JP2008065220A - Method for producing toner, 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 uniform dispersibility for particle sizes. <P>SOLUTION: A toner composition liquid obtained by dissolving or dispersing a toner composition, at least comprising a binding resin precursor and a coloring agent into a solvent and/or monomer is fed to a storage part 1, while exciting the toner composition liquid by an exciting means 2 via the storage part, the toner composition liquid is released to a granulation space 6, from a plurality of through holes 4 provided at the storage part, and the toner composition liquid is passed through a columnar state into a constricted state, so as to be converted into droplets. At least during the conversion of the toner composition liquid into the droplets or after the conversion of the toner composition liquid into the droplets, a reaction wherein the molecular weight of the binding resin precursor increases (elongation reaction), or a reaction where molecule chains are applied with a crosslinked structure (crosslinking reaction) or a reaction, where solvent insoluble components are formed (gelling reaction) is performed, so as to change the droplets into solid particles. <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.

  Toners are required to have low-temperature fixing for energy saving. Especially in full-color equipment, high gloss and color mixing are required, so the toner needs to have a low melt viscosity. Often used is a polyester resin. However, since such a toner tends to cause hot offset, conventionally, silicone oil or the like is applied to a heat roll. However, this method requires an oil tank and an oil application device, which is complicated and large.

  Due to the above-mentioned problems, it is a problem to achieve both low-temperature fixability and hot offset resistance even in recent years even when an oil application mechanism is not provided in the fixing roller. As a solution, the molecular weight of the polyester resin has a distribution of a low molecular weight component and a high molecular weight component, the low molecular weight component provides low-temperature fixability, and the high molecular weight component provides offset resistance, thereby improving the oil coating mechanism. Good fixing characteristics can be obtained even when there is no ink.

  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 the emulsion polymerization aggregation method, this method is excellent in that a resin that can be used is versatile, and that a polyester resin that is advantageous for energy saving due to low-temperature fixing 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 addition, as described above, when a resin component having a high molecular weight is included in the toner composition liquid in order to provide offset resistance, the viscosity of the toner composition liquid increases and the droplets are formed. May become difficult and clogging of the injection part is likely to occur. In particular, in order to give offset resistance, it is advantageous to increase rubber elasticity by giving a high molecular weight resin component a cross-linked structure, but when the high molecular weight component has a cross-linked structure, The increase in the viscosity of the toner composition liquid is significant, and the solubility in organic solvents also decreases, so that clogging tends to occur easily. In order to reduce the viscosity of the composition liquid, there is a means for lowering the solid content ratio in the composition liquid. However, in this case, there is a problem that productivity is deteriorated and droplets are easily coalesced.

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 for stabilizing the particle formation by curing a resin or a UV curable resin 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 above-mentioned granulation method (Patent Documents 5 to 9), the vibration part is directly in contact with the fluid, but in such a configuration, when 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 produce toner efficiently, has excellent low-temperature fixability and hot offset resistance even when no oil application mechanism is provided on the fixing heat roller, and has a single particle dispersibility. A toner production method that has no or very little variation due to particles in the conventional production methods in many characteristic values required for toners such as fluidity and charging characteristics due to the particles possessed In order to develop an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., which has both offset resistance and heat resistant storage stability without causing nozzle clogging during toner production. Manufacturing method of toner used for developer, toner manufactured thereby, toner manufacturing apparatus using the toner manufacturing method, image forming method using the toner, image And to provide an image forming apparatus using the forming method

The present inventors apply the same vibration to the raw material fluid discharged from the through hole provided in the storage portion by exciting the entire storage portion having the through hole by one vibration means. Since it is possible to generate pressure compaction and wave, it is possible to simultaneously generate 100 or more droplet formation phenomena by one vibration means. In addition, particles, particularly toners, can be produced efficiently, and particles having a monodispersibility with an unprecedented particle size are required for toners such as fluidity and charging characteristics. Develop electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., which have no or very little variation in particles due to the particle size seen in conventional manufacturing methods at many characteristic values. And it found that it toners prepared for use in a developer for, the present invention has been completed.
That is, the present invention is as follows.

[1] In a toner produced by discharging a toner composition liquid in which a toner composition containing at least a binder resin precursor and a colorant is dissolved or dispersed in a solvent and / or a monomer from a through hole to form droplets, The toner composition liquid is supplied to the storage part, and the toner composition liquid is excited through the storage part by vibration means that contacts at least a part of the storage part, and the toner is discharged from a plurality of through holes provided in the storage part. The composition liquid is discharged into the granulation space, and the toner composition liquid is formed into droplets through a constricted state from a columnar shape, and at least during the droplet formation or after droplet formation, the binder resin precursor has a reaction in which the molecular weight increases ( The droplets are transformed into solid particles in the granulation space by performing any one of an extension reaction), a reaction in which molecular chains have a crosslinked structure (crosslinking reaction), and a reaction to form the solvent-insoluble component (gelation reaction). do it A toner obtained.
[2] The toner composition liquid includes a compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group compound as the binder resin precursor. ] The toner described in the above.
[3] The toner according to [2], wherein the active hydrogen group is a functional group selected from the group consisting of an amino group, a hydroxyl group, a mercapto group, a carboxyl group, and an organic group in which they are blocked. .
[4] The toner according to [2] or [3], wherein the reactive site of the polymer is an isocyanate group and / or an epoxy group.
[5] The toner according to any one of [2] to [4], wherein the polymer is a polymer selected from the group consisting of polyester, epoxy resin, and polyurethane. [2] to [2], wherein the content of the compound obtained by the elongation reaction and the crosslinking reaction of the polymer and the polymer in the binder resin in the toner is 5 to 50% by weight. [7] The toner according to [1], wherein the toner composition liquid contains at least a vinyl polymerizable monomer as a binder resin precursor and a polymerization initiator.
[8] The above [7], wherein the toner composition liquid is a toner composition liquid obtained by dissolving or dispersing a vinyl polymerizable monomer as the binder resin precursor in another polymerizable monomer. Toner.
[9] The toner according to [7] or [8], wherein the toner composition liquid further contains a crosslinkable monomer.
[10] The toner according to any one of [1] to [9], wherein the toner composition liquid further contains a polyester resin.
[11] The toner according to [10], wherein the polyester resin has a glass transition point of 35 to 65 ° C. [12] The content of the polyester resin in the binder resin in the toner is 50 to 50%. The toner according to [10] or [11], which is 95% by weight.
[13] The toner according to any one of [1] to [12], wherein the toner composition liquid further contains a release agent.
[14] The above-mentioned [13], wherein the release agent is at least one selected from the group consisting of a fatty acid ester compound having a melting point of 50 to 120 ° C., a polyethylene compound, a polypropylene compound and a paraffin compound. Toner [15] The toner according to any one of [1] to [14], wherein the toner has a glass transition point of 40 to 70 ° C.
[16] The toner according to any one of [1] to [15], wherein an amount of the THF insoluble matter (gel content) of the toner is 5 to 60% by weight.
[17] In the molecular weight distribution measured by GPC (gel permeation chromatography) of the THF-soluble component of the toner, at least one main peak is present in the region of molecular weight of 3.0 × 10 ^{3 to} 5.0 × 10 ^4. The toner according to any one of [1] to [16], which is characterized by comprising:
[18] The toner according to any one of [1] to [17], wherein a 1/2 outflow temperature Tm obtained by an elevated flow tester of the toner is 115 to 140 ° C.
[19] The particle size distribution (weight average particle diameter D4 / number average particle diameter Dn) is in the range of 1.00 to 1.05, according to any one of the above [1] to [18] toner.
[20] The toner according to any one of [1] to [19], wherein the weight average particle diameter D4 is 1 to 20 μm.

[21] A two-component developer comprising at least a carrier comprising the toner according to any one of [1] to [20] and magnetic particles.
[22] The electrostatic image on the electrostatic image carrier is developed with the developer described in [21] to form a toner image, and a transfer unit 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.
[23] The electrostatic image on the electrostatic image carrier is developed with the toner according to any one of [1] to [20] to form a toner image, and the surface of the electrostatic image carrier is transferred via a transfer material. An image forming apparatus, wherein the toner image is electrostatically transferred onto the transfer material by bringing a transfer means into contact therewith.
[24] 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. The image forming apparatus according to [22] or [23].
[25] In a process cartridge that integrally supports an electrostatic image carrier and at least one unit selected from 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. The toner is the toner according to any one of [1] to [20].

[26] Toner for producing toner particles by discharging a toner composition solution in which a toner composition containing at least a binder resin precursor and a colorant is dissolved or dispersed in a solvent and / or a monomer from a through hole to form droplets In the manufacturing method, the toner composition liquid is supplied to the storage section, and a plurality of through holes provided in the storage section are excited while the toner composition liquid is excited through the storage section by vibration means that contacts at least a part of the storage section. The toner composition liquid is discharged from the holes into the granulation space, and the toner composition liquid is formed into droplets from a columnar shape through a constricted state, and at least during the formation of the droplets or after the droplet formation, the binder resin precursor has a molecular weight. The droplets are granulated by performing any one of an increasing reaction (elongation reaction), a reaction in which molecular chains have a crosslinked structure (crosslinking reaction), and a reaction for forming the solvent-insoluble component (gelation reaction). In space Method for producing a toner and changing the body particle.
[27] The toner manufacturing method according to [26], wherein there are a plurality of the through holes per vibration means.
[28] The toner production method as described in [26] or [27], wherein the through hole is formed of a metal plate having a thickness of 5 to 50 μm and an opening diameter thereof is 3 to 35 μm.
[29] An air stream is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the droplets are transported in the solvent removal facility by the air stream, and the solvent in the droplets is removed during the transport. The toner production method according to any one of [26] to [28], wherein the toner particles are formed by forming the toner particles.
[30] The toner production method according to [29], wherein the dry gas is one of air and nitrogen gas.
[31] The toner production method as described in [29] or [30] above, wherein the temperature of the dry gas is 40 to 200 ° C.
[32] The solvent removal facility has a transport path whose periphery is covered with an electric field curtain charged to a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. The toner production method according to any one of [29] to [31].
[33] The toner production method as described in any one of [26] to [32], wherein the solid content of the toner composition liquid is 5 to 20% by weight.
[34] The toner according to any one of [26] to [33], wherein the toner composition liquid contains at least a vinyl polymerizable monomer as a binder resin precursor and a polymerization initiator. Production method.
[35] The toner composition liquid, wherein the toner composition liquid is obtained by dissolving or dispersing at least a first vinyl polymerizable monomer as the binder resin precursor in another polymerizable monomer. [34] The method for producing a toner according to [34].
[36] The toner production method according to [34] or [35], wherein the toner composition liquid contains a crosslinkable monomer together with the vinyl-based polymerizable monomer and the polymerization initiator.
[37] The above-mentioned [34] to [36], wherein the vinyl polymerizable monomer is at least one selected from the group consisting of a styrene monomer, an acrylate monomer, and a methacrylate ester monomer. The toner manufacturing method in any one.
[38] The polymerization start temperature of the polymerization initiator is 40 to 60 ° C., and the heating temperature in the polymerization step is the same as the polymerization start temperature of the polymerization initiator used. 34] to [37].
[39] The [26], wherein the toner composition liquid includes a compound having an active hydrogen group and a polymer having a site capable of reacting with the compound having an active hydrogen group as the binder resin precursor. ] To [33] The method for producing a toner according to any one of [33].
[40] The toner production method as described in any one of [26] to [39], wherein the toner composition liquid contains at least one polyester resin as a binder resin.
[41] The toner production method as described in any one of [26] to [40], wherein the toner composition liquid contains an organic solvent, and the toner composition liquid is solidified by removing the solvent.

According to the present invention, the conventional problems can be solved, the toner can be efficiently produced, the particles have excellent low-temperature fixability and offset resistance, and have a monodispersibility with an unprecedented particle size. Therefore, in many characteristic values required for toners such as fluidity and charging characteristics, there is no or very little fluctuation range due to particles seen in the conventional production methods, and offset resistance, A toner having heat-resistant storage stability and excellent in low-temperature fixability, a developer containing the toner, an image forming apparatus using the toner or developer, and a process cartridge containing the toner can be provided.
Specifically, there are no fluctuations due to particle variations observed in the conventional production methods for pulverized toners and chemical toners, or even extremely small fluctuations that are almost negligible. Has features. 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. In addition, since the gel content is formed after nozzle discharge, the productivity and particle uniformity due to nozzle clogging due to the gel content are not reduced at all, and the gel content is very evenly and finely dispersed in the toner. It is possible to provide an excellent toner having no variation in the thermal characteristics.

(Toner production method)
In the toner production method of the present invention, a toner composition liquid in which a toner composition containing at least a binder resin precursor and a colorant is dissolved or dispersed in a solvent and / or monomer is discharged from a through hole to form droplets. In the toner manufacturing method for manufacturing particles, the toner composition liquid is supplied to the storage section, and the toner composition liquid is excited through the storage section by vibration means that contacts at least a part of the storage section. The toner composition liquid is discharged into the granulation space through a plurality of through holes provided, and the toner composition liquid is formed into droplets from a columnar shape through a constricted state, and at least during or after the droplet formation, the binder resin precursor The body is allowed to perform any one of a reaction in which the molecular weight increases (elongation reaction), a reaction in which the molecular chain has a crosslinked structure (crosslinking reaction), and a reaction to form the solvent-insoluble component (gelation reaction). Droplet And wherein the changing to the solid particles in the granulation space.

(Toner production equipment)
An apparatus used in the toner manufacturing method of the present invention (hereinafter also referred to as “toner manufacturing apparatus”) is not particularly limited as long as it is an apparatus capable of manufacturing toner by the manufacturing method, and is appropriately selected. As a preferable toner manufacturing apparatus that can be used, for example, as shown in FIG. 2, at least a storage unit 1 that stores at least the toner composition liquid as the droplet forming unit, a vibrating unit 2, , A support means 3 for holding the vibration means 2, a plate having a plurality of through holes 4 provided at the bottom of the storage portion 1, and supplying the toner composition liquid discharged from the through holes 4 to the storage portion, A device having a liquid supply means 5 for discharging from the holes 4, a solvent removal facility 6 as the toner particle forming means, and a toner collecting portion 7 is preferably mentioned.

(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, as a result of deriving the conditions for forming stable uniform particles experimentally, uniform particles can be stably formed under the condition of the following formula (3). There is.
3.5 <λ / d (jet) <7.0 (3)
Furthermore, as explained in Non-Patent Document 3, 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 follows.
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 toner manufacturing apparatus 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. For example, as shown in FIG. 3, 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 and to provide the release valve 12 for removing 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.

(Solvent removal equipment)
The solvent removal equipment 6 is not particularly limited as long as the solvent of the droplets 13 can be removed. 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.
In addition, from the viewpoint of preventing the droplet 13 from adhering to the wall surface of the solvent removal (drying) facility 6, the solvent removal facility 6 was charged with a polarity opposite to the charge of the droplet. It is preferable that an electric field curtain is provided, a conveyance path whose periphery is covered with the electric field curtain is formed, and liquid droplets are allowed to pass through the conveyance path.

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.
The droplets need not be completely solidified in the solvent removal facility 6. It is only necessary that the surface of the droplets is solidified so that the droplets do not coalesce in the collection unit in the solvent removal facility 6 and can maintain a spherical shape. The solidification reaction may further proceed in the container to form solid particles.

(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.

  In the present invention, the reaction for increasing the molecular weight (extension reaction), the reaction in which the molecular chain has a crosslinked structure (crosslinking reaction), and the reaction for forming the solvent-insoluble component (gelation reaction) are carried out in the toner collecting unit 7. There is no problem even if it is done. In that case, the toner collecting part 7 may have a heating means for heating the inside of the toner collecting part 7 to a constant temperature, and the means is not particularly limited, but dry gas is used. This is preferable because the entire collected toner can be uniformly heated. The dry gas is not particularly limited, and the same dry gas as that used for solvent removal and toner collection described above can be used. For example, in the case of a reaction in which a monomer is polymerized using a polymerization initiator, the temperature of the dry gas is preferably equal to or higher than the polymerization start temperature of the polymerization initiator used for the polymerization reaction. Therefore, specifically, the temperature of the dry gas is preferably, for example, 40 to 200 ° C, more preferably 50 to 150 ° C, and particularly preferably 75 to 85 ° C.

(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.

(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 at least one of dissolved and dispersed, and can be appropriately selected and used. 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.
However, when the toner composition liquid contains a vinyl polymerizable monomer as a binder resin precursor and contains a polymerization initiator, the temperature of the toner composition liquid is kept below the polymerization start temperature of the polymerization initiator. It is preferable. Therefore, the polymerization initiator is more preferably added after preparing a toner composition liquid composed of a toner composition other than the polymerization initiator, and dissolved or dispersed at a temperature not higher than the polymerization start temperature of the polymerization initiator. .

(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 nozzle diameter), f: vibration frequency, 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 nozzle opening diameter regardless of the vibration frequency at which the droplets are 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 nozzle 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. In addition, these external additives may reduce the adhesion between toner particles during fixing, and may impair low-temperature fixability. Therefore, the toner of the present invention can obtain good fixing characteristics without being affected by the low temperature fixability by the external additive by adding a small amount or no external additive.

(toner)
The toner of the present invention is a toner produced by the production method described above, and a toner having a monodispersed particle size distribution is obtained.
Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.05. Moreover, as a weight average particle diameter, it is preferable that it is 1-20 micrometers.

The toner obtained by the toner manufacturing method can be easily redispersed, that is, floated in an air current by electrostatic repulsion effect. For this reason, the toner can be prepared and transported to the development area without using the transport means used in the conventional electrophotographic system. That is, even a weak air current has sufficient transportability, and the toner can be transported to the development area with a simple air pump and developed as it is. Development is so-called power cloud development, and since there is no disturbance in image formation due to airflow, extremely good electrostatic latent image development can be performed. Further, the toner of the present invention can be applied without any problem even if it is a conventional development system. At this time, members such as a carrier and a developing sleeve are simply used as a toner conveying unit, and there is no need to consider a frictional charging mechanism that has been conventionally shared in function. Accordingly, since the degree of freedom of the material is greatly increased, the durability can be greatly improved, an inexpensive material can be used, and the cost can be reduced.
The toner material that can be used in the present invention is not particularly limited as long as at least a binder resin precursor, a colorant, a solvent, and / or a monomer are used as raw materials, and the same toner material as that of a conventional electrophotographic toner can be used. That is, conventionally used binder resins, mold release agents, fluidity improvers, and external additives can be used.

(Toner composition liquid)
The toner composition liquid is formed by dissolving or dispersing a toner composition containing at least a binder resin precursor and a colorant in a solvent and / or a monomer.
In the present invention, the toner composition solution is subjected to a reaction in which the molecular weight increases (extension reaction), a reaction in which the molecular chain has a cross-linked structure (cross-linking), at least during or after droplet formation. It is important that the droplets change into solid particles in the granulation space by performing either a reaction) or a reaction that forms the solvent-insoluble component (gelation reaction).
As described above, when a resin component having a high molecular weight is dissolved and dispersed in the toner composition liquid from the beginning, the viscosity of the toner composition liquid increases, making it difficult to form the droplets, and clogging of the ejecting portion. However, as in the present invention, the binder resin precursor undergoes a reaction in which the molecular weight increases (extension reaction) or a reaction in which the molecular chain has a crosslinked structure, as in the present invention. (Crosslinking reaction) or solidification by a reaction forming a solvent-insoluble component (gelation reaction) eliminates the above-described problems, and the vibration means that comes into contact with a part of the storage section causes the storage section to pass through the storage section. A liquid droplet forming method in which the toner composition liquid is discharged from a plurality of through holes provided in the storage portion into the granulation space while exciting the toner composition liquid, and the toner composition liquid is formed into droplets from a columnar shape through a constricted state. To adopt It, it is possible to achieve a high degree of single dispersibility of the resulting toner.

For example, when a polymer having a site capable of reacting with a compound having an active hydrogen group is used as the binder resin precursor, the toner composition solution dissolves the binder resin precursor and the compound having an active hydrogen group in a solvent. Or obtained by dispersing. The solvent is removed in the particle forming step to obtain a toner.
In this case, the toner composition liquid preferably further contains polyester and a release agent.
The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the toner material, and can be appropriately selected according to the purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1 , 2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like, preferably an ester solvent, Ethyl acetate is particularly preferred. These may be used individually by 1 type and may use 2 or more types together.

  When a vinyl polymerizable monomer is used as the binder resin precursor, the toner composition liquid contains a vinyl polymerizable monomer and a polymerization initiator, and is formed into droplets of toner composition liquid or dried and solidified. By heating the product, the vinyl polymerizable monomer is polymerized to obtain a toner. The polymerization step may be performed any time after the toner composition liquid is formed into droplets, and there is no problem even if it is performed simultaneously with the solvent removal in the solvent removal equipment 6.

  A crosslinkable compound may be contained in the toner composition liquid. The crosslinkable compound increases the degree of crosslinking of the gel formed by polymerizing the binder resin precursor, and even if the amount of gel formed is small, the toner has offset resistance and heat resistant storage stability. There is an effect of improving. The amount of gel formed can be measured by measuring the amount of toner insoluble in THF (tetrahydrofuran). The amount of toner insoluble in THF is preferably 5 to 60% by weight. It is preferable for obtaining offset resistance and heat resistant storage stability. When it is less than 5% by weight, the low-temperature fixability is excellent but the offset resistance is deteriorated. On the other hand, when it is more than 60% by weight, the offset resistance and heat-resistant storage stability are excellent, but the low-temperature fixability is hindered. More preferably, it is 10 to 40% by weight, and particularly preferably 15 to 25% by weight.

The toner of the present invention has at least one molecular weight distribution in the region of molecular weight of 3.0 × 10 ^{3 to} 5.0 × 10 ⁴ in the molecular weight distribution measured by GPC (gel permeation chromatography) of the THF dissolved content of the toner. It preferably has a main peak. The molecular weight distribution mainly corresponds to the molecular weight distribution of the binder resin other than the gel content. If the molecular weight distribution has a main peak in the region of at least a molecular weight of 3.0 × 10 ^{3 to} 5 × 10 ⁴ , it is optimal without impairing the low-temperature fixability even if the toner contains a gel component. It is possible to maintain a good fixing characteristic. When the molecular weight distribution has a main peak at a molecular weight greater than 5 × 10 ⁴ , the toner cannot have sufficient low-temperature fixability, which causes fixing failure. Conversely, when the molecular weight distribution has a main peak at a molecular weight of less than 3.0 × 10 ³ , there are too many low molecular weight components, so that the gel content is not exerted, and offset resistance and heat resistant storage stability. Gets worse. The molecular weight range having a main peak is more preferably 5.0 × 10 ^{3 to} 2.0 × 10 ⁴ , and particularly preferably 5.0 × 10 ^{3 to} 1.7 × 10 ⁴ . The toner in the present invention preferably has a 1/2 outflow temperature Tm determined by an elevated flow tester of 115 to 140 ° C, more preferably 120 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.

  The toner composition liquid preferably has a solid content ratio of 5 to 20% by weight. If the solid content ratio is less than 5%, the productivity is inferior, and the particles are likely to coalesce, and the particle size uniformity may be lost. On the other hand, when the content is 20% by weight or more, there is a case where it is difficult to eject with a small particle size because the viscosity of the toner composition liquid is high. In addition, nozzle clogging may easily occur.

(Active hydrogen group-containing compound)
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction, a crosslinking reaction, or the like in the toner composition liquid.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) are preferred in that they can be increased in molecular weight by reactions such as elongation reaction and crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). is there.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

  Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, aliphatic diamines, and the like. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amine (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amine group (B) The mixing equivalent ratio of amino group [NH _x ] ([NCO] / [NH _x ]) is preferably 1/3 to 3/1, more preferably 1/2 to 2/1. Particularly preferred is /1.5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NH _x ]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is low. Thus, the hot offset resistance may be deteriorated.

(Polymer capable of reacting with active hydrogen group-containing compound)
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a heating medium for fixing. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and the like are preferable. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.

Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. In some cases, the low-temperature fixability may deteriorate.

  There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.

  Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

As a mixing ratio when reacting the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Fixability may deteriorate.

The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The mass average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4,000 to 30,000 is more preferable. When the mass average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml / min, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

(Vinyl polymerizable monomer and crosslinkable monomer)
A case where the binder resin precursor is a monomer and toner particles are formed by a polymerization reaction of the monomer will be described by taking as an example a case where a vinyl polymerizable monomer is used as the monomer.
In this case, the toner composition liquid contains a vinyl polymerizable monomer and a polymerization initiator, and the vinyl polymerizability can be obtained by heating the toner composition liquid formed into droplets or the toner obtained by particle formation. Toner particles are formed through a polymerization process in which the monomer is polymerized, and a gel is formed inside the toner. The gel component formed by the vinyl-based polymerizable monomer gives the toner excellent offset resistance and heat-preserving stability while having excellent mechanical strength. For this reason, the toner of the present invention causes little toner contamination on the developer carrying member, carrier, photoconductor, etc., and can provide a high-quality image for a long period of time extremely stably.

  The polymerization process may be performed at any time after the toner composition liquid is formed into droplets, and even if the polymerization process is performed simultaneously with the solvent removal in the solvent removal equipment 6, There is no problem even if it is done. The toner collected in the toner collecting unit 7 may be transferred to a separate heating device (not shown) and heated. The heating means is not particularly limited as long as the inside of the system can be maintained at a constant temperature, and an air flow heating apparatus using various gases obtained by heating air, nitrogen, carbon dioxide gas, combustion gas or the like is generally used. The heating temperature is preferably equal to or higher than the polymerization start temperature of the polymerization initiator used. However, when the polymerization initiator temperature is too higher than the glass transition temperature of the binder resin of the toner particles, the toner particles are aggregated and bonded. Accordingly, the polymerization initiation temperature is preferably 40 to 70 ° C, more preferably 40 to 60 ° C, although it depends on the polymerization initiation temperature of the polymerization initiator used and the glass transition temperature of the binder resin.

Further, the polymerization step may be performed simultaneously with the solvent removal in the solvent removal equipment 6 (primary polymerization), and further may be performed in the toner collecting unit 7 or transferred to the heating device (secondary polymerization). . In this case, the primary polymerization is preferable because the polymerization reaction proceeds moderately in the vicinity of the surface of the toner particles and an effect of suppressing the coalescence or aggregation of the toner particles in the toner collecting portion 7 is obtained.
Further, the polymerization step may be performed after an additive added to the toner particles for the purpose of improving fluidity is added to the surface of the toner particles. In this case, an additive on the toner surface is preferable because it prevents aggregation and coalescence of toner particles caused by heating in the polymerization step.

  The vinyl polymerizable monomer used in the present invention is not particularly limited, but those usually used can be appropriately selected and used. For example, styrene monomers, acrylic monomers, methacrylic monomers and the like can be mentioned. Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, 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, p -Styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or a derivative thereof.

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

  Examples of other monomers include the following (1) to (18). (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, etc. (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 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

  These vinyl polymerizable monomers can be used alone or in a mixture of two or more. Among these, it is preferable to use one or more monomers selected from styrene monomers, acrylate monomers, and methacrylate monomers. Acrylic acid ester monomers and methacrylic acid ester monomers are excellent in mechanical strength, have good affinity with recording media such as paper, and have excellent fixability. However, in consideration of charging characteristics, environmental stability, material dispersibility, etc., in particular, styrene monomers are used in combination with acrylate monomers, methacrylate monomers, or acrylate monomers and methacrylate monomers. Is particularly preferred.

  The addition amount of the vinyl polymerizable monomer is preferably in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the binder resin. When the amount is less than 5 parts by weight, the gel content in the toner is not sufficiently formed, and the offset resistance and the heat resistant storage stability are lowered. When the amount is more than 150 parts by weight, the amount of gel formed in the toner increases, which tends to inhibit low-temperature fixability or cause toner particles to coalesce in the polymerization process. More preferably, it is 10-65 weight part, Especially preferably, it is 18-35 weight part.

  In the toner of the present invention, a crosslinkable monomer that is a crosslinker having two or more vinyl groups may be used in combination with the vinyl polymerizable monomer. A gel component in which a high-order cross-linked structure is formed with the cross-linkable monomer imparts excellent offset resistance, heat-resistant storage stability, and mechanical strength to the toner in a small amount. Examples of the crosslinkable monomer include aromatic divinyl compounds and diacrylate compounds. Examples of the aromatic divinyl compound include 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. Examples include xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate 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, those obtained by replacing acrylate of these compounds with methacrylate, and the like.

  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 crosslinkable monomers are preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the vinyl polymerizable monomer. Among these crosslinkable monomers, from the viewpoint of fixing property and offset resistance, aromatic divinyl compounds (particularly divinylbenzene), diacrylate compounds linked by a bond chain containing one aromatic group and one ether bond are more. preferable.

(Polymerization initiator)
The polymerization initiator contained in the toner composition liquid used in the present invention is not particularly limited, but a commonly used radical polymerization initiator can be appropriately selected and used. Examples of the radical polymerization initiator include azo compound polymerization initiators and organic peroxide polymerization initiators.

  Examples of the azo compound polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2′-azobis. (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexane) Carbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′, 4′-dimethyl-4′-methoxyvalero Nitrile, 2,2′-azobis (2-methylpropane), 4,4′-azobis (4-cyanopentanoic acid), 2- (tert-butylazo) -4-methoxy-2,4-dimethyl Valeronitrile, 2- (tert-butylazo) -2,4-dimethylvaleronitrile, 4- (tert-butylazo) -4-cyanopentanoic acid, 2- (tert-butylazo) -isobutyronitrile, 2- (tert -Butylazo) -2-methylbutyronitrile, 1- (tert-amylazo) cyclohexanecarbonitrile, 1- (tert-butylazo) cyclohexanecarbonitrile, 1- (tert-butylazo) formamide, and the like.

  Examples of the organic peroxide polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- ( tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoy Peroxide, 2,4-dichlorobenzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di- Isopropyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert -Butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl perpivalate, tert-butyl peroxylaurate, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di-tert- Examples thereof include butyl peroxyhexahydroterephthalate and tert-butyl peroxyazelate.

  In addition, a polyfunctional polymerization initiator may be used. For example, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert- Butyl peroxyhexane, 2,5-dimethyl-2,5-di- (tert-butyl peroxy) hexyne-3, di-tert-butyl peroxy-diisopropylbenzene, 1,1-bis (tert-butyl Peroxy) -3,3,5-trimethyl-cyclohexane, n-butyl-4,4-di- (tert-butylperoxy) valerate, and the like. Further, a polyfunctional polymerization initiator having a polymerizable unsaturated group may be used, for example, diallyl peroxydicarbonate, tert-butyl peroxymaleic acid, tert-butyl peroxyallyl carbonate, tert-butyl. Peroxyisopropyl fumarate, and the like.

  The heating temperature in the polymerization process of the present invention depends on the activation energy of the polymerization initiator, that is, the polymerization start temperature. In particular, the polymerization initiation temperature of the polymerization initiator is preferably a temperature that is not higher than the glass transition temperature of the binder resin. When the polymerization initiation temperature is higher than the glass transition temperature of the binder resin, it causes the coalescence and aggregation of the toner particles in the polymerization step, and the monodispersity of the particle size distribution which is one of the advantages of the present invention. It is easily damaged. The polymerization initiation temperature is preferably 40 to 70 ° C, more preferably 40 to 60 ° C. Among the polymerization initiators described above as more preferable polymerization initiators, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2- (tert-butylazo) -4-methoxy-2,4-dimethylvaleronitrile, Examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl perpivalate, di-isopropyl peroxydicarbonate, and the like.

  The addition amount of the polymerization initiator depends on the type of the vinyl polymerizable monomer and the crosslinkable monomer and the polymerization initiator, but from the viewpoint of crosslinking efficiency, the total amount of the vinyl polymerizable monomer and the crosslinkable monomer. It is preferable to set it as the range of 0.03-3 weight part with respect to 100 weight part.

(resin)
The toner composition liquid may contain a binder resin as another component.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. Examples thereof include a polyester polymer, a styrene monomer, an acrylic monomer, and a methacrylic resin. Vinyl polymers such as monomers, copolymers of these monomers or two or more types, 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, etc. (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 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as 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 used as the binder resin of the toner 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), 4,4′-azobis (4-cyanopenta) Acid), 2- (tert-butylazo) -4-methoxy-2,4-dimethylvaleronitrile, 2- (tert-butylazo) -2,4-dimethylvaleronitrile, 4- (tert-butylazo) -4-cyano Pentanoic acid, 2- (tert-butylazo) -isobutyronitrile, 2- (tert-butylazo) -2-methylbutyronitrile, 1- (tert-amylazo) cyclohexanecarbonitrile, 1- (tert-butylazo) cyclohexane Carbonitrile, 1- (tert-butylazo) formamide, methyl ethyl ketone peroxide, acetylacetone peroxide, ketone peroxides such as cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert- Butyl hydropao Side, 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, 2,4-dichlorobenzoyl peroxide, m- Tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-isopropyl peroxydicarbonate , Di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxide Oxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperpivalate, tert-butylperoxylaurate, tert-butylperoxybenzoate, tert -Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl -Oxyhexahydroterephthalate, tert-butyl peroxyazelate, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxy Hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, di-tert-butylperoxy-diisopropylbenzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethyl-cyclohexane, n-butyl-4,4-di- (tert-butylperoxy) valerate, diallyl peroxydicarbonate, tert-butylperoxymaleic acid, tert-butylperoxyallyl And carbonate, tert-butyl peroxyisopropyl fumarate, etc. It is done.

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.

When the binder resin is a polyester-based resin, the molecular weight distribution of the THF-soluble component of the resin component has at least one peak in the region of a molecular weight of 3.0 × 10 ^{3 to} 5.0 × 10 ⁴ . It is preferable in terms of toner fixing properties and offset resistance. As a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and a molecular weight of 5,000 to 20,000 is preferable. Binder resins having at least one peak in the region are more preferable.

Further, 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 mg KOH / g to 70 mg KOH / g, and most preferably 0.1 mg KOH / g to 50 mg KOH / 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.
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 molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.
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 S (ml), a blank is measured at the same time, and the amount of KOH solution used at this time is B (ml), which is calculated by the following equation (1). However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

  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 70 ° 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.

In the present invention, the toner composition liquid may contain a magnetic material 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, (2) metals such as iron, cobalt, nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium. (3) and mixtures thereof are used.

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

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

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | 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.

(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 to be kneaded together with the production of the master batch or the master batch, for example, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and substituted polymers thereof, in addition to the above-described polyester resin; 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-chloro Methyl methacrylate copolymer, Len-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Examples thereof include acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-50 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 weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene conversion weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.
The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

<Release agent>
Moreover, in this invention, a mold release agent can be contained with binder resin and a coloring agent.
The mold release agent of the present invention is not particularly limited and can be appropriately selected from commonly used ones. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax , Aliphatic hydrocarbon waxes such as sazol 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 based on fatty acid esters such as animal waxes such as beeswax, beeswax, lanolin, spermaceti, mineral waxes such as ozokerite, ceresin and peteratum, montanate 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 mold release agent further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandic acid, eleostearic acid, Unsaturated fatty acids such as valinal acid, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long chain alkyl alcohol, polyhydric alcohols such as sorbitol, linoleic acid amide, Fatty acid amides such as olefinic acid amide and lauric acid amide, saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide, ethylene bisoleic acid amide, hexamethylene bisio Unsaturated fatty acid amides such as inamide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasinamide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

More preferable examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefins, polyolefins polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefins obtained by thermal decomposition of high molecular weight polyolefins, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
In addition, these release agents may be obtained by using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a liquid crystal deposition method, or a low molecular weight solid fatty acid. , Low molecular weight solid alcohol, low molecular weight solid compound, and other impurities are preferably used.
The melting point of the release agent is more preferably 50 to 120 ° C. in order to balance the fixability and the offset resistance. If it is less than 50 degreeC, blocking resistance may fall, and if it exceeds 120 degreeC, an offset-resistant 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 wax is preferably 50 to 120 ° C., more preferably 50 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, Can Delila wax, rice wax or montan wax and hydrocarbon-based wax Like a combination of.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak may be in the region of 50 to 120 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 50 to 120 ° 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.

(Other ingredients)
<Career>
The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.
Examples of the resin used in the coating material include styrene-acrylic ester copolymers, styrene-acrylic resins such as styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, and the like. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as a coating (coating) material for carriers such as an ionomer resin and a polyphenylene sulfide resin can be used.
These resins may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

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

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

Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.
Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.
Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. 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.

<Fluidity improver>
A fluidity improver may be added to the toner of the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm, as an average primary particle size.

The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, 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.

<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.

  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, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.

Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., the resulting material is mechanically adjusted, or the so-called spray-drying method is used to dissolve and disperse the toner material in a solvent in which the toner binder is soluble, and then using a spray-drying device. Examples thereof include a method of removing a solvent to obtain a spherical toner and a method of forming a spherical toner by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, 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 weight of the toner, and more preferably 0.01 to 2.0% by weight.

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

(Image forming device)
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 specified in the present invention 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 sheet feeding device 6 on the upstream side of the tandem 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 sheet 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 60, a developing device 61, and a primary transfer device around a drum-shaped photoconductor 40 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 defined in the present invention 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. 8 and 9A and 9B, the induction heating means 6 that heats the heating roller 1 by electromagnetic induction includes an exciting coil 7 that is a magnetic field generating means, and the exciting coil 7 is wound around. And a coil guide plate 8. 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 on the image, 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.

  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.

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

[Example 1]
(Production of toner composition dispersion and toner)
-Synthesis of unmodified polyester (low molecular weight polyester) resin-
An unmodified polyester resin as a binder resin was synthesized.
Bisphenol A ethylene oxide 2-mole adduct 67 parts by weight Bisphenol A propion oxide 3-mole adduct 84 parts by weight terephthalic acid 274 parts by weight Dibutyltin oxide 2 parts by weight The reaction was allowed to proceed at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize unmodified polyester resin 1.
The obtained unmodified polyester resin 1 had a number average molecular weight (Mn) of 3,100, a weight average molecular weight (Mw) of 12,000, and a glass transition temperature (Tg) of 50 ° C.

-Synthesis of prepolymer (polymer having a site capable of reacting with active hydrogen group)-
A prepolymer intermediate as a binder resin precursor was synthesized.
Bisphenol A ethylene oxide 2-mole adduct 682 parts by weight Bisphenol A propylene oxide 2-mole adduct 81 parts by weight Terephthalic acid 283 parts by weight Trimellitic anhydride 22 parts by weight Dibutyltin oxide 2 parts by weight The reaction vessel was charged with a nitrogen inlet tube and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an intermediate polyester.
The resulting intermediate polyester had a number average molecular weight (Mn) of 4,000, a weight average molecular weight (Mw) of 15,000, and a glass transition temperature (Tg) of 54 ° C.

Next, a prepolymer as a binder resin precursor was synthesized.
The intermediate polyester 411 parts by weight Isophorone diisocyanate 89 parts by weight Ethyl acetate 500 parts by weight or more was charged into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Prepolymer solution 1 was synthesized.
The free isocyanate content of the obtained prepolymer solution 1 was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

-Preparation of colorant dispersion-
A carbon black dispersion was prepared as a colorant.
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. Furthermore, the carbon black dispersion liquid which passed the filter (product made from PTFE) which has a 0.45 micrometer pore and was disperse | distributed to the submicron area | region was prepared.

-Preparation of dispersion with added resin and wax-
A dispersion having the following composition to which resin and wax were added was prepared.
Unmodified polyester resin 1 85 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 2610 parts by weight The above formulation was stirred for 10 minutes using a mixer having stirring blades, Dispersed. At this time, it was possible to completely prevent pigments and the like 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. This is designated as resin and wax dispersion 1.

-Preparation of toner composition dispersion-
Next, a toner composition dispersion was prepared.
Resin and wax dispersion 1 1000 parts by weight N-behenyl-1,3-propanediamine 0.27 parts by weight The above formulation was stirred for 1 minute using a mixer having stirring blades. Thereafter, 11 parts by weight of Prepolymer Solution 1 was added, and the mixture was further stirred with a mixer having a stirring blade for 1 minute. This is designated as Toner Composition Dispersion Liquid 1. The obtained dispersion was kept at a temperature of 20 to 28 ° C. under a nitrogen atmosphere.

-Preparation of toner-
The obtained toner composition dispersion 1 was supplied to the storage unit 1 of the toner manufacturing apparatus shown in FIG. The plate having the through-holes 4 used was prepared by processing femtosecond lasers into a perfectly circular discharge hole having a diameter of 8 μm on a nickel plate having a thickness of 20 μm.
After preparing the toner composition liquid, the liquid droplets were ejected under the following toner production conditions, and the liquid droplets were dried and solidified to produce a toner.
[Toner preparation conditions]
Dry air flow rate: Orifice sheath 2.0 L / min, In-apparatus air 3.0 L / min Dry air temperature: 40-42 ° C.
In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Nozzle frequency: 220 kHz

The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. The collected toner particles were stored in a high temperature bath at 50 ° C. for 3 hours. The obtained toner particles are referred to as toner base particles 1. When the particle size distribution of the toner base particles was measured with a particle size measuring device “Multisizer III” (manufactured by Beckman Coulter, Inc.), the mass average particle size D4 was 5.00 μm, and D4 / Dn was almost monodisperse. Some toner base particles.
Using a Henschel mixer, 100 parts by weight of the toner base particles obtained above, 0.6 parts by weight of hydrophobic silica (manufactured by Clariant Japan) as an external additive, and 0.2 parts by weight of hydrophobic titanium oxide (manufactured by Teica) are used. The toner was obtained by mixing and 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 for the 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 parts by weight of the toner prepared above with respect to 100 parts by weight of the carrier. Was charged by uniformly mixing at 48 rpm for 3 minutes using a type of tumbler mixer (made by Willy et Bacofen (WAB)) in which the container was rolled and stirred. In the present invention, 200 g of carrier and 14 g of toner were placed in an ointment bottle having an internal volume of 500 ml and mixed. This developer is referred to as developer 1.
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)
About the obtained toner, the particle size distribution, the charge amount distribution, the glass transition temperature (Tg), the THF insoluble matter (gel content) amount, the main peak of the molecular weight distribution of the THF soluble matter, and the 1/2 outflow temperature are measured. The measurement results are shown in Table 1. Further, the productivity of the obtained toner and the state of nozzle contamination after toner production were examined, and the results are shown in Table 1. The toner was measured for low-temperature fixability, offset resistance, heat-resistant storage stability, and carrier contamination, and the measurement results are shown in Table 2. 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.

<Charge amount distribution>
The charge amount distribution of the toner was measured by a charge amount distribution measuring device (E-Spart analyzer, EST-2 type manufactured by Hosokawa Micron). Specifically, the prepared developer is set in a measuring machine, and the toner released from the developer by air blowing at a constant pressure is fed to the toner suction port of the measuring machine by a certain amount, whereby the charge amount distribution is measured. . As an index indicating the distribution of the charge amount, the distribution is represented by the most frequent (peak) value [q / d] and the distribution width at the half height of the most frequent, so-called half width. As for the characteristics of the toner, it is desirable that the charge amount distribution is sharper, but generally the higher the charge amount, the larger the half-value width tends to be.

<Glass transition temperature (Tg)>
The glass transition temperature (hereinafter referred to as Tg) of each toner and toner resin was measured by the following method using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
First, about 5.0 mg of resin or toner (sample) was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC by the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, and the DSC curve was measured with the differential scanning calorimeter ("DSC-60"; Shimadzu Corporation make). From the obtained DSC curve, it calculated from the intersection of the tangent of the curve before the inflection point of the resin (or toner) and the curve after the inflection point using the analysis program in the DSC-60 system. At the same time, the melting point (Tp) of the release agent can be obtained from the peak value derived from the release agent.

<Amount insoluble in THF (gel content)>
The THF-insoluble component is a polymer gel component and mainly refers to a polymer component having a molecular weight of 10 ⁷ or more. 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 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.

<Molecular weight distribution main peak of THF soluble content>
The molecular weight distribution of the THF soluble content of the toner 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. Stabilize the column in a 40 ° C. heat chamber, flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of the resin prepared to a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight main peak of the toner, the molecular weight distribution of the sample is determined from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. calculate. 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.

<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. 11, 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 (manufactured by 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. At this time, it was confirmed that the height of the toner layer was 30 mm or more. The glass container containing the toner was tapped 100 times and then left in a thermostatic bath set at a temperature of 50 ° C. for 24 hours. Thereafter, the glass container was returned to room temperature, and the penetration of the toner layer in the glass container was measured based on a penetration test (JIS K2235-1991). In Table 2, from the good ones, ◎ when the penetration is 30 mm or more, ◯ when 25 mm to 29 mm, △ when 15 mm to 24 mm, × when 10 mm to 14 mm, and In the case of 9 mm or less, it showed by xx.

<Carrier contamination>
The carrier contamination property is a characteristic that serves as an index of toner carrier contamination. The higher the mechanical strength of the toner, the less the carrier contamination.
Specifically, as an evaluation method, the developed developer was used in an evaluation machine A described later, and after running 30,000 image charts of 50% image area in the single color mode, the developer was extracted, and the developer was removed. An appropriate amount was put in a gauge with a mesh having a mesh size of 32 μm, and air blowing was performed to separate the toner and the carrier. 1.0 g of the obtained carrier was put in a 50 ml glass bottle, 10 ml of methyl ethyl ketone (MEK) was added, shaken 50 times, and allowed to stand for 10 minutes. Thereafter, the supernatant MEK solution was placed in a glass cell, and the transmittance of the MEK solution was measured using a turbidimeter. Table 1 shows that the carrier contamination is good, the transmittance is 95% or more, ◎, 90-94% is ◯, 80-89% is △, 70-79. When it was%, it was indicated by x, and when it was 69% or less, it was indicated by x.

<Low-temperature fixability / offset resistance>
Using an evaluation machine A, which will be described later, a solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² is printed on plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>). A fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the 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.

<Toner productivity>
The amount of toner particles (mg / h) produced per hour is measured from one nozzle among the plurality of nozzles (through holes) provided in the toner composition liquid reservoir, and this is used as the toner. It was evaluated as productivity. 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.

<Nozzle dirt>
The toner manufacturing apparatus was continuously operated, and the contamination of the nozzles at the time when 500 g of toner particles were produced was evaluated. In Table 2, nozzles with no nozzle dirt or clogging are marked with ◎, and some dirt is attached to the nozzle, but those with no production problems are marked with ○, and some dirt is attached to the nozzle. Some of the nozzles are clogged with some nozzles, and some of the nozzles are dirty or clogged. The case where the particle size distribution was also deteriorated was indicated by x, and the case where the nozzle particle was severely clogged and the particle size distribution of the produced toner particles was deteriorated or could not be produced at all was indicated by xx.

(Evaluation of image quality 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 the present example and the 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.
As evaluation items, image granularity / sharpness, fine line reproducibility, image density unevenness, and background stain were evaluated. The evaluation results are shown in Table 2.
The following describes the image quality evaluation method.

<Image graininess and sharpness>
Using the evaluation machine A or B, C, and D, 10,000 photographic images were output in a monochromatic mode, and the degree of graininess and sharpness was visually evaluated. The degree is ◎ for offset printing, ◯ for slightly worse than offset printing, △ for slightly better than conventional electrophotographic images, and for conventional electrophotographic images. When it was worse than x and when it was worse than a conventional electrophotographic image, it was displayed as x.

<Thin wire reproducibility>
Using the evaluation machine A or B, C, and D, after running 30,000 image charts with 50% image area in monochromatic mode, a 600 dpi fine line image was output to Ricoh type 6000 paper, The degree of bleeding was compared with a stage sample. 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. When it was rank 5, it was indicated by ◎, when it was rank 4, it was indicated by ◯, when it was rank 3, it was indicated by △, when it was rank 2, it was indicated by ×, and when it was rank 1, it was indicated by xx.

<Image density unevenness>
Using the evaluation machine A, B, C, or D, after running 30,000 image charts with 50% image area in monochromatic mode, the entire solid image is output to a Ricoh type DX OHP sheet. The degree of density unevenness was compared with the stage sample, and was evaluated in five stages of ranks 1-5. Rank 5 has the least density unevenness, and rank 1 has the lowest density unevenness. When it was rank 5, it was indicated by ◎, when it was rank 4, it was indicated by ◯, when it was rank 3, it was indicated by △, when it was rank 2, it was indicated by ×, and when it was rank 1, it was indicated by xx.

<Skin dirt>
Using an evaluation machine A, B, C, or D, after running 10,000 image charts with a 5% image area in a monochromatic mode under an environment of 10 ° C. (humidity 15RH%), a thin line of a photosensitive member 600 dpi The image was output to Ricoh type 6000 paper, and the image density of the non-image area was measured with a colorimeter X-Rite 938 (manufactured by X-Rite). When the image density is less than 0.003, ◎, when 0.003 to 0.01, ◯, when 0.011 to 0.015, Δ, when 0.015 to 0.030, ×,. In the case of 031 or more, it is indicated by xx.

[Example 2]
In the preparation of the dispersion liquid to which the resin and wax of Example 1 were added, everything was the same as Example 1 except that the unmodified polyester resin 1 was not used and the addition amount of ethyl acetate was changed to 2620 parts by weight. Resin and wax dispersion 2 were prepared.
In the preparation of the toner composition dispersion liquid of Example 1, the resin and wax dispersion liquid 2 was used instead of the resin and wax dispersion liquid 1, and the amount of N-behenyl-1,3-propanediamine added was 1. A toner composition dispersion 2 was prepared in the same manner as in Example 1 except that 88 parts by weight and the addition amount of the prepolymer solution 1 were changed to 75.3 parts by weight.
All of the obtained dispersions were treated in the same manner as in Example 1 to obtain substantially monodispersed toner base particles 2 having a mass average particle diameter D4 of 5.00 μm and D4 / Dn of 1.02. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain Toner 2. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 3]
In the preparation of the dispersion liquid to which the resin and wax of Example 1 were added, everything was carried out except that the addition amount of the unmodified polyester resin 1 was changed to 50 parts by weight and the addition amount of ethyl acetate was changed to 2615 parts by weight. Resin and wax dispersion 3 were prepared in the same manner as in Example 1.
Further, in the adjustment of the toner composition dispersion liquid of Example 1, the resin and wax dispersion liquid 3 was used instead of the resin and wax dispersion liquid 1, and the addition amount of N-behenyl-1,3-propanediamine was set to 0. Toner composition dispersion 3 was prepared in the same manner as in Example 1 except that 93 parts by weight and the addition amount of prepolymer solution 1 were changed to 37 parts by weight.
All of the obtained dispersions were treated in the same manner as in Example 1 to obtain substantially monodispersed toner base particles 3 having a mass average particle diameter D4 of 5.00 μm and D4 / Dn of 1.01. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain toner 3. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 4]
In the preparation of the dispersion liquid to which the resin and wax of Example 1 were added, everything was carried out except that the addition amount of the unmodified polyester resin 1 was changed to 95 parts by weight and the addition amount of ethyl acetate was changed to 2605 parts by weight. Resin and wax dispersion 4 were prepared in the same manner as in Example 1.
Further, in the preparation of the toner composition dispersion liquid of Example 1, the resin and wax dispersion liquid 4 was used instead of the resin and wax dispersion liquid 1, and the amount of N-behenyl-1,3-propanediamine added was changed to 0.1. A toner composition dispersion 4 was prepared in the same manner as Example 1 except that 09 parts by weight and the addition amount of the prepolymer solution 1 were changed to 3.7 parts by weight.
All of the obtained dispersions were treated in the same manner as in Example 1 to obtain toner base particles 4 that were almost monodispersed with a mass average particle diameter D4 of 5.01 μm and D4 / Dn of 1.03. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain toner 4. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 5]
In the synthesis of the unmodified polyester resin of Example 1, the reaction was carried out at 230 ° C. for 4 hours under normal pressure, and then the reaction solution was changed to react for 2 hours under a reduced pressure of 10 to 15 mmHg. The unmodified polyester resin 2 was synthesized in the same manner as in Example 1.
The obtained unmodified polyester resin 2 had a number average molecular weight (Mn) of 1,500, a weight average molecular weight (Mw) of 4,500, and a glass transition temperature (Tg) of 42 ° C.
In addition, in the preparation of the dispersion liquid to which the resin and wax of Example 1 were added, everything was the same as Example 1 except that the unmodified polyester resin 2 was used instead of the unmodified polyester resin 1. The processed toner base particles 5 were almost monodispersed having a mass average particle diameter D4 of 5.00 μm and D4 / Dn of 1.02. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain toner 5. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 6]
In the synthesis of the prepolymer of Example 1, a prepolymer solution was prepared in the same manner as in Example 1 except that the addition amount of terephthalic acid was changed to 265 parts by weight and the addition amount of trimellitic anhydride was changed to 40 parts by weight. 2 was synthesized.
The intermediate polyester of the obtained prepolymer solution 2 had a number average molecular weight (Mn) of 5,200, a weight average molecular weight (Mw) of 21,000, and a glass transition temperature (Tg) of 65 ° C.
In addition, in the preparation of the toner composition dispersion liquid of Example 1, all treatments were performed in the same manner as in Example 1 except that the prepolymer solution 2 was used instead of the prepolymer solution 1, and the mass average As a result, toner base particles 6 having a substantially monodispersed particle size D4 of 5.00 μm and D4 / Dn of 1.01 were obtained. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain toner 6. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 7]
-Synthesis of styrene-acrylic resin-
First, a styrene-acrylic resin as a binder resin was synthesized.
Styrene monomer 60 parts by weight n-butyl acrylate monomer 30 parts by weight Acrylic acid monomer 10 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 carried out by mixing in a container and refluxing at 65 ° C. for 5 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 (Mn) of 6,000, a weight average molecular weight (Mw) of 26,600, and a glass transition temperature (Tg) of 61 ° C.
In the preparation of the dispersion liquid to which the resin and wax of Example 1 were added, all treatments were performed in the same manner as in Example 1 except that the styrene-acrylic resin 1 was used instead of the unmodified polyester resin 1. Thus, completely monodispersed toner base particles 7 having a mass average particle diameter D4 of 4.98 μm and D4 / Dn of 1.00 were obtained. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain toner 7. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 8]
-Preparation of dispersion with added resin and wax-
Next, a dispersion having the following composition to which a resin as a binder resin, a vinyl polymerizable monomer, and a wax were added was prepared.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 1 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Styrene monomer 8 parts by weight n-butyl methacrylate monomer 6 parts by weight Ethyl acetate 3340 parts by weight The above formulation was stirred and dispersed for 15 minutes using a mixer having stirring blades. At this time, it was possible to completely prevent pigments and the like from aggregating due to shock caused by solvent dilution. The dispersion liquid at this stage was filtered with a 0.45 μm filter (manufactured by PTFE), but no clogging was observed, and it was confirmed that all passed.
Next, while maintaining this dispersion at 20 to 28 ° C., 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) is added as a polymerization initiator, and a mixer having stirring blades is used. And stirred for 10 minutes to obtain a dispersion. This is designated as Toner Composition Dispersion Liquid 8. The obtained dispersion was kept at a temperature of 20 to 28 ° C. under a nitrogen atmosphere.

-Preparation of toner-
The obtained toner composition dispersion 8 was supplied to the storage unit 1 of the toner manufacturing apparatus shown in FIG. The plate having the through-hole 4 used was prepared by processing a perfect circular discharge hole with a diameter of 10 μm on a nickel plate with a thickness of 20 μm by processing with a femtosecond laser.
After preparing the toner composition liquid, the liquid droplets were ejected under the following toner production conditions, and the liquid droplets were dried and solidified to produce a toner.
[Toner preparation conditions]
Dry air flow rate: Orifice sheath 2.0 L / min, In-apparatus air 3.0 L / min Dry air temperature: 80-82 ° C.
In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Nozzle frequency: 220 kHz
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. The collected toner particles were stored in a high temperature bath at 50 ° C. for 3 hours. The obtained toner base particles are referred to as toner base particles 8. The toner base particles were substantially monodisperse toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.01. The obtained toner base particles were mixed with additives in the same manner as in Example 1 to obtain toner 8. Thereafter, a developer was prepared in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.

[Example 9]
In the preparation of the dispersion to which the resin and wax of Example 8 were added, styrene-acrylic resin 1 was used instead of unmodified polyester resin 3, and 2,2′-azobis (2,4-dimethylvaleronitrile) was added. Except that the amount was changed to 0.15 parts by weight, the toner was processed in the same manner as in Example 8 and was a substantially monodispersed toner having a mass average particle diameter D4 of 6.01 μm and D4 / Dn of 1.01. Base particles were obtained. The obtained toner base particles were mixed with additives in the same manner as in Example 8 to obtain toner 9. Thereafter, a developer was produced and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Example 10]
In the preparation of the dispersion liquid to which the resin and wax of Example 8 were added, the formulation was changed to the following formulation, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Styrene monomer 10 parts by weight n-butyl methacrylate monomer 4 parts by weight Divinyl Benzene 0.4 parts by weight Ethyl acetate 3350 parts by weight Next, while maintaining this dispersion at 20 to 25 ° C., 0.1 part by weight of tert-butyl perpivalate was added as a polymerization initiator, and a mixer having stirring blades was added. The resulting mixture was stirred for 10 minutes to obtain a dispersion. The resulting dispersion was kept at a temperature of 20-25 ° C. under a nitrogen atmosphere. The obtained dispersion was treated in the same manner as in Example 8 to obtain completely monodispersed toner base particles having a toner weight average particle diameter D4 of 6.01 μm and D4 / Dn of 1.00. It was. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is designated as Toner 10. Thereafter, a developer was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 11]
In the preparation of the dispersion to which the resin and wax of Example 8 were added, the polymerization initiator used was changed to 0.15 parts by weight of 2,2′-azobisisobutyronitrile, and was collected in the preparation of the toner. Except that the toner was changed to be stored in a high-temperature bath at 60 ° C. for 5 hours, it was treated in the same manner as in Example 8, and the toner had a mass average particle diameter D4 of 6.08 μm and D4 / Dn of 1.06. Thus, substantially monodispersed toner base particles were obtained. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is referred to as Toner 11. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Example 12]
In the preparation of the dispersion liquid to which the resin and wax of Example 8 were added, the formulation was changed to the following formulation, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Paraffin wax (melting point 72 ° C.) 5 parts by weight Styrene monomer 40 parts by weight n-butyl acrylate monomer 20 parts by weight Acrylic Acid 5 parts by weight Crosslinkable monomer (trade name MANDA / manufactured by Nippon Kayaku Co., Ltd.) 1.3 parts by weight Ethyl acetate 4770 parts by weight Next, while maintaining this dispersion at 20 to 28 ° C., 2, 2 as a polymerization initiator 0.8 parts by weight of '-azobis (2,4-dimethylvaleronitrile) was added and stirred for 10 minutes using a mixer having stirring blades to obtain a dispersion. The obtained dispersion was kept at a temperature of 20 to 28 ° C. under a nitrogen atmosphere. The obtained dispersion was treated in the same manner as in Example 8 to obtain substantially monodispersed toner base particles having a toner mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.01. . The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is referred to as Toner 12. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Example 13]
In the preparation of the dispersion liquid to which the resin and wax of Example 8 were added, the formulation was changed to the following formulation, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Paraffin wax (melting point 72 ° C.) 5 parts by weight Styrene monomer 90 parts by weight n-butyl acrylate monomer 45 parts by weight Acrylic Acid 15 parts by weight Crosslinkable monomer (trade name MANDA / manufactured by Nippon Kayaku Co., Ltd.) 1.5 parts by weight Ethyl acetate 7110 parts by weight Next, while maintaining this dispersion at 20 to 28 ° C., 2, 2 as a polymerization initiator 2.3 parts by weight of '-azobis (2,4-dimethylvaleronitrile) was added and stirred for 10 minutes using a mixer having stirring blades to obtain a dispersion. The obtained dispersion was kept at a temperature of 20 to 28 ° C. under a nitrogen atmosphere. The obtained dispersion was treated in the same manner as in Example 8 to obtain completely monodispersed toner base particles having a toner mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.00. It was. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is designated as Toner 13. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Example 14]
In the preparation of the dispersion liquid to which the resin and wax of Example 8 were added, the unmodified polyester resin 4 (Mw 6,800, Tg 45 ° C./manufactured by Sanyo Chemical Industries) was used instead of the unmodified polyester resin 3. Except for the above, the same processing as in Example 8 was carried out to obtain substantially monodispersed toner base particles having a mass average particle diameter D4 of 6.00 μm and D4 / Dn of 1.02. The obtained toner base particles were mixed with additives in the same manner as in Example 8 to obtain toner 14. Thereafter, a developer was produced and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.
[Example 15]
In Example 8, evaluation was performed in the same manner as in Example 8 except that evaluation of the toner physical properties and image quality was performed using the evaluation machine B instead of the evaluation machine A. The results are shown in Tables 1 and 2.

[Example 16]
In Example 8, evaluation was performed in the same manner as in Example 8 except that evaluation of the toner physical properties and image quality was performed using the evaluation machine C instead of the evaluation machine A. The results are shown in Tables 1 and 2.

[Example 17]
In Example 8, evaluation was performed in the same manner as in Example 8 except that evaluation of the toner physical properties and image quality was performed using the evaluation machine D instead of the evaluation machine A. The results are shown in Tables 1 and 2.

[Comparative Example 1]
In the preparation of the dispersion liquid of Example 8, the formulation was changed to the following, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 2960 parts by weight In Example 1, the toner was processed in the same manner as in Example 8 except that the collected toner was changed so as not to be stored in the high-temperature bath, and the toner had a mass average particle diameter D4 of 6.01 μm and D4 / Dn of 1.00. Some completely monodispersed toner base particles were obtained. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is designated as Toner 15. Thereafter, a developer was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Comparative Example 2]
In the preparation of the dispersion liquid of Example 8, the formulation was changed to the following, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 5
(Mw 59,000, Tg 60 ° C./Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 2960 parts by weight The toner was processed in the same manner as in Example 8 except that the collected toner was changed so as not to be stored in the high-temperature bath, and the mass average particle diameter D4 of the toner was 6.00 μm and D4 / Dn was 1.01. Almost monodispersed toner base particles were obtained. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is designated as Toner 16. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Comparative Example 3]
In the preparation of the dispersion liquid of Example 8, the formulation was changed to the following, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Unmodified polyester resin 6 (gel content)
(Mw 87,000 (however, THF-soluble Mw) / manufactured by Kao) 20 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 3500 parts by weight The toner was prepared in the same manner as in Example 8, except that the collected toner was changed so that the collected toner was not stored in the high-temperature tank. However, nozzle clogging occurred several minutes after the start of droplet discharge, and the target toner (toner 17) could not be produced.

[Comparative Example 4]
In the preparation of the dispersion liquid of Example 8, the formulation was changed to the following, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Styrene-acrylic resin 1 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 2960 parts by weight In the preparation of toner, the collected toner is stored in a high-temperature tank. The toner was processed in the same manner as in Example 8 except that the amount of toner particles was changed so that substantially monodispersed toner base particles having a toner weight average particle diameter D4 of 6.01 μm and D4 / Dn of 1.02 were obtained. It was. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is designated as Toner 18. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Comparative Example 5]
-Preparation of dispersion with added resin and wax-
A dispersion having the following composition to which resin and wax were added was prepared.
Unmodified polyester resin 1 85 parts by weight Prepolymer solution 1 30 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 130 parts by weight It stirred for 1 minute using the mixer which had. Next, using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), three passes were performed under the condition that the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled. After the dispersion, 0.75 parts by weight of N-behenyl-1,3-propanediamine was added, and the mixture was further stirred for 1 minute using a mixer having a stirring blade to prepare a resin and wax dispersion 19. .

-Preparation of aqueous medium phase-
An aqueous medium phase was prepared as a dispersion medium for the resin and wax dispersion.
Suspension of 10% by weight of tricalcium phosphate 265 parts by weight Sodium dodecylbenzenesulfonate 0.2 part by weight Ion exchange water 306 parts by weight The above formulation was put into a beaker and mixed and stirred using a mixer having stirring blades. And uniformly dissolved to prepare an aqueous medium phase.

-Preparation of emulsified slurry-
150 parts by weight of the aqueous medium phase is put in a container and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and 100 parts by weight of the resin and wax dispersion 19 are added thereto. And mixed for 10 minutes to prepare an emulsified slurry.

-Removal of organic solvent-
100 parts by weight of the emulsified slurry was placed in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

-Cleaning and drying-
After 100 parts by weight of the emulsified slurry from which the organic solvent had been removed was filtered under reduced pressure, 300 parts by weight of ion-exchanged water was added to the filter cake and mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes). After that, it was filtered. An operation of adding 300 parts by weight of ion-exchanged water to the obtained filter cake, mixing with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtering was further performed twice. 20 parts by weight of a 10% by weight aqueous sodium hydroxide solution was added to the obtained filter cake, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by weight of ion-exchanged water was added, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), and then filtered. Further, 20 parts by weight of 10 wt% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a final filter cake. .
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 24 hours, and sieved with a mesh of 75 μm to obtain toner base particles 20. The toner base particles 20 had a mass average particle diameter D4 of 5.00 μm and D4 / Dn of 1.13. The obtained toner base particles were mixed with additives in the same manner as in Example 1. This toner is referred to as Toner 19. Thereafter, a developer was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Comparative Example 6]
In the preparation of the dispersion liquid of Example 8, the formulation was changed to the following, and the mixture was stirred and dispersed for 15 minutes using a mixer having stirring blades as in Example 8.
Unmodified polyester resin 3
(Mw 28,600, Tg 51 ° C./manufactured by Sanyo Chemical Industries) 100 parts by weight Carbon black dispersion 30 parts by weight Carnauba wax (melting point 80 ° C.) 5 parts by weight Ethyl acetate 2960 parts by weight

-Preparation of toner-
In place of the apparatus used in Example 8, a storage unit for storing the dispersion liquid and a head unit capable of applying a piezoelectric pulse to the storage unit by expansion and contraction of the piezoelectric body and discharging droplets from the nozzles are provided. Then, after the droplets were discharged under the following toner production conditions, the toner was produced by drying and solidifying the droplets. The apparatus of Example 8 has a structure in which vibration is applied to the nozzle itself, whereas the apparatus of Comparative Example 6 is greatly different in that a piezoelectric pulse is applied to the dispersion liquid storage unit.
[Toner preparation conditions]
Dry air flow rate: Air in the apparatus 3.0 L / min Dry air temperature: 80 to 82 ° C
In-apparatus temperature: 27-28 ° C
Dry air (dew point temperature): -20 ° C
Piezoelectric pulse frequency: 20 kHz
The dried and solidified toner particles were collected by suction using a filter having 1 μm pores, and toner base particles having a wide particle size distribution with a mass average particle diameter D4 of 7.58 μm and D4 / Dn of 1.34 were obtained. . The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is referred to as Toner 20. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Comparative Example 7]
A dispersion added with resin and wax was prepared under the same conditions as in Example 8. The obtained dispersion was treated in the same manner as in Comparative Example 6, and the obtained dried and solidified toner particles were collected by suction with a filter having 1 μm pores. The collected toner particles were stored in a high-temperature bath at 50 ° C. for 3 hours, and toner base particles having a wide particle size distribution with a mass average particle diameter D4 of 7.32 μm and D4 / Dn of 1.38 were obtained. The obtained toner was mixed with an additive in the same manner as in Example 8. This toner is referred to as Toner 21. Thereafter, a developer was prepared and evaluated in the same manner as in Example 8. The results are shown in Tables 1 and 2.

[Comparative Example 8]
A dispersion to which a resin and wax were added was prepared under the same conditions as in Comparative Example 3. A toner was prepared from the obtained dispersion in the same manner as in Comparative Example 6. However, the target toner (toner 22) could not be produced because nozzle clogging occurred approximately 1 hour after the start of droplet ejection.

  As shown in Tables 1 and 2, the toner production method of the present invention makes it possible to produce a toner having a gel content without lowering productivity such as nozzle clogging. Furthermore, the toner obtained is very monodispersed and has excellent particle uniformity. In addition, the toner has both low-temperature fixability, offset resistance, and heat-resistant storage stability and excellent mechanical strength. Therefore, an image obtained by developing with the toner is extremely faithful to an electrostatic latent image. Excellent image quality can be obtained over a long period of time.

  The toner of the present invention is excellent in low-temperature fixability, hot offset resistance, heat-resistant storage stability, and has a monodispersibility with an unprecedented particle size. Develop electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. that have no or very little variation in particles due to the conventional manufacturing methods at many required characteristics. It can be used as a developer. Further, the toner can be produced with high efficiency by using the toner production method of the present invention.

It is explanatory drawing of the droplet formation phenomenon of a liquid column. 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. 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 an explanatory diagram illustrating an outline of an IH fixing device. FIG. 2 is an explanatory diagram illustrating an outline of an IH fixing device. It is a schematic explanatory drawing which shows an example of the process cartridge of this invention. It is the schematic of the flow curve obtained by an elevated flow tester.

Explanation of symbols

[FIG. 2], [FIG. 3] 1 reservoir 2 vibration means 3 support means 4 through hole 5 liquid supply means 6 solvent removal equipment 7 toner collecting part 8 piping 9 through hole holding mechanism 10 vibration generator 11 conductive wire 12 Release valve 13 Droplet 14 Drying means 15 About toner particles [FIG. 4] to [FIG. 7] 1 Photoconductor 2 Transfer device, Primary transfer device 3 Sheet transport belt s Sheet 4 Intermediate transfer member 5 Secondary transfer device 6 Paper feed Device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer member cleaning device 10 Endless belt-like intermediate transfer member 14, 15, 16 Support roller 10 Intermediate transfer member 17 Intermediate transfer member 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 Reversing device 30 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46 Paper feed path 47 Transport roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separation roller 53 Manual feed path 55 Switching claw 56 Ejection roller 57 Ejection tray 61 Development device 62 Primary transfer device 63 Photoconductor cleaning device 64 Static elimination device 65 Developer on development sleeve 68 Agitation 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 Light 160 charging device 200 feeder table 300 scanner 400 ADF (ADF)
[FIG. 8], [FIG. 9] 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 (41)

  In the toner manufactured by discharging a toner composition liquid, in which a toner composition containing at least a binder resin precursor and a colorant is dissolved or dispersed in a solvent and / or monomer, from a through hole to form droplets, the toner composition The toner composition liquid is supplied 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 supplies the liquid to the storage section and contacts at least a part of the storage section. Release into the granulation space, the toner composition liquid is formed into a droplet from a columnar shape through a constricted state, and at least during or after the formation of the droplet, the binder resin precursor has a molecular weight increasing reaction (extension reaction) The droplets are converted into solid particles in the granulation space by performing either a reaction in which the molecular chain has a crosslinked structure (crosslinking reaction) or a reaction to form the solvent-insoluble component (gelation reaction). Is Toner, characterized in that.   2. The toner according to claim 1, wherein the toner composition liquid includes a compound having an active hydrogen group and a polymer having a site capable of reacting with the compound having the active hydrogen group as the binder resin precursor. .   The toner according to claim 2, wherein the active hydrogen group is a functional group selected from the group consisting of an amino group, a hydroxyl group, a mercapto group, a carboxyl group, and an organic group in which they are blocked. The toner according to claim 2, wherein the reactive site of the polymer is an isocyanate group and / or an epoxy group.   The toner according to claim 2, wherein the polymer is a polymer selected from the group consisting of polyester, epoxy resin, and polyurethane.   The content of the compound having an active hydrogen group and the component obtained by elongation reaction and crosslinking reaction of the polymer in the binder resin in the toner is 5 to 50% by weight. Item 6. The toner according to any one of Items 2 to 5   The toner according to claim 1, wherein the toner composition liquid contains at least a vinyl polymerizable monomer as a binder resin precursor and a polymerization initiator.   The toner according to claim 7, wherein the toner composition liquid is a toner composition liquid obtained by dissolving or dispersing a vinyl polymerizable monomer as the binder resin precursor in another polymerizable monomer.   The toner according to claim 7, wherein the toner composition liquid further contains a crosslinkable monomer.   The toner according to claim 1, wherein the toner composition liquid further contains a polyester resin.   The toner according to claim 10, wherein the polyester resin has a glass transition point of 35 to 65 ° C.   The toner according to claim 10 or 11, wherein the content of the polyester resin in the binder resin in the toner is 50 to 95% by weight.   The toner according to claim 1, wherein the toner composition liquid further contains a release agent.   The toner according to claim 13, wherein the release agent is at least one selected from the group consisting of a fatty acid ester compound having a melting point of 50 to 120 ° C., a polyethylene compound, a polypropylene compound, and a paraffin compound.   The toner according to claim 1, wherein the toner has a glass transition point of 40 to 70 ° C.   The toner according to claim 1, wherein the toner has a THF-insoluble content (gel content) of 5 to 60% by weight. In the molecular weight distribution measured by GPC (gel permeation chromatography) of the THF-soluble component of the toner, the toner has at least one main peak in the region of molecular weight of 3.0 × 10 ^{3 to} 5.0 × 10 ^4. The toner according to claim 1.   The toner according to any one of claims 1 to 17, wherein a 1/2 outflow temperature Tm obtained by an elevated flow tester of the toner is 115 to 140 ° C.   The toner according to claim 1, wherein the particle size distribution (weight average particle diameter D4 / number average particle diameter Dn) is in the range of 1.00 to 1.05.   The toner according to claim 1, wherein the weight average particle diameter D4 is 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 21 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 24. The image forming apparatus according to Item 22 or 23.   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 for manufacturing toner particles, a toner composition liquid in which a toner composition containing at least a binder resin precursor and a colorant is dissolved or dispersed in a solvent and / or monomer is discharged from a through hole to form droplets. The toner composition liquid is supplied to the storage portion, and the toner composition liquid is excited through the storage portion by vibration means that contacts at least a part of the storage portion, and the plurality of through holes provided in the storage portion A reaction in which the toner composition liquid is discharged into the granulation space, the toner composition liquid is formed into droplets from a columnar shape through a constricted state, and at least during the droplet formation or after the droplet formation, the binder resin precursor increases in molecular weight. (Extension reaction), a reaction in which the molecular chain has a cross-linked structure (cross-linking reaction) and a reaction to form the solvent-insoluble component (gelation reaction) are performed, and the droplets are solidified in the granulation space. particle Method for producing a toner and changing.   27. The toner manufacturing method according to claim 26, wherein there are a plurality of the through holes per vibration means.   28. The toner manufacturing method according to claim 26, wherein the through hole is formed of a metal plate having a thickness of 5 to 50 [mu] m, and an opening diameter thereof is 3 to 35 [mu] m.   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 manufacturing method according to claim 26, wherein toner particles are formed.   30. The toner manufacturing method according to claim 29, wherein the dry gas is one of air and nitrogen gas.   The toner production method according to claim 29 or 30, 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 electric field curtain charged to a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. The toner production method according to any one of 29 to 31.   The method for producing a toner according to any one of claims 26 to 32, wherein the solid content of the toner composition liquid is 5 to 20 wt%.   34. The method for producing a toner according to claim 26, wherein the toner composition liquid contains at least a vinyl polymerizable monomer as a binder resin precursor and a polymerization initiator.   35. The toner composition liquid according to claim 34, wherein the toner composition liquid is obtained by dissolving or dispersing at least a first vinyl polymerizable monomer as the binder resin precursor in another polymerizable monomer. Toner production method.   36. The toner manufacturing method according to claim 34 or 35, wherein the toner composition liquid contains a crosslinkable monomer together with the vinyl polymerizable monomer and the polymerization initiator.   37. The toner according to claim 34, wherein the vinyl polymerizable monomer is at least one selected from the group consisting of a styrene monomer, an acrylate monomer, and a methacrylate ester monomer. Production method.   The polymerization start temperature of the polymerization initiator is 40 to 60 ° C, and the heating temperature in the polymerization step is the same as the polymerization start temperature of the polymerization initiator used. The toner production method according to any one of the above.   34. The toner composition liquid according to claim 26, wherein the toner composition liquid contains a compound having an active hydrogen group and a polymer having a site capable of reacting with the compound having an active hydrogen group as the binder resin precursor. A method for producing the toner according to any one of the above.   40. The toner manufacturing method according to claim 26, wherein the toner composition liquid contains at least one polyester resin as a binder resin.   41. The toner manufacturing method according to claim 26, wherein the toner composition liquid contains an organic solvent, and the toner composition liquid is solidified by removing the solvent.

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