walls (30b) and (30c) having an open nozzle part, and the lid part (31) is connected to each other.
A gas blowing pipe (91) is fitted into the side surface of the shroud portion (30).
Of the double walls, the inner wall (30c) ends near the lower end of the container (13).
Out of the double walls, the outer wall (30b) wraps around to the lower part of the nozzle (15) and ends with a lower circular opening (30a) facing the nozzle (15).
The aperture (30a) has a diameter “D”, and the inner wall of the bottom (30d) of the outer wall (30b) and the lower end of the nozzle (15) maintain a clearance “G”. Since G is smaller than D, G is the main factor that determines the flow velocity of the carrier airflow.

The flow (23a) containing the droplets (23) is then guided into the shroud portion (30) having a large volume with the shroud portion (30) and the container (13) attached to the upper portion.
In the chamber part (18), a downward air flow (96) shown in FIG. 4 is formed by a chamber part outlet (93) described later.
The air flow (96) is a uniform laminar flow, and the flow (23a) including the droplets (23) is dried and solidified in a laminar flow state by the air flow (96), and the toner collecting portion (4) at the bottom. To the guide tube (92) connected to the.
The guide tube (92) is connected to a cyclone (not shown), collected while being dried, and fed to the toner reservoir (5).
A gas blowing pipe (91) is airtightly fitted on the upper side surface of the shroud portion (30).
A pressure gauge (PG1) is inserted on the opposite side surface of the chamber portion (18).
Moreover, the pressure gauge (PG2) is also inserted in the side surface of the blowing pipe of the shroud part (30).

Next, the operation of the toner manufacturing apparatus according to this embodiment will be described.
Here, the case where the toner composition liquid (10) is circulated will be described.
When the toner composition liquid (10) is accommodated in the container (13) with an appropriate pressure, the annular vibration means (17), which is a vibration means, is vibrated and driven at 100 kHz, for example, by a driving device (not shown). Then, the vibration propagates to the ejection plate (16), and the toner composition liquid (10) is ejected from the plurality of nozzles (15) at a discharge frequency that matches the vibration driving frequency.
The released initial velocity (V ₀ ) tends to decelerate due to resistance due to the viscosity of the gas in the shroud portion (30).

On the other hand, in the shroud part (30), gas is blown out by the blowing pipe (91), and the carrier airflow (95) is formed through the shroud part (30), and the chamber part (18 ).
The air flow (95) formed is uniform and downward in the circumferential direction, and the lower end of the wall (30b) of the shroud portion (30) is rounded, so the air flow smoothly changes sideways. , Merge under the nozzle (15), and further discharged from the opening (30a). If the airflow at this time is turbulent, the droplets (23) are likely to coalesce with each other.
The discharged droplet (23) rides on the carrier airflow (95) and is released from the opening (30a) into the chamber portion (18) where it rides on the laminar airflow (96) and coalesces. Without being sent to the toner collecting section (4).

In this example, the flow velocity (V ₁ ) of the carrier airflow (95) is larger than the initial velocity (V ₀ ) of the droplet (23), and the droplet (23) is accelerated and sent on the carrier airflow (95). Shows the case.
(V ₁ ) only needs to be higher than the free fall speed, and may be lower than the initial speed (V ₀ ).
An air flow (96) having a flow velocity (V ₂ ) faster than (V ₁ ) is formed in the chamber.
The flow velocity (V ₂ ) of the air flow (96) is preferably as large as possible to prevent coalescence.
The air flow (96) in the chamber portion (18) blows out gas from the blow-out pipe (93), thereby forming a uniform and uniform air flow in the circumferential direction as in the shroud portion (30).
Laminar flow is preferred in the chamber part (18). Since the flow (23a) (flow velocity is V ₁ ) of the droplet including the droplet (23) immediately after being discharged into the chamber portion (18) does not cause turbulent flow and flows down smoothly, the chamber portion ( 18) It is preferable that V ₂ ≧ V ₁ with respect to the flow velocity (V ₂ ) of the air flow (96) in the interior.

The flow rates of the carrier airflow (95) in the shroud part (30) and the airflow (96) in the chamber part (18) are managed by pressure gauges (PG1) and (PG2).
It is preferable that the pressure (P1) in the shroud part (30) and the pressure (P2) in the chamber part (18) have a relationship of P1 ≧ P2. If this relationship is not satisfied, there is a possibility that a negative pressure acts on the droplet (23) and the liquid flows backward.

As described above, the rate-determining rate of the airflow (95) in the shroud portion (30) is determined by “the diameter (D) of the opening (30a)> the clearance between the wall (30b) and the head (2a). (G) ”, it is G, that is, the clearance between the wall (30b) and the head (2a).
The above is the air flow (95) in the shroud portion (30) and the air flow (96) in the chamber portion (18), and the blowing pipe (91) and the chamber portion outlet (93) at the upper portion of the chamber portion (18). However, the air flow may be formed by suction from a pipe (92) provided at the lower part of the chamber part (18).

The cross section of the opening (30a) of the wall (30b) of the shroud (30) has a larger diameter along the gas discharge direction. That is, the taper (30e) is preferably attached in the direction in which the outer diameter increases.
Thus, by forming the taper (30e) in the opening (30a), when the droplet (23) passes through the opening (30a), the droplet (23) becomes a wall surface of the opening (30a). It is possible to avoid contact with and adhere to.

In this embodiment, nitrogen gas is used for the shroud part (30) and the chamber part (18) as the gas to be blown out. However, any gas may be used, and air or other gas may be used.
In FIG. 12, the shroud portion (30) is constituted by a double pot-shaped wall. However, the inner wall (30c) may be shared by the outer peripheral wall constituting the flow path member (13).
Further, by providing a configuration in which a plurality of droplet ejecting units (2) and a shroud portion (30) are arranged in one chamber portion (18), the toner production efficiency can be further increased.
The discharged liquid droplet (23) is removed by the solvent while passing through the particle forming section (3), and is collected in the toner storage section (5) in a solid form.

(Dry)
If necessary, secondary drying such as fluidized bed drying or vacuum drying is further performed.
If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixing properties, and charging characteristics will change over time, but the organic solvent will volatilize during fixing by heating, which will adversely affect users and peripheral devices. Thorough drying is carried out.

(toner)
Next, the toner according to the present invention will be described.
The toner according to the present invention is a toner manufactured by a toner manufacturing method using the above-described toner manufacturing apparatus, whereby a toner having a monodispersed particle size distribution is obtained.
Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.15. More preferably, it is 1.00 to 1.05. Moreover, as a weight average particle diameter, it is preferable to exist in the range of 1-20 micrometers, More preferably, it is 3-10 micrometers.

Next, the toner material (toner composition liquid) that can be used in the present invention will be described.
First, a toner composition liquid in which a toner composition is dispersed and dissolved in a solvent as described above will be described.
As the toner material, the same material as that of a conventional electrophotographic toner can be used.
That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner particles can be produced by drying and solidifying into fine droplets by the toner production method.
It is also possible to obtain a target toner by drying and solidifying a liquid obtained by dissolving or dispersing a kneaded material obtained by hot-melting and kneading the above materials in various solvents into fine droplets by the toner production method. is there.

[Toner material]
The toner material contains at least a resin and a colorant and, if necessary, other components such as a carrier and a wax.

〔resin〕
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins , Coumarone indene resin, polycarbonate resin, petroleum resin, and the like.

  Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

  Examples of acrylic monomers include acrylic acid, or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid. Examples include 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacrylic acid such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or esters thereof, and the like.

The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer.
(1) Monoolefins such as ethylene, propylene, butylene, isobutylene;
(2) Polyenes such as butadiene and isoprene;
(3) Vinyl halides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride;
(4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate;
(5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether;
(6) Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone;
(7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone;
(8) Vinyl naphthalenes;
(9) Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .;
(10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid;
(11) unsaturated dibasic acid anhydrides such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride;
(12) Maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid Monoesters of unsaturated dibasic acids such as monomethyl esters, mesaconic acid monomethyl ester;
(13) Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid;
(14) α, β-unsaturated acids such as crotonic acid and cinnamic acid;
(15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride;
(16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acid and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof;
(17) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate;
(18) Monomers having a hydroxy group such as 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

In the toner according to the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene.
Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate.

Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing acrylates of the above compounds with methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.
These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, with respect to 100 parts by weight of other monomer components.
Among these crosslinkable monomers, diacrylates bonded to a toner resin from a bond chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group, and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds.
Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 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, Ketone peroxides such as rohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl 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, di-isopropylperoxydicarbonate, di-2-ethylhexylpero Xidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate, 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.

When the binder resin is a styrene-acrylic resin, there is at least one peak in the molecular weight distribution of 3,000 to 50,000 (in terms of number average molecular weight) in the molecular weight distribution by GPC of the soluble component in tetrahydrofuran (THF) as the resin component. A resin which is present and has at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property.
Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a region having a molecular weight of 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.
The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is most preferably 0.1 mgKOH / g to 50 mgKOH / g.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as 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.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acid such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides.

  Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic 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, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

When the binder resin is a polyester resin, the molecular weight distribution of the THF soluble component of the resin component
The presence of at least one peak in the molecular weight region of 3,000 to 50,000 is preferable from the viewpoint of toner fixing property and offset resistance, and the THF-soluble component includes components having a molecular weight of 100,000 or less. A binder resin that is 100% is also preferable, and a binder resin having at least one peak in a region having a molecular weight of 5,000 to 20,000 is more preferable.
When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. Most preferably, it is g-50 mgKOH / g.

In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.
As the binder resin that can be used in the toner according to the present invention, it is also possible to use a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component. it can.
Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of use of the KOH solution at this time is S (ml), a blank is measured at the same time, the amount of use of the KOH solution at this time is B (ml), and the following formula is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W
The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

  Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium. (3) and mixtures thereof are used.

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. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used.
Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium.
The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.
As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable.
The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be determined by measuring an enlarged photograph taken with a transmission electron microscope with a digitizer or the like.
Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively.

[Colorant]
The magnetic material can also be used as a colorant.
The colorant is not particularly limited and may be appropriately selected from commonly used resins. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor 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, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
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.

The colorant used in the toner according to the present invention can also be used as a master batch combined with a resin.
In addition to the above-mentioned modified and unmodified polyester resins, for example, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and substitutes thereof are used as the binder resin to be kneaded together with the production of the masterbatch or the masterbatch. Polymers of: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-acrylic acid Ethyl copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, Styrene-α-chloromethacrylic acid methyl ester Copolymer, Styrene-acrylonitrile copolymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid copolymer Styrene copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, Examples include polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. Further, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient.
The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.
The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.
The weight average molecular weight of the dispersant is a maximum molecular weight of the main peak in terms of styrene weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There is.
The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 200 parts by mass, the chargeability may be lowered.

<Wax>
In the present invention, a wax can be contained together with the binder resin and the colorant.
The wax is not particularly limited and can be appropriately selected from those usually used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax, etc. Of aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax, Waxes mainly composed of animal waxes such as lanolin and whale wax, mineral waxes such as ozokerite, ceresin, and petrolatum, and fatty acid esters such as montanic acid ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide and other saturated fatty acid bisamides, ethylene bis oleic acid amide, hexamethylene bis Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted with aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferable examples include 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, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.

Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group.
Examples of use include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If the temperature is less than 10 ° C., the function separation effect may be difficult to appear. If the temperature exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C., more preferably 70 to 100 ° C., since the function separation effect tends to be easily exhibited.

As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exert a plastic action, and those having a more linear structure or a functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action.
Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, combinations of polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon wax Combinations thereof.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak is in the region of 70 to 110 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 70 to 110 ° C.

The total content of the wax is preferably 0.2 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a highly accurate internal heat input compensation type differential scanning calorimeter. The measurement is performed according to ASTM D3418-82.
The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

<Fluidity improver>
A fluidity improver may be added to the toner according to the present invention.
The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned.
Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm, as an average primary particle size.
The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (trade name of WACKER-CHEMIE)- N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (trade name of Dow Corning): Franco1 (trade name of Franci1), and the like.

Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable.
In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%.
Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder.
As a preferred method, a method of treating silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

Examples of organosilicon compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, 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 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si.
Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and may mix and use 2 or more types.
The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable.
The surface-treated fine powder, preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.
The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary.
These inorganic fine powders may be hydrophobized as necessary.
In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer.
For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature.
In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, or the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.
Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., and adjusting the shape mechanically, or so-called spray-drying method, the toner material is dissolved and dispersed in a solvent in which the toner binder is soluble, and then spray-dried. Examples thereof include a method of removing a solvent to obtain a spherical toner and a method of forming a spherical toner by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, more preferably 5 mμ to 500 mμ.
The specific surface area according to the BET method is preferably 20 to 500 m ² / g.
The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting resins And polymer particles.
Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity.

Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, a modified silicone oil, Etc. are preferable.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and more preferably 5 mμ to 500 mμ.
Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight of the toner, and more preferably 0.01 to 2.0% by weight.

Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. There may be mentioned polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles.
The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  The developing method using the toner according to the present invention can use all of the electrostatic latent image carriers used in the conventional electrophotography. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image, and the like. A carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

  Next, specific examples in this embodiment will be described. In addition, this invention is not limited to the following Example at all.

-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
17 parts by mass of carbon black (Regal 400; manufactured by Cabot) and 3 parts by mass of a pigment dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades.
As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion in which aggregates of 5 μm or more were completely removed.

-Preparation of wax dispersion-
Next, a wax dispersion was prepared.
Carnauba wax 18 parts by mass and wax dispersant 2 parts by mass were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades.
The primary dispersion was heated to 80 ° C. with stirring to dissolve the carnauba wax, and then the liquid temperature was lowered to room temperature to precipitate wax particles so that the maximum diameter was 3 μm or less. As the wax dispersant, a polyethylene wax grafted with a styrene-butyl acrylate copolymer was used. The obtained dispersion was further finely dispersed by a strong shearing force using a dyno mill and adjusted so that the maximum diameter was 1 μm or less.

-Preparation of toner composition dispersion-
Next, a toner composition dispersion liquid having the following composition to which a resin as a binder resin, the colorant dispersion liquid, and the wax dispersion liquid were added was prepared.
100 parts by mass of polyester resin as a binder resin, 30 parts by mass of the colorant dispersion, 30 parts by mass of the wax dispersion, 840 parts by mass of ethyl acetate, and stirring for 10 minutes using a mixer having stirring blades, Evenly dispersed. Pigments and wax particles did not aggregate due to shock due to solvent dilution.

-Preparation of toner-
500 ml of the obtained dispersion liquid was supplied to the nozzle (15) of the droplet forming means (11) in the toner production apparatus diagram (FIG. 12) described above.
The used discharge plate (16) was prepared by machining a circular discharge hole (nozzle) (15) having a diameter of 10 μm on a nickel plate having an outer diameter of 15.0 mm by electroforming.
The discharge holes were provided only in a range of about 3 mmφ at the center of the discharge plate (16) in a staggered pattern so that the distance between the discharge holes was 100 μm pitch.
The vibration means (17) is lead zirconate titanate having an inner diameter of 4 mm, a diameter of 10 mm, and a thickness of 1.5 mm. The joint surface (19b) with the discharge plate (16), and the discharge plate (16) and the frame (flow channel member) ) And 20 (20) were joined together using tin, bismuth, silver solder (melting point: 140 ° C., elastic modulus: 2.4 × 10 ^ 10 Pa, heating condition: 170 ° C. × 5 minutes).
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen in the device 30.0 L / min Temperature in the device: 27-28 ° C
Frequency: 50 kHz
Applied voltage sine wave peak value: 15.0V
The “frequency” is an input vibration frequency to the vibration means (17) by an electric drive device (not shown in FIG. 12).
Under this condition, the toner composition liquid was stably ejected without causing (clogging) nozzle clogging. The discharge amount was 3.0 g / min based on the toner composition liquid. The toner standard after drying is about 0.3 g / min.

The dried and solidified toner particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores.
Particle size of the collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions. The weight average particle size (D4) was 5.5 μm and the number average Toner base particles having a particle size (Dn) of 5.0 μm and D4 / Dn of 1.10 were obtained.
When the stability of the discharge was tested, it was operated for 2000 hours while cleaning the nozzle every 10 hours. The discharge amount immediately after the nozzle cleaning was 3.0 g / min, and the initial state was 3.0 g / min. The average particle diameter (D4) was 5.5 μm, the number average particle diameter (Dn) was 5.0 μm, and toner base particles having D4 / Dn of 1.10 were obtained, which were exactly the same as in the initial state.
Therefore, it became clear that the vibration state of the nozzle maintained the initial state sufficiently even after 2000 hours of operation.

A measurement method using a flow particle image analyzer will be described below.
The measurement of the toner, toner particles, and external additives using a flow particle image analyzer can be performed using, for example, a flow particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.
The measurement is performed by removing fine dust through a filter, and as a result, 10 ml of water having 10 or less particles in a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in 10 ⁻³ cm ³ of water. A few drops of a nonionic surfactant (preferably, Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added, 5 mg of a measurement sample is further added, and 20 kHz, 50 W / 10 cm ^{3 is obtained with an} ultrasonic dispersing device STM UH-50. in conditions, subjected to dispersion treatment for 1 minute, further, subjected to dispersion treatment in total 5 minutes, (as the target particles measuring circle-equivalent diameter range) particle concentration 4000-8000 pieces ^{/ 10} -3 cm ³ of sample The particle size distribution of particles having a circle-equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured using the sample dispersion liquid.

The sample dispersion is allowed to pass through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm).
In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other.
While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image.
From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.
In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured.
As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the 0.06-400 μm range into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

Using the same toner composition liquid as that used in Example 1, toner was prepared under the following conditions.
500 ml of the toner dispersion was supplied to the nozzle (15) of the droplet forming means (17) of the above-described toner production apparatus diagram (FIG. 12). Here, FIG. 12 is exactly the same as that of the first embodiment, but the joint surface (19b) between the vibration generating means (17) and the discharge plate (16), and the discharge plate (16) and the flow path member (frame). The part (19a) and the joint surface (19a) with (20) are both joined by using tin, copper, silver solder (melting point: 220 ° C., elastic modulus: 31 GPa) under heating conditions of 250 ° C. for 5 minutes.
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen in the device 30.0 L / min Temperature in the device: 27-28 ° C
Frequency: 50 kHz
Applied voltage sine wave peak value: 22.0V
The “frequency” is an input vibration frequency to the vibration means (17) by an electric drive device (not shown in FIG. 12).
Under this condition, the toner composition liquid was stably ejected without causing (clogging) nozzle clogging. The discharge amount was 3.0 g / min based on the toner composition liquid. The toner standard after drying is about 3.2 g / min.

The dried and solidified toner particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores.
Particle size of collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions. The weight average particle size (D4) was 5.6 μm, and the number average Toner base particles having a particle size (Dn) of 5.0 μm and D4 / Dn of 1.12 were obtained.
When the stability of the discharge was tested, it was operated for 2000 hours while cleaning the nozzle every 10 hours, and the discharge amount immediately after the nozzle cleaning was 3.0 g / min, and the initial state was 3.0 g / min. The weight average particle diameter (D4) was 5.6 μm, the number average particle diameter (Dn) was 5.0 μm, and the toner base particles having D4 / Dn of 1.12 were unchanged from the initial state.
Therefore, it became clear that the vibration state of the nozzle maintained the initial state sufficiently even after 2000 hours of operation.
The difference from Example 1 is the difference in the joining member, but in Example 2, the temperature during joining was set high, and the vibration means (17) was deteriorated. Therefore, it was necessary to set the input voltage high. It is thought that there was.

Using the same toner composition liquid as that used in Examples 1 and 2, toner was prepared under the following conditions.
500 ml of the toner dispersion was supplied to the nozzle (15) of the droplet forming means (17) of the above-described toner production apparatus diagram (FIG. 12). Here, FIG. 12 is exactly the same as that of the first embodiment, but the joint surface (19b) between the vibration generating means (17) and the discharge plate (16), and the discharge plate (16) and the flow path member (frame). The part (19a) and the joint surface (19a) with (20) are both cured with an epoxy resin adhesive (elastic modulus, 1.3 × 10 ^ 8 Pa) and heated at 150 ° C. for 60 minutes. Joined.
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen in the device 30.0 L / min Temperature in the device: 27-28 ° C
Frequency: 50 kHz
Applied voltage sine wave peak value: 12.0V
The “frequency” is an input vibration frequency to the vibration means (17) by an electric drive device (not shown in FIG. 12).
Under this condition, the toner composition liquid was stably ejected without causing (clogging) nozzle clogging.
The discharge amount was 3.0 g / min based on the toner composition liquid. The toner standard after drying is about 0.3 g / min.

The dried and solidified toner particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores.
Particle size of collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions. The weight average particle size (D4) was 5.6 μm, and the number average Toner base particles having a particle size (Dn) of 4.9 μm and D4 / Dn of 1.14 were obtained.
When the stability of the discharge was tested, it was operated for 2000 hours while cleaning the nozzle every 10 hours, and the discharge rate immediately after nozzle cleaning was 3.3 g / min, about 10% of the initial value of 3.0 g / min. As a result, toner base particles having a weight average particle diameter (D4) of 5.6 μm, a number average particle diameter (Dn) of 4.8 μm, and a D4 / Dn of 1.17 are obtained, and the particle size distribution tends to be slightly widened. Met.
The vibration state of the nozzle seemed to maintain the initial state even after 2000 hours of operation, but seemed to vary slightly.
Although the difference from Example 1 is the difference in the joining member, in Example 3, the epoxy resin was used for the joining member, and the vibration means (17) and the frame were not sufficiently fixed. As a result, the amplitude increased. The discharge amount increases and the input voltage tends to be kept low, but the uniformity of the vibration state is lowered, so that the particle size distribution is considered to be slightly lower than that of Example 1.
With regard to stability after 2000 hours, it is considered that the epoxy resin as a joining member was softened by long-time discharge, resulting in an increase in the amplitude of the discharge plate and an increase in satellite generation.
Since voltage adjustment is possible in actual manufacturing, this is not a problem, but it is inferior to a metal bonding member in terms of long-term stability.

(Comparative example)
Using the same toner composition liquid as that used in Examples 1, 2, and 3, toner was prepared under the following conditions.
500 ml of the toner dispersion was supplied to the nozzle (15) of the droplet forming means (17) of the above-described toner production apparatus diagram (FIG. 12). Here, FIG. 12 is exactly the same as that of the first embodiment, but the joint surface (19b) between the vibration generating means (17) and the discharge plate (16), and the discharge plate (16) and the flow path member (frame). The part (19a) and the joint surface (19a) with (20) are both bonded by using a silicone resin adhesive (elastic modulus 1.4 × 10 ^ 7 Pa) and curing the adhesive under heating conditions 150 ° C. × 60 minutes. did.
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen in the device 30.0 L / min Temperature in the device: 27-28 ° C
Frequency: 50 kHz
Applied voltage sine wave peak value: 10.0V
The “frequency” is an input vibration frequency to the vibration means (17) by an electric drive device (not shown in FIG. 12).
Under this condition, the toner composition liquid was stably ejected without causing (clogging) nozzle clogging.
The discharge amount was 3.0 g / min based on the toner composition liquid. The toner standard after drying is about 0.3 g / min.

The dried and solidified toner particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores.
Particle size of collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions. The weight average particle size (D4) was 5.6 μm, and the number average Toner base particles having a particle size (Dn) of 4.6 μm and D4 / Dn of 1.21 were obtained, and the particle size distribution was much wider than that of the example. This is thought to be because the generation of satellites increased because the vibration state of the discharge plate was not uniform.
When the stability of the discharge was tested, it was operated for 2000 hours while cleaning the nozzle every 10 hours, and the discharge rate immediately after nozzle cleaning was 3.2 g / min, which was higher than the initial 3.0 g / min. It was. The weight average particle diameter (D4) was 5.6 μm, the number average particle diameter (Dn) was 4.6 μm, and toner base particles having D4 / Dn of 1.21 were obtained, which was equivalent to the initial state.
The difference from Example 1 is the difference in the joining member, but in the comparative example, silicone resin is used for the joining member, and the vibration means (17) and the frame are not sufficiently fixed, and the fulcrum is not fixed in vibration. It is predicted that concentric vibrations cannot be obtained and the discharge particle size varies depending on the nozzle position.
In addition, since the discharge plate is not sufficiently fixed, the amplitude itself increases, and thus the input voltage tends to be kept low.
As for the stability after 2000 hours, it is considered that as a result of the softening or partial peeling of the silicone resin as the joining member due to the long-time discharge, the amplitude of the discharge plate is increased and the generation of satellites is increased.
In actual production, since the particle size distribution of the obtained toner is wide, it can be determined that the merit of the jet granulation method cannot be obtained.

  As described above, the toner production method according to the present invention and the toner produced thereby can efficiently produce the toner and develop an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. Can be used as a developer.

(About FIGS. 1 to 11)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
3A Top surface portion of particle forming portion 4 Toner collecting portion 5 Tube 6 Toner storage portion 7 Raw material storage portion 8 Piping 8A Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Discharge plate 12A Discharge plate peripheral portion 12C Convex shape portion 13a Discharge plate Joining part 13b Vibration means joining part 14 Storage part 15 Flow path member (frame)
16 droplet forming means 17 vibration generating means (electromechanical conversion means)
18 Liquid supply tube 19 Bubble discharge tube 20 Support member 23 AC power supply 24 Electric circuit 31 Liquid droplet 35 Air flow 41 Air flow path forming member 42 Air flow path 43 Static elimination device T Toner particle (about FIG. 12)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 2a Head 3 Chamber area (particle solidification area)
4 Toner Collection Portion 5 Toner Storage Portion 6 Raw Material Storage Portion 7 Liquid Supply Pipe 9 Drainage Pipe 10 Toner Composition Liquid (Material Liquid)
11 Droplet Means 12 Reservoir 13 Liquid Chamber (Container)
DESCRIPTION OF SYMBOLS 15 Nozzle 16 Discharge plate 17 Vibrating means 18 Chamber part 19a Outermost junction part 19b of discharge plate Vibrating means junction part 20 Flow path member (part of frame)
21 discharge hole 23 droplet 23a droplet flow 30 shroud portion 30a opening 30b wall 30c wall 30d bottom 30e taper 31 lid portion 32 valve 91 ejection pipe 92 guide pipe 93 ejection port 95 carrier airflow 96 airflow PG1 pressure gauge PG2 Pressure gauge 100 pump

JP-A-7-152202 Japanese Patent Publication No.57-201248 Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP 2006-293320 A JP 2008-281915 A

Claims (13)

  A liquid droplet is formed by introducing a toner composition liquid in which a toner material containing at least a binder resin, a colorant, and a wax is dissolved or dispersed in a solvent into a liquid chamber and ejecting the liquid from the liquid chamber; A method for producing toner, comprising the step of removing the solvent from the solidified toner composition liquid and solidifying the droplets to produce toner particles, wherein the liquid chamber is provided on one surface of the toner composition liquid, and a plurality of nozzles The material toner composition liquid is ejected as droplets by vibration by an annular vibration means disposed in the outer peripheral area on one surface side of the discharge plate having the discharge plate. It is fixed to the annular vibration means in the arranged region, and is fixed to the frame of the liquid chamber on the outer region and on the opposite side, and is fixed to the annular vibration means and the annular vibration. Bullets of joining members used for fixing means Method for producing a toner, wherein the rate is 1.0 × 10 ^ 8 or more.   The method for producing a toner according to claim 1, wherein the bonding agent is a metal material having a melting temperature of 230 ° C. or less.   The toner manufacturing method according to claim 1, wherein the bonding agent is mainly composed of tin, bismuth, and silver.   The toner manufacturing method according to claim 1, wherein the bonding agent is mainly composed of tin, copper, and silver.   The discharge plate is formed in a convex shape in a direction in which the droplets are discharged, and the plurality of nozzles are formed in a portion formed in the convex shape. And a method for producing the toner according to claim 3.   The said annular vibration means is what vibrates the said discharge plate in the vibration mode which does not have a node in a diameter direction, The Claim 1, 2, 5 and Claim 3 or 4 characterized by the above-mentioned. Toner manufacturing method.   The toner manufacturing method according to claim 1, wherein a nozzle diameter of the discharge plate is 5 to 15 μm.   The ring-shaped vibrating means is a piezoelectric element, and the discharge condition of droplets from the discharge plate to be controlled is a voltage applied to the element. Item 5. The toner production method according to any one of Items 3 and 4.   The said annular vibration means is a piezoelectric element, and the discharge condition of the droplet from the said discharge plate to be controlled is the frequency of the voltage applied to this element, The claim 1, 2, 5 thru | or 8 and claim | claim Item 5. The toner production method according to any one of Items 3 and 4.   The discharge speed of the liquid droplets is increased or decreased by a conveying airflow after the material liquid is discharged as liquid droplets from the discharge plate. The toner production method described in 1.   A toner produced according to any one of claims 1 to 10.   The toner according to claim 11, wherein a particle size distribution (weight average particle diameter / number average particle diameter) is in a range of 1.00 to 1.15.   The toner according to claim 11, wherein the toner has a weight average particle diameter of 3 to 10 μm.

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