JP2009020349A - Method for producing toner, toner and developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing toner, capable of efficiently producing a toner without clogging of an injection part, and to provide the toner usable in an image forming apparatus using a fixing heat roller having no oil application mechanism. <P>SOLUTION: The method for producing toner comprises quantitatively supplying a toner composition liquid containing at least a binder resin and a coloring agent to a storage part; discharging the toner composition liquid through a plurality of through-holes provided in the storage part while exciting the toner composition liquid through the storage part by a vibration means which is partially in contact with the storage part to form droplets thereof through a columnar state and a constriction state, and changing the droplets to solid particles in a granulation space. The toner composition liquid is obtained through a master batch process for preliminarily dispersing at least the coloring agent and a first resin to form a master batch and a toner composition liquid producing process for preparing the toner composition liquid from at least the master batch and a toner material containing the binder resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  Conventionally, as a developer used in an electrophotographic image forming apparatus, a magnetic toner and a non-magnetic toner such as a two-component developer composed of a carrier and a toner, or a one-component developer that does not require a carrier are known. It has been. For the toner used in these developers, a production method by a polymerization method such as a suspension polymerization method or an emulsion polymerization aggregation method is used. In addition, a method for producing a developer accompanied by volume shrinkage called a polymer dissolution suspension method is also known.

As a toner production method different from these production methods, a so-called “new granulation method” (hereinafter referred to as the present specification), in which fine droplets are formed using piezoelectric pulses, and the formed fine droplets are dried and solidified to form a toner. Is known as a “new granulation method” (Patent Documents 1 to 5).
The known production methods using these new granulation methods have a problem that productivity is poor because the number of droplets that can be ejected from one nozzle per unit time is limited. In addition, in such a manufacturing method, the droplets are coalesced and the particle size distribution is widened, so that a toner having a wide particle size distribution can be obtained, and a toner excellent in monodispersibility cannot be obtained. there were.
Further, in the above-described new granulation method (Patent Documents 1 to 5), in the case of a configuration in which the vibration unit directly touches the fluid, when the number of pores for forming droplets and the number of vibration units match, A toner having a sharp particle size distribution can be obtained, but when a large number of pores are excited by a single vibrating portion, depending on the distance between the pore position and the vibrating portion, Since the size of the ejected droplets changes, the resulting toner particles are produced as an aggregate of toner particles having a wide particle size distribution among a plurality of orifices. There is.

JP 2003-262976 A JP 2003-280236 A JP 2006-0775708 A JP 2006-077252 A JP 2006-167593 A

  The present invention has been made in view of the problems of the prior art in the so-called new granulation method, and is a method for producing a toner that can efficiently produce toner without clogging of the ejecting portion in the droplet forming step. The purpose is to provide. Further, the developer using the toner obtained by the present invention can be used in an image forming apparatus using a fixing heat roller not provided with an oil application mechanism, and has excellent low-temperature fixability and hot offset resistance. Another object of the present invention is to provide a toner that has no or very little variation between toner particles in physical characteristics such as fluidity and charging characteristics. Furthermore, the present invention provides a toner that can be used in a general image forming apparatus, and has toner properties as other electrophotographic toners in addition to the above-described toner properties, and also has excellent monodispersibility. The purpose is to do.

In order to solve the above problems, the present invention has the following problem solving means.
<1> In a toner production method for producing toner particles by discharging a toner composition liquid containing a toner material containing at least a binder resin and a colorant from a through hole and forming droplets.
The toner composition liquid is quantitatively supplied to the storage section, and the plurality of through holes provided in the storage section are excited while the toner composition liquid is excited through the storage section by vibration means that contacts a part of the storage section. A toner manufacturing method in which the toner composition liquid is discharged into a granulation space to form droplets from a columnar shape through a constricted state, and the droplets are changed into solid particles in the granulation space;
The toner composition liquid is
A master batch process in which at least a colorant and the first resin are dispersed in advance to form a master batch;
A toner composition liquid manufacturing step using a toner composition containing at least the master batch and the binder resin as a toner composition liquid;
The toner production method according to claim 1, wherein:
<2> The method for producing a toner according to <1>, wherein the first resin and the resin constituting the binder resin are the same resin.
<3> The method for producing a toner according to <1> or <2>, wherein the toner composition liquid contains an organic solvent, and a toner material is dissolved or dispersed. .
<4> The toner production method according to any one of <1> to <3>, wherein the step of changing to the solid particles is a step of removing the organic solvent from the droplets.
<5> The toner according to any one of <1> to <4>, wherein the droplet formation is performed by applying vibration having a constant frequency in a range of 100 kHz to 10 MHz by the vibration unit. It is a manufacturing method.
<6> The toner production method according to any one of <1> to <5>, wherein a solid content ratio of the toner composition liquid is 5 to 20% by weight.
<7> A toner obtained by discharging a toner composition liquid containing a toner material containing at least a binder resin and a colorant from a through hole and forming droplets,
The toner composition liquid using a toner material including at least a masterbatch in which a colorant and a first resin are dispersed in advance and the binder resin is quantitatively supplied to a storage unit and is in contact with a part of the storage unit The toner composition liquid is discharged from the plurality of through-holes provided in the storage portion into the granulation space while exciting the toner composition liquid through the storage portion by vibration means to form droplets from a columnar shape through a constricted state. A toner obtained by changing the droplets to solid particles in a granulation space.
<8> The toner according to <7>, wherein the toner composition liquid contains an organic solvent, and the solidification is a solvent removal.
<9> The toner according to any one of <7> to <8>, wherein the vibration unit is in contact with at least the through-hole or the storage portion and directly vibrates.
<10> The toner according to any one of <7> to <9>, wherein there are a plurality of the through holes per vibration means.
<11> The toner according to any one of <7> to <10>, wherein the toner has a volume average particle diameter (Dv) of 1 to 20 μm.
<12> The toner according to <7>, wherein the toner has a ratio (Dv / Dn) of a volume average particle diameter (Dv) to a number average particle diameter (Dn) in a range of 1.00 to 1.05. > To <11>.
<13> A developer using the toner according to any one of <7> to <12>.

According to the present invention, the vibrating means is in contact with a part of the reservoir that stores the toner composition liquid, and vibrates the toner composition liquid that is quantitatively fed through the reservoir, thereby allowing one reservoir to Since the toner composition liquid discharged from a plurality of through holes (nozzle discharge ports) provided in the same can be collectively vibrated, more than 100 droplets are generated simultaneously by one vibration means. It becomes possible.
According to the present invention, various problems in the prior art can be solved at once, and there is no blockage at the discharge port (through hole) portion of the nozzle, so that the toner is excellent in productivity and monodispersed (monodispersed). Can be produced efficiently. Since the toner obtained by such a manufacturing method is a particle having a monodispersibility with a particle size not found in conventional particles, in many characteristic values required for the toner such as fluidity and charging characteristics, There is no or only a small range of variation between particles as seen in the previous production methods, and the toner is very narrow. The toner of the present invention can be used as a developer. According to the present invention, the production of a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc. A method and toner produced thereby can be provided.

(Toner production method)
The toner production method of the present invention is a toner production method for producing toner particles by discharging a toner composition liquid from a through hole and forming droplets.
The toner composition liquid is quantitatively supplied to the storage part (storage process), and a plurality of parts provided in the storage part are excited while the toner composition liquid is excited through the storage part by vibration means in contact with a part of the storage part. The toner composition liquid is discharged from the nozzle discharge port (through hole) into the granulation space and is formed into droplets from a columnar shape through a constricted state (droplet forming step), and the droplets are changed into solid particles in the granulation space ( Particle forming step) a toner production method,
The toner composition liquid is obtained by a master batch in which at least a colorant and a first resin are dispersed in advance, and a toner composition liquid manufacturing step in which a toner material containing the binder resin is used as a toner composition liquid. .

The storage process described above is a process of transporting the toner composition liquid to the storage part described above by the liquid transport unit, and the droplet forming process penetrates the toner composition liquid transported by the storage process as shown in FIG. Power is supplied to the vibration application unit 2 to the storage unit 1 provided with a plurality of holes to apply vibration to the storage unit, and preferably vibration is applied in the droplet generation direction (droplet falling direction: vertical direction). This is a step in which the toner composition liquid is continuously discharged to form a columnar state, and then monodispersed droplets are gradually generated due to the influence of vibration application, droplet surface tension, and gravity.
In the particle forming step, the monodispersed droplets are removed from the droplet forming step together with the dry air by the solvent removal unit 6 of the manufacturing apparatus to remove the solvent which is a volatile component in the droplets. ) Is solidified to produce particulate toner.

-Action-
According to the toner manufacturing method of the present invention, the number of droplets generated from the discharge port (through hole 4) of the nozzle is very large, tens of thousands to several million per second, and more discharge holes are provided. It is also easy to do. Moreover, it can be said that it is one of the most suitable methods for producing toner from the viewpoint of obtaining particles having a very uniform droplet diameter and substantially the same shape and having sufficient productivity. In the production method of the present invention, the particle diameter of the finally obtained toner 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)
In the above formula (1), Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow rate and nozzle 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).
Solid content volume concentration (volume%) = (solid particle diameter / droplet diameter) ³ (2)

That is, the diameter of the toner particles obtained by the present invention is twice the nozzle opening diameter regardless of the vibration frequency at which the droplets are ejected. Therefore, it is possible to obtain toner particles having a target solid particle diameter by obtaining and adjusting the solid content concentration in advance from the relationship of the above formula (2). For example, when the nozzle diameter is 7.5 μm, the droplet diameter is 15 μm. Therefore, if the solid content volume concentration is 6.40% by volume, 6.0 μm solid particles can be obtained. In this case, the vibration frequency is preferably higher from the viewpoint of productivity, but Q (liquid flow rate) is determined from the calculation formula (1) according to the vibration frequency determined here.
In the conventional manufacturing method, the particle size has changed greatly depending on the material used. In the manufacturing method of the present invention, the droplet diameter at the time of ejection and the solid content concentration in the toner composition liquid are controlled. It is possible to obtain particles having a set particle size continuously, preferably in large quantities (in an amount suitable for mass production).

  Further, since the toner obtained by the toner production method of 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 with an extremely small amount of addition. From the viewpoint of deterioration of the external additive due to load (stress) and the safety of the fine particles to the human body, the addition of the external additive can be suppressed as much as possible in the toner obtained by the production method of the present invention. In addition, the addition of these external additives can suppress the decrease in adhesion between toner particles and the inhibition of low-temperature fixability, has more stable low-temperature fixability, and has adhesive properties at the time of fixing (to a recording medium such as paper) A toner having excellent fixing characteristics can be obtained. Such toner has very little variation in the expression of the adhesive force due to fixing. In other words, the toner obtained by the production method of the present invention has little variation in the temperature at which low-temperature fixability develops due to its uniform particle size and the suppression of the addition of external additives, and at the same time fixing strength (adhesion) There is almost no variation in force), low-temperature fixability, and excellent image stability and high sensitivity.

A preferable manufacturing apparatus used in the toner manufacturing method of the present invention will be described below.
-Device-
An example of a toner production apparatus used in the toner production method of the present invention is shown in FIG.
As shown in FIG. 1, the toner manufacturing apparatus includes at least a storage unit 1 that stores a toner composition liquid of a fluid that is a raw material, a vibration application unit 2 that uses a piezoelectric element that is a vibration application unit, and a vibration application unit 2. At the bottom of the support part 3 to be held and the storage part 1, a plurality of through holes 4 and toner particles that are solidified into a monodispersed toner composition liquid, which is a raw material in droplet form, are solidified and granulated It has a forming unit 6 and a toner collecting unit 16 for collecting the granulated monodispersed toner. The toner collecting unit 16 is provided at the bottom of the toner manufacturing apparatus. Then, as shown in FIG. 4, the toner composition liquid used in the toner manufacturing method of the present invention is quantitatively fed from the liquid supply means 5 and supplied to the reservoir 1 having a through hole at the bottom. The toner composition liquid, which is a raw material used in the method for producing the fed toner, is transferred from a plurality of through holes provided at the bottom of the storage unit 1 through the through holes 4 provided at the bottom of the storage unit 1. It is discharged continuously in a columnar shape. The released columnar composition liquid falls and drops into a monodispersed (monodispersed) particle diameter in which the particle diameter is gradually uniformed from the columnar shape. Volatile components in the droplets are evaporated and solidified to form a monodispersed (monodispersed) toner, which is accumulated in the toner collecting unit 16.
Each part of such a toner manufacturing apparatus will be described below. 3 shows an example in which the vibration applying unit 2 is provided so as to come into contact with the head of the storage unit 1, the vibration applying unit 1 of the toner manufacturing apparatus penetrates the bottom of the storage unit 1. It can also be provided in contact with the hole.

--Reservoir 1--
The storage unit 1 is formed of a material such as SUS (stainless steel) or metal such as aluminum because at least the toner composition liquid that is a raw material needs to be held in a pressurized state.
Such a reservoir 1 desirably has a pressure resistance of about 10 MPa, for example. Further, as illustrated in FIG. 3, it is desirable to have a holding portion (holding mechanism) 9 that is connected to a supply pipe 12 that supplies a liquid to the storage portion and holds a bottom plate-like body having a through hole. . A vibration application unit 2 that vibrates the entire storage unit 1 is provided in contact with the storage unit 1. The vibration applying unit 2 includes a vibration generating unit 10 having an electrode, and a conductive wire 11 is connected to the electrode. The vibration application unit 2 is controlled by a signal (for example, a pulse signal or a waveform signal) applied by a control unit (not shown). The storage unit 1 is provided with an open valve 17 for adjusting the pressure in the storage unit and removing bubbles in the storage unit. The open / close valve is automatically controlled, or a threshold value such as a pressure is provided to open the valve appropriately. It is also possible to perform control such as closing or closing.

--- Vibration application section 2--
As shown in FIGS. 1 and 3, the vibration application unit 2 has at least one vibration exciter, and preferably forms the droplets by exciting the entire storage unit 1 having the through holes, preferably substantially simultaneously. . For this purpose, the excitation of the vibration applying unit 2 is preferably controlled so that the same pressure is applied to the plurality of through holes existing at the bottom almost simultaneously.
The vibration application unit 2 that applies vibration to the storage unit 1 can generate pressure or vibration generated by applying a certain waveform by a signal (pulse signal or waveform signal) from the control unit. . As such a material, an inorganic piezoelectric element, an organic piezoelectric element, a pyroelectric element, or the like is used. From the viewpoint described above, for example, the through-hole applies a controlled stress to the reservoir 1 or the bottom of the reservoir 1 provided with the through-hole due to expansion and contraction of a piezoelectric body (or a pyroelectric body). The toner composition liquid as a raw material is preferably discharged because it is controlled to be constant, thereby forming monodisperse particles.

Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT), and other examples include inorganic piezoelectric materials such as quartz, single crystals such as LiNbO ₃ , LiTaO ₃ , and KNbO ₃ . Moreover, organic piezoelectric (or pyroelectric) materials, such as piezoelectric polymers, such as polyvinylidene fluoride (PVDF), are mentioned. In particular, a piezoelectric body formed by stacking may be used.
The constant frequency applied to the reservoir by such a vibration application unit is not particularly limited and can be appropriately selected according to the purpose, but is preferably 100 kHz to 10 MHz, and has a very uniform particle size. From the viewpoint of generating droplets, a frequency in the range of 200 kHz to 2 MHz is more preferable.

The vibration application unit 2 is provided in contact with the storage unit 1, and the storage unit 1 is preferably a plate-like portion having a through hole and is preferably held at the bottom of the storage unit 1. The vibration applying unit 2 and the plate-like part having the through hole are parallel to the bottom plate-like part from the viewpoint of uniformly applying vibration in order to discharge the raw material from the through hole in a liquid column shape. It is most preferable that they are arranged in the area. In this way, the arrangement relationship is based on the steady position, and the tangential component between the vibration application unit 2 and the storage unit 1 or between the vibration application unit 2 and the storage unit bottom is k1 (tangential component of the vibration application unit 2), The reservoir (the tangential component m ^{1 on} the upper surface of the reservoir and the bottom (plate-like) tangential component m ² ) is preferably within 10 ° (10 degrees). Alternatively the unit direction component n1 traveling direction of the vibration generated, that the normal component m ₂ of the normal component m ₁ or bottom of the upper surface of the reservoir is either a ± 10 ° or 180 ± 10 ° desirable.
A plurality of through-holes 4 are provided from the viewpoint of efficiently generating minute droplets in order to reduce the production cost in large quantities or to reduce production costs, rather than providing only one through-hole 4 at the bottom. It is preferable to form the droplets discharged from the through holes by discharging them to the solvent removing unit 6 which is one solvent removing unit and drying it.

  From the viewpoint of further improving productivity, a plurality of storage units having the vibration applying unit 2 may be provided, or the storage unit is divided into a plurality of parts, and the divided storage units 1, 1,. The application unit 2 can also be provided independently. With this configuration, the number of toner particles per unit time is determined by the product of the frequency, the number of vibration application units (or the number of storage units), and the number of through holes provided in each storage unit. The For this reason, the productivity is improved in proportion to the number of through-holes in each reservoir, but the uniformity of the particle diameter cannot be maintained beyond a certain range. Accordingly, it is preferable that the number of through holes in one vibration application unit is in the range of 10 to 10,000 from the viewpoint of productivity and controllability. Further, in order to reliably generate a uniform particle diameter, it is more preferable that the number of through holes is 10 to 1,000. The waves having a constant frequency described above are preferably applied to the plurality of through holes provided in the same waveform and in the same phase. As a result, it is applied to all the through-holes with the same waveform and the same phase, and the toner composition liquid is ejected into the granulation space with substantially the same diameter, so that a column state having substantially the same shape is formed for each through-hole. The columnar toner composition liquid that has been discharged into the granulation space due to the excitation force and dropping force from the vibration application unit and the surface tension of the columnar toner composition is twisted from the column state. Through the process, droplets are formed into a monodispersed particle size almost simultaneously.

--Supporting means--
As shown in FIG. 3, the vibration unit 2 and the storage unit 1 are supported by a support unit 3. Such a support portion 3 is provided so that the vibration applying portion 2 is in close contact with the storage portion 1 and this storage portion is fixed in the toner manufacturing apparatus. The material of the support portion 3 is not particularly limited, but a rigid body such as a metal is used, and a vibration reducing material such as a rubber material or a resin material or an elastic body such as a spring is used so as to prevent disturbance of the storage portion due to resonance. The used damping material can also be provided in a part of the support portion, for example.

--- Through hole--
The through-hole 4 is preferably provided at the bottom of the storage unit 1 to discharge the raw toner composition liquid that has been fed and stored in the storage unit. As the material and hole shape of the plate material provided with the through holes 4, for example, a metal plate material having a thickness of 5 to 50 μm is used, and the opening diameter is preferably 1 to 40 μm. By adopting such a shape, a very uniform particle size can be obtained without being blocked by a fine particle dispersion of 1 μm or less contained in the raw toner composition liquid and by applying vibrations having a frequency of 100 kHz or more. It is preferable because fine droplets can be generated. This is because a raw toner composition liquid is ejected into a columnar shape from a through-hole by application of vibration, and then droplets are stably obtained (see FIG. 2). At this time, the frequency suitable for being applied to form droplets substantially tends to decrease as the diameter of the through hole increases. For this reason, it is preferable to apply a vibration frequency of 100 kHz or more in consideration of the productivity of the manufactured toner. The opening diameter means a diameter in the case of a perfect circle, and a short diameter in the case of an ellipse.

-Liquid feeding means, liquid supply means-
As shown in FIG. 1, the liquid transport unit 5 for supplying the liquid to the common liquid chamber has a metering pump such as a tube pump, a gear pump, a rotary pump, a syringe pump, or the raw toner composition liquid is air. Or the like. By these liquid transport sections 5, the raw toner composition liquid is fed into the common liquid chamber, and the pressure can be increased so as to form liquid droplets. The liquid pressure can be adjusted by measuring or monitoring with a pressure gauge or pressure sensor attached to the liquid feeding section. It is preferable to send these liquid feeding amounts quantitatively, but in the present invention, the liquid feeding amounts may be changed and supplied.

--Toner particle forming section 6--
As shown in FIG. 1, the toner particle forming unit 6 is a unit in which the solvent (solvent) in the droplet 13 is diffused and solidifies (particles) from the droplet 13, and the droplet 13 flies in this unit. The dry gas 14 flows out in the same direction as the direction (falling direction) to generate an air flow, and the droplets 13 are transported. During this transport, the solvent in the droplets 13 is diffused and removed, and the toner particles 15 are removed. It is formed. The “dry gas” for generating the airflow used here is a gas having a dew point under atmospheric pressure of −10 ° C. or lower. Examples of such a dry gas include air and nitrogen gas, but are not particularly limited as long as the dew point is −10 ° C. or lower.
Further, as shown in FIG. 1, from the viewpoint of preventing droplets 13 from adhering to the wall surface of the solvent removal (drying) facility 6 on the inner wall surface of the solvent removal facility 6 that is also the toner particle forming portion. The electric field curtain 8 charged with a polarity opposite to the electric charge of the droplet may be provided to form a conveyance path covered with the electric field curtain, and the droplet may pass through the conveyance path. it can.

-Toner collecting part 16-
As shown in FIG. 4, the toner collecting unit 16 is a unit that efficiently collects and transports the toner formed by the toner particle forming unit 6. From such a viewpoint, the toner collecting unit 16 Provided at the bottom.
Such a toner collecting portion 16 is provided on the bottom portion 7 of the toner manufacturing apparatus from the viewpoint described above, and has a tapered surface whose opening diameter is gradually reduced as shown in FIG. A toner fluid is formed in which the toner particles 15 are flowed by a dry gas, and the toner particles are thereby transferred to a toner storage container (not shown).
When the toner fluid is sent to the storage container, as shown in the figure, the toner fluid 15 is sent by dry gas, or the toner storage container side is set to a pressure lower than the pressure in the apparatus to send the toner particles 15 into the storage container. Further, it is also possible to carry out the transfer with the dry gas and the reduced pressure inside the storage container. As shown in FIG. 4, the toner collecting unit 16 may be constituted by a cyclone, for example.

In order to fluidize the toner particles 15 with the dry gas, it is possible to transfer the toner particles 15 in a vortex by applying a centrifugal force by a cyclone shown in FIG.
Furthermore, from the viewpoint of transferring the toner particles 15 more efficiently, the toner collecting portion and the toner collecting container may be formed of a conductive material and connected to the ground. The toner manufacturing apparatus preferably has an exposure specification.

--- Static eliminator--
The toner manufacturing apparatus used in the present invention may have static elimination at the bottom. Such a static eliminator removes the charge of the toner particles 15 formed by passing the droplets 13 through the transport path to neutralize the toner particles 15 and accommodates the toner particles 15 in a toner storage container (not shown). Can do.
There is no restriction | limiting in particular as the method of static elimination by a static elimination device, The method known normally can be selected suitably and can be used. Since efficient charge removal is possible, for example, it is preferable to irradiate light such as visible light, ultraviolet light, and soft X-ray, or irradiate plasma.

--- Droplet--
As described above, a large number of droplets 13 are generated by causing a toner composition liquid containing a specific substance to vibrate at a constant frequency and ejecting it from the ejection ports (through holes) 4 of a plurality of nozzles. In the present invention, as described above, a plurality of through holes provided in the nozzle are provided as shown in FIGS. The toner composition liquid and the like will be described later.
The toner composition liquid, which is a raw material for generating droplets, dissolves or disperses the toner material. From the viewpoint of maintaining a high charge amount, the toner composition liquid preferably has an electrolytic conductivity of 1.0 × 10 ⁻⁷ S / m or more.
From the same point of view, the electrolytic conductivity of the solvent or dispersion medium used for the dissolution or dispersion is also preferably 1.0 × 10 ⁻⁷ S / m or more. The toner composition liquid is formed by dissolving or dispersing a toner material.

Hereinafter, the toner composition liquid used in the toner production method of the present invention will be described. First, the colorant used in the toner composition liquid will be described.
Colorant In the method for producing a toner of the present invention, a colorant such as a dye or a pigment is used.
The colorant such as dye or pigment is not particularly limited and can be appropriately selected and used. Examples thereof include 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, phisay Red, parachlor ortho nitroaniline red, risor fast scarlet G, brilliant fast scarlet, brilliant carmine BS, permanent red (F2R, F4R, FRL, FRLL, F4RH), fast scarlet VD, velkan fast rubin B, brilliant scarlet G , Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment 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, quinacrid Red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, 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 Lake, Ma Lakite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon, and a mixture thereof may be mentioned. These dyes or pigments are used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the method for producing a toner of the present invention is preferably a masterbatch that is used as a masterbatch in which the resin and a dye or pigment (at least one of a dye or a pigment) are dispersed in advance.
In such a master batch, the dye or the pigment is sufficiently dispersed in the resin.
In the present invention, a dispersion liquid in which the dispersion liquid is a primary dispersion liquid can be used as a master batch. However, a secondary dispersion liquid subjected to secondary dispersion by applying a high tensile force is used as a master batch. You can also Further, the secondary dispersion described above for the masterbatch used in the present invention is passed through a filter having pores of submicron (less than 1 μm: for example 0.8 μm or less, for example 0.6 μm or less, for example 0.5 μm or less). A submicron dispersion can also be used as a masterbatch. In this specification, the master batch refers to the primary dispersion, but in the present invention, these secondary dispersion and submicron dispersion are also included in the concept of the master batch.
The resin to be kneaded together with the production of the primary dispersion masterbatch or the primary dispersion masterbatch is more preferably a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, or a substituted product thereof; 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-chloromethacrylic acid Methyl copolymer, styrene-acrylonitrile Copolymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid copolymer, Styrene-maleic acid ester copolymer Styrene copolymers such as polymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin Rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The resin contained in the master batch has a weight average molecular weight of gel permeation chromatography, the maximum value of the main peak is the molecular weight (molecular weight in terms of styrene), and preferably 500 to 100,000, and from the viewpoint of the dispersibility of the dye or pigment From 3000 to 100,000 is more preferable. 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 masterbatch may decrease, and when the molecular weight exceeds 100,000, the dispersibility of the masterbatch may decrease.

The resin contained in the master batch has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and is preferably used by dispersing the master batch. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the master batch 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 resin in the masterbatch in terms of pigment dispersibility. Specific commercial products include “Azisper PB821”, “Azisper PB822” (Ajinomoto Fine Techno Co., Ltd.). Product), “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like. These dispersants can also be used when preparing a toner composition liquid.

  The addition amount of the dispersant is preferably 1 to 50 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the dye or pigment. If it is less than 1 part by weight, the dispersibility may be lowered, and if it exceeds 50 parts by weight, the chargeability may be lowered.

  The masterbatch used in the method for producing a toner of the present invention can be obtained by mixing and kneading the above-described dye or pigment and the above-described resin while applying a high shearing force. In this case, a solvent, moisture, or the like can be added in order to uniformly disperse the dye or pigment in the resin so as not to cause so-called “dama” between the dye or pigment and the resin. By doing so, the dye or pigment is wetted into a paste form, and the paste dye or pigment, the resin and the organic solvent are mixed and kneaded together, so that the dye or pigment and the resin can be easily blended. In particular, when the dye or pigment is in the form of a wet cake, since the solvent and the dye or pigment are familiar, they can be used as they are, which is convenient for the global environment. For the mixing and kneading for producing the master batch, a high shear dispersing device such as a roll mill or a pulverizer can be suitably used.

-Toner composition liquid-
The toner composition liquid used in the method for producing a toner of the present invention is obtained by using at least the above-described master batch and a binder resin and dissolving or dispersing them in a solvent (solvent). As described above, the masterbatch used in the present invention is a masterbatch comprising at least a resin and a colorant obtained by previously dispersing a resin and a dye or pigment.
--Binder resin--
Examples of the binder resin used in the toner composition liquid include two or more kinds of acrylic acid and acrylate polymer, vinyl polymer such as methacrylic acid and methacrylic acid ester, and raw material monomers of these polymers. Copolymer, styrene polymer, polyester (co) polymer, polyol resin, phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate Examples thereof include resins and petroleum resins.

Examples of the styrenic polymer include styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer. Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic copolymer Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinylmethylke Styrene copolymer such as styrene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Coalescence is mentioned.
In addition, the acrylic acid and the acrylic ester polymer may contain an acrylic binder. Examples of such an acrylic binder include polymethyl methacrylate and polybutyl methacrylate. Vinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic Group petroleum resin, chlorinated paraffin, paraffin wax, and the like.

  Examples of the acrylic acid and methacrylic acid ester polymers include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, and n-acrylate. -Homopolymers made from dodecyl, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof, and the like, 2 of these materials (monomers) Examples include copolymers of more than seeds.

  Examples of the methacrylic acid and methacrylic acid ester-based polymers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, and n-methacrylate. Homopolymers such as dodecyl, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. Is mentioned.

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

  In the description of the binder resin, the monomer or the portion indicated by the monomer is described as a raw material component of the binder resin. That is, when the description is given by using a monomer or monomer as a raw material of the polymer, these are used as a raw material of a homopolymer or one component of a copolymer. In the present invention, one of these monomers is used. The portion may be used as a binder resin and may be present as a monomer component in the manufactured toner. These monomer components have a binding effect for binding to a recording medium (for example, paper) more firmly in the fixing process in electrophotographic printing, and these monomers are also included in the binder resin. There is.

  Among such binder resins, there are resins having low reactivity, but they may be used in combination with the above resins. For example, styrene monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl styrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.

Examples of other monomers forming the vinyl polymer or copolymer include monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene.
The monomer constituting the polyester polymer is composed of a dihydric or higher alcohol component and a divalent or higher acid component (including an acid anhydride), and includes the following.
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, anhydrides thereof, partial lower alkyl esters and the like.

  When the binder resin is a polyester resin, the molecular weight distribution of the soluble component in the THF-soluble component of the resin component is preferably a molecular weight of 100,000 or less, and at least one in a region having a molecular weight of 3,000 to 50,000. The presence of a peak is preferable from the viewpoint of toner fixing properties and offset resistance, and a binder resin having at least one peak in a molecular weight region of 5,000 to 20,000 is more preferable. From another viewpoint, the molecular weight distribution of the soluble component is such that at least one peak exists in the molecular weight region of 3,000 to 50,000 and the component having a molecular weight of 100,000 or less is 60 to 100% by weight. A binder resin is preferable, and a resin in which at least one peak exists in a molecular weight region of 5,000 to 20,000 and a component having a molecular weight of 100,000 or less is 60 to 100% by weight is more preferable.

In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF (tetrahydrofuran) as a solvent.
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.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 weight% 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 is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when the acid value of the binder resin is measured from the toner, the acid value and content of the master batch or the 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 (4/1 by volume) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l (0.1 M) KOH.
(4) The amount of KOH solution used at this time is S (ml), the amount of blank KOH solution used is B (ml), and the acid value (mgKOH / g) is calculated using the following formula (1). To do. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

  The above-mentioned binder resin preferably has a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of the storage stability of the toner after it is produced. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated. In addition, it is preferable to select a resin that can be easily mixed with the binder resin as the resin in the masterbatch used in the present invention. In this case, the same resin or a similar resin can be selected as the resin used for the binder resin and the masterbatch. Therefore, as the resin used in the masterbatch, the resin described in the section of the binder resin can also be selected as the resin of the masterbatch.

The toner composition liquid used in the method for producing a toner of the present invention is obtained by using the above-described master batch and the above-described binder resin and preparing them with a solvent or a dispersion medium.
The solvent or dispersion medium used in the toner production method of the present invention is not particularly limited as long as it is a solvent or dispersion medium that can dissolve or disperse the masterbatch and the binder resin. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, acetic acid And methyl, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. For example, an ester solvent is preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

The toner composition liquid used in the toner production method of the present invention is preferably 5 to 20% by weight in terms of solid content. If the solid content ratio is less than 5% by weight, the productivity is inferior, and the particles tend to stick together, so the particle size uniformity may be lost. On the other hand, if it exceeds 20% by weight, the viscosity of the toner composition liquid becomes high and it may be difficult to eject with a small particle diameter. In addition, nozzle clogging may easily occur. In addition, the toner composition liquid used in the toner production method of the present invention uses at least the master batch and the binder resin. As described above, the resin (first resin) in the masterbatch and the binder resin may be the same, and a combination in which the binder resin and the masterbatch are uniformly dissolved or dispersed is selected. Is done. These solid content ratios can be determined according to a normal method. For example, a certain amount (for example, about 1 g) of the toner composition liquid is weighed on a watch glass and the like, and dried in a constant temperature drying oven at, for example, 100 ° C. or lower (about 40 to 60 ° C.) (for example, dried for about 2 hours). It can be obtained by weighing. Alternatively, the value obtained by (B / A) × 100 can be used as the solid content ratio (% by weight) by the remaining amount B obtained by subtracting the weight of the solvent from the toner composition liquid weight A.
Master Badge

<Release agent>
In the present invention, a release agent can be contained in the toner composition liquid together with the binder resin and the master batch. Such a mold release agent can also be added to the primary dispersion which is the aforementioned master batch. Such a release agent is not particularly limited and may be appropriately selected from those usually used. Examples thereof include low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, and 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. Plant waxes, animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and waxes based on fatty acid esters such as montanic ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  Further, examples of the release agent include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amides, lauric acid amides, saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide, ethylene bis oleic acid amide, hexamethylene bis olei Unsaturated fatty acid amides such as acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid amide Such as aromatic bisamides such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate and other fatty acid metal salts, and aliphatic hydrocarbon waxes grafted with vinyl monomers such as styrene and acrylic acid. And fatty acid such as behenic acid monoglyceride and partial ester compound of polyhydric alcohol, and methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oil.

  More preferably, 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, catalysts such as Ziegler catalysts and metallocene catalysts under low pressure are used as release agents. Polymerized polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by pyrolyzing high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, Synthetic hydrocarbon wax synthesized by the Age method, synthetic wax using a compound having one carbon atom as a monomer, hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon wax and a functional group Mixture of hydrogen 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 mold release agents use the press sweating method, the solvent method, the recrystallization method, the vacuum distillation method, the supercritical gas extraction method (including the method of extracting using a supercritical chromatograph) or the liquid crystal deposition method. Thus, a release agent from which the molecular weight distribution is sharpened, low molecular weight solid fatty acid, low molecular weight solid alcohol, low molecular weight solid compound, and other impurities are removed can also be used.

Further, by using a release agent that uses two or more different types of waxes in combination, a plasticizing action and a 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 difference in melting point 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, combinations of polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Candelilla wax, rice wax or montan wax and hydrocarbon wax The combination of the scan and the like.

  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.

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.
In the present invention, the melting point of the wax is defined as the peak top temperature at the maximum peak of the endothermic peak of the wax measured by DSC.

The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.
The total content of the release agent is preferably 0.2 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total of the masterbatch resin and the binder resin.

(toner)
The toner of the present invention is a toner manufactured by the toner manufacturing method of the present invention, preferably using the above-described manufacturing apparatus, and preferably has a monodispersed particle size distribution.
The toner of the present invention is a toner obtained by discharging a toner composition liquid containing a toner material containing at least a binder resin and a colorant from a through hole to form droplets, and at least the colorant and the first resin The toner composition liquid using a toner material containing a masterbatch in which is dispersed in advance and the binder resin is supplied to the storage portion, and the toner composition is passed through the storage portion by vibration means that contacts a part of the storage portion. While exciting the liquid, the toner composition liquid is discharged into the granulation space from a plurality of through-holes provided in the reservoir, and is converted into droplets from a columnar shape through a constricted state, and the droplets are changed into solid particles in the granulation space. It is preferable to obtain it.
The toner of the present invention has a particle size distribution in which the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.05. preferable. The toner of the present invention preferably has a volume average particle size of 1 to 20 μm.

  The toner of the present invention can be easily re-dispersed, that is, suspended in an air stream, due to the electrostatic repulsion effect. For this reason, the toner can be easily transported to the developing region without using a transporting unit used in a 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, when the toner of the present invention is used as a developer, it may be a conventional development system and can be applied to these development systems. At this time, members such as a carrier and a developing sleeve are simply used as a toner conveying unit, and it is not necessary to consider a frictional charging mechanism that has been conventionally shared in function. Therefore, since the degree of freedom of the material is greatly increased, the durability can be greatly improved, and the toner can be manufactured using an inexpensive material, which not only reduces the manufacturing cost but also suits the charging method. The materials can also be selected as appropriate.

-Other ingredients-
<Fluidity improver>
When the toner of the present invention is used as a developer (electrostatic image developing toner), a fluidity improver may be added. Such a fluidity improver improves the fluidity of the toner (becomes easier to flow) by adding it after the toner has been produced.
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.

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

Examples of the organosilicon compound 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 2 or more types may be mixed and used for them.
The number average particle size of the fluidity improver is preferably 5 to 100 nm, and 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 weight with respect to 100 parts by weight of the toner particles.

  When the toner of the present invention is used as a developer (electrostatic image developing toner), as an additive, electrostatic latent image carrier / carrier protection, improved cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics Various metal soaps, fluorine surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity-imparting agents Inorganic fine powders such as titanium oxide, aluminum oxide, and alumina can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. Also, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white and black fine particles having opposite polarity to the toner particles Can also be used in small amounts as a developability improver.

These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.
In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.

Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a master batch 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.

When the toner of the present invention is used as a developer, it is not necessary to use an external additive, but when it is used, inorganic fine particles are preferably used as the external additive.
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, pengallaba, 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 weight of the toner, and more preferably 0.01 to 2.0% by weight.
In addition, polymer-based fine particles such as soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polycondensation system such as methacrylate, acrylate ester copolymer, silicone, benzoguanamine, nylon (polyamide resin), The polymer particle by a thermosetting resin is mentioned.
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, and modified silicone oil. 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, for example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate fine particles. And polymer fine particles produced by soap-free emulsion polymerization such as 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.

<Career>
The toner of the present invention and a carrier may be mixed and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite, and resin-coated carriers can also 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.
Also, a binder type carrier core in which magnetic powder is dispersed in a resin can be used.

In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating agent, a method in which the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable.
The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on 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 silicone oil (weight ratio 1: 5) with respect to 100 parts by weight of titanium oxide fine powder. Treated with 12 parts by weight of the mixture,
(2) The thing processed with 20 weight part of the mixture of dimethyldichlorosilane and dimethyl silicone oil (weight ratio 1: 5) with respect to 100 weight part of silica fine powders is mentioned.

Among the resins of the resin-coated carrier, 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 weight ratio 10:90 to 90:10), styrene-acrylic acid 2-ethylhexyl copolymer (copolymerization weight ratio 10:90 to 90:10) and styrene- A mixture with acrylic acid-2-ethylhexyl-methyl methacrylate copolymer (copolymer weight ratio 20 to 60: 5 to 30:10:50) can be 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 (1) magnetic iron oxide such as magnetite, maghemite, and ferrite, and iron oxide containing other metal oxides, and (2) iron-rich ferrite, iron, cobalt, nickel, etc. Metals 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 Fe ₃ O ₄ (iron trioxide) and γ-Fe ₂ O ₃ (iron trioxide) are particularly preferable.
The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

As the different elements, salts of the different elements can be mixed at the time of production of the magnetic substance, and taken into the particles by 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 weight part of magnetic bodies are preferable with respect to 100 weight part of binder resin, and 20-150 weight part is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be determined by measuring an enlarged photograph taken with a transmission electron microscope with a digitizer or the like.

Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively.
The carrier resistance value is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness on 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.

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 magnetic material can also be used as a colorant pigment.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to the following Example and is not interpreted.

(Example 1)
(Preparation of toner composition liquid)
-Synthesis of master batch-
Carbon black (Cabot, Regal 400R) 39 parts by weight, polyester resin (Sanyo Kasei, RS801) 60 parts by weight, water 30 parts by weight are added, and the mixture is mixed with a Henschel mixer (Mitsui Mining). Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

-Preparation of dispersion with added resin and wax-
Next, a toner composition liquid having the following composition to which a resin as a binder resin and a wax were added was prepared.
As a binder resin, 100 parts by weight of a polyester resin, 12 parts by weight of the above [Masterbatch 1], 5 parts by weight of carnauba wax are mixed with 1,000 parts by weight of ethyl acetate, and a mixer having stirring blades as in the preparation of the masterbatch. And stirred for 10 minutes to disperse. It was possible to completely prevent the pigments in the master batch from aggregating without being shocked by solvent dilution. The electrolytic conductivity of this dispersion was 3.6 × 10 ⁻⁷ S / m. This is referred to as resin and [toner composition liquid 1].

-Preparation of toner-
The obtained [Toner Composition Liquid 1] was diluted with ethyl acetate so that the solid content was 6.0% by weight, and the toner composition liquid was supplied to the storage section 1 of the toner manufacturing apparatus shown in FIG. The nozzles used were 500 concentric circles formed by removal processing (laser ablation) by a mask reduction projection method using a femtosecond laser on a 20 μm-thick nickel plate and a femtosecond laser. . The portion where the through-hole was present was a square area with a side of 0.5 mm.
After preparing the toner composition liquid, droplets were ejected under the following toner production conditions, and then the droplets were dried and solidified to produce a toner.

-Preparation of toner-
[Toner preparation conditions]
Toner composition liquid density: ρ = 1.888 g / cm ³
Dry air flow rate: Orifice sheath 2.0 L / min (2.0 liters per minute),
Air in the device 3.0L / min (3.0 liters per minute)
In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Nozzle frequency: 220 kHz
Liquid supply condition to the toner reservoir: 400 ml / hr
The dried and solidified toner particles were collected by a cyclone. When the particle size distribution of the collected particles was measured by a flow particle image analyzer (FPIA-2000), the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn was 1.02, and the number average 26.5 g of toner base particles having a particle size of 5.0 μm was obtained in 1 hour of production. An optical micrograph of the obtained particles is shown in FIG.

(Example 2)
[Masterbatch 2] was prepared in the same manner as in Example 1 except that in “Masterbatch synthesis”, 29 parts by weight of carbon black (Cabot Corp., Regal 400R) and 70 parts by weight of polyester resin (Sanyo Kasei, RS801) were used. The toner base particles of Example 2 were prepared in the same manner as in Example 1 except that 12 parts by weight of [Masterbatch 1] prepared and added to “Preparation of toner composition liquid” was changed to 15 parts by weight of [Masterbatch 2]. 2] was created.

(Example 3)
[Masterbatch 3] in the same manner as in Example 1 except that in “Masterbatch synthesis”, carbon black (Cabot, Regal 400R) 49 parts by weight and polyester resin (Sanyo Chemicals, RS801) 50 parts by weight were used. [Master batch 1] 12 parts by weight added to “Preparation of toner composition liquid” was changed to [Master batch 3] 9 parts by weight in the same manner as in Example 1 except that [Toner matrix] Particle 3] was created.

(Comparative Example 1)
-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 1 is greatly 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 by a flow type particle image analyzer (FPIA-2000). The volume average particle size was 4.8 μm, and Dv / Dn (volume average particle size / The ratio of the number average particle diameter) was 1.32 and the average circularity was 0.98. The toner base particles have a wide particle size distribution. The production amount per hour was 24.8 g. An optical micrograph of the obtained particles is shown in FIG.

(Comparative Example 2)
-Preparation of dispersion of colorant (dispersion without resin: dispersion without masterbatch)-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 15 parts by weight and a pigment dispersant 3 parts by weight were primarily dispersed in 82 parts by weight 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 (made of PTFE (polytetrafluoroethylene)) and passing through the filter to a submicron region was prepared.

-Preparation of dispersion with added resin and wax (dispersion as a toner composition without using a masterbatch)-
-Preparation of toner-
Toner particles were obtained in the same manner as in Example 1 except that the master batch as the colorant used in Example 1 was replaced with the dispersion shown in the comparative example.
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 by a flow type particle image analyzer (FPIA-2000). The volume average particle size was 4.8 μm and Dv / Dn was 1.09. Thus, toner base particles having a wide particle size distribution were obtained. The production amount per hour was 24.8 g.

-External additive treatment-
With respect to 100 parts by weight of the obtained toner base particles of Example 1 and Comparative Examples 1 and 2, 1.0 part by weight of hydrophobic silica (“H2000”; manufactured by Clariant Japan) as an external additive was added to a Henschel mixer (Mitsui). The toner of Example 1 and Comparative Examples 1 and 2 was 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.

Next, a carrier was produced as follows.
To 100 parts by weight of toluene, 100 parts by weight of a silicone resin (“organostraight silicone”, 5 parts by weight of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by weight 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 weight of spherical magnetite with a particle size of 50 μm using a fluidized bed coating apparatus.

5 parts by weight of each of the toners of Example 1 and Comparative Examples 1 and 2 having been subjected to external additive treatment and 95 parts by weight of the carrier were mixed by a ball mill, and the two-component developers of Example 1 and Comparative Examples 1 and 2 were mixed. Manufactured.

[Evaluation methods]
(Evaluation item)
(1) Measurement of nozzle clogging After toner preparation, the nozzle clogging of the used toner production apparatus is measured.
The central part of the nozzle was magnified 100 times with a microscope (Keyence VHX-100) and evaluated visually. The nozzles were less clogged and evaluated from the good ones as 、, ○, Δ, and ×.

(2) Measurement of volume average particle diameter and ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) Volume average particle diameter (Dv) and number average particle diameter (Dn) are It can be measured by the Coulter counter method. Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include a method of measuring using a Coulter counter TA-II or Coulter Multisizer II (both manufactured by Coulter, Inc.).
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 measuring device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate distribution and number distribution. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) 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-type particle image analyzer (Flow
The measurement method using the Particle Image Analyzer will be described below.
The measurement of toner, toner particles and external additives using a flow type particle image analyzer can be performed using, for example, a flow type 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 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) in 10 ml of water having 20 or less particles. A few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) are added, 5 mg of a measurement sample is further added, and 20 kHz, 50 W / 10 cm ^{3 is obtained with an} ultrasonic dispersing device STM UH-50.
The dispersion treatment was performed for 1 minute under the above conditions, and the dispersion treatment was further performed for a total of 5 minutes, so that the particle concentration of the measurement sample was 4000 to 8000 particles / 10 ⁻³ cm ³
The particle size distribution of particles having a circle-equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured using the sample dispersion liquid (for particles in the measurement circle-equivalent diameter range).

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.
Table 1 shows the evaluation results of the toners of Examples 1 to 3 and Comparative Examples 1 and 2.

  As shown in Table 1, according to the present invention, the clogging of the nozzle is small, and the toner can be efficiently formed.

  The toner of the present invention is a particle having unprecedented particle size and monodispersibility. In many physical property values required for the toner such as fluidity and charging characteristics, the particles found in the conventional production methods are used. There are no or very little fluctuations. Therefore, such a toner can be used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. The toner manufacturing method of the present invention is an epoch-making manufacturing method because mass production, which is important in the manufacturing method, can produce toner with high efficiency and less nozzle clogging.

1 is a schematic view of a toner manufacturing apparatus. It is the figure which showed the process in which it changes from the liquid column shape in the injection apparatus containing a nozzle to a particle shape. It is the figure which showed the structure of the part of the apparatus containing a nozzle. FIG. 2 is a schematic view of a toner manufacturing apparatus, and schematically shows each part of the apparatus together with its function. (A) is an optical micrograph of the toner particles prepared in Example 1, and (b) is an optical micrograph of the toner particles prepared in Comparative Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Storage part 2 Vibration application part 3 Support part 4 Through-hole 5 Liquid conveyance part 6 Toner particle formation part 8 Electric field curtain 13 Droplet 14 Drying gas 15 Toner particle 16 Toner collection part 18 Transfer means

Claims (13)

In a toner production method for producing toner particles by discharging a toner composition liquid containing a toner material containing at least a binder resin and a colorant from a through-hole and forming droplets,
The toner composition liquid is quantitatively supplied to the storage section, and the plurality of through holes provided in the storage section are excited while the toner composition liquid is excited through the storage section by vibration means that contacts a part of the storage section. A toner manufacturing method in which the toner composition liquid is discharged into a granulation space to form droplets from a columnar shape through a constricted state, and the droplets are changed into solid particles in the granulation space;
The toner composition liquid is
A master batch process in which at least a colorant and the first resin are dispersed in advance to form a master batch;
A toner composition liquid manufacturing step using a toner composition containing at least the master batch and the binder resin as a toner composition liquid;
A method for producing a toner obtained by   The method for producing toner according to claim 1, wherein the first resin and the resin constituting the binder resin are the same resin.   The method for producing a toner according to claim 1, wherein the toner composition liquid contains an organic solvent, and a toner material is dissolved or dispersed.   4. The toner manufacturing method according to claim 1, wherein the step of changing to the solid particles is a step of removing the organic solvent from the droplets.   5. The toner manufacturing method according to claim 1, wherein the droplet formation is performed by applying vibration having a constant frequency in a range of 100 kHz to 10 MHz by the vibration unit.   6. The method for producing a toner according to claim 1, wherein a solid content ratio of the toner composition liquid is 5 to 20% by weight. A toner obtained by discharging a toner composition liquid containing a toner material containing at least a binder resin and a colorant from a through hole and forming droplets,
The toner composition liquid using a toner material including at least a masterbatch in which a colorant and a first resin are dispersed in advance and the binder resin is quantitatively supplied to a storage unit and is in contact with a part of the storage unit The toner composition liquid is discharged from the plurality of through-holes provided in the storage portion into the granulation space while exciting the toner composition liquid through the storage portion by vibration means to form droplets from a columnar shape through a constricted state. A toner obtained by changing the droplets to solid particles in a granulation space.   The toner according to claim 7, wherein the toner composition liquid contains an organic solvent, and the solidification is a solvent removal.   The toner according to claim 7, wherein the vibration unit is in contact with at least the through-hole or the storage portion and directly vibrates.   The toner according to claim 7, wherein there are a plurality of the through holes per vibration means.   The toner according to claim 7, wherein the toner has a volume average particle diameter (Dv) of 1 to 20 μm.   12. The toner according to claim 7, wherein a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.05. The toner according to any one of the above.   A developer using the toner according to claim 7.