JP2008065006A - Toner, and image forming apparatus and process cartridge using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner particles having low temperature fixability and hot-offset resistance, and also having single dispersibility for particle size. <P>SOLUTION: In the toner, produced in such a manner that a toner composition liquid comprising a toner composition, at least containing a resin and a coloring agent is released from through holes, and is converted into droplets, the toner is produced by a toner production method where the toner composition liquid is fed to a storage part; and while exciting the toner composition liquid by a vibration means, at least in contact with the storage part via the storage part, the toner composition liquid is released from a plurality of the through holes provided at the storage part into a granulation space, and is passed from a columnar state into a constricted state so as to be converted into droplets, and the droplets are changed into solid particles in the granulation space, in a molecular weight distribution measured by the GPC (gel permeation chromatography) of the THF (tetrahydrofuran) soluble content in the toner, the weight average molecular weight (M<SB>w</SB>) is 2.5×10<SP>4</SP>to 1.0×10<SP>5</SP>, and the THF insoluble content (gel content) in the toner is 10 wt.% or lower. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., a toner produced thereby, and the toner production method described above. The present invention relates to an image forming apparatus using the toner, an image forming method using the toner, a copying machine using the image forming method, a laser printer, and a plain paper fax machine.

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.
Conventional dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are those obtained by melt-kneading a toner binder such as a styrene resin and a polyester resin together with a colorant and finely pulverizing them, so-called pulverized 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, since the above-described polymerization type toner is premised on the use of a dispersant in an aqueous medium, a dispersant that impairs the charging characteristics of the toner remains on the toner surface and the environmental stability is impaired. It is known that a defect occurs or a very large amount of washing water is required to remove this, and it is not always satisfactory as a manufacturing method.

  As an alternative method for producing toner, a method has been proposed in which fine droplets are formed using a piezoelectric pulse and then dried and solidified to form a 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). However, in these methods, the number of droplets that can be ejected from one nozzle per unit time is small, and there is a problem that productivity is low, and at the same time, the spread of particle size distribution due to coalescence of droplets is unavoidable, Also in terms of monodispersity, it was not satisfactory.

In these methods, since the toner material is melted or dissolved or dispersed in an organic solvent or the like is discharged from the nozzle, it is necessary to uniformly dissolve or disperse the toner material. In particular, since the toner is required to have properties such as offset resistance during heat fixing and heat-resistant storage stability, a high molecular weight component (gel content) having a weight average molecular weight exceeding 10 ⁷ may be contained in the toner. It is common. However, such a high molecular weight component is difficult to dissolve in a solvent or the like, and requires high-temperature heating to be melted, which is difficult from the viewpoint of the heat resistance of other toner raw materials and production equipment. Further, when the high molecular weight component is dispersed in the toner material, there is a serious problem that nozzle clogging occurs and it becomes difficult to form fine droplets.
Using a toner material containing a thermosetting resin or UV curable resin as a dispersoid, a dispersion finely dispersed in a dispersion medium is intermittently ejected as droplets from a nozzle, and then the droplets are aggregated and thermally cured A method of stabilizing the particle formation by curing a resin or a UV curable resin or a method of solidifying droplets has also been proposed (see Patent Documents 5 to 9). However, these methods also have low productivity and are insufficient in terms of monodispersibility as in Patent Documents 1 to 4. Moreover, although resin is hardened after particle | grain formation, the subject regarding the fixing characteristic as mentioned above was not solved.
In the case of the granulation method described above (Patent Documents 5 to 9), it is characterized in that the vibration part directly touches the fluid, but in such a configuration, if the number of pores and vibration parts match, it is sharp. In the case of a large number of pores and one excitation part, the size of the liquid droplets ejected from the pores depends on the distance between the positions of the pores and the excitation part. It has been found that the toner particles produce different particle sizes between multiple orifices with different toner particles.

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2006-28432 A JP 2006-28433 A JP 2006-0775708 A JP 2006-075252 A JP 2006-167593 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can efficiently produce a toner, and further has a single particle dispersibility with a particle size that has never been obtained so that many characteristic values required for the toner such as fluidity and charging characteristics are obtained. However, there is no or very little variation in the particle size observed in the conventional production methods, and the toner has both anti-offset properties and heat-resistant storage stability. Method for producing toner used as developer for developing electrostatic image in electroprinting, toner produced by the same, toner production apparatus using the toner production method, and image formation using the toner It is an object of the present invention to provide a method and an image forming apparatus using the image forming method.

  The present inventors supply a toner composition liquid containing a toner composition containing at least a resin and a colorant to a storage part, and the toner composition liquid is passed through the storage part by vibration means that contacts a part of the storage part. The toner composition liquid is discharged into a granulation space from a plurality of through-holes provided in the reservoir, and the toner composition liquid is converted into droplets from a columnar shape through a constricted state. It has been found that a toner having excellent monodispersibility can be produced by changing to solid particles.

In this method, the entire storage part having the through hole is excited by a single vibration means, so that the raw material fluid discharged from the through hole provided in the storage part is equally vibrated and pressure-concentrated. Since it is possible to generate waves, it is possible to simultaneously generate 100 or more droplet formation phenomena by one vibration means, and this makes it possible to prevent various problems such as blockage of the through-hole portion, productivity, and stability. The problem can be solved, particles, particularly toners can be produced efficiently, and the particles having a monodispersibility with an unprecedented particle size are required for toners such as fluidity and charging characteristics. Develops electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc., which have no or very little variation in the characteristic values due to particles seen in conventional manufacturing methods. A method for producing a toner to be used in order for the developer.
The present invention is a toner having the following constitution obtained by using this production method, and has the constitution as described below.

<1> In a toner produced by discharging a toner composition liquid containing a toner composition containing at least a resin and a colorant from a through hole into droplets, the toner composition liquid is supplied to a storage section, and at least the storage section The toner composition liquid is discharged into the granulation space from a plurality of through-holes provided in the storage section while exciting the toner composition liquid through the storage section by a vibrating means in contact with a part of the toner composition liquid. Is formed into a droplet from a columnar shape through a constricted state, and the droplet is changed into a solid particle in a granulation space. In the molecular weight distribution measured by gel permeation chromatography), the weight average molecular weight (M _w ) is 2.5 × 10 ^{4 to} 1.0 × 10 ⁵ , and A toner having a toner insoluble content (gel content) of 10% by weight or less.
<2> The toner according to <1>, wherein the toner composition liquid contains an organic solvent, and the toner is obtained by solidifying particles by removing the droplets.
<3> In the molecular weight distribution of the THF-soluble component of the toner, the content ratio of the polymer having a molecular weight of 1.0 × 10 ⁵ or more is 3 to 20 area% <1>, <2> Toner.
<4> The ratio M _w / M _n of the weight average molecular weight (M _w ) and the number average molecular weight (M _n ) of the toner dissolved in THF is from 8 to 75. The toner according to any one of 1 to 3.
<5> The toner according to any one of claims 1 to 4, wherein the toner contains a release agent.
<6> The toner according to <1> to <5>, wherein the toner has a number average molecular weight _Mn dissolved in THF of 5.0 × 10 ² to 5.0 × 10 ³ .
<7> The weight average molecular weight (M _w ) of at least one kind of binder resin contained in the toner is 1.0 × 10 ^{5 to} 4.5 × 10 ⁵ <1> to <6 > Toner.
<8> The toner according to <1> to <7>, wherein at least one kind of binder resin contained in the toner is made of a polyester resin.
<9> The toner according to <1> to <8>, wherein a 1/2 outflow temperature Tm, which is obtained by the toner high flow tester, is 120 to 140 ° C.
<10> The toner according to <1> to <9>, wherein the through hole is formed in a metal plate having a thickness of 5 to 50 μm, and an opening diameter thereof is 1 to 40 μm.
<11> An air flow is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the air stream causes the droplets to be transported in a solvent removal facility, and the solvent in the droplets is removed during the transport. The toner according to <1> to <10>, wherein toner particles are formed by the treatment.
<12> The toner according to <11>, wherein the dry gas is either air or nitrogen gas.
<13> The toner according to <11> or <12>, wherein the temperature of the dry gas is 40 to 200 ° C.
<14> The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged in the opposite polarity to the charge of the droplet, and allows the droplet to pass through the transport path. The toner according to <11> to <13>.
<15> The toner according to <1> to <14>, wherein the particle size distribution (mass average particle size / number average particle size) is in the range of 1.00 to 1.05.
<16> The toner according to <1> to <15>, wherein the toner has a mass average particle diameter of 1 to 20 μm.
<17> A two-component developer comprising at least a carrier comprising the toner according to <1> to <16> and magnetic particles.
<18> The electrostatic image on the electrostatic image carrier is developed with the developer according to <17> to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image carrier through a transfer material. An image forming apparatus that electrostatically transfers a toner image onto the transfer material.
<19> The electrostatic image on the electrostatic image carrier is developed with the toner described in <1> to <16> to form a toner image, and a transfer unit is applied to the surface of the electrostatic image carrier via a transfer material. An image forming apparatus, wherein the toner image is electrostatically transferred to the transfer material by contact.
<20> A heating roller made of a magnetic metal and heated by electromagnetic induction on a recording medium on which an unfixed image is formed, a fixing roller arranged in parallel to the heating roller, the heating roller, and the fixing roller And an endless belt-like toner heating medium that is heated by the heating roller and rotated by these rollers, and is pressed against the fixing roller via the toner heating medium, and is also applied to the toner heating medium. In contrast, in a fixing unit having a pressure roller that rotates in the forward direction to form a fixing nip portion, the unfixed image is heated and fixed by passing between the toner heating medium and the pressure roller. <18> and the image forming apparatus according to <19>.
<21> In a process cartridge that integrally supports an electrostatic charge image carrier and at least one unit selected from a charging unit, a developing unit, and a cleaning unit and is detachable from the main body of the image forming apparatus, the developing unit holds toner. A process cartridge, wherein the toner is the toner according to <1> to <16>.
<22> In a toner manufacturing method in which a toner composition liquid including a toner composition containing at least a resin and a colorant is discharged from a through-hole to form droplets, the toner composition liquid is supplied to a reservoir. The toner composition liquid is discharged into the granulation space from a plurality of through holes provided in the storage section while exciting the toner composition liquid through the storage section by vibration means that contacts at least a part of the storage section. In the molecular weight distribution measured by GPC (gel permeation chromatography) of the THF-dissolved component, the toner composition liquid is formed into droplets from a columnar shape through a constricted state, and the droplets are changed into solid particles in the granulation space. The weight average molecular weight (M _w ) is 2.5 × 10 ^{4 to} 1.0 × 10 ⁵ , and the THF insoluble content (gel content) of the toner is 10% by weight or less. A method for producing a toner comprising obtaining a toner.

  According to the present invention, the conventional problems can be solved, the toner can be produced efficiently, and the particles having a monodispersibility with an unprecedented particle size can be used. In many of the characteristic values required for the toner, there is no or very little variation in the particle size observed in the conventional production methods, and it is difficult for the toner production method to contain a large amount in the toner. Develops electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc. with minimal gel content, without use, with anti-offset and heat-resistant storage properties and excellent low-temperature fixability To provide a toner used as a developer, a developer including the toner, an image forming apparatus using the toner or the developer, and a process cartridge including the toner. Kill.

  Specifically, there are no fluctuations due to particle variations seen in the conventional production methods for pulverized toners and chemical toners, or even extremely small fluctuations that can be almost ignored. Has characteristics. Furthermore, according to the present invention, excellent offset resistance can be exhibited in a fixing process by a contact heating method performed using a heating member such as a heat roller. It also has excellent heat-resistant storage stability, prevents toner blocking even during long-term storage in a high-temperature environment, and does not impair various toner qualities. Furthermore, offset toner resistance and trade-off characteristics due to the effect of the toner being closely and uniformly arranged on the recording medium by the optimum molecular weight design of the toner and the excellent monodispersibility of the particle size distribution. Low temperature fixability could also be achieved.

[Toner production method]
The toner of the present invention supplies a toner composition liquid containing a toner composition containing at least a resin and a colorant to a storage part, and the toner composition is passed through the storage part by vibration means that contacts at least a part of the storage part. While exciting the liquid, the toner composition liquid is discharged into the granulation space from a plurality of through holes provided in the storage portion, and the toner composition liquid is converted into droplets from a columnar shape through a constricted state, and the droplets are formed into the granulation space To produce solid particles.

[Toner production equipment]
The apparatus used for producing the toner of the present invention (hereinafter also referred to as “toner production apparatus”) is not particularly limited as long as it is an apparatus capable of producing the toner of the present invention, and is appropriately selected. Can be used, but a storage part for storing a toner composition liquid containing a toner composition containing at least a resin and a colorant, a plurality of through holes provided in the storage part, and one of the storage parts Vibrating means that excites the toner composition liquid through the storage section by contacting and vibrating to discharge the toner composition liquid continuously from the through-hole to the granulation space to form droplets from the columnar state through the constricted state And toner particle forming means for changing the droplets into solid particles in the granulation space.

  As a preferable toner manufacturing apparatus, for example, as shown in FIG. 1, at least a storage unit 1 that stores at least the toner composition liquid as the droplet forming unit, a vibrating unit 2, and the vibrating unit are held. Support means 3 A liquid supply means 5 having the plurality of through-holes 4 for supplying the toner composition liquid discharged from the through-holes to the reservoir and releasing the liquid from the through-holes, and the toner particle forming means An apparatus having a solvent removal facility 6 and a toner collecting unit 7 is preferably used.

(Dropping phenomenon)
The liquid column droplet formation phenomenon will be described with reference to FIG.
As explained in Non-Patent Document 1 below, the wavelength condition λ at which the liquid column is most unstable is expressed by the following equation (1) using the liquid column diameter d (jet). It is represented by
λ = 4.5d (jet) (1)
Here, the frequency f of the disturbance phenomenon that occurs can be expressed by the following equation (2), where v is the velocity of the liquid column.
f = v / λ (2)
Further, as described in Non-Patent Document 2 below, as a result of deriving conditions for forming uniform particles stably experimentally, it is possible to stably form uniform particles under the condition of the following formula (3). It is said that.
3.5 <λ / d (jet) <7.0 (3)
Furthermore, as explained in Non-Patent Document 3 below, based on the energy conservation law, the minimum jet velocity v (min) at which the liquid discharged from the through hole forms a liquid column is expressed by the following equation (4): It is expressed as
v (min) = (8σ / ρd (jet)) ^1/2 (4)
In Equation (4), σ represents the surface tension of the liquid, ρ represents the liquid density, and d (jet) represents the diameter of the liquid column. The conditional expressions (1) to (4) are useful for estimating the conditions for reproducing such a phenomenon. However, we consider that these relational expressions are the types of liquid substances, mixtures, and dispersions. However, the phenomenon that the liquid column is formed into droplets by the above disturbance by attaching the vibrator to the liquid chamber and vibrating the vibrator at the frequency f has been confirmed. Was established.

[Non-Patent Document 1] Rayleigh, Lord “On the Instability of Jets” Proc. London Math. Soc. 110: 4 [1878]
[Non-Patent Document 2] Schneider J. et al. M.M. , C.I. D. Hendricks, Rev. Instrum. 35 (10), 1349-50 [1964]
[Non-Patent Document 3] Lindblad N. et al. R. and J. et al. M.M. Schneider, J.A. Sci. Instrum. 42, 635 [1965]

Hereinafter, the apparatus for producing the toner of the present invention will be described in detail for each member. (Reservoir)
Since the storage part needs to be held at least in a state where the toner composition raw material fluid is pressurized, it is made of a member such as a metal such as SUS or aluminum and preferably has a pressure resistance of about 10 MPa. However, it is not limited to this. In addition, for example, as shown in FIG. 2, a structure provided with a mechanism 9 that holds a plate having a through-hole connected by a pipe 8 that supplies a liquid to the reservoir is desirable. Moreover, the vibration means 2 which vibrates the whole storage part is in contact with the said storage part. The vibration means is connected to the vibration generator 10 and the conductive wire 11 and is preferably controlled. In order to stably form the liquid column, it is preferable to adjust the pressure in the reservoir or to provide the release valve 12 for removing the bubbles inside.

(Vibration means)
It is preferable that the vibration means 2 excites the whole storage part having the through hole by one vibration means.
The vibrating means is in contact with a part of the reservoir and applies vibrations to the raw material fluid via the reservoir, so that the raw material fluid discharged from the through hole provided in one reservoir is collectively equivalent. Since it is possible to generate a pressure density wave by applying vibration, it is possible to simultaneously generate 100 or more droplet forming phenomena by one vibration means.
The vibrating means 2 for applying vibration to the storage unit 1 is not particularly limited as long as it can provide reliable vibration at a constant frequency, and can be appropriately selected and used. For example, it is preferable that the through hole is vibrated at a constant frequency by expansion and contraction of the piezoelectric body.
The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, it is expanded and contracted by applying a voltage, and the through hole can be vibrated by the 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 fixed frequency is not particularly limited and may be appropriately selected according to the purpose. However, 100 kHz to 10 MHz is preferable, and 200 kHz to 2 MHz is preferable from the viewpoint of generating micro droplets having a very uniform particle diameter. More preferred.
The vibration means 2 is in contact with the storage portion, and the storage portion holds a plate having a through hole, and the vibration means and the plate having the through hole uniformly vibrate the liquid column generated from the through hole. From the viewpoint of giving, it is most preferable that they are arranged in parallel, and even if deformation occurs in the vibration process, it is desirable that the relationship be maintained within an inclination of 10 °.
Even if only one through hole 3 is provided, particle production is possible. However, from the viewpoint of efficiently generating micro droplets having a very uniform particle diameter, a plurality of through holes 3 are provided and liquid discharged from each through hole is provided. The droplets are preferably dried with one solvent removal facility, in the example shown, the solvent removal facility 5.

  From the viewpoint of further improving productivity, it is more preferable to provide a plurality of reservoirs having the vibration means. At this time, the productivity of the toner particles is determined by the product of the number of droplets (frequency) generated per unit time, the number of vibration means, and the number of through-holes acting by one vibration means. From the viewpoint of operability, it is sufficient that the number of through-holes acted by one vibration means as much as possible, that is, the number of through-holes possessed by one reservoir is as large as possible. Not. Therefore, the number of through-holes associated with one reservoir that is vibrated by the one vibrating means is preferably 10 to 10,000 from the viewpoint of productivity and controllability. In order to more surely generate fine droplets having a very uniform particle size, it is more preferably 10 to 1,000.

(Supporting means)
The support means 3 for fixing and supporting a part of the vibration means 2 is provided for fixing the storage section and the vibration means to the apparatus. The material is not particularly limited, but may be a rigid body such as metal. That's fine. If necessary, a rubber material, a resin material, or the like as a vibration reducing material may be provided in part so as not to disturb the vibration of the reservoir due to excessive resonance.

(Through hole)
As described above, the through hole 4 is a member that discharges the toner composition raw material fluid as a liquid column. There is no restriction | limiting in particular as a material and shape of the said through-hole, Although it can be set as the shape selected suitably, For example, a discharge hole is formed with a metal plate with a thickness of 5-50 micrometers, and the opening diameter is 1. The fine liquid droplets having an extremely uniform particle size can be generated at a vibration frequency of 100 kHz or more without clogging the fine particle dispersion of 1 μm or less contained in the toner composition raw material fluid. From the viewpoint of achieving both. This is because the frequency region in which droplets can be stably obtained by the droplet formation phenomenon decreases substantially as the diameter of the through-hole increases, so that the vibration frequency of 100 kHz or more is considered in consideration of productivity. Is assumed. The opening diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

(Liquid feeding / pressurizing means)
The means 5 for supplying the liquid to the common liquid chamber is preferably a metering pump such as a tube pump, a gear pump, a rotary pump, or a syringe pump. Moreover, the pump of the type pressurized and sent with compressed air etc. may be used. With these liquid supply means, the common liquid chamber is filled with the toner composition raw material fluid, and the pressure can be increased to a pressure at which droplets can be formed. The liquid pressure can be measured with a pressure gauge attached to the pump or a dedicated pressure sensor.

(electrode)
An electrode can be provided to charge the droplets 11 discharged from the through holes to form monodisperse particles.
The electrodes are a pair of members disposed so as to face the through holes, and the shape thereof is not particularly limited and can be appropriately selected. However, the electrodes are preferably formed in a ring shape.
A charging method using the electrode (hereinafter also referred to as “ring electrode”) is not particularly limited, but a constant charge amount can always be given to the droplet 13 discharged from the through hole. Therefore, for example, it is preferable to give a positive charge or a negative charge to the droplet 13 by induction charge. More specifically, the dielectric charging is preferably performed by passing the droplet through a ring electrode to which a DC voltage is applied.
Further, as the method of inductive charging, a direct current voltage is directly applied to the through hole, and a potential difference is provided with respect to the ground arranged at the bottom of the drying equipment to charge the droplet. In this case, a potential can be applied through the conductive toner composition liquid in the toner composition liquid storage section 1. If the liquid supply to the toner composition liquid storage unit 1 is insulated by using air pressure or the like, induction charging can be achieved relatively easily.
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.

(Staticizer)
After neutralizing the electric charge of the toner particles 15 formed by passing the droplets 13 through the conveyance path, a static eliminator is provided as a member for accommodating the toner particles 15 in the toner storage container. I can do it.
There is no particular limitation on the method of static elimination by the static eliminator, and a conventionally known method can be appropriately selected and used. However, since neutralization can be efficiently performed, for example, soft X-ray irradiation , Plasma irradiation, etc. are preferable.

(Solvent removal equipment)
The solvent removal equipment 6 is not particularly limited as long as the solvent of the droplets 13 can be removed, but an air flow is generated by flowing a dry gas in the same direction as the droplet 13 discharge direction. The toner particles 15 are preferably formed by transporting the droplets 13 in the solvent removal equipment 6 and removing the solvent in the droplets 13 during the transportation. 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 that can dry the droplets 13, and examples thereof include air and nitrogen gas.
Although there is no restriction | limiting in particular as a method of flowing the said dry gas to the solvent removal installation 6, For example, the method of connecting a dry gas supply tube to a solvent removal installation and flowing a dry gas in a solvent removal installation is mentioned.

The temperature of the drying gas is preferably higher in terms of drying efficiency, and even if a drying gas having a boiling point higher than the solvent used is used due to the characteristics of spray drying, the constant rate drying region during drying is used. Thus, the droplet temperature does not rise above the boiling point of the solvent, and the resulting toner is not thermally damaged. However, since the main constituent material of the toner is a thermoplastic resin, when it is exposed to a dry gas that is higher than the boiling point of the resin to be used after drying, that is, in the rate-decreasing drying region, the toner is liable to be thermally fused. There is a risk that the monodispersibility may be impaired. Therefore, specifically, the temperature of the dry gas is preferably, for example, 40 to 200 ° C, more preferably 60 to 150 ° C, and particularly preferably 75 to 85 ° C.
In addition, an electric field curtain charged with a polarity opposite to the electric charge of the droplets is provided on the inner wall surface of the solvent removal facility 6 from the viewpoint of preventing the droplets 13 from adhering to the wall surface of the solvent removal facility 6. It is preferable to form a transport path whose periphery is covered with the electric field curtain, and allow droplets to pass through the transport path.

(Toner collecting part)
The toner collecting unit 7 is a member provided at the bottom of the toner particle manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner.
The structure of the toner collecting portion 7 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 15 are formed from the outlet portion whose opening diameter is smaller than that of the inlet portion, the dry gas 14 is used to form the flow of the dry gas, and the toner particles are stored in the toner by the flow of the dry gas. It is preferably transferred to a container.
As the transfer method, as shown in the illustrated example, the toner particles 15 may be pumped to the toner storage container by the dry gas 14, or the toner particles 15 may be sucked from the toner storage container side.
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 15 reliably, it is preferable that it is a vortex | eddy_current.

Furthermore, from the viewpoint of more efficiently transporting the toner particles 15, the toner collection unit 7 and the toner collection container are formed of a conductive material and are connected to the ground. More preferred. The toner manufacturing apparatus preferably has an exposure specification.

(Droplet)
As described above, the droplet 13 is generated by discharging a toner composition liquid containing a specific substance from the through-hole 4 provided in the storage unit 1 oscillated at a constant frequency. The toner material will be described in a separate “toner” section.

The toner composition liquid is not particularly limited as long as the toner material is dissolved and / or dispersed, and can be appropriately selected and used. Further, from the viewpoint of maintaining a high charge amount, the electrolytic conductivity is preferably 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.

(Function)
According to the toner production method of the present invention described in detail above, the number of droplets generated from the through hole 4 is very large, tens of thousands to several million per second, and more discharge holes are provided. It is also easy to do. In addition, it can be said to be the most suitable method for producing toner from the viewpoint of obtaining a very uniform droplet diameter and sufficient productivity. Further, in this production method, the particle diameter of the toner finally obtained can be accurately determined by the following calculation formula (1), and there is almost no change in the particle diameter depending on the material used.
〔a formula〕
Dp = (6QC / πf) ^(1/3) (1)
Where Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow rate and through-hole diameter), f: vibration frequency, and C: volume concentration of solid content.
The toner particle diameter can be accurately calculated only by the above formula (1), but more simply can 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 toner particles obtained by the present invention is twice the opening diameter of the through hole regardless of the vibration frequency at which the droplet is ejected. Therefore, the target solid particle diameter can be obtained by obtaining and adjusting the solid content concentration in advance from the relationship of the above formula (2). For example, when the through-hole diameter is 7.5 μm, the droplet diameter is 15 μm. Therefore, if the solid content volume concentration is 6.40% by volume, 6.0 μm solid particles can be obtained. In this case, the vibration frequency is preferably higher from the viewpoint of productivity, but Q (liquid flow rate) is determined from the calculation formula (1) according to the vibration frequency determined here.

In the conventional manufacturing method, the particle size often varies greatly depending on the material used. In this manufacturing method, the particle size as set is controlled by managing the droplet diameter and solid content concentration at the time of discharge. It becomes possible to continuously obtain particles having a diameter.
Further, since the toner obtained by the present invention has a very uniform particle size, the fluidity in the toner base is very high. Therefore, even when an external additive is added for the purpose of reducing the adhesive force to a manufacturing apparatus or the like, the effect can be exhibited in an extremely small amount. Considering the deterioration of external additives due to stress and the safety of fine particles to the human body, it is preferable not to use such external additives as much as possible, which is also an advantage of the present invention.

[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 (mass average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.05. Moreover, as a mass mean 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 due to the 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 developing 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 has a weight-average molecular weight _Mw of a THF-soluble component of the obtained toner of 2.5 × 10 ^{4 to} 1.0 × 10 ⁵ , and a THF-insoluble amount (gel) of the toner. If the condition that the amount) is 10% by weight or less can be satisfied, the same toner as the conventional electrophotographic toner can be used. That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. Desired toner particles can be produced by drying and solidifying into fine droplets by a 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.

The toner manufacturing method of the present invention uses a toner composition solution in which the toner material is dissolved or dispersed in various organic solvents. However, when the toner material contains undissolved residue, the dispersion diameter of the toner material is smaller than the through-hole diameter. In the case of a large size, in the liquid column and droplet formation process from the through hole, the through hole is clogged, and not only uniform particles cannot be formed continuously, but also toner production becomes difficult. In particular, high molecular weight resin having a weight average molecular weight as the gel fraction exceeds 10 ^7, dissolved or finely dispersed in an organic solvent is difficult, tends to cause the through-hole clogging. Therefore, the amount of gel contained in the toner is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less.

Further, when the amount of gel used in the present invention is extremely small, the weight average molecular weight _{Mw of} the toner dissolved in THF is 2.5 × 10 ⁴ to 1 from the viewpoint of offset resistance and heat resistant storage stability. Must be 0 × 10 ⁵ . A toner satisfying this condition exhibits sufficiently excellent offset resistance and heat-resistant storage stability, and exhibits excellent fixing characteristics that do not impair low-temperature fixability. When it is smaller than 2.5 × 10 ⁴ , the low-temperature fixability is excellent, but the offset resistance is deteriorated. On the other hand, when it is larger than 1.0 × 10 ⁵ , not only the low-temperature fixability is inhibited but also the worst penetration. It can be a cause of clogging.
In the molecular weight distribution of the toner dissolved in THF, the content ratio of the polymer having a molecular weight of 1.0 × 10 ⁵ or more is preferably 3 to 20 area%. When it is less than 3 area%, the offset resistance and heat-resistant storage stability deteriorate, and when it exceeds 20 area%, the low-temperature fixability deteriorates. More preferably, it is 5-15 area%, Most preferably, it is 10-15 area%.

Further, the number-average molecular weight M _n of the toner dissolved in THF is preferably 5.0 × 10 ^{2 to} 5.0 × 10 ³ , more preferably 1.0 × 10 ^{3 to} 3.0 × 10 ³ . is there. By setting it within this range, it is possible to obtain a toner excellent in low-temperature fixability. When it is smaller than this range, the heat resistant storage stability is deteriorated. Further, the offset weight and the low-temperature fixability are more favorable when the ratio M _w / M _n of the weight average molecular weight M _w and the number average molecular weight M _n is 8 to 75. M _w / M _n is more preferably 10 to 40, and particularly preferably 20 to 30.

In the present invention, the molecular weight distribution of the toner dissolved in THF is measured by gel permeation chromatography (GPC) using THF as a solvent.
Further, the toner in the present invention preferably has a ½ outflow temperature Tm calculated by a Koka flow tester of 120 to 140 ° C., more preferably 128 to 135 ° C. The 1/2 outflow temperature is one of characteristic values representing the thermoplasticity of the toner, and is closely related to the fixing characteristics and the like. When the ½ outflow temperature is lower than 120 ° C., the low-temperature fixability is excellent, but the heat-resistant storage stability is deteriorated and toner blocking tends to occur. Moreover, when it exceeds 140 degreeC, although it is advantageous to offset resistance and heat-resistant storage stability, low temperature fixability is impaired.

(Toner material)
The toner material contains at least a resin and a colorant and, if necessary, other components such as a carrier and a wax.
(resin)
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins , Coumarone indene resin, polycarbonate resin, petroleum resin, and the like. Among these, polyester polymers are particularly excellent in low-temperature fixability and are preferably used as a binder resin from the viewpoint of energy saving. When used in full-color toners, they are excellent in transparency and color development.

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and 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 , Styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic. Examples include 2-ethylhexyl acid, 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. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 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 and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene 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 and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, 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 anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 Monomers having a hydroxy group such as 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 cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass, with respect to 100 parts by mass of the other monomers forming the vinyl polymer or copolymer. More preferred. 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, Ketone peroxides such as rohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylpero Xidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di- tert- butylperoxy to hexa hydro terephthalate, tert- butylperoxy azelate, and the like.

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, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, 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.

  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.

Even if these binder resins are used in combination with a plurality of types of resins, and the binder resin has any molecular weight distribution, the final molecular weight distribution and gel content of the toner satisfy the conditions of the present invention. There is no problem as long as it is satisfied. However, when the weight average molecular weight _Mw of the binder resin to be used is 1.0 × 10 ^{5 to} 4.5 × 10 ⁵ , the offset resistance and the heat resistant storage stability are further improved without impairing the low-temperature fixability. Can be improved. More preferably, it is 2.0 × 10 ^{5 to 3.5} × 10 ⁵ .

  From the viewpoint of affinity with fixing paper and dispersibility with other toner materials, when the binder resin is a polyester resin, the acid value thereof is preferably 0.1 mgKOH / g to 100 mgKOH / g. It is more preferably 0.1 mgKOH / g to 70 mgKOH / g, and most preferably 0.1 mgKOH / g to 50 mgKOH / g. 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. It is more preferable that the concentration is 0.1 mgKOH / g to 50 mgKOH / g. Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is set to S (ml), a blank is measured at the same time, the amount of KOH solution used at this time is set to B (ml), and the following calculation formula (3) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (3)

  The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

(Coloring agent)
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 with the master batch, in addition to the modified and unmodified polyester resins mentioned above, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted polymers; 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-chloromethacrylate Methyl acid copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. 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 mass average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, and is preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 1,000 is more preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.
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)
<Release agent (wax)>
In the present invention, a wax may be contained together with the binder resin and the colorant.
In particular, the toner of the present invention is preferably used in combination with a wax, since offset resistance and releasability from a fixing member can be further improved.
The wax of the present invention is not particularly limited and can be selected and used as appropriate. 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 fatty acids such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnapyl 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 sepasic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted with aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

More 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. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Hydrocarbon wax synthesized by the above, synthetic wax using a compound having one carbon atom as a monomer, hydrocarbon wax having a functional group such as hydroxyl group or carboxyl group, hydrocarbon wax and hydrocarbon having functional group 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 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, Candelilla wax, Rice wax or montan wax and hydrocarbon 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 raising and lowering the temperature once and taking a previous history.

(Magnetic material)
In the present invention, a magnetic substance can be contained together with the binder resin and the colorant.
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 these A mixture of

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

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

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge NEG VP2036 of quaternary ammonium salt, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone, Zone-based pigment, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the like, and is not uniquely limited. It is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded together with the masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent. Further, after the toner base particles are prepared, they may be fixed on the surface thereof.

(Application of additives, etc.)
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, Examples include finely powdered non-alumina, treated silica obtained by subjecting them to a surface treatment with a silane coupling agent, a titanium coupling agent or silicone oil, treated titanium oxide, and treated alumina. 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, for example, 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.
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. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, or the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.
Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.

A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., 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, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, more preferably 5 mμ to 500 mμ.
The specific surface area according to the BET method is preferably 20 to 500 m ² / g.
The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation 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 mμ to 2 μm, and more preferably 5 mμ to 500 mμ. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

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. Examples thereof include polymer 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.
In the developing method of the present invention, all of the electrostatic latent image carriers used in the conventional electrophotographic methods 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.

[Developer]
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 of 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 attached to the applied carrier core, or a method in which the resin 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 substance is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethylsilicone 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. Of 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 preferred.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier, or a non-magnetic toner.

[Image forming apparatus]
Hereinafter, an image forming apparatus using the electrophotographic toner of the present invention or a two-component developer composed of the toner and a carrier will be described. Note that the image forming apparatus of the present invention is not limited to the one described below, and any image forming apparatus can be used as long as the conditions shown in the claims are satisfied.

(Tandem type color image forming device)
An embodiment of a tandem type color image forming apparatus used in the present invention will be described. As shown in FIG. 4, the tandem type electrophotographic apparatus includes a direct transfer system that sequentially transfers an image on each photoconductor 1 to a sheet s conveyed by a sheet conveying belt 3 by a transfer apparatus 2. As shown in FIG. 5, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2 and then the image on the intermediate transfer member 4 is transferred to the sheet s by the secondary transfer device 5. There are indirect transfer systems that perform batch transfer. The transfer device 5 is a transfer conveyance belt, but there are also roller shapes and methods.

Comparing the direct transfer type and the indirect transfer type, the former arranges the paper feeding device 6 on the upstream side of the tandem type image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The paper feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveyance direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. Due to the speed difference between the sheet conveying speed when passing through the apparatus 7 and the sheet conveying speed by the transfer conveying belt, there is a drawback that the fixing device 7 tends to affect the image formation on the upstream side. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that allows the sheet s to bend, so that the fixing device 7 hardly affects the image formation.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.

  In this type of color electrophotographic apparatus, as shown in FIG. 5, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 6 shows an embodiment of the present invention, which is a tandem indirect transfer type electrophotographic apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) further mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.

Then, as shown in FIG. 6, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so that it can be rotated and conveyed clockwise in the figure.
In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.
Among the three images, four images of yellow, cyan, magenta, and black are formed on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.
An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.

A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.
The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, under such a secondary transfer device 22 and a fixing device 25, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet in parallel with the tandem image forming device 20 described above. Is provided.

Now, when making a copy using this color electrophotographic apparatus, a document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.
When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer body 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan single color images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.
Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  In the tandem image forming apparatus 20 described above, the individual image forming means 18 includes, for example, a charging device 160, a developing device 61, and a primary transfer device around a drum-shaped photoconductor 140 as shown in FIG. 62, a photoconductor cleaning device 63, a charge removal device 64, and the like. Referring to the reference numerals shown in FIG. 7, 65 is a developer on the developing sleeve, 68 is a stirring paddle, 69 is a partition plate, 71 is a toner concentration sensor, 72 is a developing sleeve, 73 is a doctor, 75 is a cleaning blade, and 76 is A cleaning brush, 77 is a cleaning roller, 78 is a cleaning blade, 79 is a toner discharge auger, and 80 is a driving device.

(Fixing device)
The fixing device in the present invention is not limited to the one described below, and there is no problem with any fixing device as long as the conditions of the claims are satisfied.
In the following, as shown in FIG. 8, the heating means is a means for generating Joule heat by an eddy current generated in the magnetic metal member by an alternating magnetic field and causing the heating body including the metal member to generate heat by electromagnetic induction. An embodiment of a heating type fixing device will be described.

  The fixing device shown in FIG. 8 is stretched between the heating roller 1 heated by electromagnetic induction of the induction heating means 6, the fixing roller 2 arranged in parallel with the heating roller 1, and the heating roller 1 and the fixing roller 2. An endless belt-like heat-resistant belt (toner heating medium) 3 that is heated by the heating roller 1 and rotates in the direction of arrow A by at least one of these rollers, and the fixing roller 2 via the belt 3 And a pressure roller 4 that rotates in the forward direction with respect to the belt 3. The heating roller 1 is made of a hollow cylindrical magnetic metal member such as iron, cobalt, nickel or an alloy of these metals, and has a low heat capacity and a high temperature rise. The fixing roller 2 includes a metal core 2a made of, for example, stainless steel, and an elastic member 2b in which a heat-resistant silicone rubber is solid or foamed and covered with the core 2a. In order to form a contact portion having a predetermined width between the pressure roller 4 and the fixing roller 2 by the pressing force from the pressure roller 4, the outer diameter is made larger than that of the heating roller 1. With this configuration, the heat capacity of the heating roller 1 becomes smaller than the heat capacity of the fixing roller 2, and the heating roller 1 is rapidly heated to shorten the warm-up time. The belt 3 stretched between the heating roller 1 and the fixing roller 2 is heated at the contact portion W1 with the heating roller 1 heated by the induction heating means 6. The inner surface of the belt 3 is continuously heated by the rotation of the rollers 1 and 2, and as a result, the entire belt is heated. The pressure roller 4 includes a cored bar 4a made of a cylindrical member made of a metal having high thermal conductivity such as copper or aluminum, and an elastic member having high heat resistance and toner releasability provided on the surface of the cored bar 4a. 4b. In addition to the above metal, SUS may be used for the core metal 4a. The pressure roller 4 presses the fixing roller 2 via the belt 3 to form the fixing nip portion N, but in this embodiment, the pressure roller 4 is harder than the fixing roller 2. As a result, the pressure roller 4 bites into the fixing roller 2 (and the belt 3), and the recording material 11 follows the circumferential shape of the surface of the pressure roller 4 by this biting. Has the effect of facilitating.

  As shown in FIGS. 8A, 9A, and 9B, the induction heating means 6 that heats the heating roller 1 by electromagnetic induction includes an excitation coil 7 that is a magnetic field generation means, and an excitation coil 7. The coil guide plate 8 is wound around. The coil guide plate 8 has a semi-cylindrical shape arranged close to the outer peripheral surface of the heating roller 1, and as shown in FIG. 9B, the excitation coil 7 is formed of a single long excitation coil wire. 8 is alternately wound in the axial direction of the heating roller 1. The exciting coil 7 is connected to a driving power source (not shown) whose oscillation circuit has a variable frequency. Outside the excitation coil 7, a semi-cylindrical excitation coil core 9 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 10 and is disposed close to the excitation coil 7. In the present embodiment, the exciting coil core 9 has a relative permeability of 2500. A high frequency alternating current of 10 kHz to 1 MHz, preferably a high frequency alternating current of 20 kHz to 800 kHz is supplied to the exciting coil 7 from a driving power source, thereby generating an alternating magnetic field. The alternating magnetic field acts on the heat generating layer of the heating roller 1 and the belt 3 in the contact area W1 between the heating roller 1 and the heat-resistant belt 3 and the vicinity thereof, and in the direction B that prevents the change of the alternating magnetic field inside these. Eddy current I flows. This eddy current I generates Joule heat corresponding to the resistance of the heat generating layer of the heating roller 1 and the belt 3, and the belt having the heating roller 1 and the heat generating layer mainly in the contact area between the heating roller 1 and the belt 3 and in the vicinity thereof. 3 is heated by electromagnetic induction.

The belt 3 heated in this way is detected by temperature detecting means 5 comprising a thermosensitive element such as a thermistor arranged in contact with the inner surface side of the belt 3 in the vicinity of the inlet side of the fixing nip N. The belt inner surface temperature is detected.
Of course, the fixing device used in the present invention is not limited to the fixing device as described above. However, a high-quality image having particularly excellent color reproducibility and color developability can be obtained, and fixing using a heat roller system is possible. It is preferable to use the present fixing device because the heat transfer efficiency is higher than that of the apparatus, the warm-up time can be shortened, and an image forming apparatus using a fixing device capable of quick start and energy saving can be obtained.

[Process cartridge]
FIG. 10 shows a schematic configuration of an image forming apparatus having a process cartridge used in the embodiment of the present invention. In the drawing, a represents the entire process cartridge, b represents a photoreceptor, c represents a charging unit, d represents a developing unit, and e represents a cleaning unit.
In the present invention, at least the photosensitive member b and the developing unit d are integrally combined as a process cartridge among the above-described components such as the photosensitive member b, the charging device unit c, the developing unit d, and the cleaning unit e. The process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.
In the image forming apparatus having the process cartridge using the electrophotographic toner of the present invention, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the charging unit, and then receives image exposure light from an image exposing unit such as slit exposure or laser beam scanning exposure. An electrostatic image is sequentially formed on the peripheral surface of the body, and the formed electrostatic image is then developed with toner by a developing unit, and the developed toner image is exposed between the photosensitive member and the transfer unit from the paper feeding unit. The transfer material is sequentially transferred to the transfer material fed in synchronization with the rotation of the body. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing toner remaining after transfer by a cleaning unit, and after further static elimination, it is repeatedly used for image formation.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all.

[Example 1]
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400 / Cabot) 15 parts by weight Pigment dispersant (Ajisper PB821 / Ajinomoto Fine Techno Co., Ltd.) 3 parts by weight Ethyl acetate 82 parts by weight Using a mixer with stirring blades, primary dispersion It was. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Further, a carbon black dispersion liquid, which is a liquid dispersed through the filter (made of PTFE) having a pore size of 0.45 μm and dispersed to the 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.
Polyester resin 1
( _Mw 28,000, _Mn 3,700 / manufactured by Sanyo Chemical Industries) 70 parts by weight polyester resin 2
( _Mw 150,000, _Mn 8,000 / manufactured by Sanyo Chemical Industries) 30 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1630 parts by weight At the time of preparing the colorant dispersion Similarly, the mixture was stirred for 15 minutes using a mixer having a stirring blade 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.

-Preparation of toner-
The obtained dispersion was supplied to the storage unit 1 of the toner manufacturing apparatus shown in FIG. The used plate having through-holes is a concentric circle having a through-hole of 8.0 μm in a perfect circle formed on a nickel plate having a thickness of 20 μm by removal processing (laser ablation) by a mask reduction projection method using a femtosecond laser. Individually produced. The portion where the through-hole was present was a square area with a side of 0.5 mm.
After the dispersion was prepared, droplets were formed under the following toner production conditions, and then the droplets were dried and solidified to produce a toner.
[Toner preparation conditions]
Dispersion solid content: 6.25% by weight
Dispersion specific gravity: 1.185 g / cm ³
Liquid flow rate: 400 ml / hr
Dry air flow rate: Sheath 2.0 L / min, Air in device 20 L / min Temperature in device: 27-28 ° C
Dew point temperature: -20 ° C
Common liquid chamber vibration frequency: 601.0 kHz

The dried and solidified toner particles were collected by a cyclone. When the particle size distribution of the collected particles was measured with a particle size analyzer Multisizer III (manufactured by Beckman Coulter, Inc.), the mass average particle diameter D4 was 6.01 μm, and D4 / Dn was 1.01. Base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG. Further, an optical micrograph of the toner base is shown in FIG.
100 parts by weight of the toner base obtained above, 0.5 parts by weight of hydrophobic silica (manufactured by Clariant Japan) as an external additive, and 0.3 parts by weight of hydrophobic titanium oxide (manufactured by Teika) are mixed using a Henschel mixer. Then, the toner was obtained by passing through a sieve having an opening of 38 μm. This toner is referred to as Toner 1.

-Preparation of two-component developer-
As a carrier used in a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin with an average thickness of 0.5 μm is used, and 7 weight of the toner prepared above with respect to 100 parts by weight of the carrier. A developer was prepared by uniformly mixing and charging the part using a tumbler mixer of the type in which the container rolls and stirs.
The carrier was prepared as follows. As a core material, 5000 parts of Mn ferrite particles (weight average diameter: 35 μm), and as a coating material, 450 parts of toluene, 450 parts of silicone resin SR2400 (made by Toray Dow Corning Silicone, nonvolatile content 50%), aminosilane SH6020 ( Using a coating liquid prepared by dispersing 10 parts of Toray Dow Corning Silicone) and 10 parts of carbon black with a stirrer for 10 minutes, the core material, the coating liquid, and a rotating bottom plate disk in the fluidized bed The coating liquid was applied to the core material by applying it to the coating apparatus for coating while forming a swirling flow provided with stirring blades. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

-Evaluation of toner properties-
The obtained toner was measured for particle size distribution, molecular weight distribution, gel content, and ½ outflow temperature, and the measurement results are shown in Table 1. Further, the heat resistant storage stability of the toner was measured, and the measurement results are shown in Table 2. In addition, productivity of the obtained toner and through-hole contamination after toner preparation were also evaluated, and the evaluation results are shown in Table 1. Details of each measurement method are described below.

<Particle size distribution>
The weight average particle diameter (D4) and number average particle diameter (Dn) of the toner of the present invention were measured with an aperture diameter of 100 μm using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.), and analysis software ( The analysis was performed with a Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted. After measuring the volume and number of toner particles or toner, the volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained. As an index of the particle size distribution, D4 / Dn obtained by dividing the weight average diameter (D4) of the toner by the number average particle diameter (Dn) is used. If it is completely monodisperse, it becomes 1, and the larger the value, the wider the distribution.

<Molecular weight distribution (weight average molecular weight _Mw , number average molecular weight _Mn )>
The molecular weight distribution of the toner dissolved in THF was measured by GPC (gel permeation chromatography) measuring apparatus GPC-150C (manufactured by Waters). KF801-807 (made by Shodex) was used for the column. The measurement is performed by the following method. The column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min. After 0.05 g of toner is sufficiently dissolved in 5 g of THF, it is filtered through a pretreatment filter (for example, a pore diameter of 0.45 μm Chromatodisc (manufactured by Kurabo Industries)), and finally the sample concentration is 0.05 to 0.6% by weight. Inject 50 to 200 μl of a THF sample solution of the prepared resin and measure. In measuring the weight average molecular weight M _w and the number average molecular weight M _n of the THF-dissolved part of the toner, the molecular weight distribution of the sample is expressed by the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Calculate from the relationship. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or a molecular weight of 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 1.1 × 10 ⁵ , manufactured by Toyo Soda Kogyo Co., Ltd. It is appropriate to use 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
Further, the content ratio of the polymer in a specific molecular weight range can be easily calculated from the obtained molecular weight distribution. The content ratio (area%) of the polymer having a molecular weight of 1.0 × 10 ⁵ or more in the present invention is the integrated value of the molecular weight of 1.0 × 10 ⁵ or more in the obtained molecular weight distribution as the total integrated value of the molecular weight distribution. It was calculated by dividing.
Further, the molecular weight distribution of the sample other than the toner was measured by the same measurement method as described above.

<Amount insoluble in THF (gel content)>
The THF-insoluble component is a polymer gel component having a weight average molecular weight exceeding 10 ⁷ . In the present invention, the gel content was measured as follows.
1 g of toner is weighed, 100 g of THF is added thereto, and the mixture is stirred at 10 ° C. using a stirrer for 15 minutes, and then left at 10 ° C. for 20 to 30 hours. After 20 to 30 hours, the gel component which is insoluble in THF absorbs THF as a solvent, swells and settles, and is separated by filter paper. The filter paper is FILTER PAPER No. 7 (manufactured by Advantech) was subjected to suction filtration while thoroughly washing the gel fraction separated on the filter paper with THF. The separated gel is heated at 120 ° C. for 3 hours to volatilize the absorbed THF, and the weight of the gel is weighed. The gel amount (% by weight) in the present invention is determined by the weighed value (g) × 100 of the gel content.

<1/2 outflow temperature>
The 1/2 outflow temperature Tm in the present invention was measured using a Koka type flow tester CFT-500C (manufactured by Shimadzu Corporation). The flow curve obtained by this measurement is a curve as shown in FIG. 12, and the 1/2 outflow temperature can be read. In the figure, the melting temperature in the 1/2 method is the T1 / 2 outflow temperature. The measurement conditions were a load of 20 kg, a die diameter of 1 mm, a die length of 10 mm, and a heating rate of 3 ° C./min.

<Heat resistant storage stability>
The heat-resistant storage stability was measured using a penetration tester (Nikka Engineering). Specifically, 10 g of toner is weighed and placed in a 30 ml glass container (screw vial) in an environment of temperature 20 to 25 ° C. and humidity 40 to 60%, and the lid is closed. The glass container containing the toner was tapped 100 times and then left for 24 hours in a thermostatic bath set at a temperature of 50 ° C., and the penetration was measured with a penetration meter. In Table 2, from the good ones, it is ◎ for 30 mm or more, ◯ for 20 mm to 29 mm, △ for 15 mm to 19 mm, x for 8 mm to 14 mm, and 7 mm or less. Is indicated by xx.

<Toner productivity>
The amount of toner particles (mg / h) produced per hour is measured from one through-hole among the plurality of through-holes provided in the toner composition liquid reservoir, and this is used as the toner productivity. As evaluated. Table 2 shows that the toner productivity is good, the case of 200 mg / h or more is ◎, the case of 150 to 199 mg / h is 、, the case of 100 to 149 mg / h is △, and 50 to 99 mg / h. In the case of x, it was indicated by x, and in case of 49 mg / h or less, it was indicated by x.

<Dirt through hole>
The toner manufacturing apparatus was continuously operated to evaluate through-hole contamination at the time when 500 g of toner particles were produced. In Table 2, if the through-hole is not soiled or clogged at all, it is ◎, and some dirt is attached to the through-hole. If some of the through-holes are clogged with some clogging, it is △, and some of the through-holes are clogged with dirt or clogged. In the case where the particle size distribution of the toner particles deteriorated is x, the clogging is severe, and the particle size distribution of the produced toner particles deteriorates or cannot be produced at all.

-Image quality evaluation using copied images-
In the toner and the two-component developer obtained above, the four-color developing unit sequentially develops each developer on one belt photosensitive member, sequentially transfers it to an intermediate transfer member, and collectively transfers the four colors onto paper or the like. Full-color laser printer of type Imagio Neo C285 (manufactured by Ricoh) (evaluator A), and evaluator B modified to transfer the toner directly to the development site by airflow and develop it with a powder cloud An evaluation machine C in which the fixing device of the evaluation machine A is modified to an oil-less IH fixing device, and the evaluation machine A is integrally coupled as a process cartridge with a photosensitive member, a charging device, a developing means, and a cleaning device. Evaluation was performed by an evaluation machine D modified to be configured. In this example and comparative example, the developer was put in one of the four color developing units, and the image quality and the like were evaluated in the single color mode.

The following describes the image quality evaluation method.
<Image graininess and sharpness>
Using the evaluation machine A, 10,000 sheets of photographic images were output in monochromatic mode, and the degree of graininess and sharpness was visually evaluated. In Table 2, the degree is ◎ when the level is equivalent to offset printing, ◯ when it is slightly worse than offset printing, and △ when it is slightly better than the conventional electrophotographic image. In the case of grade, it was indicated by ×, and in the case of worse than the conventional electrophotographic image, it was indicated by ××.

<Thin wire reproducibility>
Using Evaluator A, after running 30,000 image charts with 50% image area in monochrome mode, output a 600 dpi thin line image to Ricoh type 6000 paper, and compare the degree of fine line bleeding with the step sample. did. Evaluation is made in five stages of ranks 1 to 5, rank 5 is the best in fine line reproducibility, and rank 1 is the worst. In Table 2, it is ◎ if it is rank 5, ◯ if it is rank 4, △ if it is rank 3, ３ if it is rank 2, and xx if it is rank 1. Displayed.

<Low-temperature fixability and hot offset resistance>
Using Evaluation Machine A, a solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was created on plain paper and cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh Copied Printing Paper <135>), A fixing test was performed by changing the temperature of the fixing belt, and an upper limit temperature at which hot offset did not occur on plain paper was defined as an upper limit fixing temperature. Further, the solid image was created on a plain paper at a position 3.0 cm from the front end in the paper passing direction. Further, the minimum fixing temperature was measured with a thick paper. The fixing lower limit temperature was drawn on the surface of the obtained fixed image using a drawing tester AD-401 (manufactured by Ueshima Seisakusho) with a ruby needle (tip radius 260 to 320 μmR, tip angle 60 degrees) and a load of 50 g. The drawing surface was strongly rubbed 5 times with Hanikot # 440 (manufactured by Honeylon), and the fixing belt temperature at which image shaving was almost eliminated was determined as the minimum fixing temperature. Table 2 shows low-temperature fixability when the fixing lower limit temperature is 130 ° C. or less, ◎, 131-140 ° C., 141-155 ° C., 156-160 ° C., x, 161 ° C. In the above case, it is indicated by xx. As for hot offset resistance, ◎ when the upper limit fixing temperature is 220 ° C. or higher, ○ when 200 to 219 ° C., Δ when 180 to 199 ° C., × when 170 to 179 ° C., 169 ° C. or lower. In the case of, it is indicated by xx.

[Example 2]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.26% by weight and a specific gravity of 1.187 g / cm ^3. Except that they were used, the same procedure as in Example 1 was carried out to obtain completely monodispersed toner base particles having a mass average particle diameter D4 of 6.01 μm and D4 / Dn of 1.00. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 2. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 3
( _Mw 416,000, _Mn 6,500 / manufactured by Kao) 60 parts by weight Polyester resin 4
( _Mw 15,000, M _n 3,500 / manufactured by Kao) 40 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1628 parts by weight

[Example 3]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.23 wt% and a specific gravity of 1.181 g / cm ^3. Except that they were used, the same as in Example 1, completely monodispersed toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.00 were obtained. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 3. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 65
( _Mw 25,000, _Mn 1,100 / manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1637 parts by weight

[Example 4]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.27% by weight and a specific gravity of 1.189 g / cm ^3. Except that it was used, the same as in Example 1, completely monodispersed toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.00 were obtained. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 4. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 6 ( _Mw 87,000 / manufactured by Kao) 85 parts by weight Polyester resin 7 ( _Mw 5,300 / manufactured by Kao) 15 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1625 parts by weight

[Example 5]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.30% by weight and a specific gravity of 1.195 g / cm ^3. Except that they were used, the same procedure as in Example 1 was carried out to obtain completely monodispersed toner base particles having a mass average particle diameter D4 of 6.01 μm and D4 / Dn of 1.00. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 5. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 8
( _Mw 84,000, _Mn 9,500 / manufactured by Kao) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1617 parts by weight

[Example 6]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.26% by weight and a specific gravity of 1.185 g / cm ^3. Except for the use, substantially the same monodispersed toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.02 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 6. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 3
( _Mw 416,000, _Mn 6,500 / manufactured by Kao) 45 parts by weight polyester resin 4
( _Mw 15,000, M _n 3,500 / manufactured by Kao) 55 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1630 parts by weight

[Example 7]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.25% by weight and a specific gravity of 1.187 g / cm ^3. Except for the use, substantially the same monodispersed toner base particles having a mass average particle diameter D4 of 6.02 μm and D4 / Dn of 1.02 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 7. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 9
( _Mw 59,000, _Mn 2,200 / manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1628 parts by weight

[Example 8]
-Synthesis of styrene-acrylic resin-
First, a styrene-acrylic resin as a binder resin was synthesized.
Styrene monomer 65 parts by weight N-butyl acrylate monomer 30 parts by weight Acrylic acid monomer 15 parts by weight 2,2′-azobisisobutyronitrile 1.5 parts by weight Tetrahydrofuran 500 parts by weight The above formulation was reacted in a nitrogen atmosphere. The polymerization reaction was performed by mixing in a container and refluxing at 65 ° C. for 6 hours. Next, the solvent was removed to obtain a styrene-n-butyl acrylate-acrylic acid copolymer. This was designated as styrene-acrylic resin 1.
The obtained styrene-acrylic resin 1 had a number average molecular weight (M _n ) of 8,700 and a weight average molecular weight (M _w ) of 56,000.
Subsequently, in the preparation of the dispersion to which the resin and the wax of Example 1 were added, a dispersion having a solid content of 6.28% by weight and a specific gravity of 1.190 g / cm ³ was changed to the following formulation. Except for the use thereof, substantially the same monodispersed toner base particles having a mass average particle diameter D4 of 6.02 μm and D4 / Dn of 1.02 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 8. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Styrene-acrylic copolymer resin 1
( _Mw 56,000, _Mn 8,700) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1622 parts by weight

[Example 9]
In Example 1, except that the evaluation machine B was used in place of the evaluation machine A, the above evaluation was performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
[Example 10]
In Example 1, except that the evaluation machine C was used instead of the evaluation machine A, the above evaluation was performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
[Example 11]
In Example 1, except that the evaluation machine D was used instead of the evaluation machine A, the above evaluation was performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

[Comparative Example 1]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.23 wt% and a specific gravity of 1.181 g / cm ^3. Except for the use, substantially the same monodispersed toner base particles having a mass average particle diameter D4 of 6.01 μm and D4 / Dn of 1.01 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 9. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 10
(M _w 22,000, M _n 1,200 / manufactured by Kao) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1637 parts by weight

[Comparative Example 2]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.27% by weight and a specific gravity of 1.189 g / cm ^3. Except for the use, toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.12 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the target toner 10. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 11 ( _Mw 70,000 / manufactured by Kao) 30 parts by weight polyester resin 9
( _Mw 59,000, _Mn 2,200 / manufactured by Sanyo Chemical Industries) 70 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1625 parts by weight

[Comparative Example 3]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.27% by weight and a specific gravity of 1.189 g / cm ^3. Except for the use, toner base particles having a mass average particle diameter D4 of 5.72 μm and D4 / Dn of 1.34 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the target toner 11. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2. Further, when the through hole was confirmed after the toner was manufactured, clogging occurred inside the through hole.
Polyester resin 11 ( _Mw 70,000 / manufactured by Kao) 45 parts by weight Polyester resin 9
( _Mw 59,000, _Mn 2,200 / manufactured by Sanyo Chemical Industries) 55 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1625 parts by weight

[Comparative Example 4]
In the preparation of the dispersion to which the resin and wax of Example 1 were added, the following formulation was changed to obtain a dispersion having a solid content of 6.25% by weight and a specific gravity of 1.186 g / cm ^3. Except for the use, substantially the same monodispersed toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.03 were obtained in the same manner as in Example 1. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 12. The obtained toner was evaluated as described above. The results are shown in Tables 1 and 2.
Polyester resin 1
( _Mw 28,000, _Mn 3,700 / manufactured by Sanyo Chemical Industries) 20 parts by weight polyester resin 2
( _Mw 150,000, _Mn 8,000 / manufactured by Sanyo Chemical Industries) 80 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax 5 parts by weight Ethyl acetate 1630 parts by weight

[Comparative Example 5]
In place of the toner manufacturing apparatus used in the first embodiment, a storage portion for storing the dispersion liquid, and a pressure pulse is applied to the storage portion by expansion and contraction of the piezoelectric body, thereby discharging the liquid substance as droplets from the through hole. A toner manufacturing apparatus provided with a head portion capable of the above was used. The apparatus of Comparative Example 6 is significantly different from the structure of Example 1 in that the piezoelectric element is in direct contact with the through-hole portion, and the pressure pulse due to the expansion and contraction of the piezoelectric body vibrates the through-hole portion itself. Except for the difference in the droplet forming portion, the droplets were ejected under the same toner production conditions as in Example 1, and the droplets were dried and solidified, whereby the mass average particle diameter D4 was 5.30 μm and D4 / Dn was Toner base particles having a broad particle size distribution of 1.35 were obtained. An optical micrograph of the toner base is shown in FIG. In addition, the same plate as in Example 1 was used as the plate having the through holes of the droplet discharge portion used in this comparative example. The obtained toner base particles were treated with an external additive in the same manner as in Example 1 to obtain the intended toner 13.

  As shown in Tables 1 and 2, the image obtained by developing with the toner prepared in the present invention is extremely excellent in image quality faithful to the electrostatic latent image, and has low temperature fixability and offset resistance. It was compatible.

It is explanatory drawing of an example of the toner particle manufacturing apparatus for implementing this invention. It is explanatory drawing of an example of the storage part in this invention. It is a figure explaining the droplet formation phenomenon of a liquid column. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. FIG. 2 is a schematic explanatory diagram of an IH fixing device. FIG. 2 is a schematic explanatory diagram of an IH fixing device. It is a schematic explanatory drawing which shows an example of the process cartridge of this invention. 2 is a scanning electron micrograph of the toner base produced in Example 1. FIG. It is the schematic of the flow curve obtained by an elevated flow tester. FIG. 3 is an optical micrograph of the toner obtained in Example 1. 7 is an optical micrograph of the toner obtained in Comparative Example 5. FIG.

Explanation of symbols

(About Fig. 1 and Fig. 2)
DESCRIPTION OF SYMBOLS 1 Storage part 2 Vibrating means 3 Support means 4 Through-hole 5 Liquid supply means 6 Solvent removal equipment 7 Toner collection part 8 Piping 9 Through-hole holding mechanism 10 Vibration generator 11 Conductive wire 12 Release valve 13 Droplet 14 Drying means 15 Toner Particles (Figures 4-7)
DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer apparatus, Primary transfer apparatus 3 Sheet conveyance belt s Sheet 4 Intermediate transfer body 5 Secondary transfer apparatus 6 Paper feed apparatus 7 Fixing apparatus 8 Photoconductor cleaning apparatus 9 Intermediate transfer body cleaning apparatus 10 Endless belt-shaped intermediate Transfer body 14, 15, 16 Support roller 10 Intermediate transfer body 17 Intermediate transfer body cleaning device 18 Image forming means 20 Tandem image forming device 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 42 Paper feeding roller 43 Paper bank 44 Paper feeding cassette 45 Separating roller 46 Paper feeding path 47 Conveying roller 48 Feeding Paper path 49 Registration roller 50 Paper feed roller 51 Hand Paper tray 52 separation roller 53 manual paper feed path 55 switching claw 56 discharge roller 57 paper discharge tray 61 developing device 62 primary transfer device 63 photoconductor cleaning device 64 static eliminator 65 developer on developing sleeve 68 stirring paddle 69 partition plate 71 toner Density sensor 72 Developing sleeve 73 Doctor 75 Cleaning blade 76 Cleaning brush 77 Cleaning roller 78 Cleaning blade 79 Toner discharge auger 80 Drive device 100 Copying device main body 140 Photoconductor 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
(About FIGS. 8 and 9)
DESCRIPTION OF SYMBOLS 1 Heating roller 2 Fixing roller 2a Core metal 2b Elastic member 3 Heat resistant belt (toner heating medium)
DESCRIPTION OF SYMBOLS 4 Pressure roller 6 Induction heating means W1 Contact part 4a Core metal 4b Elastic member 11 Recording material 7 Excitation coil 8 Coil guide plate 9 Excitation coil core 10 Excitation coil core support member

Claims (22)

In a toner produced by discharging a toner composition liquid containing a toner composition containing at least a resin and a colorant from a through hole into droplets, the toner composition liquid is supplied to a storage part, and at least a part of the storage part The toner composition liquid is discharged into the granulation space from a plurality of through holes provided in the storage portion while exciting the toner composition liquid through the storage portion by the vibration means in contact with the storage portion. A toner manufactured by a toner manufacturing method characterized by forming droplets through a constricted state and changing the droplets into solid particles in a granulation space, wherein the toner has a GPC (gel permeation) content in THF. in the molecular weight distribution measured by chromatography), the weight average molecular weight _{(M w)} is the ^{2.5 × 10 4 ~1.0 × 10 5} , and, in the toner Toner, wherein the HF insoluble content (gel content) is 10% by weight or less.   The toner according to claim 1, wherein the toner composition liquid contains an organic solvent, and the toner is obtained by solidifying particles by removing the droplets. 3. The toner according to claim 1, wherein in the molecular weight distribution of the THF-soluble component of the toner, the content ratio of the polymer having a molecular weight of 1.0 × 10 ⁵ or more is 3 to 20 area%. 4. The ratio M _w / M _n of the weight average molecular weight (M _w ) and the number average molecular weight (M _n ) of the THF-soluble component of the toner is 8 to 75. 5. Toner.   The toner according to claim 1, wherein the toner contains a release agent. 6. The toner according to claim 1, wherein the toner has a number-average molecular weight M _n dissolved in THF of 5.0 × 10 ² to 5.0 × 10 ³ . The weight average molecular weight (M _w ) of at least one kind of binder resin contained in the toner is 1.0 × 10 ^{5 to} 4.5 × 10 ^5. The toner described.   The toner according to claim 1, wherein at least one binder resin contained in the toner is made of a polyester resin.   The toner according to any one of claims 1 to 8, wherein a 1/2 outflow temperature Tm obtained by the high flow type flow tester of the toner is 120 to 140 ° C.   The toner according to claim 1, wherein the through-hole is formed in a metal plate having a thickness of 5 to 50 μm, and an opening diameter thereof is 1 to 40 μm.   By causing a dry gas to flow in the same direction as the droplet discharge direction, an air flow is generated, and the air flow causes the droplets to be transported in the solvent removal equipment, and the solvent in the droplets is removed during the transport. The toner according to claim 1, wherein toner particles are formed.   The toner according to claim 11, wherein the dry gas is one of air and nitrogen gas.   The toner according to claim 11 or 12, wherein the temperature of the dry gas is 40 to 200 ° C.   The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged to a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. Item 14. The toner according to any one of Items 11 to 13.   The toner according to claim 1, wherein the particle size distribution (mass average particle diameter / number average particle diameter) is in the range of 1.00 to 1.05.   The toner according to claim 1, wherein the toner has a mass average particle diameter of 1 to 20 μm.   A two-component developer comprising at least a carrier comprising the toner according to claim 1 and magnetic particles.   An electrostatic charge image on the electrostatic charge image bearing member is developed with the developer according to claim 17 to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic charge image bearing member via a transfer material so that the toner image is formed. An image forming apparatus for electrostatic transfer to the transfer material.   An electrostatic image on the electrostatic image carrier is developed with the toner according to claim 1 to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image carrier via a transfer material. An image forming apparatus, wherein the toner image is electrostatically transferred onto the transfer material.   A recording medium on which an unfixed image is formed is stretched between a heating roller made of magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel to the heating roller, and the heating roller and the fixing roller. And is heated by the heating roller and rotated by the endless belt-like toner heating medium, and is pressed against the fixing roller via the toner heating medium, and in turn with respect to the toner heating medium. A fixing unit having a pressure roller that rotates in a direction to form a fixing nip portion passes the toner heating medium and the pressure roller to heat and fix the unfixed image. Item 20. The image forming apparatus according to Item 18 or 19.   In a process cartridge that integrally supports at least one unit selected from an electrostatic charge image carrier and a charging unit, a developing unit, and a cleaning unit, and is detachable from the image forming apparatus main body, the developing unit holds toner, A process cartridge, wherein the toner is the toner according to claim 1. In a toner manufacturing method in which a toner composition liquid including a toner composition containing at least a resin and a colorant is discharged from a through hole to form droplets, the toner composition liquid is supplied to a storage section, and at least stored. The toner composition liquid is discharged into the granulation space from a plurality of through-holes provided in the storage section while exciting the toner composition liquid through the storage section by vibration means in contact with a part of the storage section. In the molecular weight distribution measured by GPC (gel permeation chromatography) of the THF-dissolved liquid, the liquid is formed into droplets from a columnar shape through a constricted state, and the droplets are changed into solid particles in the granulation space. _{(M w)} is the ^{2.5 × 10 4 ~1.0 × 10 5} , and, THF insoluble content of the toner (gel content) is 10 wt% or less toner Toner production method characterized by obtaining.