JP4594789B2 - Particle manufacturing apparatus and particle group manufacturing method - Google Patents

Description

The present invention relates to the production how the apparatus for producing particles and particle groups.

There have been industrial products using micro powders. For example, there are developers such as carrier particles and toner particles used in image forming apparatuses such as cosmetics, pharmaceuticals, electrophotography, electrostatic recording, and electrostatic printing.
As for cosmetics, it is said that the light is more diffused by the finer formation of the foundation, and as a result, the unevenness of the skin is less noticeable. Therefore, recently, a technique has been developed that uses uniform particles of several μm to several tens of nm as the foundation.

  As for pharmaceuticals, it is necessary to create particles of several μm in order to reach the lungs and bronchi, and if the targeted diameter can be created with high accuracy, it will be possible to produce pharmaceuticals with high therapeutic effects. At the same time, it can contribute to the reduction of manufacturing costs and the cost of pharmaceuticals.

  Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are temporarily attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed in the development process. Then, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known. When the development process and the transfer process are performed using electrostatic force, if the particle size distribution width is large with respect to the target toner particle diameter, the amount of charge is likely to vary, resulting in a problem in image uniformity. In addition, in the case where an adhesive transfer process is used or in the fixing process, when the particle size distribution width is large, the contact between the toner particles, the transfer body, and the fixing member varies, resulting in an image that lacks uniformity. In addition, when the particle size distribution width of the carrier particles is large, the electric field uniformity between the magnetic brush tip and the photoconductor is insufficient, and there is still a problem in image uniformity.

  As another example, a technique for improving braking performance during sudden braking by spraying fine particles between wheels and rails has already been put into practical use.

As described above, in various products using the fine powder, it is important to control the particle size and distribution of the particles to be used in order to realize the function and stability of the product. For this reason, various manufacturing apparatuses have been used to produce particles having a uniform diameter.
For example, conventionally, dry toners used for electrophotography, electrostatic recording, electrostatic printing, etc., a toner binder such as a styrene resin, a polyester resin, and the like are melt-kneaded with a colorant and finely pulverized, so-called pulverization type Toner is widely used.

  Recently, a toner production method using a suspension polymerization method or an emulsion polymerization aggregation method, so-called polymerization type toner, has been studied. In addition to this, a method called volumetric shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. Unlike the suspension polymerization method and emulsion polymerization aggregation method, this method is a versatile resin that can be used, and in particular, a polyester resin useful for a full color process that requires transparency and smoothness of the image area after fixing. It is excellent in that it can be used.

However, in the above pulverized toner, it is difficult to uniformly control the particle size of the toner.
In addition, the above-described polymerization toner is not perfect in terms of uniformity of toner particle size, and further improvement is demanded. In addition, since it is assumed that the dispersant is used in an aqueous medium, the dispersant that impairs the charging characteristics of the toner remains on the surface of the toner, causing problems such as loss of environmental stability and removal. It is known that a very large amount of washing water is required to do so, and it is not always satisfactory as a production method.

  As a method for producing toner in place of each of the above-described methods, there has been proposed a method of forming fine droplets using piezoelectric pulses and further drying and solidifying the droplets to form toner (see Patent Document 2). Furthermore, a method has also been proposed in which fine droplets are formed by utilizing thermal expansion in the nozzle, and this is dried and solidified to form a toner (see Patent Document 3). Furthermore, a method for performing the same processing using an acoustic lens has been proposed (see Patent Document 4).

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977

  However, these methods may cause the spread of the particle size distribution due to the coalescence of the droplets, and there is a problem in terms of monodispersibility. In order to solve this problem, in Patent Document 4 in paragraph 0085 and in Patent Document 3 in paragraph 0083, in each head section, in order to prevent liquid droplets discharged from adjacent head sections from joining together, It discloses that the discharge timing is different. However, in this method, it is necessary to provide a vibration source or a heating source for each head, and there is a problem that the cost of the apparatus becomes high. At the same time, it is assumed that each head operates uniformly. Even problems arise. In addition, when a part of the head fails, there is a problem that the production amount of particles is affected.

  For the purpose of controlling the particle size with higher reliability, the present inventor makes a discharge member provided on the discharge member by bringing the discharge member into contact with a liquid such as a solution or dispersion of a toner material and vibrating the discharge member. A particle manufacturing apparatus that discharges liquid from a hole to form droplets and dries the droplets has been studied. The difference between this method and Patent Document 4 is that, in the method of Patent Document 4, the discharge member itself having the discharge hole does not vibrate, and another member is vibrated to discharge the droplet, whereas in this method, the discharge hole is discharged. This is a point that the discharge member itself having a vibration is vibrated as a vibration member. As a result, the vibration source is unified, and a particle manufacturing apparatus excellent in economic efficiency and reliability can be realized.

The present invention further improves the above-described particle production apparatus, and is a simple and reliable method for ensuring uniformity of particle size by controlling the coalescence of droplets and for precise control of particle size distribution. in Hisage a method of manufacturing apparatus for producing particles, and the particles to achieve Kyosu an object Rukoto.

The particle manufacturing apparatus according to the invention of claim 1 provided to solve the above problems includes a discharge member having a plurality of discharge holes, vibration applying means for applying vibration to the discharge member at a predetermined frequency, and a solid A liquid tank storing a liquid in which a component is dissolved or dispersed in a solvent in contact with the discharge member, and the plurality of discharge holes are point- symmetric on the plate surface of the discharge member And the center of symmetry of the point is substantially the same as the center position of the plate surface of the discharge member, and the discharge area has at least two different opening areas, and the opening area Are arranged so that the distance between the discharge holes having substantially the same opening area is longer than the distance between the different discharge holes, and the liquid is discharged as droplets from the discharge holes by the vibration applied by the vibration applying means. Let Characterized in that to obtain solid particles of the droplets by drying.

  The particle manufacturing apparatus according to the invention of claim 2 provided to solve the above-described problem is the invention according to claim 1, wherein the opening area of the discharge hole provided in the discharge member, the vibration applied by the vibration applying means, A solid particle group having a predetermined particle size distribution is manufactured by setting one or more of the following parameters: frequency, solid content volume concentration of the liquid, and the amount of liquid passing through the discharge hole per unit time. Features.

The particle manufacturing apparatus according to the invention of claim 3 provided to solve the above-mentioned problem is that, in the invention of claim 1, the frequency of vibration applied by the vibration applying means is variable, and the liquid is used as droplets. It is characterized in that the particle size of the solid particle group is continuously changed only by changing the frequency of the vibration during discharging.

The particle manufacturing apparatus according to the invention of claim 4 provided to solve the above-mentioned problem is the invention of claim 3 , wherein the frequency of the vibration after the change is a natural number times or a natural number of the frequency of the vibration before the change. It is characterized by that.

In order to solve the above problem, the particle production apparatus according to the invention of claim 5 is provided in the invention of claim 1, wherein the liquid tank is divided into a plurality of region units, and the solid content volume concentration for each region. The liquids having different (vol%) are stored in contact with the ejection member.

The particle manufacturing apparatus according to the invention of claim 6 provided to solve the above-mentioned problem is the invention according to claim 1, wherein the liquid tank is divided into a plurality of regions, and the liquid is discharged into the discharge member for each region. The amount of the liquid that passes through the discharge hole per unit time is controlled to be different for each region.

The method for producing a particle group according to the invention of claim 7 provided to solve the above-described problem includes a discharge member having a plurality of discharge holes, and a vibration applying unit that vibrates the discharge member at a predetermined frequency. A liquid tank that stores a liquid in which a solid component is dissolved or dispersed in a solvent in contact with the discharge member, and the plurality of discharge holes are point- symmetric on the plate surface of the discharge member. The point-symmetric symmetry center is arranged so as to be substantially the same as the plate surface center position of the discharge member , and the discharge hole has at least two different opening areas. A particle group manufacturing method using a particle manufacturing apparatus arranged such that a distance between discharge holes having substantially the same opening area is longer than a distance between discharge holes having different opening areas, the discharge member having The solids are dissolved in the solvent. In a state contacting the dispersed liquid, by vibrating the said discharge output member, ejecting the liquid as droplets, wherein the droplets are dried in flight of two or more different particle size solid It is characterized by obtaining a particle group.

The method for producing a particle group according to the invention of claim 8 provided to solve the above-mentioned problem is the invention of claim 7 , wherein the opening area of the discharge hole provided in the discharge member, the frequency of vibration of the discharge member, The particle size distribution of the particle group is controlled by setting one or more of the parameters of the solid volume concentration of the liquid and the amount of liquid passing through the discharge hole per unit time.

A method for producing a particle group according to an invention of claim 9 provided to solve the above-described problem is that, in the invention of claim 7 , the liquid is ejected as droplets while changing the frequency of vibration of the ejection member. Thus, a group of particles having different particle sizes is obtained.

The method for producing a particle group according to the invention of claim 10 provided to solve the above-mentioned problem is the invention according to claim 9 , wherein the frequency of vibration after the change is a natural number multiple of the frequency of vibration before the change or It is characterized by a natural fraction.

The method for producing a particle group according to the invention of claim 11 provided to solve the above-described problem is that, in the invention of claim 7 , the liquids having different solid content volume concentrations (volume%) of 2 or more are simultaneously dropped. It is discharged by, and wherein the obtaining a particle group composed of different grain size as a.

The method for producing a particle group according to the invention of claim 12 provided to solve the above-mentioned problem is that in the invention of claim 7 , the amount of the liquid passing through the discharge hole per unit time is different by 2 or more. by ejecting liquid as each simultaneously droplets as characterized by obtaining the particle group consisting of grain size different.

Method for producing particles according to the invention of claim 13, provided in order to solve the above problems, in the invention of claim 7, by electrostatic induction in the droplets discharged from the discharge hole, positive or negative charge It is characterized by giving.

According to the first and seventh aspects of the invention, a desired particle size distribution can be obtained by a simple method in the configuration in which the ejection member is vibrated by a single vibrating member. Since droplet discharge is performed by a single vibration applying member, the reliability is higher than in the conventional method in which individual pressure is applied to each droplet.
Further, the particle diameter can be varied by changing the opening area of the discharge hole. In particular, in this production apparatus, particles having different particle shapes are produced at the same time, so that the mutual dispersibility of particles having different particle shapes is improved. Furthermore, since the coordinates in the traveling direction of the droplet become closer as the droplet diameter is closer, the droplets that are closer to the droplet diameter are spaced apart from each other, so that the droplets in flight can be joined together. In this way, a particle manufacturing apparatus in which the density of the discharge holes is high (that is, the particle productivity per vibration is good) and the coalescence is suppressed can be realized. A specific example is a houndstooth arrangement.
In addition, according to the second and eighth aspects of the invention, the coalescence of droplets can be suppressed by changing the particle size distribution. Also in this case, since the coalescence can be suppressed by a simple method of changing the droplet diameter, the droplet discharge is performed by a single vibration applying member as compared with the conventional method in which the discharge timing is changed for each droplet. Highly reliable.
Further, according to the inventions of claims 3, 4 , 9, and 10, the particle diameter can be varied by changing the frequency. In particular, according to this method, since the particle size can be changed only by switching the frequency, it is not necessary to prepare the manufacturing apparatus in advance to set the opening area, and the particle size is continuously changed. I can do it. In addition, according to this method, it is easy to manufacture a particle group in which particles having different particle diameters have poor mutual dispersibility, or to store particles having different particle diameters in different storage locations.
According to the fifth and eleventh aspects of the present invention, the particle size can be varied by changing the solid content volume concentration (volume%) for each liquid belonging to each region. In particular, in this production apparatus and method, particles having different particle shapes are produced at the same time, so that the mutual dispersibility of particles having different particle shapes is improved.
According to the sixth and twelfth aspects of the present invention, for each discharge hole belonging to each region, the pump flow velocity and the nozzle diameter can be changed to change the Q in the equation (1), thereby making it possible to vary the particle size. In particular, in this production apparatus and method, particles having different particle shapes are produced at the same time, so that the mutual dispersibility of particles having different particle shapes is improved.
According to the invention of claim 13 , it is possible to prevent the droplets from being joined together.
In addition, according to the present invention, a predetermined number of particles having different particle diameters can be reliably produced by a simple method. Thereby, for example, it is possible to control the particle size distribution with high accuracy so that the particle group has a predetermined function or to suppress coalescence in a droplet state.

An example in which the present invention is applied to a dry toner for electrophotography will be described.
(Toner production method)
-Device-
A toner manufacturing apparatus that is an aspect of the particle manufacturing apparatus of the present invention includes a droplet forming unit that forms a droplet by discharging a solution or dispersion of a toner material containing a resin and a colorant from a discharge hole; Toner particle forming means for drying the droplets by removing the solvent contained in the droplets to form toner particles. It should be noted that configurations other than the manufacturing apparatus of the present embodiment can be employed without departing from the spirit of the invention.

  Specifically, as shown in FIG. 1, a liquid tank 10 for storing a liquid, a discharge member 11 that is vibrated while being in contact with the liquid stored in the liquid tank, and a droplet provided on the discharge member It has a discharge hole (hereinafter referred to as “nozzle”) 1 as a forming means, an electrode 2, a solvent removal equipment 3, a charge eliminator 4, and a toner collecting portion 5 as the toner particle forming means.

  In the toner manufacturing apparatus shown in FIG. 1, the dissolved or dispersed liquid is ejected from the nozzle 1 as droplets 6, the droplets 6 are charged by the electrodes 2, and then the solvent is removed by the solvent removal equipment 3. Thus, the toner particles 7 are collected by the toner collecting unit 5 after being neutralized by the static eliminator 4 and conveyed to the toner reservoir.

Hereinafter, the toner manufacturing apparatus will be described in detail for each member.
−−Nozzle−−
As described above, the nozzle 1 is a member that discharges a solution or dispersion of a toner material into droplets.

  There is no restriction | limiting in particular as the material and shape of the said discharge member 11, Although it can be set as the shape selected suitably, for example, the discharge member 11 is formed with a metal plate with a thickness of 5-50 micrometers, and the opening diameter is 3-3. A thickness of 35 μm is preferable from the viewpoint of generating a microdroplet having a very uniform particle diameter by applying a shearing force to the nozzle 1 itself when jetting the solution from the nozzle 1 and applying a shearing force. Here, the opening diameter is a length corresponding to the diameter of a perfect circle having the same area as the opening area.

  As the means for applying vibration to the nozzle 1, it is desirable to stably apply the assumed vibration. In the present embodiment, a form in which vibration is caused by expansion and contraction of the piezoelectric body is employed. However, the present invention is not limited to vibration by a piezoelectric body.

The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, it can be expanded and contracted by applying a voltage, and the nozzle can be vibrated by this expansion and contraction.
Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). Generally, since the amount of displacement is small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.

  The frequency of vibration applied to the nozzle 1 is not particularly limited and may be appropriately selected according to the purpose. However, 50 kHz to 50 MHz is preferable, and from the viewpoint of generating micro droplets having a very uniform particle size, 100 kHz to 10 MHz. Is more preferable.

  In the present invention, a plurality of the nozzles 1 are provided, and the droplets 6 discharged from each nozzle are dried by one solvent removal equipment, in the illustrated example, by the solvent removal equipment 3.

  If the ejection member 11 is vibrated by one piezoelectric body as in the present embodiment, and droplets are ejected from a plurality of nozzles by this single vibration, the vibration source is provided for each nozzle. Reliability is improved. The reason is that when there are multiple vibration sources, each vibration source may fail independently, and as a result, the particle size distribution of the ejected droplets may change. This is because this problem can be avoided. In view of such a point of view, reliability increases as the number of ejection holes on which one vibration source acts is most preferable, and one set of a predetermined particle size distribution described later is most preferably obtained by a single vibration source. . However, the present invention is not limited to the case where one set of a predetermined particle size distribution is obtained by a single vibration source.

  The number of nozzles vibrated by the one piezoelectric body is not particularly limited, but from the viewpoint of suppressing disturbance applied to the discharge member 11, it is desirable that the distribution of the opening area is not extremely biased. This will be described later together with the targeted particle size distribution.

  Further, the distance between the nozzles needs to be set from the viewpoint of preventing adhesion. This condition varies depending on the vibration state, the droplet diameter, the droplet density, the airflow state in the solvent removal equipment 3, and the like. However, even if the most ideal condition, that is, there is no fluctuation in the vibration direction and no airflow in the direction different from the droplet flying direction is generated in the solvent removal equipment 3, The distance is preferably greater than the sum of the radii of the droplets ejected from adjacent nozzles. Moreover, it is preferable that the closest distance between nozzles for producing particles having the same particle diameter is more than the diameter of the formed droplet.

--- Electrode--
The electrode 2 is a member for charging the droplet 6 discharged from the nozzle into monodispersed particles.
The electrode 2 is a pair of members installed facing the nozzle 1, and the shape thereof is not particularly limited and can be appropriately selected. For example, the electrode 2 is preferably formed in a ring shape. .

  The charging method using the electrode 2 is not particularly limited, but a constant charge amount can always be given to the droplet 6 discharged from the nozzle. It is preferable to give a positive charge or a negative charge by charging. More specifically, it is preferable that the dielectric charging is performed by passing the droplet between a pair of electrodes 2 and 2 to which a DC voltage is applied. It has already been proved that droplets in an air stream are in a highly charged state by electrospray method or fine particle production by electrostatic spraying. In this case, it is possible in principle to maintain a charge amount higher than the charge to the solid from the effect of reducing the surface area of the droplet by evaporation of the volatile component, and it is possible to obtain solid particles with higher charge.

--Solvent removal equipment--
The solvent removal equipment 3 is not particularly limited as long as the solvent of the droplet 6 can be removed, but an air stream is generated by flowing a dry gas in the same direction as the droplet 6 discharge direction. The toner particles 7 are preferably formed by transporting the droplet 6 in the solvent removal equipment 3 and removing the solvent in the droplet 6 during the transport. Here, “dry gas” means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure.
The dry gas is not particularly limited as long as it is a gas capable of drying the droplets 6, and examples thereof include air and nitrogen gas.

  In the case of simultaneously producing particles having different particle diameters as described in a part of application examples of the present invention described later, the air flow is used from the viewpoint of suppressing variation in flight paths between particles due to the difference in particle diameters. Is preferably present.

  Further, as shown in the example, from the viewpoint of preventing the droplet 6 from adhering to the inner wall surface of the solvent removal equipment 3 from the wall surface of the solvent removal equipment 3, the polarity is opposite to the charge of the droplet. It is preferable that a charged electrostatic curtain 8 is provided, a transport path whose periphery is covered with the electrostatic curtain is formed, and droplets are allowed to pass through the transport path.

--- Static eliminator--
The static eliminator 4 temporarily neutralizes the charge of the toner particles 7 formed by allowing the droplets 6 to pass through the conveyance path, and then accommodates the toner particles 7 in the toner collecting unit 5. It is a member for.
There is no particular limitation on the method of static elimination by the static eliminator 4, and a conventionally known method can be appropriately selected and used. However, since neutralization can be performed efficiently, for example, soft X-rays can be used. Irradiation, plasma irradiation. It is preferable to do so.

-Toner collection part-
The toner collecting unit 5 is a member provided at the bottom of the toner manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner.
The structure of the toner collecting portion 5 is not particularly limited as long as the toner can be collected and can be appropriately selected. From the above viewpoint, a tapered surface whose opening diameter is gradually reduced is provided as in the illustrated example. The toner particles 7 are formed from the outlet portion whose opening diameter is smaller than that of the inlet portion, using the dry gas to form the flow of the dry gas, and the toner particles are transferred to the toner storage container by the flow of the dry gas. It is preferable to transport it.

As the transfer method, as shown in the illustrated example, the toner particles 7 may be pumped to the toner storage container by a dry gas through the pumping tube 9, or the toner particles 7 may be sucked from the toner storage container side. Good.
Although there is no restriction | limiting in particular as a flow of the said dry gas, From a viewpoint which can generate the centrifugal force and can convey the toner particle 7 reliably, it is preferable that it is a vortex | eddy_current.

  Further, from the viewpoint of more efficiently transporting the toner particles 7, the toner collecting portion 5, the pressure feeding tube 9, and the toner collecting container are formed of a conductive material, and these are connected to the ground. More preferably. The toner manufacturing apparatus preferably has an exposure specification.

--- Droplet--
As described above, the droplet 6 is generated by discharging a solution or dispersion of a toner material containing a specific substance from the nozzle 1 oscillated at a constant frequency. The toner material will be described in a separate “toner” section.

The toner material dissolving or dispersing liquid is not particularly limited as long as the toner material is at least one of dissolved and dispersed, and can be appropriately selected and used. From the viewpoint of maintaining, it is preferable that the electrolytic conductivity is 1.0 × 10 ⁻⁷ S / m or more.
From the same viewpoint, the electrolytic conductivity as a solvent of the dissolved or dispersed liquid is preferably 1.0 × 10 ⁻⁷ S / m or more.

  The method for dissolving or dispersing the toner material is not particularly limited, and a commonly used method can be appropriately selected. Specifically, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin may be melt-kneaded with a colorant or the like and finely pulverized, or obtained during the production. The kneaded product may be once dissolved in an organic solvent in which the resin component is soluble and then processed as fine droplets.

-Action-
According to the toner manufacturing apparatus described in detail above, the number of droplets generated from one discharge hole of the nozzle can be increased to tens of thousands to several million per second, which is a viewpoint of productivity. Is excellent from.

  Moreover, according to this method, the particle diameter can be controlled with extremely high accuracy. If the variation in particle diameter is small, the fluidity of the particles themselves is high. Therefore, even when an external additive is added for the purpose of suppressing adhesion to a production apparatus or the like, the effect can be exhibited even in a very small amount. Considering the decrease in reliability due to peeling of the external additive and the safety of the peeled fine particles to the human body, there are advantages if it is possible to control the external additive with a small amount.

  By the way, according to the study by the present inventor, the particle diameter of the finally obtained solid particles can be determined with high accuracy by the following calculation formula (1) or (2). If the values of the parameters appearing in the equation are the same, there is almost no change in the particle size due to the molecular structure of the material used. Some of the production equipment so far has a large change in particle size depending on the material used. In this production equipment, by appropriately controlling the parameters appearing in the following two equations, It becomes possible to obtain solid particles having

〔a formula〕
Dp = (6 × Q × C / π / f) ^1/3 (1)
However, Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow velocity and nozzle diameter), f: vibration frequency, C: volume concentration of solid content, and π: circumference.

  The particle diameter can be calculated by the above formula (1), but can also be obtained by the following formula (2).

〔a formula〕
Solid content volume concentration (volume%) = (solid particle diameter / droplet diameter) ³ (2)

  That is, the diameter of the solid particles obtained by the present invention can also be controlled by adjusting the droplet diameter and the solid content concentration.

  The present invention utilizes these properties to easily produce a particle group having a predetermined particle size distribution. Specifically, in the present embodiment, the methods described in the following application examples can be considered. Note that these methods can be used simultaneously.

(Application example 1)
In the first application example, by forming a plurality of discharge holes with different nozzle diameters in the discharge member, the parameter Q of the formula (1) is changed for each discharge hole, thereby changing the diameter of the powder particles to be manufactured. .

  As an application example of this method, it is conceivable that the toner particle group has a predetermined particle size distribution. For example, in Japanese Patent Application Laid-Open No. 2003-255589, the toner particle size distribution is set to 40 to 80% by number of toner having a weight average particle size of 6.0 to 8.0 μm and 5 μm or less. And two properties of fluidity can be compatible (see paragraph 0015 of JP-A-2003-255589).

  Japanese Patent Application Laid-Open No. 2003-263019 discloses that, for example, two particle size distribution peaks of 8.5 μm and 1.6 μm are provided in order to reduce the jamming of the developer onto the developer carrying member. Has been.

  As described above, considering overall high image quality and reliability in the image forming process, it may be preferable that the particle diameter of the toner particles has a predetermined distribution depending on the image forming process.

However, in Japanese Patent Application Laid-Open No. 2003-255589, since granulation is performed by a pulverization step, it is difficult to stably produce a toner particle group having a target particle size distribution.
In JP 2003-263019 A, as shown in FIG. 5 of the publication, there are many particles having an intermediate particle size between two peaks of the particle size distribution. If there is an increase or decrease in the abundance, there is a risk that the targeted effect cannot be obtained.

  Therefore, in this application example, the area of the plurality of nozzles is changed in order to accurately and stably obtain a particle distribution that meets the conditions. As an example of the particle size distribution, a distribution “a toner having a weight average particle size of 6.0 to 8.0 μm and a weight average particle size of 5 μm or less is 40 to 80% by number” described in Japanese Patent Application Laid-Open No. 2003-255589 is described. Think about getting.

As shown in FIG. 2, one discharge member (vibration member) is provided with NA first discharge holes 1A having a diameter A [μm] and NB second discharge holes 1B having a diameter B [μm]. . Further, when the diameter of the nozzle is x [μm], the diameter of the obtained solid particles is assumed to be a function f (x) [μm] of x. Here, the toner shape is calculated as a true sphere to simplify the calculation, but other shapes can also be calculated.
The number% of toner particles having a particle size f (B) [μm] is given by the following equation (3).

      NB / (NA + NB) × 100 [%] (3)

  Further, the weight average particle diameter Mw of the particle group is given by the following formula (4), where the density of the solid particles is μ.

Mw = [NA × f (A) ⁴ + NB × f (B) ⁴ ] / [NA × f (A) ³ + NB × f (B) ³ ]
... (4)

As shown in FIG. 2, it is assumed that NA = NB in this example.
In this case, if f (B) = 4 [μm], there are 50 number% of toner particles of 4 [μm] from the formula (3), and “40 to 80 number% of toner of 5 μm or less” is obtained. Fulfill.
Further, when f (A) = 7.47 [μm] is obtained by substituting f (B) = 4 [μm] into the formula (4) and obtaining Mw = 7 [μm], f (A) = 7.47 [μm] is obtained. .
Therefore, if A is a nozzle diameter such that f (A) = 7.47 [μm], the condition “the particle size distribution of the toner is 6.0 to 8.0 μm” is satisfied.

  Here, the function form of f (x) can be experimentally obtained in advance. It is clear from the study by the present inventors that the condition can be approximated to f (x) = 2 × x by adjusting the conditions. In such a case, the nozzle diameter may be set to s / 2 [μm] in order to obtain a particle size of s [μm], so the two types of nozzle diameters in FIG. 2 are set to A = 3.735. By setting [μm] and B = 2 [μm], it is possible to accurately produce the particle size distribution described in Japanese Patent Application Laid-Open No. 2003-263019. (In Fig. 3, the width of the distribution is made by the ability of the table creation software, but in reality there is almost no distribution width)

  The particle size distribution obtained in this example is shown in FIG. As described above, according to this production method, a particle size distribution having a peak at a predetermined particle size and almost no other particle size, which is difficult with the conventional production method, can be easily obtained. . In addition, the reason for describing “almost” in “almost no other particle size” is that a small number of particles having a particle size other than the target particle size may be generated due to the coalescence of droplets. is there.

  Further, according to this method, for example, a particle group having a complicated particle size distribution as shown in FIG. 4 can be manufactured with high accuracy and stability. For example, as shown in FIG. 5, the particle size distribution is controlled by providing N1 nozzles 1C having a nozzle diameter R1 at a distance L1 from the center of a disk-type discharge member, and nozzles 1D having a nozzle diameter R2 at a distance L2 from the center. This is achieved by increasing the index concentrically with N2 nozzles and N3 nozzles 1E having a nozzle diameter R3 at a distance L3 from the center. Of course, the arrangement of the nozzles is not limited to that shown in FIG. 5, and a predetermined number of nozzles having a predetermined nozzle diameter may be provided on the ejection member. FIG. 5 is merely an example.

  As described above, since it is possible to stably produce even a particle group having a complicated particle size distribution by using the present invention, it becomes easy to impart a target function to the particle group, and the conventional production apparatus can be used. There are very significant advantages compared to this.

  Moreover, since particles having different particle sizes are generated at the same time, the mutual dispersibility of particles having different particle sizes is good. In other words, the smaller the particle size, the greater the adhesion between the particles. Therefore, if there is an aggregate of only small particles, the particles tend to agglomerate with each other, making it difficult for particles with different particle sizes to mix evenly (interdispersibility is low). Deteriorate). However, in this method, particles having different particle diameters are generated at the same time, so that particles having the same particle diameter are prevented from being gathered together in a dense manner, and mutual dispersibility can be ensured.

  By the way, according to the production apparatus of the present invention, it is possible to obtain a characteristic particle size distribution which is not present in the past. Specifically, as shown in FIGS. 3 and 4, a sharp distribution centering on a predetermined particle size is formed discretely, and the target particle size distribution is formed as a whole by collecting the discrete distributions. Is done. Such a distribution is difficult to obtain with a conventional manufacturing apparatus, and is possible for the first time by the present invention.

  For example, in Japanese Patent Application Laid-Open No. 2003-263019, as shown in FIG. 5 of the publication, there are a large number of particles having an intermediate particle size between two peaks of the particle size distribution. By using the present invention, a characteristic distribution as shown in FIGS. 3 and 4 can be easily obtained with respect to such a distribution.

  The case where the target particle size distribution is formed as a whole by the collection of discrete distributions and the case where there are many particles in particle sizes other than the peak of the particle size distribution as in the past are logically considered. Although it is difficult to separate, the particle size distribution that can be obtained by the present invention is specified as follows in order to clarify the range.

In the particle size distribution of the particle group, when the particle size value corresponding to the peak (maximum value of the particle size distribution) is Z, N particles having the particle size value Z are counted. At this time, if the number of particles having a particle size different from Z by 1%, ie, (1 + 0.01) × Z or (1-0.01) × Z, is N / 2 or less ( Hereinafter, it is referred to as “condition S”), and it can be said that this particle group has a particle size distribution peculiar to the above-described production method. A sharp distribution at a level where the number of counted particles is less than half when only 1% deviates from the peak of the particle size distribution is a particle size distribution unique to the present invention that is difficult to obtain with a conventional manufacturing apparatus.
Therefore, the particle size distribution unique to the present invention is a particle size distribution in which two or more peaks of the particle size distribution satisfying the above condition S exist.

  Note that even if the particle size value Z has a peak, the size cannot be strictly equal if it is measured infinitely finely to the molecular level. In many actual particle size measuring apparatuses, a predetermined particle size width is set, and those having a particle size not less than the lower limit value and less than the upper limit value are often counted. Therefore, when confirming the success or failure of Condition S, the particle size width, which is a unit for counting the number at the time of measurement, is set to 0.1% or more and less than 10% of the weight average particle size, and includes the peak particle size. The success or failure of Condition S is measured between the particle size range and the particle size range adjacent thereto. If the particle size width is changed in the range of 0.1% or more and less than 10% of the weight average particle size and there is at least one particle size width satisfying the condition S, the condition S is assumed to be satisfied.

  As described above, the toner particles have been described as an example in the present example. However, it is needless to say that such accurate particle size distribution can be applied to granulation in other fields such as pharmaceuticals. Therefore, the method of this application example is not limited to toner particle production.

  In addition, as in this example, it is desirable from the viewpoint of disturbance suppression that the nozzle opening area is distributed so that the force toward the direction other than the discharge direction is not exerted on the discharge member 11 (see FIG. 2).

  To generalize the discussion, the position of the center of gravity of the discharge member 11 when projected onto a cross section orthogonal to the discharge direction is defined as a point O. Then, each nozzle is replaced with a single density substance, and the position of the center of gravity of the substance when projected onto a cross section orthogonal to the ejection direction is defined as a point P. At this time, the greater the distance between the point O and the point P, the more disturbance may occur. For example, if the nozzle is unevenly distributed only at one end of the discharge member 11, the discharge member 11 may be inclined due to a change in pressure due to the presence or absence of discharge.

  Of course, if a member having a large inertia is used as the vibration member, such a fear is reduced. However, since the thickness of the discharge member 11 is desirably 5 to 50 μm as described above, there is a limit to increasing the inertia.

From this point of view, it is desirable that point P and point O be as close as possible, but if a definition is provided to clarify the scope of rights, the distance between point P and point O will replace the discharge member with a disk of the same area. From the viewpoint of stable granulation, it is desirable that the radius is equal to or less than the radius of the disk.
This point is the same when there are a large number of nozzle diameters. The point P and the point O are obtained by the above definition, and the distance may be set to be equal to or less than the radius of the above disk.

(Application example 2)
In this application example, by forming a plurality of ejection holes with different nozzle diameters in the ejection member, the parameter Q in Expression (1) is changed for each ejection hole, thereby suppressing the coalescence of the generated droplets.
In this application example, the droplets ejected from the nozzles fly through the solvent removal equipment 3 to suppress coalescence by utilizing the behavior until solid particles are formed.

  As a specific example, a discharge member having a nozzle arrangement shown in FIG. 6 is used. In FIG. 6, nozzles 1F having a nozzle diameter R1 and nozzles 1G having a nozzle diameter R2 (here, R2 = R1 × 0.8) are arranged in a staggered pattern.

  According to the study of the present inventor, when the flying states of droplets ejected simultaneously from a nozzle having a relatively small opening area and a nozzle having a relatively large opening area are compared, the former is earlier to the static elimination member 4. And reach. This is the effect of air resistance.

  That is, the droplets discharged from the nozzles having different opening areas have different sizes and thus have different weights. On the other hand, the air resistance is determined by the velocity and the projected area of the liquid droplet projected onto a plane orthogonal to the ejection direction. Since the weight and the air resistance received depend on the size of the droplet, it is considered that the deceleration acceleration due to the air resistance varies depending on the size of the droplet. As a result of this new study, the present inventor has come to realize that droplet coalescence can be suppressed by changing the opening area of the nozzle.

  In this application example, nozzles having different opening areas are arranged in a staggered pattern as shown in FIG. 6, so the distance between nozzles having different opening areas is small, but the distance between nozzles having the same opening area is Relatively large. With this arrangement, the diameter of the liquid droplets ejected from the nozzle closest to the one nozzle is different from the diameter of the liquid droplets ejected from the one nozzle. Therefore, even if they are ejected at the same time, the distance in the traveling direction increases during the flight, and the coalescence of the droplets is suppressed.

  Further, FIG. 7 shows the state of a droplet during ejection. Experience has shown that the distance between the “point at which the droplet breaks” shown in this diagram and the ejection member 11 decreases as the nozzle opening area decreases. I know. Considering this together, droplets ejected from a nozzle with a relatively small opening area are closer to the ejection member than the droplets ejected from a nozzle with a relatively large opening area. Deceleration due to air resistance is great.

  Therefore, when a droplet ejected from a nozzle with a relatively small opening area and a droplet ejected from a nozzle with a relatively large opening area are ejected at the same time, the two droplets may come closer together Becomes lower. This effect is achieved if the opening areas are slightly different, and is more reliably achieved as the difference in the opening areas increases. Actually, the opening area may be varied depending on the allowable variation in particle diameter.

  As described above, in this application example, it is possible to suppress the coalescence of droplets by a simple method in which the opening areas of the nozzles are different, and it is possible to suppress the production of solid particles greatly deviating from the target particle size distribution.

  In addition, although the solid particle diameter produced | generated from the nozzle from which opening area differs is naturally different, what is necessary is just to set this difference in particle diameter in an allowable range. Compared with the case where the particle volume is doubled or tripled by coalescence, the difference in the particle diameter is small, and it is not a problem because it can be controlled.

(Application example 3)
In this application example, by changing the frequency f of the piezoelectric material applied to the discharge member 11, the parameter Q of the equation (1) is changed for each discharge hole, thereby changing the diameter of the produced powder particles.
Since the solid particle diameter is proportional to 1/3 of 1 / f, the solid particle diameter can be continuously changed by changing the frequency.

  FIG. 8 shows the discharge member 11 used in this example. In FIG. 8, all nozzles have the same opening area. Accordingly, the same size droplets are ejected from each nozzle, and the size of the droplets ejected from each nozzle is kept equal by changing the vibration frequency f applied to the ejection member. The droplet diameter changes as it sags.

The particle size distribution may be controlled as follows.
The solid particle diameter obtained at the frequency f calculated by the equation (1) is represented as Dp (f). When the liquid flow rate Q and the solid volume concentration C are constant, if the frequency f1 is applied to the piezoelectric body for the time t1 [sec], solid particles having a particle diameter Dp (f1) are generated by f1 × t1 per nozzle. The Therefore, in the case of ejection members having the same opening area of the nozzle 1 as shown in FIG. 8, assuming that the number of nozzles is N, N × f1 × t1 solid particles having a particle diameter Dp (f1) are generated.

  Next, when the frequency is switched to the second frequency f2 and oscillated t2 [sec] at the frequency f2, N × f2 × t2 solid particles having a particle diameter Dp (f2) are generated.

  According to this method, since the particle size can be changed only by switching the frequency, it is not necessary to prepare the manufacturing apparatus in advance to set the opening area, and the particle size is continuously changed. I can do it.

  On the other hand, since particles having different particle sizes cannot be generated at the same time, the mutual dispersibility of particles having different particle sizes is poor. From this point of view, it is preferable to finely switch the frequency in order to improve the mutual dispersibility. Specifically, as described above, when N × f1 × t1 solid particles having a particle size Dp (f1) are generated and N × f2 × t2 solid particles having a particle size Dp (f2) are generated If the frequency f1 is applied continuously over the time t1 and then the frequency f2 is applied continuously over the time t2, the mutual dispersion is poor. Therefore, the frequency f1 is changed to the time t1 as a whole while switching the frequencies f1 and f2 in a short cycle. The frequency f2 is preferably applied only for the time t2.

  Conversely, when it is desired to suppress the mutual dispersion, the frequency f2 may be applied continuously over the time t2 after the frequency f1 is applied continuously over the time t1.

  In addition, when it is desired to individually obtain a particle group for each particle diameter, the frequency f1 is continuously applied over the time t2 after the frequency f1 is continuously applied over the time t1, and the particles are switched at the timing of frequency switching. What is necessary is just to change the storage location. At this time, if it is desired to more surely prevent the mixing of the particle diameters, the particles generated before and after the frequency switching are not stored, and other particles may be stored in each storage destination.

  By the way, when switching the frequency, there is no problem if the vibration state of the discharge member smoothly shifts to the vibration at the new frequency, but in fact, it vibrates at the original frequency until the transition to the steady state after switching. There is a possibility that interference occurs between the vibrating member and the piezoelectric body vibrating at a new frequency, and solid particles having an unexpected particle size may be generated.

  Therefore, in this application example, in order to reduce such a problem, the frequency after switching is changed so as to be a natural number times or a fraction of the natural number of the frequency before switching. In this way, there is little interference between the frequencies before and after switching, and the frequency can be switched smoothly.

  When this suitable frequency is switched, as is clear from the equation (1), the particle size corresponding to the original frequency is multiplied by “(natural number) times (1/3)” or “(1 / The particle size can be changed by (natural number) times (1/3) ". For example, they are 0.63 times, 0.69 times, 0.79 times, 1.26 times, 1.44 times, and the like.

  In this way, the particle size distribution is such that the peaks of the particle size distribution are mutually “(natural number) times (1/3)” or “(1 / natural number) times (1/3)”, and What satisfies the above-described condition S is obtained for the first time by the present invention.

  Note that it is also possible to combine the method of making the opening areas of the nozzles different from each other as shown in Application Examples 1 and 2 and the method of making the vibration frequency f variable as shown in Application Example 3. For example, by using a discharge member in which the opening areas of the nozzles are different from each other as shown in FIGS. 2 and 5, and by changing the vibration frequency to be applied, the “(natural number) of the opening area of each nozzle is changed. It is possible to produce particles having a particle size that is ((1/3) power) times or ((1 / natural number) times (1/3) power).

(Application example 4)
In this application example, by changing the solid content volume concentration (volume%), the diameter of the solid particles is changed according to the equation (2).

FIG. 9 shows a manufacturing apparatus used in this application example. This manufacturing apparatus is substantially the same as the apparatus shown in FIG. 1, and members having the same functions are given the same numbers as those in FIG.
The difference between FIG. 1 and FIG. 9 is that the liquid tank 10 is divided into a plurality of small liquid tanks, and each small liquid layer has a different solid content volume concentration (volume%) dissolved or dispersed liquid (dissolved or dispersed liquid 1 to 1). 4) is supplied. In this example, as a member that separates the liquid tank 10, a separation member 11 </ b> A integrated with the discharge member 11 is provided. However, the liquid tank can be separated by other methods. The volume of each small liquid tank may be the same or different.

In such a configuration, when the ejection member 11 is vibrated by one piezoelectric body, solid particles having different particle diameters are obtained from the respective nozzles due to the difference in solid content volume concentration (volume%). In this example, since the nozzle diameter is the same for each nozzle, the obtained solid particle diameter can be controlled according to the formula (2) only by the solid content volume concentration (volume%). However, even if the nozzle diameter is different for each nozzle, the solid particle diameter obtained from each nozzle when using a solution or dispersion having a specific solid content volume concentration (volume%) should be known in advance by experiments. Based on this, the solid particle diameter after changing the solid content volume concentration (volume%) can be calculated from the equation (2).
Since particles having different particle sizes are generated at the same time, similar to Application Example 1, the particles having different particle sizes have good mutual dispersibility.

(Application example 5)
In this application example, the same apparatus as in application example 4 is used. The difference from the application example 4 is that the solid content volume concentration (volume%) of the dissolved or dispersed liquid sent to each small liquid tank is the same, and the flow velocity to be fed is different. If the flow rate is different, the liquid flow rate Q in the formula (1) changes. Therefore, if the relationship between the flow rate and the liquid flow rate Q is experimentally obtained in advance, the solid particle diameter obtained is changed by changing the flow rate. I can do it.

  In this example, since the nozzle diameter is the same for each nozzle, the obtained solid particle diameter can be controlled only by the flow velocity. However, even if the nozzle diameter is different for each nozzle, if the solid particle diameter obtained from each nozzle when the flow velocity is changed is known in advance by experiment, the flow velocity can be controlled based on that data. Can change the solid particle size. Since particles having different particle sizes are generated at the same time, similar to Application Example 1, the particles having different particle sizes have good mutual dispersibility.

  According to the application example described above, a target particle size distribution can be easily obtained with the apparatus configuration in which vibration is applied to one ejection member by one piezoelectric body.

(toner)
The toner of the present invention is a toner manufactured by the toner manufacturing method of the present invention described above.

As the toner, a toner having a monodispersed particle size distribution can be obtained by the toner manufacturing method.
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 1.05. Moreover, as a weight average particle diameter, it is preferable that it is 1-20 micrometers.

  The toner obtained by the toner manufacturing method can be easily redispersed, that is, floated in an air current by electrostatic repulsion effect. For this reason, the toner can be prepared and transported to the development area without using the transport means used in the conventional electrophotographic system. That is, even a weak air current has sufficient transportability, and the toner can be transported to the development area with a simple air pump and developed as it is. Development is so-called power cloud development, and since there is no disturbance in image formation due to airflow, extremely good electrostatic latent image development can be performed. Further, the toner of the present invention can be applied without any problem even if it is a conventional development system. At this time, members such as a carrier and a developing sleeve are simply used as a toner conveying unit, and there is no need to consider a frictional charging mechanism that has been conventionally shared in function. Accordingly, since the degree of freedom of the material is greatly increased, the durability can be greatly improved, an inexpensive material can be used, and the cost can be reduced.

  The toner material that can be used in the present invention can be the same as the conventional electrophotographic toner. 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 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 of 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 acrylates of the above compounds in place of 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 mass, more preferably 0.03 to 5 parts by mass, with respect to 100 parts by mass of other monomer components. Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one 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, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Rupaokishi, tert- butylperoxy azelate, and the like.

  When the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) has at least one peak in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). 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 molecular weight region 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 toner has fixability and offset resistance because at least one peak exists in the molecular weight range of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. More preferable is a binder resin.

  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 of the present invention, 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 can also be used. . 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 the acid value of the binder resin is measured 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 KOH solution used at this time is S (ml), a blank is measured at the same time, the amount of KOH solution used at this time is B (ml), and the following equation (5) is used for calculation. However, f is a factor of KOH.

      Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (5)

  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 under 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 iron trioxide 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 | grains 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 obtained by measuring a 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.
The magnetic material can also be used as a colorant.

--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 present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene and other styrene and its substitutes Polymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-Chloromethyl methacrylate Polymer, 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, polyvinyl Examples include 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 shear force. At this time, an organic solvent can be used 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. Also, 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 the maximum molecular weight of the main peak in terms of styrene conversion 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 becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.

  The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 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 50 parts by mass, the chargeability may be lowered.

-Other ingredients-
<Career>
The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.

  The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.

Examples of the resin used in the coating material include styrene-acrylic ester copolymers, styrene-acrylic resins such as styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, and the like. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as a coating (coating) material for carriers such as an ionomer resin and a polyphenylene sulfide resin can be used. These resins may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

  In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating agent, a method in which the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable.

  The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.

  Examples of use in which a magnetic material is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.

  Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.

  Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50) is mentioned.

  Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.

  Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.

  Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the unevenness of the surface of the carrier and the amount of resin to be coated.

  The carrier having a particle size of 4 to 200 μm can be used, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.

  In the two-component developer, it is preferable to use 1 to 200 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. More preferable

<Wax>
In the present invention, a wax may be contained together with the binder resin and the colorant.
The wax of the present invention is not particularly limited, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sax. Plant waxes such as aliphatic hydrocarbon waxes such as sol wax, oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Waxes mainly composed of animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and fatty acid esters such as montanic 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 onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using 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 preferred 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. Polyolefins, polyolefins polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefins obtained by thermal decomposition of high molecular weight polyolefins, 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 it is less than 10 ° C., the function separation effect may be difficult to appear, and if it 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, and more preferably 70 to 100 ° C, because 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 exhibit 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, 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-based wax Like a combination of.

  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 high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out 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 of 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-CHEMIEGMBH)- 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 a 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.
As 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 of 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, adjustment of softening point, improvement of fixing rate For purposes such as various types of metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. A body etc. can be added as needed. These inorganic fine powders may be hydrophobized as necessary. Also, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white and black fine 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, and the rotation 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., the resulting material is mechanically adjusted, or the so-called spray-drying method is used to dissolve and disperse the toner material in a solvent in which the toner binder is soluble, and then using a spray-drying device 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, quartz 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 μm to 2 μm, and more preferably 5 μm to 500 μm.

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 system such as silicone, benzoguanamine and nylon, thermosetting resin 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 μm to 2 μm, and more preferably 5 μm to 500 μm. 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.

  For the toner of the present invention, all of the electrostatic latent image carriers used in conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, and a selenium static image carrier. An electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

Next, an image forming apparatus and a process cartridge that perform image formation using these toners will be described.
FIG. 10 shows an example of an image forming apparatus to which the present invention can be applied. In a normal image forming operation, a transfer material such as a recording sheet supplied from the paper feeding device 25 is attracted to the transfer material transport belt 22 as a transfer body by applying a predetermined voltage to the suction roller 22a. The transfer material moves together with the transfer material conveyance belt while being carried on the transfer material conveyance belt 22, and the toner images are transferred from the process cartridges 21K, 21M, 21C, and 21Y as image forming means during the movement. When the transfer material passes through the conveyance belt 22 and reaches the fixing device 23, the toner image on the transfer material is heated while being sandwiched between the heating roller 23a and the pressure roller 23b, and is fixed on the transfer material. A visible image is formed on the material. In the mode for adjusting the color misregistration and toner density of each color toner image, a toner image having a predetermined pattern is directly formed on the transfer material conveying belt 22 from the process cartridges 21K, 21M, 21C, and 21Y, and is applied by the P sensor 22b. The toner pattern is detected, and the writing timing and development bias are changed based on the detection result, so that an optimum color image can be obtained. Thereafter, the toner pattern on the transfer material conveyance belt 22 is collected in the process cartridges 21K, 21M, 21C, and 21Y, whereby the transfer material conveyance belt 22 is cleaned. This cleaning operation will be described later. Here, 21K, 21M, 21C, and 21Y are toner cartridges for forming toner images of black, magenta, cyan, and yellow, respectively.

In this case, in particular, the process cartridge is included in the toner cartridge, and thus the process cartridge. Therefore, the toner cartridge will be described below using the term “process cartridge”. That is, in this specification, “process cartridge” is a subordinate concept of “toner cartridge”. The "toner cartridge" is a subordinate concept of "container storing the particles." In the present invention, particles that are not toner particles can be produced, and particles that are not toner particles can have a characteristic particle size distribution. It is not limited, and the capsule etc. which stored the pharmaceutical etc. also correspond. It can be flexible.

  As shown in FIG. 12, the process cartridge can be detached from the space opened by the retraction of the transfer material conveyance belt 22, and can be replaced by the user. During image formation, writing devices 24K, 24M, 24C, and 24Y irradiate process cartridges 21K, 21M, 21C, and 21Y with writing light corresponding to black, magenta, cyan, and yellow image information. The process cartridge forms a toner image corresponding to the writing light and transfers it to a transfer material. The writing devices 24K, 24M, 24C, and 24Y are devices for writing a latent image on the charged image carrier 31 according to image information. Various devices such as an optical scanning device using a polygon and an LED array can be used.

  Next, the process cartridge of this example will be described with reference to FIG. Since the process cartridges 21K, 21M, 21C, and 21Y have the same structure, only one will be described. The image carrier 31 is a negatively charged organic photoreceptor, and is provided so as to be rotated in the arrow direction, that is, in the counterclockwise direction by a rotation driving mechanism (not shown). The cleaning device 34 includes a cleaning blade 34 a that is brought into contact with a counter with respect to the rotation direction of the image carrier 31, and a waste toner storage portion 34 b that stores the cleaned toner particles as waste toner.

  The contact charging member 32 is a flexible charging in which a medium-resistance foamed urethane layer 32b in which a urethane resin, carbon black as conductive particles, a sulfurizing agent, a foaming agent, etc. are formulated in a roller shape is formed on a core metal 32a. Laura. The material of the medium resistance layer formed on the core metal in the charging roller 32 is not limited to the above, but urethane, ethylene-propylene-diene polyethylene (EPDM), butadiene acrylonitrile rubber (NBR), silicone rubber, A rubber material in which a conductive material such as carbon black or a metal oxide is dispersed in order to adjust resistance in isoprene rubber or the like, or a foamed material of these materials can be used.

  The developing means 13 is rotated clockwise to be in contact with the image carrier 31, the developing roller 33a, the supply roller 33b for coating the developing roller 33a with toner particles, and the thickness of the toner particles coated on the developing roller 33a. An elastic blade 33c that negatively charges the toner particles by friction while restricting the toner particles, and a stirring member 33d that moves the toner particles in the process cartridge toward the supply roller while stirring. In addition, a DC bias can be applied to the developing roller 33a from a power source, which will be described later, in a state where the process cartridge is mounted on the image forming apparatus main body.

Specifically, a DC bias is applied to the developing roller from the power source on the apparatus main body side by contacting an electrical contact provided on the side of the process cartridge 1 with an electric contact on the image forming apparatus main body side. Further, toner particles (not shown) are stored in the developing means 33 that also serves as an unused toner storage unit. The transfer roller 22b facing the image carrier 31 via the transfer material conveying belt has at least a cored bar and a conductive elastic layer covering the cored bar. The conductive elastic layer is made of polyurethane rubber, ethylene-propylene-diene. Mixing and dispersing a conductivity imparting agent such as carbon black, zinc oxide, tin oxide, etc. in an elastic material such as polyethylene (EPDM), the electrical resistance value (volume resistivity) is 10 ⁶ to 10 ¹⁰ Ω · cm. It is a transfer roller which is an adjusted elastic body.

Next, the operation of the process cartridge will be described.
The image forming apparatus of this example is an image forming apparatus that can function as a copying machine and a printer. When functioning as a copier, the image information read from the scanner is subjected to various image processing such as A / D conversion, MTF correction, gradation processing, etc., and converted into writing data. When functioning as a printer, image information in a format such as a page description language or a bitmap transferred from a computer or the like is subjected to image processing and converted into write data.

  Prior to image formation, the image carrier 31 starts to rotate in the direction of the arrow in FIG. 11, that is, in the counterclockwise direction so that the moving speed of the surface becomes a predetermined measure. The charging roller 32 is rotated about the image carrier 31. At this time, a DC voltage of -1000 V is applied to the core of the charging roller 32 from a charging bias application power source, whereby the surface of the image carrier 31 is charged to about -400 V. The writing device 24 (24C, 4m, 24Y, 24K) exposes the charged image carrier 31 according to the writing data. That is, by changing the potential of the image portion by light irradiation, a difference from the potential of the non-image portion not irradiated with light is generated, and an electrostatic latent image is formed by this potential contrast.

  The electrostatic latent image formed on the image carrier by the writing device 24 is developed one component by the developing device 33 and is visualized on the image carrier 31 as a toner image when toner particles adhere to the image portion. The developing device 33 of this example forms a toner image on the image carrier 31 by a contact-type nonmagnetic one-component developing method.

  Specifically, the developing roller 33a is rotated clockwise, and the supply roller 13b made of an elastic body rotating clockwise is brought into contact with the developing roller 33a to coat the toner particles on the supplying roller on the developing roller 33a. . The toner particles coated on the developing roller 33a are negatively charged by friction with the elastic blade 33c while the thickness thereof is regulated by the elastic blade 33c, and then conveyed to a portion facing the image carrier 31 according to the rotation of the developing roller 33a. It is done. At the opposite portion between the developing roller 33a and the image carrier 31, a DC electric field is applied between the developing roller 33a and the image carrier 31 by applying a DC bias of −300V to the developing roller 33a from a power source described later. The formed negatively charged toner particles are selectively attached only to the image portion on the image carrier by this direct current electric field to form a toner image.

  The transfer material is conveyed from the paper feeding device 25 in synchronization with the timing at which the toner image formed on the image carrier 31 reaches the transfer portion that is the opposite portion between the transfer roller 22b and the image carrier 31. The toner image on the carrier 31 is transferred to the transfer material by the voltage applied to the transfer roller. The transferred toner image is fixed on the transfer material by the fixing device 23 and an image is output.

  On the other hand, the toner (transfer residual toner) remaining on the image carrier 31 without being transferred is cleaned by the cleaning device 34, and the cleaned image carrier surface is used for the next image formation.

Example 1
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 15 parts by mass and pigment dispersant 3 parts by mass were primarily dispersed in 82 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 rainbow dispersion in which aggregates were completely removed. Further, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
Next, a dispersion liquid having the following composition to which a resin as a binder resin and a wax were added was prepared.
100 parts by mass of polyester resin as a binder resin, 30 parts by mass of the carbon black dispersion, and 5 parts by mass of carnauba wax are mixed with 1000 parts by mass of ethyl acetate, and a mixer having stirring blades is used as in the preparation of the colorant dispersion. Then, the mixture was stirred for 10 minutes and dispersed. It was possible to completely prevent pigments from aggregating due to shock caused by solvent dilution. The dispersion liquid at this stage was filtered with a 0.45 μm filter (made by PTFE) in the same manner as in the preparation of the colorant dispersion liquid, but it was confirmed that no clogging occurred and all passed. The electrolytic conductivity of this dispersion was 3.5 × 10 ⁻⁷ S / m.

-Preparation of toner-
The obtained dispersion was supplied to the toner production apparatus shown in FIG. The discharge member used was a nickel plate having a thickness of 20 μm, and a perfect circular discharge hole with a diameter of 10 μm and a perfect circular discharge hole with a diameter of 20 μm were produced by processing with a femtosecond laser.
After the dispersion liquid was prepared, the liquid droplets were discharged under the following toner production conditions, and then the liquid droplets were dried and solidified to produce a toner.

[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: Orifice sheath 2.0 L / min, In-apparatus air 3.0 L / min In-apparatus temperature: 27-28 ° C.
Dew point temperature: -20 ° C
Nozzle frequency: 220 kHz

  The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. When the particle size distribution of the collected particles is analyzed by a flow type particle image analyzer (FPIA-2000), there are peaks in the particle sizes of 6.0 μm and 12.0 μm, and toners having other particle sizes. There were almost zero particles.

-Toner evaluation-
The charge amount of the obtained toner was evaluated.
It was measured with a suction type charge amount measuring device. Specifically, the toner is sucked into a Faraday cage equipped with a filter that can collect the toner, an electrometer is connected to this, the total charge amount of the sucked toner is measured, and the toner weight on the filter is measured. The total charge amount was divided by the collected toner weight to obtain the charge amount per unit weight.
As a result, a charge amount of −35 [μC / g] was obtained, and it was found that the charge amount was suitable for use in the above-described image forming apparatus.

(Example 2 (reference example) )
In Example 1, the other conditions were the same as in Example 1, and only one discharge hole having a diameter of 10 μm was used. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The weight average particle size was 6.0 μm, and the number average particle size was 6.0 μm. Toner base particles that were completely monodispersed were obtained. Next, a similar experiment was performed with the nozzle frequency set at 110 kHz. As a result, toner base particles having a weight average particle diameter of 4.8 μm and a number average particle diameter of 4.8 μm were obtained.

(Example 3)
In Example 1, the target toner was obtained in the same manner as Example 1 except that the nozzle frequency was 440 kHz and the liquid flow rate supplied from the syringe pump was doubled. When the particle size distribution of the collected particles is analyzed by a flow type particle image analyzer (FPIA-2000), there are peaks in the particle sizes of 6.0 μm and 12.0 μm, and toners having other particle sizes. There were almost zero particles.

Example 4
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was 1333 parts by mass. When the particle size distribution of the collected particles is analyzed by a flow type particle image analyzer (FPIA-2000), there are peaks in the particle sizes of 5.0 μm and 10.0 μm, and toners having other particle sizes. There were almost zero particles.

(Example 5)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was changed to 1666 parts by mass. When the particle size distribution of the collected particles is analyzed by a flow type particle image analyzer (FPIA-2000), there are peaks in the particle sizes of 4.0 μm and 8.0 μm, and toners having other particle sizes. There were almost zero particles.

(Example 6)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was 2000 parts by mass. When the particle size distribution of the collected particles is analyzed by a flow type particle image analyzer (FPIA-2000), there are peaks in the particle sizes of 3.0 μm and 6.0 μm, and toners having other particle sizes. There were almost zero particles.

It is sectional drawing which shows the structural example 1 of the particle manufacturing apparatus (toner manufacturing apparatus) which concerns on this invention. It is the schematic which shows the discharge hole pattern 1 of the discharge member used by this invention. FIG. 3 is a diagram showing a particle size distribution of toner particles obtained by the ejection hole pattern of FIG. 2. It is a figure which shows the example of the particle size distribution of the toner particle which can be implement | achieved by this invention. It is the schematic which shows the discharge hole pattern 2 of the discharge member used by this invention. It is the schematic which shows the discharge hole pattern 3 of the discharge member used by this invention. It is a figure which shows the mode of the droplet discharged from the discharge hole of a discharge member. It is the schematic which shows the discharge hole pattern 4 of the discharge member used by this invention. It is sectional drawing which shows the structural example 2 of the particle manufacturing apparatus (toner manufacturing apparatus) which concerns on this invention. It is sectional drawing which shows the structural example of the image forming apparatus which can apply the particle group of this invention. It is sectional drawing which shows the structure of the process cartridge which is one aspect | mode of the storage body which stored the particle group of this invention. 2 is a cross-sectional view illustrating a configuration of an image forming apparatus in a state where a transfer material conveyance belt is retracted. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,1A, 1B, 1C, 1D, 1E, 1F, 1G Discharge hole 2 Electrode 3 Solvent removal apparatus 4 Charger 5 Toner collection part 6 Droplet 7 Toner particle 8 Electrostatic curtain 9 Pressure feed tube 10 Liquid tank 11 Discharge member 11A Separating member 21K, 21M, 21C, 21Y Process cartridge 22 Transfer material conveying belt 22a Adsorption roller 22b P sensor 23 Fixing device 23a Heating roller 23b Pressure roller 24K, 24M, 24C, 24Y Writing device 25 Paper feeding device 31 Image carrier Body 32 Contact charging member (charging roller)
32a Metal core 32b Urethane foam layer 33 Developing means 33a Developing roller 33b Supply roller 33c Elastic blade 33d Stirring member 34 Cleaning device 34a Cleaning blade 34b Waste toner storage unit

Claims (13)

A discharge member having a plurality of discharge holes;
Vibration applying means for applying vibration to the discharge member at a predetermined frequency;
A liquid tank for storing a liquid in which a solid component is dissolved or dispersed in a solvent in contact with the discharge member, and
The plurality of discharge holes are arranged so as to be point- symmetric on the plate surface of the discharge member, and are arranged so that the center of symmetry of the point symmetry is substantially the same as the center position of the plate surface of the discharge member. And at least two or more different opening areas, and arranged such that the distance between the discharge holes having substantially the same opening area is longer than the distance between the discharge holes having different opening areas.
A particle manufacturing apparatus characterized in that solid particles are obtained by discharging the liquid as droplets from a discharge hole by the vibration applied by the vibration applying means and drying the droplets.   1 of each parameter of the opening area of the discharge hole provided in the discharge member, the frequency of vibration applied by the vibration applying means, the solid volume concentration of the liquid, and the amount of liquid passing through the discharge hole per unit time The particle production apparatus according to claim 1, wherein a plurality of particles are produced to produce a group of solid particles having a predetermined particle size distribution.   The frequency of the vibration applied by the vibration applying means is variable, and the particle size of the solid particle group is continuously changed only by changing the frequency of the vibration while discharging the liquid as droplets. The particle manufacturing apparatus according to claim 1. 4. The particle manufacturing apparatus according to claim 3 , wherein the frequency of the vibration after the change is a natural number times or a fraction of the natural number of the frequency of the vibration before the change.   The liquid tank is divided into a plurality of area units, and the liquid having different solid content volume concentration (volume%) for each area is stored in contact with the ejection member. The particle manufacturing apparatus according to 1. The liquid tank is divided into a plurality of area units, and the liquid is stored in contact with the discharge member for each area,
The particle manufacturing apparatus according to claim 1, wherein the amount of the liquid that passes through the ejection hole per unit time is controlled to be different for each region. A discharge member having a plurality of discharge holes, a vibration applying means that vibrates the discharge member at a predetermined frequency, and a liquid in which a solid component is dissolved or dispersed in a solvent is stored in contact with the discharge member. It includes a liquid tank which, a plurality of discharge holes while being disposed so as to be point symmetrical on the plate surface of the discharge member, the plate surface center position of the symmetry center of the point symmetry said discharge member Are arranged so as to be substantially the same as each other, and are composed of at least two discharge holes having different opening areas, and the distance between the discharge holes having substantially the same opening area as compared to the distance between the discharge holes having different opening areas. A method for producing a particle group using a particle production apparatus arranged to be long ,
The liquid is discharged as droplets by vibrating the discharge member in a state where the liquid in which the solid component is dissolved or dispersed in the solvent is in contact with the discharge member.
A method for producing a particle group, wherein the droplets are dried during flight to obtain a solid particle group having two or more different particle sizes . One or more parameters of the opening area of the discharge hole provided in the discharge member, the vibration frequency of the discharge member, the solid volume concentration of the liquid, and the amount of liquid passing through the discharge hole per unit time are set. The particle group production method according to claim 7 , wherein a particle size distribution of the particle group is controlled. The method for producing a particle group according to claim 7 , wherein the particle group having different particle diameters is obtained by discharging the liquid as droplets while changing the frequency of vibration of the discharge member. 10. The method for producing a particle group according to claim 9 , wherein a frequency of the vibration after the change is set to a natural number times or a fraction of a natural number of the frequency of the vibration before the change. By solid volume concentration (vol%) is discharged at least two different said liquid as a droplet simultaneously each particle group of claim 7, characterized in that to obtain a particle group composed of different particle size Production method. By discharging a respective liquid droplets simultaneously the liquid amount of the liquid as two or more different ones passing through the discharge holes per unit time, wherein, characterized in that obtaining a particle group composed of different particle size Item 8. A method for producing a particle group according to Item 7 . The method for producing a particle group according to claim 7 , wherein a positive charge or a negative charge is applied to the liquid droplets ejected from the ejection holes by electrostatic induction.

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