JP2008065005A - Electrostatic charge image development toner, and method for producing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner particles having low temperature fixability and hot-offset resistance, and also having the uniform dispersibility of particle sizes. <P>SOLUTION: In the method for producing toner where a toner composition liquid obtained by dissolving and/or dispersing a toner composition at least comprising a resin, a coloring agent and one or more kinds of inorganic particulates into a solvent is ejected from through holes, and is converted into droplets, so as to produce toner particles, the toner composition liquid is fed to a storage part, and, while exciting the toner composition liquid by a vibration means at least in contact with the storage part via the storage part, the toner composition liquid is ejected from a plurality of the through holes provided at the storage part into a granulation space, the toner composition liquid is passed through a columnar state into a constricted state, so as to be converted into droplets, and the droplets are changed into solid particles in the granulation space, so as to produce the toner. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  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.

  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.

  On the other hand, an electrophotographic toner comprising at least one or more inorganic fine particles inside the toner base particles is disclosed, and the inorganic fine particles added internally to the toner particles are uniformly present inside the particles. In this way, the presence of inorganic fine particles inside the particles can stabilize the charging characteristics and prevent the external additive from being buried, thereby improving the fluidity and improving the offset resistance. It is known that it can be made (refer patent document 2).

  As an alternative toner manufacturing method, 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 3). Further, a method has been proposed in which thermal droplets in the nozzle are used to form fine droplets, which are then dried and solidified to form a toner (see Patent Document 4). Furthermore, a method for performing the same processing using an acoustic lens has been proposed (see Patent Document 5). 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.

Using a toner material containing a thermosetting resin or UV curable resin as a dispersoid, a dispersion finely dispersed in a dispersion medium is intermittently ejected as droplets from a nozzle, and then the droplets are aggregated and thermally cured. A method of stabilizing the particle formation by curing a resin or a UV curable resin or a method of solidifying droplets has also been proposed (Patent Documents 6 to 10). However, these methods also have low productivity and are insufficient in terms of monodispersibility as in Patent Documents 1 to 4. Moreover, although resin is hardened after particle | grain formation, the subject regarding the fixing characteristic as mentioned above was not solved.
In the case of the granulation method described in Patent Documents 6 to 10 described above, the vibration part is in direct 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.

  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. Further, when the toner composition liquid contains inorganic fine particles, there is a problem that the particle size distribution is not sharp and the nozzles are easily clogged with inorganic fine particles.

JP-A-7-152202 International Publication No. 2004/086149 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. Due to the possessed particles, 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, electrophotography, It is an object of the present invention to provide a method for producing a toner used as a developer for developing an electrostatic charge image in electrostatic recording, electrostatic printing or the like.

The present inventors supply a toner composition liquid containing a toner composition containing at least a resin and a colorant to a storage part, and the toner composition liquid is passed through the storage part by vibration means that contacts a part of the storage part. The toner composition liquid is discharged into a granulation space from a plurality of through-holes provided in the reservoir, and the toner composition liquid is converted into droplets from a columnar shape through a constricted state. It has been found that a toner having excellent monodispersibility can be produced by changing to solid particles. In this method, the entire storage part having the through hole is excited by a single vibration means, so that the raw material fluid discharged from the through hole provided in the storage part is equally vibrated and pressure-concentrated. Since it is possible to generate waves, it is possible to simultaneously generate 100 or more droplet formation phenomena by one vibration means, and this makes it possible to prevent various problems such as blockage of the through-hole portion, productivity, and stability. The problem can be solved, particles, particularly toners can be produced efficiently, and the particles having a monodispersibility with an unprecedented particle size are required for toners such as fluidity and charging characteristics. Develops electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc., which have no or very little variation in the characteristic values due to particles seen in conventional manufacturing methods. It is useful as a method for producing a toner to be used in order for the developer. By using this production method, the present invention has been completed by finding that even when the toner composition liquid contains inorganic fine particles, the particle size distribution is sharp and the through-holes are not clogged with inorganic fine particles.
Means for solving the problems are as follows.

[1] A toner composition solution in which a toner composition containing at least a resin, a colorant, and one or more kinds of inorganic fine particles is dissolved and / or dispersed in a solvent is discharged from a through-hole to form droplets to produce toner particles. In the toner manufacturing method, the toner composition liquid is supplied to the storage unit, and a plurality of units provided in the storage unit are excited while the toner composition liquid is excited through the storage unit by vibration means that contacts at least a part of the storage unit. The toner composition liquid is discharged into the granulation space from the through-holes, and the toner composition liquid is changed from a columnar shape to a droplet through a constricted state, and the droplet is changed into solid particles in the granulation space to produce a toner. And a method for producing the toner.
[2] The method for producing a toner according to [1], wherein the total amount of inorganic fine particles determined by X-ray fluorescence analysis is 0.1 to 50 wt% with respect to the toner composition.
[3] The method for producing a toner according to [1] or [2], wherein the inorganic fine particles are produced using an organosol body.
[4] The method for producing a toner according to [1] to [3], wherein the solvent is removed from the droplets to form solid particles.
[5] The method for producing a toner according to [4], wherein the solvent is an organic solvent.
[6] The method for producing a toner according to [1] to [5], wherein a solid content ratio of the toner composition liquid is 5 to 20% by weight.
[7] The toner manufacturing method according to [1] to [6], wherein a plurality of the through holes are present for each of the vibration means.
[8] The toner manufacturing method as described in [1] to [7], wherein an opening diameter of the through hole is 1 to 40 μm.
[9] The toner production method according to [1] to [8], wherein the liquid droplets discharged from the through holes are given a positive charge or a negative charge by induction charge.
[10] An air stream is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the air stream causes the droplets to be transported in a solvent removal facility, and the solvent in the droplets is removed during the transport. The toner production method according to any one of [1] to [9], wherein the toner particles are formed.
[11] The toner production method according to [10], wherein the dry gas is either air or nitrogen gas.
[12] The toner production method according to [11], [12], wherein the temperature of the dry gas is 40 to 200 ° C.
[13] An electrostatic charge image developing toner produced by the toner production method according to any one of [1] to [12].
[14] The electrostatic image developing toner according to [13], wherein the particle size distribution (volume average particle size / number average particle size) is in the range of 1.00 to 1.05.
[15] The toner for developing an electrostatic charge image according to [13], [14], wherein the volume average particle diameter is 1 to 20 μm.

  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 toner such as fluidity and charging characteristics, there is no or very little variation due to particles as seen in conventional manufacturing methods. Electrophotography, electrostatic recording Further, it is possible to provide a toner used as a developer for developing an electrostatic charge image in electrostatic printing or the like.

[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 resin, a colorant, and one or more kinds of inorganic fine particles is dissolved and / or dispersed in a solvent is discharged from a through hole to form droplets. In the toner manufacturing method for manufacturing toner particles, the toner composition liquid is supplied to the storage part, and the toner composition liquid is stored while being excited through the storage part by vibration means that contacts at least a part of the storage part. The toner composition liquid is discharged into a granulation space through a plurality of through holes provided in the section, and the toner composition liquid is formed into droplets from a columnar shape through a constricted state, and the droplets are changed into solid particles in the granulation space. A toner is obtained.

[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. A storage unit that stores a toner composition solution in which a toner composition containing at least a resin, a colorant, and one or more kinds of inorganic fine particles is dissolved and / or dispersed in a solvent; and at least a part of the storage unit The toner composition liquid is discharged into the granulation space through a plurality of through holes provided in the storage portion while exciting the toner composition liquid through the storage portion, and the toner composition liquid is constricted from the columnar shape. A toner manufacturing apparatus comprising: vibration means for forming droplets; and toner particle forming means for drying the droplets to form toner particles by removing the solvent contained in the droplets discharged into the granulation space. It is preferable that.
As the preferred toner manufacturing apparatus, for example, as shown in FIG. 1, at least a storage unit 1 that stores at least the toner composition liquid as the droplet forming unit, a vibrating unit 2, and the vibrating unit are held. A supporting means 3 having a plurality of through holes 4, a liquid supply means 5 for supplying the toner composition liquid discharged from the through holes to the reservoir and releasing it from the through holes, and the toner particle formation A device having a solvent removal facility 6 and a toner collecting unit 7 as means is preferably mentioned.

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. In addition, for example, as shown in FIG. 2, a structure provided with a mechanism 9 that holds a plate having a through-hole connected by a pipe 8 that supplies a liquid to the reservoir is desirable. Moreover, the vibration means 2 which vibrates the whole storage part is in contact with the said storage part. The vibration means is connected to the vibration generator 10 and the conductive wire 11 and is preferably controlled. In order to stably form the liquid column, it is preferable to adjust the pressure in the reservoir or to provide the release valve 12 for removing the bubbles inside.

(Vibration means)
It is preferable that the vibration means 2 excites the whole storage part having the through hole by one vibration means.
The vibrating means is in contact with a part of the reservoir and applies vibrations to the raw material fluid via the reservoir, so that the raw material fluid discharged from the through hole provided in one reservoir is collectively equivalent. Since it is possible to generate a pressure density wave by applying vibration, it is possible to simultaneously generate 100 or more droplet forming phenomena by one vibration means.
The vibrating means 2 for applying vibration to the storage unit 1 is not particularly limited as long as it can provide reliable vibration at a constant frequency, and can be appropriately selected and used. For example, it is preferable that the through hole is vibrated at a constant frequency by expansion and contraction of the piezoelectric body.
The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, it is expanded and contracted by applying a voltage, and the through hole can be vibrated by the expansion and contraction.

Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). Generally, since the amount of displacement is small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The fixed frequency is not particularly limited and may be appropriately selected according to the purpose. However, 100 kHz to 10 MHz is preferable, and 200 kHz to 2 MHz is preferable from the viewpoint of generating micro droplets having a very uniform particle diameter. More preferred.
The vibration means 2 is in contact with the storage portion, and the storage portion holds a plate having a through hole, and the vibration means and the plate having the through hole uniformly vibrate the liquid column generated from the through hole. From the viewpoint of giving, it is most preferable that they are arranged in parallel, and even if deformation occurs in the vibration process, it is desirable that the relationship be maintained within an inclination of 10 °.
Even if only one through hole 3 is provided, particle production is possible. However, from the viewpoint of efficiently generating micro droplets having a very uniform particle diameter, a plurality of through holes 3 are provided and liquid discharged from each through hole is provided. The droplets are preferably dried with one solvent removal facility, in the example shown, the solvent removal facility 5.

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

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

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

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

(electrode)
An electrode can be provided as a member for charging 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 there is no particular limitation on the shape thereof, and can be selected as appropriate. For example, the electrodes are preferably formed in a ring shape.
The charging method using the electrode is not particularly limited, but a constant charge amount can always be given to the droplet 13 discharged from the through hole. It is preferable to give a positive charge or a negative charge. More specifically, it is preferable that the dielectric charging is performed by passing the droplet between a pair of electrodes to which a DC voltage is applied. It has already been proved that droplets in an air stream are in a highly charged state by electrospray method or fine particle production by electrostatic spraying. In this case, it is possible in principle to maintain a charge amount higher than the charge to the solid from the effect of reducing the surface area of the droplet by evaporation of the volatile component, and it is possible to obtain solid particles with higher charge.

(Solvent removal equipment)
The solvent removal equipment 6 is not particularly limited as long as the solvent of the droplets 13 can be removed, but an air flow is generated by flowing a dry gas in the same direction as the droplet 11 discharge direction. The toner particles 6 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.

(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. be able to.
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.

(Toner collecting part)
The toner collecting unit 7 is a member provided at the bottom of the toner manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner.
The structure of the toner collecting portion 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, using the dry gas to form the flow of the dry gas, and the toner particles are transferred to the toner storage container by the flow of the dry gas. It is preferable to transport it.
As the transfer method, as in the illustrated example, the toner particles 15 may be pumped to the toner storage container by a dry gas, 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.
Further, from the viewpoint of more efficiently transporting the toner particles 15, it is more preferable that the toner collecting portion 7 and the toner collecting container are formed of a conductive material and are connected to the ground. preferable. The toner manufacturing apparatus preferably has an exposure specification.

(Droplet)
As described above, the droplet 13 is generated by discharging a toner composition liquid containing a specific substance from the through-hole 4 provided in the storage unit 1 oscillated at a constant frequency. The toner material will be described in a separate “toner” section.
The toner composition liquid is not particularly limited as long as the toner material is 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. Specifically, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin may be melt-kneaded with a colorant or the like and finely pulverized, or obtained during the production. The kneaded product may be once dissolved in an organic solvent in which the resin component is soluble and then processed as fine droplets.

(Function)
According to the toner production method of the present invention described in detail above, the number of droplets generated from the through hole 4 is very large, tens of thousands to several million per second, and more discharge holes are provided. It is also easy to do. In addition, it can be said to be the most suitable method for producing toner from the viewpoint of obtaining a very uniform droplet diameter and sufficient productivity. Further, in this production method, the particle diameter of the toner finally obtained can be accurately determined by the following calculation formula (1), and there is almost no change in the particle diameter depending on the material used.

〔a formula〕
Dp = (6QC / πf) ^(1/3) (1)
Where Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow rate and through-hole diameter), f: vibration frequency, and C: volume concentration of solid content.
The toner particle diameter can be accurately calculated only by the above formula (1), but more simply can be obtained by the following formula (2).
〔a formula〕
Solid content volume concentration (volume%) = (solid particle diameter / droplet diameter) ³ (2)

That is, the diameter of the toner particles obtained by the present invention is twice the opening diameter of the through hole regardless of the vibration frequency at which the droplet is ejected. Therefore, the target solid particle diameter can be obtained by obtaining and adjusting the solid content concentration in advance from the relationship of the above formula (2). For example, when the through-hole diameter is 7.5 μm, the droplet diameter is 15 μm. Therefore, if the solid content volume concentration is 6.40% by volume, 6.0 μm solid particles can be obtained. In this case, the vibration frequency is preferably higher from the viewpoint of productivity, but Q (liquid flow rate) is determined from the calculation formula (1) according to the vibration frequency determined here.
In the conventional manufacturing method, the particle size often varies greatly depending on the material used. In this manufacturing method, the particle size as set is controlled by managing the droplet diameter and solid content concentration at the time of discharge. It becomes possible to continuously obtain particles having a diameter.

  Further, since the toner obtained by the present invention has a very uniform particle size, the fluidity in the toner base is very high. Therefore, even when an external additive is added for the purpose of reducing the adhesive force to a manufacturing apparatus or the like, the effect can be exhibited in an extremely small amount. Considering the deterioration of external additives due to stress and the safety of fine particles to the human body, it is preferable not to use such external additives as much as possible, which is also an advantage of the present invention. 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 (volume average particle size / number average particle size) of the toner is preferably in the range of 1.00 to 1.05. Moreover, as a volume 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 it contains at least a resin and a colorant, and further contains at least one kind of inorganic fine particles. The same toner material as that of a conventional electrophotographic toner can be used. That is, a toner binder such as a polyester resin, a styrene acrylic resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner particles can be produced by drying and solidifying into fine droplets by the toner production method.
It is also possible to obtain a target toner by drying and solidifying a liquid obtained by dissolving or dispersing a kneaded material obtained by hot-melting and kneading the above materials in various solvents into fine droplets by the toner production method. is there.

[Toner composition liquid]
The toner composition liquid is formed by dissolving or dispersing at least a resin and a colorant in a solvent.
The toner composition liquid is preferably prepared by dissolving or dispersing the toner material in the organic solvent. The organic solvent is removed by the particle forming step.
The organic 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 are preferable, and ester solvents are preferable. Ethyl acetate is particularly preferred. These may be used individually by 1 type and may use 2 or more types together.
The toner composition liquid preferably has a solid content ratio of 5 to 20%. 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. If it is 20% or more, since the viscosity of the toner composition liquid is high, ejection with a small particle size may be difficult. In addition, nozzle clogging may easily occur.

(resin)
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. 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.

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.

When the binder resin is a polyester resin, the toner has fixability and offset resistance because at least one peak exists in the molecular weight range of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. More preferable is a binder resin.
When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. Most preferably, it is g-50 mgKOH / g.
In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

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

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

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

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

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

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | 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 particle 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 is 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. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

In addition, these 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, since the function separation effect tends to be easily exhibited, the melting point of at least one wax is preferably 50 to 120 ° C, and more preferably 50 to 100 ° C.

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.

(Inorganic fine particles)
In the present invention, the toner composition liquid contains at least one kind of inorganic fine particles. By containing the inorganic fine particles used in the present invention inside the toner, the charging characteristics of the toner base can be stabilized, and a decrease in charging ability due to long-time toner stirring in the developing machine can be suppressed.
The inorganic fine particles exposed on the toner base surface not only prevent the external additive from being buried, but also function as a lubricant and exhibit excellent fluidity.

As the inorganic fine particles in the present invention, for example, silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, Metal oxides such as samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy Calcium carbonate, light calcium carbonate, metal carbonate such as zinc carbonate, barium carbonate, dosonite, hydrotalcite, metal sulfate such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, Metal silicates such as leh, talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes, metal nitrides such as aluminum nitride, boron nitride, silicon nitride, titanic acid Metal titanates such as potassium, calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metals such as tricalcium phosphate Examples thereof include metal sulfides such as phosphate and molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, and other inorganic fine particles.
Of these, metal oxides are preferable, and silica, alumina, and titania are more preferable.

Further, as the inorganic fine particles in the present invention, layered inorganic mineral fine particles obtained by modifying at least a part of ions between layers of the layered inorganic mineral with organic ions can be used.
A layered inorganic mineral refers to an inorganic mineral formed by superposing layers having a thickness of several nanometers, and modifying means introducing an organic ion into ions existing between the layers. Specifically, it is described in JP-T-2006-500605, JP-T-2006-503313, and JP-A-2003-202708. This is called intercalation in a broad sense. As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By doing so, the hydrophilicity becomes high, and it is easily deformed during granulation, dispersed and refined, and the charge adjusting function is sufficiently exhibited. Such a modified inorganic mineral is refined and deformed during the production of the toner, and is particularly present in the surface portion of the toner particles, so that it performs a charge control function and contributes to low-temperature fixing. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 5% by weight.

The modified layered inorganic mineral used in the present invention is desirably one having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.
Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates or phosphates are raised. A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 5% by weight.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) is, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
Formula (1) R ₁ (OR ₂ ) _n OSO ₃ M
[Wherein, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]
By using a modified layered inorganic mineral, the toner phase and / or the oil phase containing the toner composition precursor has a non-Newtonian viscosity in the production process of the toner having moderate hydrophobicity, and the toner is deformed. Can be

The inorganic fine particles used in the present invention may be resin particles composed of inorganic fine particles and a resin described in JP-A-2005-49858.
The resin particles have a volume average particle diameter of 3 to 10 μm and a shape factor (SF-2) of 110 to 300, and are composed of a resin (a) and inorganic fine particles (b), and from at least a part of (b) The outer shell layer (S). Here, containing (b) is a state in which (b) exists in the interior from the surface of the resin particles (A). When (b) is exposed to the outside of the resin particles (A) or adsorbed to the surface of (A), the surface and bulk properties of (A) are predominantly the properties of (b), and the resin (a ) Is less likely to be exhibited. On the contrary, when (b) is contained in the particles, the characteristics of (a) are easily developed. That is, (a) is present on the surface of (A), and the outer shell layer (S) also has a portion occupied by (a), so that the low-temperature fixability is improved. When (A) contains a wax, the wax oozes out from the portion occupied by (a) described above at the time of thermal fixing, so that the hot offset resistance is improved.
The content of (b) in (A) is preferably 0.01 to 50%, more preferably 0.05 to 45%, and particularly preferably 0.1 to 40%.
In (b), the one forming the outer shell layer (S) is expressed as (b *), and the content of (b *) in (A) is preferably 0.01 to 20%, more preferably 0.8. 05 to 18%, particularly preferably 0.1 to 15%.
Further, the ratio of (b *) in (b) is preferably 10% or more, more preferably 20% or more.

The inorganic fine particles used in the toner of the present invention are those that have been surface treated with a hydrophobizing agent. As the hydrophobic treatment agent, for example, 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 and the like are preferable surface treatment agents. It is done. A sufficient effect can be obtained even when a silicone oil is used as a hydrophobizing agent and subjected to a surface treatment.
The inorganic fine particles used in the toner of the present invention are preferably hydrophobized as described above, and the degree of hydrophobicity by methanol titration is preferably 15 to 55%.
The degree of hydrophobicity was measured by the following method. First, 50 ml of ion-exchanged water and 0.2 g of a sample are placed in a beaker, and methanol is added dropwise while stirring. Next, as the methanol concentration in the beaker increases, the external additive gradually settles, and the mass fraction of methanol in the mixed solution of methanol and water at the end point when the total amount of the additive has settled is expressed as the degree of hydrophobicity (%). did.

Further, the silica used in the present invention is preferably used in the form of an organosol. In order to obtain an organosol of silica, for example, a silica hydrogel dispersion synthesized by a wet method (hydrothermal synthesis method, sol-gel method, etc.) is hydrophobized with a surface treatment agent, and water is treated with methyl ethyl ketone, The method of substituting with organic solvents, such as ethyl acetate, is mentioned.
As a specific method for producing the organosol, for example, the method described in JP-A-11-43319 can be preferably used.
By mixing the organosilica sol obtained as described above in the toner oil phase, silica can be dispersed in the toner oil layer in a state of high dispersion stability.

In addition, the dispersion method of the inorganic fine particles containing silica described above and internally added in the toner is not particularly limited, and a known method can be applied. For example, the following dispersion method can be used.
(1) A method in which a binder resin and inorganic fine particles are melt-kneaded with a kneader in the presence of a solvent and / or a dispersing agent as required to obtain a master batch in which the inorganic fine particles are dispersed in the binder resin.
(2) A method in which inorganic fine particles are dissolved or suspended in a solvent together with a binder resin as necessary, and then mechanically wet pulverized or crushed by a disperser.
(3) A method of adding and mixing inorganic fine particles synthesized in a solvent.
(4) A method in which inorganic fine particles dispersed in water are subjected to a wet treatment by adding a treating agent, and then an organosol substituted with a solvent is added and mixed.
Among these, from the viewpoint of dispersion stability, a method in which inorganic fine particles dispersed in water are wet-treated by adding a treating agent, and then a solvent-substituted organosol is added and mixed is preferable.

By making the content of the inorganic fine particles in the toner base particles 0.1 to 50 wt%, preferably 0.5 to 10 wt% with respect to the toner, the effects of the present invention can be further exhibited. When the addition amount is within this range, the toner base can have good charging characteristics, and there is an effect of preventing the charging ability from being lowered due to burying or liberation of the external additive at the time of toner strong stirring deterioration. Further, the inorganic fine particles exposed on the toner surface can sufficiently exhibit the effect as a lubricant and can have excellent fluidity.
If it is smaller than this range, it will be difficult to exhibit sufficient charging ability and fluidity, and if it is larger than this range, the amount of inorganic fine particles exposed on the toner surface will increase, not only deteriorating the circularity of the toner particles. Inorganic fine particles act as a fixing inhibitor, and the minimum fixing temperature is increased, so that the low-temperature fixing property is impaired.

  The content of inorganic fine particles in the toner base particles is determined by fluorescent X-ray analysis. A calibration curve is prepared by fluorescent X-ray analysis using toner base particles in which the content of inorganic fine particles is clear in advance, and the content of inorganic fine particles in the toner base particles is obtained by fluorescent X-ray analysis using the calibration curve. . For example, ZSX-100E manufactured by Rigaku Corporation can be used as the fluorescent X-ray apparatus. Further, when two or more kinds of inorganic fine particles were used, the total of the analysis values of the inorganic fine particle content was used as the inorganic fine particle content in the toner base particles.

(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.

<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.

  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.

  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]
(Preparation of toner composition liquid)
-Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 1,800, a weight average molecular weight (Mw) of 4,800, and a glass transition temperature (Tg) of 50 ° C.

-Synthesis of prepolymer (polymer having a site capable of reacting with active hydrogen group)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The obtained intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized. This is designated Prepolymer Solution 1.
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-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 15 parts by mass and pigment dispersant 3 parts by mass were primarily dispersed in 82 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Further, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
Next, a dispersion liquid having the following composition to which a resin as a binder resin and a wax were added was prepared.
100 parts by mass of the unmodified polyester resin as a binder resin, 30 parts by mass of the carbon black dispersion, and 5 parts by mass of carnauba wax are mixed with 1000 parts by mass of ethyl acetate, as in the preparation of the colorant dispersion. Using a mixer, the mixture was stirred for 10 minutes and dispersed. It was possible to completely prevent pigments from aggregating due to shock caused by solvent dilution. The dispersion liquid at this stage was filtered with a 0.45 μm filter (made by PTFE) in the same manner as in the preparation of the colorant dispersion liquid, but it was confirmed that no clogging occurred and all passed. The electrolytic conductivity of this dispersion was 3.5 × 10 ⁻⁷ S / m. This is designated as resin and wax dispersion 1.

-Preparation of toner composition liquid-
To 1000 parts by mass of the obtained resin and wax dispersion, 0.6 parts by mass of inorganic fine particles (organosilica sol MEK-ST-UP (ER = 20%), manufactured by Nissan Chemical Co., Ltd.) are added, and TK homomixer (special Mix by machine). The rotation speed of the mixer is preferably in the range of 5000 to 12000 rpm, and the time is preferably about 5 to 20 minutes. Further, 0.75 parts of N-behenyl-1,3-propanediamine was added as an active hydrogen group-containing compound, and the mixture was stirred for 1 minute using a mixer, and then 30 parts by mass of prepolymer solution 1 was added. The mixture was stirred with a mixer having a stirring blade for a minute. This is designated as Toner Composition Liquid 1.

-Preparation of toner-
The obtained dispersion was further diluted with ethyl acetate so that the solid content was 6.0%, and the liquid was supplied to the storage unit 1 of the toner production apparatus shown in FIG. The used plate having through-holes is a concentric circle having a through-hole of 8.0 μm in a perfect circle formed on a nickel plate having a thickness of 20 μm by removal processing (laser ablation) by a mask reduction projection method using a femtosecond laser. Individually produced. The portion where the through-hole was present was a square area with a side of 0.5 mm.
After the dispersion was prepared, droplets were formed under the following toner production conditions, and then the droplets were dried and solidified to produce a toner.
[Toner preparation conditions]
Dispersion solid content: 6.0%
Liquid flow rate: 400 ml / hr
Dry air flow rate: Sheath 2.0 L / min, Air in device 20 L / min Temperature in device: 27-28 ° C
Dew point temperature: -20 ° C
Common liquid chamber vibration frequency: 601.0 kHz
The dried and solidified toner particles were collected by a cyclone to obtain toner base particles 1 of Example 1. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn was 1 A toner base particle having a number average particle size of 6.0 μm and 0.02 μm was obtained in 2 hours. An optical micrograph of the obtained particles is shown in FIG.

[Example 2]
The same procedure as in Example 1 was conducted except that 3 parts by mass of inorganic fine particles (organosilica sol MEK-ST-UP (ER = 20%), manufactured by Nissan Chemical Co., Ltd.) to be added in the “preparation of toner composition” was used. Toner base particles 2 of Example 2 were prepared.
[Example 3]
The same procedure as in Example 1 was conducted except that 50 parts by mass of the inorganic fine particles (organosilica sol MEK-ST-UP (ER = 20%), manufactured by Nissan Chemical Co., Ltd.) to be added at the “preparation of toner composition” was used. Toner base particles 3 of Example 3 were prepared.
[Example 4]
The same procedure as in Example 1 was performed except that 500 parts by mass of inorganic fine particles (organosilica sol MEK-ST-UP (ER = 20%), manufactured by Nissan Chemical Co., Ltd.) to be added at the time of “preparing the toner composition liquid” was used. Toner base particles 4 of Example 4 were prepared.

[Example 5]
The toner base particles 5 of Example 5 were prepared in the same manner as in Example 1 except that 10 parts by mass of hydrophobic fine titanium oxide (MT-150AFM, manufactured by Teica) was added as an inorganic fine particle to be added in the “preparation of toner composition”. Created.
[Example 6]
3 parts by weight of inorganic fine particles (organosilica sol MEK-ST-UP (ER = 20%), manufactured by Nissan Chemical Co., Ltd.) and hydrophobic titanium oxide (MT-150AFM, taker) to be added in the “preparation of toner composition” Product) Toner base particles 6 of Example 6 were prepared in the same manner as in Example 1 except that the amount was 0.6 parts by mass.
[Example 7]
In “Synthesis of prepolymer (polymer having a site capable of reacting with active hydrogen group)”, an intermediate polyester having Mn = 5,200, Mw = 21,000, Tg = 65 ° C. was synthesized and used instead. A toner base particle 7 of Example 7 was produced in the same manner as in Example 1 except that.
[Example 8]
In Example 1, the amount of ethyl acetate added in the “preparation of toner composition” was 1760 parts, and the diameter of the through hole was changed to 8 μm in the “preparation of toner”. Toner base particles 8 of Example 8 were prepared.

[Comparative Example 1]
Comparison was made in the same manner as in Example 1 except that 0 part by mass of inorganic fine particles (organosilica sol MEK-ST-UP (ER = 20%), manufactured by Nissan Chemical Co., Ltd.) to be added in the “preparation of toner composition liquid” was compared. Toner base particles 9 of Example 1 were prepared.

-External additive treatment-
With respect to 100 parts by mass of the obtained toner base particles of Examples 1 to 8 and Comparative Example 1, 1.0 part by mass of hydrophobic silica (“H2000”, manufactured by Clariant Japan) as an external additive was added to a Henschel mixer (Mitsui). The toners of Examples 1 to 8 and Comparative Example 1 were manufactured by performing 5 cycles of mixing at a peripheral speed of 30 m / s for 30 seconds and resting for 1 minute, and sieving with an opening of 35 μm mesh.

[Comparative Example 2]
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.
-Preparation of toner-
A storage unit for storing the dispersion liquid used in Example 1 and a head unit capable of applying a pressure pulse to the storage unit by expansion and contraction of the piezoelectric body and thereby discharging the liquid substance as droplets from the nozzle are provided. The apparatus of Comparative Example 2 is significantly different from the structure of Example 1 in that the piezoelectric element is in direct contact with the nozzle part and the pressure pulse generated by the expansion and contraction of the piezoelectric body vibrates the nozzle part itself. Except for the difference in the droplet forming portion, the toner was prepared by discharging the droplet under the same toner preparation conditions as in Example 1 and drying and solidifying the droplet. Further, the number of nozzles of the droplet discharge section used in this comparative example was 500 as in the first embodiment.
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The volume average particle size was 4.8 μm and Dv / Dn was 1.32. The toner base particles had a wide distribution. The production amount per hour was 24.8 g. An optical micrograph of the obtained particles is shown in FIG.

Next, a carrier was produced as follows.
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”, 5 parts by mass of r- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added, and the mixture was mixed with a homomixer for 20 minutes. A magnetic layer was prepared by coating the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluidized bed coating apparatus.
5 parts by mass of each of the toners of Examples 1 to 8 and Comparative Example 1 that have been treated with the external additive and 95 parts by mass of the carrier are ball mill mixed to produce the two-component developers of Examples 1 to 8 and Comparative Example 1. did.

[Evaluation methods]
(Evaluation item)
(1) Measurement of content of inorganic fine particles in toner base particles The content of inorganic fine particles in the toner base particles in the present invention can be measured by the following method. A calibration curve is prepared by fluorescent X-ray analysis using toner base particles in which the content of inorganic fine particles is clear in advance, and the content of inorganic fine particles in the toner base particles is obtained by fluorescent X-ray analysis using the calibration curve. . For example, ZSX-100E manufactured by Rigaku Corporation can be used as the fluorescent X-ray apparatus. Further, when two or more kinds of inorganic fine particles were used, the total of the analysis values of the inorganic fine particle content was used as the inorganic fine particle content in the toner base particles.

(2) Volume average particle diameter and measurement of (Dv / Dn) Volume average particle diameter (Dv) and number average particle diameter (Dn) can be measured by a Coulter counter method. Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter of the toner can be obtained.

  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; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

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

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

(4) Charging rising property (TA15)
Under an environment of a temperature of 20 ° C. and a humidity of 50%, 100 parts of the carrier and 5 parts of the toner of the present invention were charged into a stainless steel pot and rotated and mixed at 300 rpm on a ball mill stand. The developer was stopped 15 seconds after the start of rotation, and the charge amount of the resulting developer was measured with a blow-off device.

(5) Saturation chargeability (TA600)
The chargeability of the developer material after 10 minutes was measured with a blow-off device in the same manner as in the charging start-up.

(6) Glass transition temperature (Tg) The glass transition temperature (hereinafter referred to as Tg) of each toner and toner resin is determined by the following method using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). It was measured by.
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. The results are shown in Table 1.

(7) Toner fluidity A powder tester (PT-N type, manufactured by Hosokawa Micron) is loaded with meshes of 75 μm, 45 μm, and 22 μm openings in order from the top, and 2 g of the toner base is put on the uppermost 75 μm mesh. Then, a vibration of 1 mm in the vertical direction was applied for 10 seconds, and the fluidity (cohesion degree) of the toner base was calculated from the residual amount of toner on each mesh.
Aggregation degree (%) = (5 × (remaining toner amount (g) on 75 μm mesh))
+ 3 × (residual toner amount on 45 μm mesh (g))
+ (Residual toner amount on 22 μm mesh (g))) × 10
When the degree of aggregation was 8% or less, ◎, when it was 8 to 16%, ◯, when it was 16 to 25%, Δ, and when it was 25% or more, ×.

(8) Image density After running 150,000 image charts of 50% image area in monochromatic mode using Ricoh's imgio Neo 450, the solid image was output to 6000 paper manufactured by Ricoh, and the image density was set to X Measurement was performed by -Rite (manufactured by X-Rite). This was performed for four colors alone, and the average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

(9) Image granularity and sharpness Using a Ricoh imagio Neo 450, a photographic image was output in a single color, and the degree of granularity and sharpness was visually evaluated. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.

(10) Fixing property Using a RICOH Imagio Neo 450, a plain image and a cardboard transfer paper (Ricoh, Type 6200 and NBS Ricoh copy printing paper <135>), a solid image of 0.85 ± 0.1 mg / Fixing evaluation was performed with a toner adhesion amount of cm ² . A fixing test was performed by changing the temperature of the fixing belt, and an upper limit temperature at which hot offset did not occur on plain paper was defined as an upper limit fixing temperature. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The upper limit fixing temperature was ◎ for 190 ° C or higher, ○ for 190-180 ° C, △ for 180-170 ° C, and x for 170 ° C or lower. The lower limit fixing temperature was ◎ for 135 ° C. or less, ◯ for 135 to 145 ° C., Δ for 145 to 155 ° C., and × for 155 ° C. or more. Table 1 shows the characteristics of the toners used, and Table 2 shows the evaluation results of these toners.

  As shown in Table 2, according to the present invention, the toner fluidity, the image density, the image graininess / sharpness, the fixing minimum temperature, the hot offset occurrence temperature are excellent, and the toner can be efficiently converted into a toner. . Further, it has been found that an image obtained by developing using the toner produced in the present invention is extremely excellent in image quality faithful to an electrostatic latent image and can greatly reduce power consumption.

  The toner of the present invention is excellent in toner fluidity, image density, image graininess / sharpness, minimum fixing temperature and hot offset generation temperature, and has a monodispersibility with a particle size never seen before. Therefore, in many of the characteristic values required for the toner, such as fluidity and charging characteristics, there is no or very little variation in the particle size observed in the conventional production methods. Electrophotography, electrostatic recording, electrostatic It can be used as a developer for developing an electrostatic image in printing or the like. Further, the toner can be produced with high efficiency by using the toner production method of the present invention.

It is explanatory drawing of an example of the toner particle manufacturing apparatus for implementing this invention. It is explanatory drawing of an example of the storage part in this invention. It is a figure explaining the droplet formation phenomenon of a liquid column. 3 is a view showing a micrograph of the toner obtained in Example 1. FIG. 6 is a micrograph of the toner obtained in Comparative Example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Storage part 2 Vibration means 3 Support means 4 Through-hole 5 Liquid supply means 6 Solvent removal equipment 7 Toner collection part 8 Piping 9 Through-hole holding mechanism 10 Vibration generator 11 Conductive wire 12 Release valve 13 Droplet 14 Drying means 15 Toner particle

Claims (15)

  Toner production in which a toner composition liquid in which a toner composition containing at least a resin, a colorant, and one or more kinds of inorganic fine particles is dissolved and / or dispersed in a solvent is discharged from a through hole to form droplets. In the method, the toner composition liquid is supplied to the storage portion, and a plurality of through holes provided in the storage portion are excited while the toner composition liquid is excited through the storage portion by vibration means that contacts at least a part of the storage portion. Further, the toner composition liquid is discharged into a granulation space, the toner composition liquid is changed from a columnar shape into droplets through a constricted state, and the toner is manufactured by changing the droplets into solid particles in the granulation space. A method for producing toner.   The method for producing a toner according to claim 1, wherein the total amount of inorganic fine particles obtained by X-ray fluorescence analysis is 0.1 to 50 wt% with respect to the toner composition.   The method for producing a toner according to claim 1, wherein the inorganic fine particles are produced using an organosol body.   The toner production method according to claim 1, wherein the solvent is removed from the droplets to form solid particles.   The method for producing a toner according to claim 4, wherein the solvent is an organic solvent.   The toner production method according to claim 1, wherein a solid content ratio of the toner composition liquid is 5 to 20% by weight.   The toner manufacturing method according to claim 1, wherein there are a plurality of the through holes per vibration means.   The toner manufacturing method according to claim 1, wherein an opening diameter of the through hole is 1 to 40 μm.   The toner manufacturing method according to claim 1, wherein a positive charge or a negative charge is given to the droplets discharged from the through holes by induction charge.   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 1, wherein toner particles are formed.   The toner manufacturing method according to claim 10, wherein the dry gas is one of air and nitrogen gas.   The toner manufacturing method according to claim 11 or 12, wherein the temperature of the dry gas is 40 to 200 ° C.   An electrostatic image developing toner produced by the method for producing a toner according to claim 1.   14. The electrostatic image developing toner according to claim 13, wherein the particle size distribution (volume average particle size / number average particle size) is in the range of 1.00 to 1.05. The toner for developing an electrostatic charge image according to claim 13 or 14, wherein the toner has a mass volume average particle diameter of 1 to 20 µm.