JP2005215090A - Method for manufacturing toner and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner having excellent durability and having properties, such as excellent fixing properties and electrostatic charge properties, and provide a toner. <P>SOLUTION: In the method for manufacturing the toner prepared by adding resin particulates 4B mainly composed of a flourine-based resin to toner base particles 4A, a first dispersion liquid 3A prepared by finely dispersing a first dispersoid 311A containing resin a binder resin into a first dispersion medium 32A and a second dispersion liquid 3B prepared by finely dispersing a second dispersoid 31B containing resin particulates into a second dispersion medium 32B are discharged from respectively different nozzles M2 and M2' in a particulate form into a solidifying section M3 generated therein with a gaseous air current. A granular substance is obtained by solidifying the first dispersion liquid 3A of the particulate form to form the toner base particles 4A and imparting the resin particulates to the toner base particles 4A. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner manufacturing method and a toner.

A number of methods are known as electrophotographic methods. In general, a process (exposure process) of forming an electrical latent image on a photoconductor by various means using a photoconductive substance, A developing step of developing the latent image with toner, a transferring step of transferring the toner image onto a transfer material such as paper, and a step of fixing the toner image by heating, pressing, etc. using a fixing roller. doing.
The toner used in such a method is required to have performance such as predetermined charging characteristics and fixing characteristics in order to obtain an excellent image. Therefore, conventionally, a toner is known in which fine particles composed of a fluororesin having excellent releasability and chargeability are added to toner base particles mainly composed of a binder resin (see, for example, Patent Document 1). .)

For example, in Patent Document 1, fine particles composed of a fluororesin and toner base particles are simply mixed with an airflow stirring type mixer or the like to attach the fine particles to the surface of the toner base particles. Yes.
However, since the toner according to Patent Document 1 is obtained by mixing and adhering the fine particles to the toner base particles simply by an air flow stirring mixer or the like, the fixing strength of the fine particles to the toner base particles is relatively small. Therefore, the fine particles easily fall off from the toner base particles when subjected to an external force by stirring or frictional charging in the developing device. As a result, such toner cannot improve the performance for a long time due to the fine particles, and is inferior in durability. Further, since the fluororesin tends to aggregate without being uniformly dispersed only by the mixing, the obtained toner has a variation in chargeability and is inferior in charging characteristics.

JP 2000-284524 A (10th and 12th paragraphs)

  An object of the present invention is to provide a toner production method and a toner having excellent durability and characteristics such as excellent fixing characteristics and charging characteristics.

Such an object is achieved by the present invention described below.
The toner manufacturing method of the present invention is a method of manufacturing a toner in which resin fine particles mainly composed of a fluorine-based resin are added to toner base particles,
A first dispersion liquid in which the first dispersoid containing the binder resin is finely dispersed in the first dispersion medium, and a second dispersion material in which the second dispersoid containing the resin fine particles is finely dispersed in the second dispersion medium. 2 dispersion liquids are discharged from different nozzles into the solidified part where the gas stream is generated,
The first dispersion liquid in the form of fine particles is solidified to form the toner base particles, and the resin fine particles are applied to the toner base particles to obtain a granular material.

  As a result, a large amount of resin fine particles are present on the outer periphery of the toner base particles or in the vicinity thereof, so that the resin fine particles exhibit their functions sufficiently, and the obtained toner has excellent characteristics such as fixing characteristics and charging characteristics. be able to. Since the fluororesin constituting the resin fine particles has particularly excellent releasability and chargeability, the obtained toner has extremely excellent fixing characteristics and charging characteristics. In the obtained toner, since the resin fine particles are not so much present in the toner base particles, but are present in the outer periphery of the toner base particles or in the vicinity thereof, the resin fine particles have the mechanical strength of the toner base particles. Excellent durability without lowering. Furthermore, since the toner base particles and the resin fine particles are welded or fused to each other, the obtained toner has a relatively strong adhesive force between them, and this point is also highly durable. It will be a thing. Therefore, it is possible to manufacture a toner having excellent durability and charging characteristics, such as excellent fixing characteristics and charging characteristics, while exhibiting excellent durability.

In the method for producing a toner of the present invention, the first dispersion in the form of fine particles is solidified to form the toner base particles, and the resin fine particles are fixed or embedded on the outer periphery of the toner base particles or in the vicinity thereof. It is preferable to obtain a granular material.
As a result, it is possible to produce a toner having particularly excellent durability and the function of the resin fine particles more fully, and having particularly excellent characteristics such as fixing characteristics and charging characteristics.

In the toner production method of the present invention, the binder resin is preferably a thermoplastic resin.
As a result, the mechanical stability of the toner particles can be further improved, and as a result, the toner particles have particularly excellent durability.
In the method for producing a toner of the present invention, the average particle size of the resin fine particles is preferably 0.04 to 1.0 μm.
As a result, the resin fine particles can be efficiently attached in the recesses near the surface of the toner base particles. As a result, the obtained toner has an appropriate degree of circularity, excellent properties and uniformity in shape among the particles, and particularly excellent mechanical stability.

In the method for producing a toner of the present invention, it is preferable that the first dispersion medium and the second dispersion medium are aqueous dispersion media.
Thereby, the dispersibility of the dispersoids in the first dispersion liquid and the second dispersion liquid can be further enhanced, and these dispersoids have a relatively small particle diameter and a particularly small variation in size. Can be. In addition, since the first dispersion liquid and the second dispersion liquid can be prepared without substantially using an organic solvent or using an extremely small amount of an organic solvent, it has an adverse effect on the environment. The toner can be manufactured by a difficult method.
In the toner production method of the present invention, the first dispersion preferably contains an adhesive resin.
Thereby, the mechanical stability of the toner particles can be further improved.

In the method for producing a toner of the present invention, the adhesive resin is preferably an epoxy resin.
Thereby, the mechanical stability of the toner particles can be further improved.
In the method for producing a toner of the present invention, the temperature of the gas stream is preferably 40 to 200 ° C.
As a result, it is possible to efficiently solidify the fine particulate first dispersion while sufficiently preventing modification of the constituent material of the toner.

The toner of the present invention is manufactured by the toner manufacturing method of the present invention.
As a result, it is possible to produce a toner having excellent durability and the function of the resin fine particles, and having excellent characteristics such as fixing characteristics and charging characteristics.
The toner of the present invention is a toner obtained by adding resin fine particles mainly composed of a fluorine-based resin to toner base particles,
The toner base particles are mainly composed of a binder resin, and at least a part of the outer periphery of the toner base particles or the vicinity thereof is composed of an adhesive resin.
The resin fine particles are adhered to the adhesive resin.
As a result, the dispersion of characteristics such as charging characteristics and fixing characteristics among the toner particles is particularly small, and the resolution of the image formed by the toner is sufficiently high while the reliability of the entire toner is particularly high. Can be.

In the toner of the present invention, the average particle diameter is preferably 2 to 20 μm.
As a result, variations in characteristics such as charging characteristics and fixing characteristics among the toner particles are particularly reduced, and the reliability of the toner as a whole is further improved.
In the toner of the present invention, it is preferable that the standard deviation of the particle diameter between each particle is 1.5 μm or less.
Thereby, the transfer efficiency and mechanical strength of the toner particles can be made particularly excellent while the particle diameter of the toner particles is sufficiently small. Also, the fluidity of the toner is improved.

In the toner of the present invention, the average circularity R represented by the following formula (I) is preferably 0.95 or more.
R = L ₀ / L ₁ (I)
(Where, L ₁ [μm] is the circumference of the projected image of the toner particles to be measured, and L ₀ [μm] is the circumference of a perfect circle having an area equal to the area of the projected image of the toner particles to be measured) Represents length)
As a result, it is possible to produce a toner having excellent durability and the function of the resin fine particles, and having excellent characteristics such as fixing characteristics and charging characteristics.

Hereinafter, preferred embodiments of a toner production method and a toner according to the present invention will be described in detail with reference to the accompanying drawings.
As will be described in detail later, the toner production method of the present invention comprises a first dispersion liquid in which a first dispersoid containing a binder resin is finely dispersed in a first dispersion medium, and mainly a fluororesin. The second dispersoid containing the dispersed resin fine particles and the second dispersion finely dispersed in the second dispersion medium are discharged from different nozzles into the solidified portion where the gas stream is generated in the form of fine particles. The first dispersion liquid is solidified to form the toner base particles, and the resin fine particles are applied to the toner base particles. As a result, it is possible to produce a toner having excellent durability and the function of the resin fine particles, and having excellent characteristics such as fixing characteristics and charging characteristics. Since the fluororesin constituting the resin fine particles is particularly excellent in releasability and chargeability, the toner obtained has extremely excellent fixing characteristics and charging characteristics. More specifically, for example, the resin fine particles 4B adhere to the outer periphery of the toner (toner particles) configured as shown in FIG. 1, that is, the toner base particles 4A mainly composed of the binder resin (this embodiment). The toner particles 100 that are fixed or embedded in the form can be preferably produced. The toner particles thus produced have particularly excellent durability, and the toner in which the resin fine particles adhere to the outer periphery of the toner base particles or in the vicinity thereof has a sufficient function of the resin fine particles. In particular, it has excellent characteristics such as fixing characteristics and charging characteristics. In the following, prior to the description of the toner production method, a preferred embodiment of the toner of the present invention will be described first.

[Toner particles]
FIG. 1 is a sectional view schematically showing a preferred embodiment of the toner (toner particles) of the present invention, and FIG. 2 is a flowchart for softening point analysis.
As shown in FIG. 1, the toner particle 100 is composed of a granular body 4 including toner base particles 4 </ b> A and resin fine particles 4 </ b> B fixed or embedded near the outer periphery thereof, and an external additive (not shown). The toner base particles 4A are composed of a joined body (aggregate) 40 formed by melting and joining a plurality of fine particles (hereinafter referred to as binder resin fine particles) made of a binder resin, and an adhesive resin phase 42. Has been. Hereinafter, the bonded body 40, the adhesive resin phase 42, the resin fine particles 4B, and the external additive will be described in detail. The toner constituent materials (joined body 40, adhesive resin phase 42, resin fine particles 4B, and external additive constituent materials) will be described in detail later.

<Joint body 40>
The joined body (aggregate) 40 is formed by joining at least a plurality of binder resin fine particles. The binder resin fine particles (joined body 40) are mainly composed of a binder resin (binder resin).
Thus, the joined body 40 is formed by joining at least a plurality of binder resin fine particles. Thereby, the circularity of the toner particles 100 can be set to an appropriate size. As a result, the triboelectric chargeability is improved and the charging characteristics of the toner are particularly excellent. Further, since the resin fine particles 4B and the external additive can be reliably supported near the surface of the toner base particles (granular body 4), the functions of the resin fine particles 4B and the external additive can be more effectively exhibited. Further, the characteristics and reliability of the toner as a whole are improved. In particular, when the joined body 40 is obtained by melting and integrating a plurality of binder resin fine particles, even if the toner particles 100 have a relatively small particle size, the degree of circularity can be relatively easily and reliably. In addition, since the boundary (interface) between the binder resin fine particles does not substantially exist, the mechanical stability as the toner particle 100 is improved.

  Further, as described above, the binder resin fine particles (bonded body 40) may be any material as long as it is mainly composed of the binder resin. However, the constituent components of the toner other than the binder resin (for example, , Colorants, waxes, charge control agents, etc.). As described above, when the binder resin fine particles (the bonded body 40) contain constituent components of the toner other than the binder resin, for example, the dispersibility of the constituent components in the toner particles can be made particularly high. In other words, a toner in which constituent components are uniformly mixed can be easily obtained, and the reliability of the obtained toner is particularly excellent.

  In particular, when the binder resin fine particles contain a colorant, the dispersibility of the colorant in the toner particles 100 can be made particularly easy. Further, when the binder resin fine particles contain a colorant, it is possible to effectively prevent the colorant from exuding to the outside of the toner particles 100 (exudation of unintentional colorant). As a result, it is possible to effectively prevent the occurrence of so-called streaks in an image formed using toner, and it is also effective to prevent dirt from adhering to constituent members of an image forming apparatus such as a photoreceptor. Can be prevented.

  Further, when the binder resin fine particles contain wax, the dispersibility of the wax in the toner particles 100 can be made particularly high with relative ease. Further, when the binder resin fine particles contain wax, it is possible to effectively prevent the wax from exuding to the outside of the toner particles 100 (unintentional exudation of wax). As a result, it is possible to effectively prevent dirt from adhering to the constituent members of the image forming apparatus such as the photosensitive member.

  Note that toner constituents other than the binder resin, such as a colorant, wax, and charge control agent, may not be included in the binder resin fine particles. For example, when the toner particle 100 (the bonded body 40) has fine particles other than the binder resin fine particles, components other than the binder resin as described above may be included as a constituent component of the fine particles. . When such fine particles other than the binder resin fine particles are included, it is preferable that substantially no boundary (interface) between the fine particles is present as described above.

<Adhesive resin phase 42>
In the present embodiment, the toner base particles 4A are provided with an adhesive resin phase (complementary phase) 42 as shown in FIG. The adhesive resin phase 42 is mainly composed of an adhesive resin, and is a recess formed near the surface of the bonded body 40 (particularly, a recess formed in a portion corresponding to the bonded portion of the adjacent binder resin fine particles). ) Or in the vicinity of the joint between the binder resin fine particles, etc., and in the unjoined part (for example, a crevasse-like unjoined part) where the joining has not progressed sufficiently. As a result, the mechanical stability and durability of the toner particles can be made excellent while sufficiently exhibiting the effects of being produced from a plurality of binder resin fine particles.

  Further, by having the adhesive resin phase 42, the unevenness in the vicinity of the surface of the toner particle 100 can be made relatively small. Thereby, the circularity of the toner particles 100 can be made relatively large, the transfer efficiency and the mechanical strength of the toner particles 100 are particularly excellent, and the toner cleaning property (attached to the photoreceptor or the like). The toner can be easily removed). Also, the fluidity of the toner is improved.

  Further, as described above, since the mechanical stability of the toner particles 100 is improved by having the adhesive resin phase 42, the toner manufacturing process such as an external addition process and a classification process (a process in which a relatively large external force is applied). In this case, it is possible to effectively prevent the toner particles 100 (the granular body 4 having the bonded body 40 and the adhesive resin phase 42) from collapsing (decomposing). For this reason, the yield of the production of toner as a final product is improved, and the amount of toner raw materials (collapsed toner particles 100) to be discarded can be suppressed. Therefore, the present invention is preferable from the viewpoint of resource saving and environmental protection.

  The adhesive resin constituting the adhesive resin phase 42 may be any resin as long as it has adhesiveness, but is preferably mainly composed of a thermosetting resin. Thereby, the mechanical stability of the toner particles 100 can be made particularly excellent, and the adhesive resin phase 42 can be easily formed at the time of production of the toner. The adhesive resin phase 42 only needs to have a function of adhering unbonded portions of the binder resin fine particles in the final toner (toner particles 100). For example, the adhesive resin phase 42 is in a state of being almost completely cured. It may be in a semi-cured state or in an uncured state. When the adhesive resin constituting the adhesive resin phase 42 is in a semi-cured or uncured state, for example, the adhesive resin can be almost completely cured by heating or the like in the fixing process. The fixing strength to the recording medium can be made particularly excellent.

  The adhesive resin is preferably mainly composed of an epoxy resin. Thereby, the mechanical stability of the toner particles 100 can be further improved, and the adhesive resin phase can be more easily formed at the time of toner production. Epoxy resins are particularly excellent in affinity with polyester resins, styrene- (meth) acrylic acid ester copolymers, and the like. Therefore, when the binder resin (binder resin) is made of such a material, the adhesive strength between the bonded body 40 and the adhesive resin phase 42 is particularly excellent. The mechanical stability can be further improved. The constituent material of the adhesive resin phase 42 will be described in detail later.

<Resin fine particles 4B>
The toner particles 100 are provided with resin fine particles 4 </ b> B mainly composed of a fluorine-based resin near the surface of the toner base particles 4 </ b> A composed of the joined body 40 and the adhesive resin phase 42. Thus, since the resin fine particles 4B are provided in the vicinity of the surface of the toner base particles 4A, the resin fine particles 4B sufficiently perform their functions, and various characteristics required for the toner (for example, charging characteristics, fluidity, release properties). The balance of the property etc.) is particularly excellent. Since the fluororesin constituting the resin fine particles 4B has particularly excellent releasability and chargeability, the toner particles 100 have extremely excellent fixing characteristics and charging characteristics.

Further, since the resin fine particles 4B do not exist so much in the toner base particles 4A and exist in the vicinity of the surface in this way, the mechanical strength of the granular material 4 is reduced due to the releasability of the resin fine particles 4B. Is prevented.
Such resin fine particles 4B are preferably fixed or embedded in the vicinity of the surface of the toner base particles 4A. As a result, the resin fine particles 4B are less likely to fall off from the toner base particles 4A, and the decrease in the mechanical strength of the granular material 4 is more reliably prevented. In particular, in the present embodiment, since the resin fine particles 4B are mainly fixed or embedded in the adhesive resin phase 42 of the toner base particles 4A, the resin fine particles 4B are particularly difficult to drop off from the toner base particles 4A. 4 is further reliably prevented from lowering the mechanical strength.

<Granular body 4>
The granular body 4 is composed of the toner base particles 4A including the joined body 40 and the adhesive resin phase 42 as described above, and the resin fine particles 4B.
The average particle diameter D of the granular material 4 is preferably 2 to 20 μm, and more preferably 3 to 8 μm. When the average particle diameter D of the granular material 4 is less than the lower limit value, it becomes difficult to uniformly charge the toner particles 100 and attach to the surface of the electrostatic latent image carrier (for example, a photoreceptor). The adhesion force increases, and as a result, there may be an increase in transfer residual toner and a decrease in transfer efficiency. In addition, it becomes difficult to manufacture the granular material 4 (toner particles 100). On the other hand, if the average particle diameter D of the granular material 4 exceeds the above upper limit value, the average particle diameter of the toner particles 100 also increases. The reproducibility at is reduced. As a result, the resolution is reduced.
Further, the standard deviation of the particle size between the particles of the granular material 4 is preferably 1.6 μm or less, more preferably 1.5 μm or less, and further preferably 1.3 μm or less. When the standard deviation of the particle diameter between the particles of the granular material 4 is 1.6 μm or less, variations in charging characteristics, fixing characteristics and the like are particularly small, and the reliability of the entire toner is further improved.

  The granular material 4 may have a configuration (configuration not shown) other than the bonded body 40, the adhesive resin phase 42, and the resin fine particles 4B. The granular material 4 may be provided with fine particles other than the binder resin fine particles, for example. More specifically, the granular material 4 may include, for example, a colorant fine particle mainly composed of a colorant, a wax fine particle mainly composed of a wax, or the like as a structure (not shown).

<External additive>
In the present embodiment, the toner particle 100 has an external additive (not shown) in addition to the granular body 4. That is, the toner particles 100 are obtained by adding an external additive to the vicinity of the surface of the granular body 4 composed of the toner base particles 4A and the resin fine particles 4B. As described above, when the external additive is added, the balance of various characteristics (for example, charging characteristics, fluidity, releasability, etc.) required for the toner is particularly excellent.

<Toner particles>
The toner particle 100 has a coating ratio of the external additive (the ratio of the area covered by the external additive in the surface area of the granule 4, and the sphere corresponding to the average particle diameter of the external additive is 6 spheres corresponding to the average particle diameter of the toner. It is preferable that the calculated covering ratio when coating with closest packing is 100 to 300%, and more preferably 120 to 220%. When the coverage of the external additive is less than the lower limit, the function of the external additive may not be sufficiently exhibited. On the other hand, when the coverage of the external additive exceeds the upper limit, the toner fixability tends to decrease.

  Further, the toner particles 100 preferably have an average circularity R represented by the following formula (I) of 0.91 to 0.99, and more preferably 0.93 to 0.98. When the average circularity R is less than 0.91, it becomes difficult to sufficiently reduce the difference in charging characteristics between the individual toner particles 100, and the developability on the photoreceptor tends to be lowered. On the other hand, if the average circularity R is too small, toner adhesion (filming) is likely to occur on the photoreceptor, and the toner transfer efficiency may be reduced. On the other hand, when the average circularity R exceeds 0.99, the transfer efficiency and mechanical strength are increased, but there is a problem that the average particle diameter is increased by promoting granulation (joining of particles). If the average circularity R exceeds 0.99, for example, it becomes difficult to remove the toner adhering to the photoreceptor or the like by cleaning.

R = L ₀ / L ₁ (I)
(Where, L ₁ [μm] is the circumference of the projected image of the toner particles to be measured, and L ₀ [μm] is a perfect circle having an area equal to the area of the projected image of the toner particles to be measured (completely (Represents the perimeter of a geometric circle)
In addition, the standard deviation of the circularity between the toner particles 100 is preferably 0.05 or less, more preferably 0.03 or less, and further preferably 0.02 or less. When the standard deviation of the circularity between the toner particles 100 is 0.05 or less, variations in charging characteristics, fixing characteristics and the like are particularly small, and the reliability of the toner as a whole is further improved.

Further, the average particle diameter D ″ of the toner particles 100 is preferably 2 to 20 μm, and more preferably 3 to 8 μm. When the average particle diameter D ″ of the toner particles 100 is less than the lower limit, it is difficult to uniformly charge the toner particles 100 and the adhesion force to the surface of the electrostatic latent image carrier (for example, a photoreceptor) is large. As a result, there may be an increase in residual toner and a decrease in transfer efficiency. In addition, it becomes difficult to manufacture the toner particles 100 (granular bodies 4). On the other hand, when the average particle diameter D ″ of the toner particles 100 exceeds the upper limit, the reproducibility of the contour portion of the image formed using the toner, particularly the development of the character image or the light pattern is lowered. As a result, the resolution is reduced.
Further, the standard deviation of the particle diameter between the toner particles 100 is preferably 1.6 μm or less, more preferably 1.5 μm or less, and further preferably 1.3 μm or less. When the standard deviation of the particle diameter between the toner particles 100 is 1.6 μm or less, variations in charging characteristics, fixing characteristics and the like are particularly reduced, and the reliability of the toner as a whole is further improved.

<Constituent materials of toner>
Next, the constituent material of toner (toner particles) (material used for toner production) will be described.
1. Binder resin (binder resin)
The binder resin (binder resin) is a component that greatly contributes to the characteristics required of the toner, such as the fixing characteristics, elastic modulus, and charging characteristics of the toner, and is the main component of the toner.
The binder resin is a main component constituting the binder resin fine particles (the bonded body 40) in the toner particles 100.

Examples of the binder resin include polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, Styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-acrylic copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester-methacrylic acid ester Single unit containing styrene or styrene substitution product with styrene resin such as copolymer, styrene-α-chloromethyl acrylate copolymer, styrene-acrylonitrile-acrylic ester copolymer, styrene-vinyl methyl ether copolymer Copolymer or copolymer, styrene-acrylic Rylic acid ester copolymer, styrene-acrylic copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester-methacrylic acid ester copolymer, styrene-α-methyl chloroacrylate copolymer, styrene- Vinyl resin such as acrylic resin such as acrylonitrile-acrylic acid ester copolymer, polyester resin, epoxy resin, urethane modified epoxy resin, silicone modified epoxy resin, vinyl chloride resin, rosin modified maleic acid resin, phenyl resin, polyethylene , Polypropylene, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin Amine resins, natural rubber and the like, and these can be used singly or in combination of two or more of them. Two or more different components as the binder resin (for example, resin type (classification), molecular weight, constituent monomer type / existence ratio, melting point, softening point, glass transition point, crystallinity (easiness to crystallize), etc. By using a combination of different components, the advantages of each component can be obtained, and various properties required as a toner can be simultaneously improved. More specifically, toner fixing characteristics (width of good fixing temperature range), mechanical strength (mechanical stability), chargeability (ease of chargeability and maintainability), heat resistance (storability), coloring Further improvement of various properties required for toner such as property (color reproducibility) and the balance of the properties can be made particularly excellent.
The “binder resin” used in the production of the toner may be the “binder resin” itself constituting the finally obtained toner, or a precursor of the binder resin (for example, a corresponding monomer, Dimer, trimer, oligomer, prepolymer, etc.).

2. Adhesive Resin The adhesive resin is the main component constituting the adhesive resin phase 42 described above.
The adhesive resin may be anything as long as it can constitute the adhesive resin phase 42 as described above, but is preferably mainly composed of a thermosetting resin. Thereby, the mechanical stability of the toner particles 100 can be made particularly excellent, and the adhesive resin phase 42 can be easily formed at the time of production of the toner. The adhesive resin is not particularly limited as long as it exhibits a function of adhering unbonded portions of the binder resin fine particles in the final toner particles 100. For example, the adhesive resin is in an uncured state when the toner is manufactured. It may be in a semi-cured state. Further, the adhesive resin may be liquid (having fluidity) when the toner is manufactured. As described above, when the adhesive resin used for the production of the toner is in a liquid state, it is excellent in handleability without using a solvent material as described later or by using a relatively small amount of solvent material (appropriate The first dispersion 3A can be prepared easily and reliably. Further, when the first dispersion 3A described later is used in the production of the toner, the adhesive resin is included in the first dispersion 3A as a material constituting at least a phase other than the first dispersoid 311A. It is preferable. Thus, the toner particles 100 (granular body 4) having the above-described configuration can be easily and reliably manufactured by a method described later.

Specific examples of the adhesive resin include polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, and styrene-vinyl chloride copolymer. Polymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester-methacrylic acid ester copolymer, styrene -Styrene resins such as methyl α-chloroacrylate copolymer, styrene-acrylonitrile-acrylate ester copolymer, styrene-vinyl methyl ether copolymer, vinyl resins such as acrylic resin and methacrylic resin, polyester Resin, epoxy resin, urethane Resin, hydrocarbon resin, amine resin, natural rubber, and the like. Among these, one kind or two or more kinds can be used in combination. Among these, it is preferable that the adhesive resin is mainly composed of an epoxy resin. Thereby, the mechanical stability of the toner particles 100 can be further improved, and the adhesive resin phase can be more easily formed at the time of toner production. Epoxy resins are particularly excellent in affinity with polyester resins, styrene- (meth) acrylic acid ester copolymers, and the like. Therefore, when the binder resin (binder resin) is made of such a material, the adhesive strength between the bonded body 40 and the adhesive resin phase 42 is particularly excellent. The mechanical stability can be further improved.
The “adhesive resin” used for toner production (used as a toner production material) may constitute the first dispersoid in the first dispersion described later, It may constitute a dispersion medium.

  Further, as the adhesive resin, a water-soluble resin (water-soluble resin) can be used at the time of toner production (adhesive resin used as a raw material for toner production). When the adhesive resin used as a raw material for toner production is a water-soluble resin, the toner can be suitably produced without using an organic solvent in the method described below. In other words, by using a water-soluble adhesive resin, the toner can be suitably manufactured by an environmentally friendly method. Further, when the adhesive resin is a water-soluble resin, the adhesive resin can be unevenly distributed in the dispersion medium in a dispersion liquid (aqueous dispersion liquid) used in a method described later. Thereby, an adhesive resin phase can be formed in a more suitable form. That is, it is possible to form an adhesive resin phase that can more effectively exhibit the function of bonding the unbonded portion of the bonded body.

Further, the adhesive resin used as a raw material for toner production has a softening point Tf _1/2 (flow 1/2 softening temperature) lower than that of the above-described binder resin (binder resin used as a raw material for toner production). Is preferred. As a result, the toner particles 100 having the above-described structure can be easily and reliably manufactured. The softening point Tf _1/2 is, for example, a flow tester, sample amount: 1 g, die hole diameter: 1 mm, die length: 1 mm, load: 20 kgf, preheating time: 300 seconds, measurement start temperature: 50 ° C., The temperature rise rate can be obtained as the temperature of a point on the flow curve corresponding to h / 2 in the flowchart for analysis as shown in FIG. 2 obtained when measured under the condition of 5 ° C./min.
The “adhesive resin” used in the production of the toner may be the “adhesive resin” itself constituting the finally obtained toner, or a precursor (for example, a corresponding monomer, dimer, trimer) of the adhesive resin. , Oligomers, prepolymers, etc.).

3. Colorant The toner (toner particles 100) usually contains a colorant. As the colorant, for example, a pigment, a dye, or the like can be used. Examples of such pigments and dyes include carbon black, spirit black, lamp black (CI No. 77266), magnetite, titanium black, chrome lead, cadmium yellow, mineral fast yellow, navel yellow, and naphthol yellow S. , Hansa Yellow G, Permanent Yellow NCG, Chrome Yellow, Benzidine Yellow, Quinoline Yellow, Tartrazine Lake, Red Mouth Lead, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, methyl violet lake, bitumen, cobalt blue, al Reblue Lake, Victoria Blue Lake, First Sky Blue, Indanthrene Blue BC, Ultramarine Blue, Aniline Blue, Phthalocyanine Blue, Calco Oil Blue, Chrome Green, Chrome Oxide, Pigment Green B, Malachite Green Lake, Phthalocyanine Green, Final Yellow Green G, Rhodamine 6G, quinacridone, rose bengal (C.I. No. 45432), C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 184, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 5: 1, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 162, nigrosine dye (CI No. 50415B), metal complex dye, silica, aluminum oxide, magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, Examples thereof include metal oxides such as magnesium oxide and magnetic materials containing magnetic metals such as Fe, Co, and Ni, and one or more of these can be used in combination. As the colorant, various color formers, fluorescent substances, phosphorescent substances, and the like may be used.

4). Wax The toner (toner particle 100) may contain a wax as a constituent component.
By including wax in the toner (toner particles 100), for example, the releasability of the toner particles can be improved.

  Examples of the wax include hydrocarbon waxes such as ozokerite, ceresin, paraffin wax, microwax, microcrystalline wax, petrolatum, Fischer-Tropsch wax, carnauba wax, rice wax, methyl laurate, methyl myristate, palmitic acid. Methyl, methyl stearate, butyl stearate, candelilla wax, cotton wax, wood wax, beeswax, lanolin, montan wax, fatty acid ester ester wax, polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax Olefin waxes such as 12-hydroxy stearamide, stearamide, phthalic anhydride amide wax, Lauro , Ketone waxes such as stearone, ether waxes, and the like, can be used singly or in combination of two or more of them.

Melting point _{T m} of a wax is not particularly limited, but is preferably 30 to 160 ° C., and more preferably 50 to 100 ° C.. Note that, for example, by differential scanning calorimetry (DSC), the temperature is increased to 200 ° C. at a temperature increase rate of 10 ° C./min, and further the temperature decrease rate is 10 ° C./min, and then the temperature increase rate is 10 ° C./min. The melting point T _m and the heat of fusion can be determined from the measurement under the condition of increasing the temperature at

5). Resin Fine Particles The toner (toner particle 100) includes resin fine particles 4B mainly composed of a fluorine-based resin.
Various fluororesins can be used as the fluororesin constituting the resin fine particles 4B. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene Hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTTE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF) ), Polyvinyl fluoride (PVF) and the like, or a combination of two or more thereof. Among these, polytetrafluoroethylene (PTFE) and tetrafluoroethylene / ethylene copolymer (ETFE) are preferable because they are particularly excellent in releasability and chargeability.

  Further, the fluororesin constituting the resin fine particles may include other resins, for example, a polymer alloy as long as the fluororesin is contained as described above. Examples of such polymer alloys include a blend of a fluororesin and a different polymer, a block copolymer obtained by chemically bonding a fluororesin and a different polymer, a copolymer such as a graft copolymer, and the like. It is done. When the resin fine particles are composed of polymer alloy or the like, the fluorine resin constituting the resin fine particles preferably has a fluorine resin content of 50% or more, more preferably 70% or more, and 85%. The above is more preferable. Thereby, the fluororesin in the resin fine particles can sufficiently exhibit its function, and the chargeability and releasability of the obtained toner can be made excellent.

6). External Additive The toner (toner particles 100) may contain an external additive as a constituent component.
Examples of the external additive include titanium oxide, silica (positively charged silica, negatively charged silica, etc.), aluminum oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, zinc oxide, alumina, magnetite, and the like. Fine particles composed of inorganic materials such as oxides, nitrides such as silicon nitride, carbides such as silicon carbide, metal salts such as calcium sulfate, calcium carbonate, and aliphatic metal salts, acrylic resins, fluororesins, polystyrene resins, polyesters Examples include resins and organic metal materials such as aliphatic metal salts (for example, magnesium stearate).

Among the external additives, examples of the titanium oxide that can be used as the external additive include rutile type titanium oxide, anatase type titanium oxide, and rutile anatase type titanium oxide.
The rutile anatase type titanium oxide has a rutile type titanium oxide (titanium dioxide) and a crystal structure anatase type titanium oxide (titanium dioxide) in the same particle. That is, the rutile anatase type titanium oxide has a mixed crystal type titanium oxide (titanium dioxide) of a rutile type crystal and an anatase type crystal.
Rutile-type titanium oxide usually has the property of easily forming spindle-shaped crystals. In addition, anatase type titanium oxide has the property of easily depositing fine crystals and being excellent in affinity with a silane coupling agent or the like used for hydrophobizing treatment or the like.

  And since rutile anatase type titanium oxide has a mixed crystal type titanium oxide of a rutile type crystal and an anatase type crystal, the advantage of the rutile type titanium oxide and the advantage of the anatase type titanium oxide And have both. That is, in the rutile-anatase type titanium oxide, a minute anatase-type crystal is mixed between the rutile-type crystals (inside the rutile-type crystal), and as a whole has a substantially spindle shape, The rutile-anatase type titanium oxide powder is less likely to be embedded in the particles 4A (granular body 4) and has excellent affinity with the silane coupling agent as the whole rutile-anatase-type titanium oxide. A uniform and stable hydrophobic film (silane coupling film) is easily formed on the surface of the film. Therefore, the toner obtained by containing the rutile-anatase type titanium oxide has a uniform charge distribution (the charge distribution of the toner particles is sharp), a stable charge characteristic, environmental characteristics (especially moisture resistance), and fluidity. And excellent caking resistance.

The abundance ratio of the rutile-type titanium oxide and the anatase-type titanium oxide in the rutile-anatase-type titanium oxide is not particularly limited, but is preferably 5:95 to 95: 5 by weight, and 50:50 More preferably, it is -90: 10. By using such a rutile-anatase type titanium oxide, the effect by using the above-mentioned rutile-anatase type titanium oxide becomes more remarkable.
Further, the rutile-anatase type titanium oxide preferably absorbs light in a wavelength region of 300 to 350 nm. Thereby, the toner has excellent light resistance (particularly, light resistance after fixing on a recording medium).

The shape of the rutile-anatase type titanium oxide is not particularly limited, but it is generally a spindle shape.
When the rutile-anatase type titanium oxide has a substantially spindle shape, the average major axis diameter is preferably 10 to 100 nm, and more preferably 20 to 50 nm. When the average major axis diameter is in such a range, the rutile-anatase type titanium oxide can sufficiently exhibit the above-described functions, and is contained in the toner base particles 4A (granular bodies 4). It is difficult to be buried and difficult to release. As a result, the stability of the toner against mechanical stress is further improved.

  The content of the rutile-anatase type titanium oxide in the toner is not particularly limited, but is preferably 0.1 to 2.0 wt%, and more preferably 0.5 to 1.0 wt%. If the content of the rutile-anatase type titanium oxide is less than the lower limit, the effect of using the rutile-anatase type titanium oxide as described above may not be sufficiently exhibited. On the other hand, when the content of the rutile-anatase type titanium oxide exceeds the upper limit, the toner fixing property tends to be lowered.

  Such a rutile-anatase type titanium oxide may be prepared by any method, but can be obtained, for example, by firing anatase-type titanium oxide. By using such a method, the abundance ratio of the rutile-type titanium oxide and the anatase-type titanium oxide in the rutile-anatase-type titanium oxide can be controlled relatively easily and reliably. When obtaining a rutile-anatase type titanium oxide by such a method, it is preferable that a calcination temperature is about 700-1000 degreeC. By setting the firing temperature within this range, it is possible to more easily and reliably control the abundance ratio of rutile titanium oxide and anatase titanium oxide in rutile anatase titanium oxide. Become.

  Among the external additives, examples of silica that can be used as the external additive include positively charged silica and negatively charged silica. The positively chargeable silica can be obtained, for example, by subjecting negatively chargeable silica to a surface treatment with a silane coupling agent having a functional group such as an amino group. When negatively chargeable silica is used as the external additive, the charge amount (absolute value) of the toner particles can be increased. As a result, a stable negatively chargeable toner can be obtained, and the toner control of the image forming apparatus can be easily performed.

Further, when negatively chargeable silica is used in combination with the rutile-anatase type titanium oxide described above, a particularly excellent effect is obtained. In other words, by using negatively-charged silica and rutile-anatase type titanium oxide in combination, the fluidity and environmental characteristics (especially moisture resistance) of the toner can be further improved, and more stable tribocharging can be exhibited. Thus, the occurrence of so-called fog can be more effectively prevented. Further, by using negatively-charged silica and rutile-anatase type titanium oxide in combination, the obtained toner can have a large charge amount (absolute value) and a sharper charge distribution.
When the average major axis diameter of the substantially spindle-shaped rutile-anatase type titanium oxide is D ₁ [nm] and the average particle diameter of the negatively chargeable silica is D ₂ [nm], 0.2 ≦ D ₁ / D ₂ ≦ It is preferable that the relationship of 15 is satisfied, and it is more preferable that the relationship of 0.4 ≦ D ₁ / D ₂ ≦ 5 is satisfied. By satisfying such a relationship, the effect of using negatively charged silica and rutile-anatase type titanium oxide in combination becomes even more remarkable. In the present specification, the “average particle diameter” refers to a volume-based average particle diameter.

Further, when positively chargeable silica is used as the external additive, for example, the positively chargeable silica can function as a microcarrier, and the chargeability of the toner particles themselves can be further improved. In particular, by using the positively chargeable silica in combination with the aforementioned rutile-anatase type titanium oxide, the toner obtained can have a large charge amount (absolute value) and a sharper charge distribution. .
When positively charged silica is included, the average particle size is preferably 30 to 100 nm, and more preferably 40 to 50 nm. When the average particle diameter of the positively chargeable silica is in such a range, the above-described effect becomes more remarkable.

Examples of the external additive include liquid external additives such as straight silicone oil, polyether-modified silicone oil, carboxyl-modified silicone oil, epoxy-modified silicone oil, methacryl-modified silicone oil, amino-modified silicone oil, and aminopolyether silicone oil. An agent may be used.
Further, as the external additive, HMDS, a silane coupling agent (for example, one having a functional group such as an amino group), titanate coupling agent on the surface of the fine particles composed of the above-described materials. In addition, a surface treatment (for example, a hydrophobization treatment or the like) with a fluorine-containing silane coupling agent, silicone oil, or the like may be used.
Further, some of the components used as external additives may be contained in the toner particles in the finally obtained toner.

7). Other Components The toner (toner particles 100) may contain components other than the binder resin, adhesive resin, colorant, wax, and external additive as its constituent components. Examples of such components include a charge control agent, a dispersant, and magnetic powder.
Examples of the charge control agent include benzoic acid metal salts, salicylic acid metal salts, alkyl salicylic acid metal salts, catechol metal salts, metal-containing bisazo dyes, nigrosine dyes, tetraphenylborate derivatives, quaternary ammonium salts, Examples thereof include alkyl pyridinium salts, chlorinated polyesters, and nitrohumic acid.

Examples of the dispersant include metal soap, inorganic metal salt, organic metal salt, and polyethylene glycol.
Examples of the metal soap include tristearic acid metal salts (for example, aluminum salts), distearic acid metal salts (for example, aluminum salts, barium salts, etc.), stearic acid metal salts (for example, calcium salts, lead salts, zinc salts, etc.) ), Linolenic acid metal salts (eg, cobalt salts, manganese salts, lead salts, zinc salts, etc.), octanoic acid metal salts (eg, aluminum salts, calcium salts, cobalt salts, etc.), oleic acid metal salts (eg, calcium salts) , Cobalt salts, etc.), palmitic acid metal salts (eg, zinc salts, etc.), naphthenic acid metal salts (eg, calcium salts, cobalt salts, manganese salts, lead salts, zinc salts, etc.), resinic acid metal salts (eg, calcium Salt, cobalt salt, manganese salt, lead salt, zinc salt, etc.).

Examples of the inorganic metal salt and the organic metal salt include a cation of an element selected from the group consisting of metals of Group IA, Group IIA, and Group IIIA of the periodic table as a cationic component, and an anion Examples of the property component include salts containing an anion selected from the group consisting of halogen, carbonate, acetate, sulfate, borate, nitrate, and phosphate.
Examples of the magnetic powder include magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, and other metal oxides such as Fe, Co, and Ni. The thing comprised with the magnetic material containing a magnetic metal etc. are mentioned.

In addition to the above materials, for example, zinc stearate, zinc oxide, cerium oxide, iron oxide, fatty acid, fatty acid metal salt and the like may be used as the additive.
Further, for example, the toner may contain at least a part of components (for example, a solvent, a dispersion medium, a dispersant, a dispersion aid, an emulsifier, etc.) used at the time of preparing a dispersion described later. Good.

[Toner Production Method]
Next, an example of a method for producing the toner (aggregate of toner particles 100) as described above will be described.
FIG. 3 is a longitudinal sectional view schematically showing an example of the configuration of a kneader and a cooler for producing a kneaded product used for the preparation of the first dispersion, and FIG. 4 is an apparatus for preparing the dispersion. FIG. 5 is an enlarged sectional view of the vicinity of the chamber of the apparatus shown in FIG. 4, and FIG. 6 is a preferred embodiment of the toner manufacturing apparatus used for manufacturing the toner of the present invention. Fig. 7 is a longitudinal sectional view schematically showing the embodiment, Fig. 7 is a sectional view showing a preferred embodiment of a nozzle for injecting a dispersion liquid as fine particles, and Figs. 8, 9 and 10 inject the dispersion liquid as fine particles. Sectional drawing which shows other embodiment of a nozzle, FIG. 11 is principal part expanded sectional view of the nozzle shown in FIG. 10, FIG. 12 is expanded sectional view which shows the inner side intermediate ring front-end | tip part of the nozzle shown in FIG. Is a sectional view showing another embodiment of a nozzle for injecting a dispersion liquid as fine particles. 14 and FIG. 14 are enlarged cross-sectional views of the main part of the nozzle shown in FIG. 13, FIG. 15 is an enlarged cross-sectional view showing the tip of the inner intermediate ring of the nozzle shown in FIG. 13, and FIG. FIG. 17 is a plan view of the gas separation recess shown in FIG. 16, and FIG. 18 is a cross-sectional view showing another embodiment of the nozzle that ejects the dispersion liquid as fine particles. Hereinafter, in FIG. 3, the left side is assumed to be “base end” and the right side is assumed to be “tip”.

  The toner manufacturing method of the present embodiment includes a first dispersion liquid in which a first dispersoid containing a binder resin is finely dispersed in a first dispersion medium, and resin fine particles mainly composed of a fluororesin. The second dispersion, in which the second dispersoid is finely dispersed in the second dispersion medium, is ejected from different nozzles into the solidified portion where the gas stream is generated, and the fine particles are dispersed in the first dispersion. A step of solidifying the liquid to form the toner base particles and applying the resin fine particles to the toner base particles. The first dispersion liquid in the present embodiment may be at least one containing a binder resin. However, in the following description, as a constituent component of the first dispersion liquid, the binder resin and an adhesive are mainly used. The case where resin is included is demonstrated. In addition, the second dispersion liquid in the present embodiment only needs to include at least resin fine particles mainly composed of a fluorine-based resin. Examples of the first and second dispersions include emulsions (emulsions) and suspensions (suspensions). Among these, suspensions are preferably used. By using the suspension, variation in shape among the toner particles 100 can be easily reduced in the finally obtained toner. Further, it is possible to more effectively prevent the solvent and the like from remaining in the finally obtained toner. In this specification, “suspension” refers to a dispersion (including a suspended colloid) in which a solid (solid) dispersoid (suspended particle) is dispersed in a liquid dispersion medium. The term “emulsified liquid (emulsion, emulsion, milky liquid)” refers to a dispersion in which a liquid dispersoid (dispersed particles) is dispersed in a liquid dispersion medium. In the following description, a case where a suspension is used as a dispersion will be described as a representative.

<Kneaded material>
In the present embodiment, first, a kneaded material K7 is obtained using a raw material K5 containing at least a binder resin among the toner constituent materials described above.
The kneaded material K7 can be manufactured using, for example, an apparatus as shown in FIG.

<Kneading process>
As described above, the raw material K5 subjected to kneading includes at least a binder resin as a constituent material of the toner, but includes components other than the binder resin such as a colorant, a wax, and a charge control agent. Is preferred. Thereby, for example, the dispersibility of the constituent components in the finally obtained toner particles 100 can be made particularly high. In other words, a toner in which constituent components are uniformly mixed can be easily obtained, and the reliability of the obtained toner can be made particularly excellent. Moreover, it is preferable that the raw material K5 used for kneading is obtained by previously mixing these components. Thereby, the effect mentioned above becomes further remarkable.

This embodiment demonstrates the structure which uses a biaxial kneading extruder as a kneading machine.
The kneading machine K1 includes a process part K2 for kneading while conveying the raw material K5, a head part K3 for extruding the kneaded raw material (kneaded material K7) into a predetermined cross-sectional shape, and a raw material K5 in the process part K2. And a feeder K4 to be supplied.
The process part K2 includes a barrel K21, a screw K22 and a screw K23 inserted into the barrel K21, and a fixing member K24 for fixing the head part K3 to the tip of the barrel K21.
In the process part K2, when the screw K22 and the screw K23 rotate, a shearing force is applied to the raw material K5 supplied from the feeder K4, and a uniform kneaded material K7 (especially a binder resin (binder resin as a main component) ) Contains two or more components, a kneaded material K7) in which these resin components are sufficiently finely dispersed or compatibilized is obtained.

  The total length of the process part K2 is preferably 50 to 300 cm, and more preferably 100 to 250 cm. When the total length of the process part K2 is less than the lower limit, for example, when the raw material K5 contains two or more components that are difficult to disperse or compatible with each other, these components are sufficiently finely dispersed or compatibilized. May be difficult. On the other hand, when the total length of the process part K2 exceeds the upper limit, depending on the temperature in the process part K2, the number of rotations of the screw K22, the screw K23, and the like, the material K5 is easily denatured by heat, and finally obtained. It may be difficult to sufficiently control the physical properties of the toner.

  Moreover, although the raw material temperature at the time of kneading | mixes changes with compositions etc. of the raw material K5, it is preferable that it is 80-260 degreeC, and it is more preferable that it is 90-230 degreeC. Note that the raw material temperature in the process part K2 may be uniform or may vary depending on the part. For example, the process unit K2 includes a first region having a relatively low set temperature and a second region that is provided on the base end side from the first region and whose set temperature is higher than the first region. You may have.

  In addition, the residence time (time required for passage) of the raw material K5 in the process part K2 is preferably 0.5 to 12 minutes, and more preferably 1 to 7 minutes. When the residence time in the process part K2 is less than the lower limit, for example, when the raw material K5 contains two or more components that are difficult to disperse or compatible with each other, these components are sufficiently finely dispersed or phased. It may be difficult to solubilize. On the other hand, if the residence time in the process part K2 exceeds the upper limit, the production efficiency is reduced. Depending on the temperature in the process part K2, the rotational speed of the screw K22, the screw K23, etc., the heat of the raw material K5 Modification tends to occur, and it may be difficult to sufficiently control the physical properties of the finally obtained toner.

  The number of rotations of the screw K22 and the screw K23 varies depending on the composition of the binder resin and the like, but is preferably 50 to 600 rpm. When the rotational speed of the screw K22 and the screw K23 is less than the lower limit, for example, when the raw material K5 contains two or more components that are difficult to disperse or compatible with each other, these components are sufficiently finely dispersed or Compatibilization may be difficult. On the other hand, when the rotation speed of the screw K22 and the screw K23 exceeds the upper limit, the molecular chain of the binder resin may be cut by shearing, and the properties of the binder resin may be deteriorated.

  Further, in the kneader K1 used in the present embodiment, the inside of the process unit K2 is connected to the pump P via the deaeration port K25. Thereby, the inside of the process part K2 can be degassed, and an increase in the pressure in the process part K2 due to heating or heat generation of the raw material K5 (kneaded material K7) can be prevented. As a result, the kneading process can be performed safely and efficiently. Further, since the inside of the process part K2 is connected to the pump P via the deaeration port K25, it is possible to effectively prevent bubbles (particularly relatively large bubbles) from being contained in the obtained kneaded material K7. And the properties of the finally obtained toner can be made more excellent.

<Extrusion process>
The kneaded material K7 kneaded in the process part K2 is pushed out of the kneader K1 through the head part K3 by the rotation of the screw K22 and the screw K23.
The head part K3 has an internal space K31 into which the kneaded material K7 is fed from the process part K2, and an extrusion port K32 from which the kneaded material K7 is extruded.

The temperature of the kneaded material K7 in the internal space K31 (at least the temperature near the extrusion port K32) is not particularly limited, but is preferably 80 to 150 ° C, more preferably 90 to 140 ° C. When the temperature of the kneaded material K7 in the internal space K31 is a value within the above range, the kneaded material K7 does not solidify in the internal space K31 and is easily extruded from the extrusion port K32.
In the illustrated configuration, the internal space K31 has a cross-sectional area gradually decreasing portion K33 in which the cross-sectional area gradually decreases in the direction of the extrusion port K32. By having such a cross-sectional area gradually decreasing portion K33, the extrusion amount of the kneaded material K7 extruded from the extrusion port K32 is stabilized, and the cooling rate of the kneaded material K7 in the cooling step described later is stabilized. As a result, the toner produced using the toner has a small variation in characteristics among the toner particles, and has excellent overall characteristics.

《Cooling process》
The softened kneaded material K7 extruded from the extrusion port K32 of the head part K3 is cooled by the cooler K6 and solidified.
The cooler K6 includes rolls K61, K62, K63, and K64, and belts K65 and K66.

The belt K65 is wound around a roll K61 and a roll K62. Similarly, the belt K66 is wound around the roll K63 and the roll K64.
The rolls K61, K62, K63, and K64 rotate about the rotation axes K611, K621, K631, and K641 in the directions indicated by e, f, g, and h in the drawing. Thereby, the kneaded material K7 extruded from the extrusion port K32 of the kneading machine K1 is introduced between the belt K65 and the belt K66. The kneaded material K7 introduced between the belt K65 and the belt K66 is cooled while being formed into a plate shape having a substantially uniform thickness. The cooled kneaded material K7 is discharged from the discharge portion K67. The belts K65 and K66 are cooled by a method such as water cooling or air cooling. If such a belt type is used as the cooler, the contact time between the kneaded product extruded from the kneader and the cooling body (belt) can be extended, and the cooling efficiency of the kneaded product is particularly excellent. Can be.

  By the way, in the kneading process, since a shearing force is applied to the raw material K5, even if the raw material K5 contains two or more components that are difficult to disperse or compatible with each other, phase separation (particularly, macrophase separation). However, the kneaded product K7 that has finished the kneading process is not subjected to a shearing force. Therefore, if it is left for a long period of time, it may cause phase separation (macro phase separation) again. is there. Therefore, it is preferable to cool the kneaded material K7 obtained as described above as soon as possible. Specifically, the cooling rate of the kneaded material K7 (for example, the cooling rate when the kneaded material K7 is cooled to about 60 ° C.) is preferably −3 ° C./second or more, and is preferably −5 to −100 ° C. / More preferably it is seconds. Further, the time required from the end of the kneading step (when the shearing force is no longer applied) to the completion of the cooling step (for example, the time required for cooling the temperature of the kneaded product K7 to 60 ° C. or lower) is 20 seconds. Or less, more preferably 3 to 12 seconds.

In the above description, in the embodiment, the configuration using a continuous twin-screw kneading extruder as the kneading machine has been described, but the kneading machine used for kneading the raw materials is not limited to this. For kneading the raw materials, for example, various kneaders such as a kneader, a batch type triaxial roll, a continuous biaxial roll, a wheel mixer, and a blade type mixer can be used.
In the illustrated configuration, the kneader having two screws has been described. However, the number of screws may be one or three or more. Further, the kneading apparatus may have a disc (kneading disc) portion.

Further, in the present embodiment, the configuration using one kneader has been described, but kneading may be performed using two kneaders. In this case, the heating temperature of the raw material, the rotational speed of the screw, and the like may be different between one kneader and the other kneader.
In the above description, the belt-type configuration is used as the cooler. However, for example, a roll-type (cooling roll-type) cooler may be used. Further, the cooling of the kneaded product extruded from the extrusion port K32 of the kneader is not limited to the one using the above-described cooler, and may be performed by, for example, air cooling.

<< Crushing process >>
Next, the kneaded material K7 that has undergone the cooling process as described above is pulverized. Thus, by pulverizing the kneaded material K7, the dispersibility of the dispersoid 31A (first dispersoid 311A) in the first dispersion 3A (droplets 9A) described later may be made particularly excellent. it can. Therefore, even in the finally obtained toner, variations in composition and characteristics among the toner particles are reduced. As a result, the obtained toner has particularly excellent overall characteristics.

The pulverization method is not particularly limited, and for example, it can be performed using various pulverizers such as a ball mill, a vibration mill, a jet mill, and a pin mill, and a crusher.
The pulverization process may be performed in multiple steps (for example, two stages of a coarse pulverization process and a fine pulverization process).
In addition, after such a pulverization step, a classification process or the like may be performed as necessary.
For the classification treatment, for example, a sieve, an airflow classifier or the like can be used.

In the present embodiment, the first dispersion is prepared using the kneaded material as described above.
By using the kneaded material K7 for the preparation of the first dispersion 3A, the following effects can be obtained. That is, each component in the kneaded material obtained by kneading even if the toner constituent material (constituting material of the binder resin fine particles) contains components that are difficult to disperse or compatible with each other. Is sufficiently compatible and finely dispersed. As a result, even if the component material of the toner contains a component that is inferior in dispersibility with respect to the first dispersion medium of the first dispersion described later (hereinafter also referred to as “hardly dispersible component”). The dispersibility of the dispersoid 31A (first dispersoid 311A) in the first dispersion 3A (droplet 9A) can be made particularly excellent. As a result, even in the finally obtained toner, variations in composition and characteristics among the toner particles are reduced. As a result, the obtained toner has particularly excellent overall characteristics.

<First dispersion>
Next, a method for preparing the first dispersion 3A and the first dispersion 3A prepared using the kneaded material (cooled and solidified kneaded material) as described above will be described.
<< Configuration of First Dispersion >>
First, the configuration of the first dispersion 3A will be described.
The first dispersion 3A has a configuration in which the first dispersoid (dispersion phase) 31A is finely dispersed in the first dispersion medium 32A. The first dispersion 3A includes at least a first dispersoid 311A mainly composed of a binder resin as the dispersoid 31A. In particular, in the present embodiment, as the dispersoid 31A, the first dispersion 3A including the first dispersoid 311A and the dispersoid 312A mainly composed of an adhesive resin is used.

1. First Dispersion Medium The first dispersion medium 32A may be any material as long as it can disperse the dispersoid 31A, which will be described later. It is preferably composed of “solvent material”.
Examples of such materials include inorganic solvents such as water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, Ketone solvents such as 3-heptanone and 4-heptanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, t-butanol, 3-methyl-1-butanol, 1-pentanol, 2- Alcohol solvents such as pentanol, n-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol, 2-methoxyethanol, allyl alcohol, furfuryl alcohol, phenol, diethyl ether, dipropyl ether Ether solvents such as diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), 2-methoxyethanol Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, methylcyclohexane, octane, didecane, methylcyclohexene, isoprene, toluene, xylene, benzene, ethylbenzene , Aromatic hydrocarbon solvents such as naphthalene, pyridine, pyrazine, furan, pyrrole, thiophene, 2-methylpyridine, 3-methylpyridine, 4-methyl Aromatic heterocyclic compound solvents such as pyridine and furfuryl alcohol, amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), dichloromethane, chloroform, 1,2-dichloroethane, Halogenated solvents such as trichloroethylene and chlorobenzene, acetylacetone, ethyl acetate, methyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, ethyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, ethyl formate, isobutyl formate, ethyl acrylate, methacrylic acid Ester solvents such as methyl acid and ethyl benzoate, amine solvents such as trimethylamine, hexylamine, triethylamine and aniline, nitrile solvents such as acrylonitrile and acetonitrile, nitromethane, Examples include nitro solvents such as nitroethane, organic solvents such as aldehyde solvents such as acetaldehyde, propionaldehyde, butyraldehyde, pentanal, and acrylic aldehyde. A mixture of one or more selected from these is used. be able to.

  Among the above materials, the first dispersion medium 32A is mainly water and / or water-soluble liquid (liquid having excellent compatibility with water (for example, liquid having a solubility in 100 g of water at 25 ° C. of 30 g or more)). It is preferable that it is comprised by these. Thereby, for example, the dispersibility of the dispersoid 31A (first dispersoid 311A) in the first dispersion medium 32A can be improved, and the particle size of the dispersoid 31A in the first dispersion 3A is compared. And small variation in size. As a result, the obtained granular material 4 (toner base particles 4A) has a small variation in size and shape among the particles and a relatively large circularity. In particular, when the first dispersion medium 32A is made of water, for example, in the toner manufacturing process, the organic solvent can be substantially prevented from volatilizing. As a result, the toner can be produced by a method that hardly causes adverse effects on the environment, that is, an environmentally friendly method.

  When a mixture of a plurality of components is used as the constituent material of the first dispersion medium 32A, the constituent material of the first dispersion medium 32A is an azeotropic mixture between at least two kinds of components constituting the mixture. It is preferable to use one that can form (the lowest boiling azeotrope). This makes it possible to efficiently remove the first dispersion medium 32A in a solidifying section or the like of a toner manufacturing apparatus described later. In addition, it becomes possible to remove the first dispersion medium 32A at a relatively low temperature in a solidifying section or the like of a toner manufacturing apparatus to be described later, and the deterioration of the characteristics of the obtained granular material 4 (toner base particles 4A) is more effective. Can be prevented. For example, liquids that can form an azeotrope with water include carbon disulfide, carbon tetrachloride, methyl ethyl ketone (MEK), acetone, cyclohexanone, 3-heptanone, 4-heptanone, ethanol, n-propanol, Isopropanol, n-butanol, i-butanol, t-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, n-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol 2-methoxyethanol, allyl alcohol, furfuryl alcohol, phenol, dipropyl ether, dibutyl ether, 1,4-dioxane, anisole, 2-methoxyethanol, hexane, heptane, cyclohexane, methylcyclohexane, octane, dideca , Methylcyclohexene, isoprene, toluene, benzene, ethylbenzene, naphthalene, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, furfuryl alcohol, chloroform, 1,2-dichloroethane, trichloroethylene, chlorobenzene, acetylacetone, acetic acid Ethyl acetate, methyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, ethyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, ethyl formate, isobutyl formate, ethyl acrylate, methyl methacrylate, ethyl benzoate, trimethylamine, hexylamine, triethylamine Aniline, acrylonitrile, acetonitrile, nitromethane, nitroethane, acrylic aldehyde and the like.

In addition, the boiling point of the first dispersion medium 32A (the first dispersion medium 32A to be removed in a later step) is not particularly limited, but is preferably 180 ° C. or lower, and more preferably 150 ° C. or lower. Preferably, it is 35-130 degreeC. As described above, when the boiling point of the first dispersion medium 32A is relatively low, the first dispersion medium 32A can be removed relatively easily in a solidifying section or the like of a toner manufacturing apparatus described later. . Further, by using such a material as the first dispersion medium 32A, the residual amount of the first dispersion medium 32A in the obtained granular material 4 can be made particularly small. As a result, the reliability as a toner is further increased.
The first dispersion medium 32A may contain components other than the materials described above. For example, in the first dispersion medium 32A, some constituents of the dispersoid 31A, inorganic fine powders such as silica, titanium oxide, and iron oxide, fatty acids, fatty acid metal salts, polymer polymerization fine powders, etc. Various additives such as organic fine powder may be included.

2. Dispersoid In this embodiment, the first dispersion 3A includes, as the dispersoid 31A, at least a first dispersoid 311A mainly composed of a binder resin and a dispersoid 312A mainly composed of an adhesive resin. It is a waste.
2-1. First dispersoid 311A
The first dispersoid 311A is made of a material containing at least a binder resin (binder resin), and is usually made of a material containing most of the components of the kneaded material K7 described above.

The content of the binder resin in the first dispersoid 311A is not particularly limited, but is preferably 1 to 99 wt%, and more preferably 15 to 90 wt%. When the content of the binder resin in the first dispersoid 311A is less than the lower limit value, the bonding strength (fixing strength) of the finally obtained toner to a recording medium such as paper is lowered and the binding is reduced. Since components (additives such as a colorant) other than the resin are easily detached from the finally obtained toner particles, the photoreceptor and the like are easily contaminated, and durability may be reduced. On the other hand, when the content of the binder resin in the first dispersoid 311A exceeds the upper limit, the content of the colorant in the finally obtained toner is relatively lowered, so that the colorability is insufficient. However, the image density may not be sufficiently obtained.
In addition, when the raw material K5 containing the colorant is used for the preparation of the kneaded material K7 described above, the colorant is usually contained in the first dispersoid 311A in the first dispersion 3A (droplet 9A). include.

The content of the colorant in the first dispersion 3A is not particularly limited, but is preferably 0.1 to 10 wt%, and more preferably 0.3 to 3.0 wt%. When the content of the colorant is less than the lower limit, it may be difficult to form a visible image having a sufficient density depending on the type of the colorant. On the other hand, if the content of the colorant exceeds the upper limit, the fixing characteristics and charging characteristics of the finally obtained toner may be deteriorated.
When the raw material K5 containing wax is used for the preparation of the kneaded material K7, the wax is usually contained in the first dispersoid 311A in the first dispersion 3A (droplet 9A). It is.

The wax content in the first dispersion 3A is not particularly limited, but is preferably 1.0 wt% or less, and more preferably 0.5 wt% or less. When the content of the wax is too large, the wax is liberated and coarsened in the finally obtained toner particles, and the toner seeps into the toner particle surface and the transfer efficiency of the toner tends to decrease. Indicates.
In addition, the first dispersoid 311A dispersed in the first dispersion medium 32A may have, for example, substantially the same composition or different composition among the respective particles. May be.

The average particle diameter d ₁ of the first dispersoid 311A in the first dispersion 3A is not particularly limited, but is preferably 0.04 to 1.0 μm, and preferably 0.10 to 0.80 μm. Is more preferable. When the average particle diameter d1 of the _first dispersoid 311A is in such a range, the finally obtained granular material 4 has an appropriate degree of circularity, and has characteristics and shapes between the particles. Excellent uniformity. On the other hand, if the average particle diameter d1 of the _first dispersoid 311A in the first dispersion 3A is too small, the particle size (toner base particles) 4 obtained becomes too small, The fluidity of the dispersion 3A may be reduced, and it may be difficult to eject the droplets 9A having a sufficiently uniform size in the granular material manufacturing process described later. On the other hand, if the average particle diameter d1 of the _first dispersoid 311A in the first dispersion 3A is too large, the particle diameter of the resulting granule 4 (toner base particle 4A) becomes too large, or the granule 4 There is a possibility that it is difficult to sufficiently increase the circularity of the (toner mother particles 4A).

Further, when the average particle diameter of the first dispersoid 311A in the first dispersion 3A is d ₁ [μm] and the average particle diameter of the granular material 4 is D [μm], 2 ≦ D / d ₁ ≦ The relationship of 200 is preferable, the relationship of 3 ≦ D / d ₁ ≦ 150 is more preferable, and the relationship of 4 ≦ D / d ₁ ≦ 100 is more preferable. By satisfying such a relationship, the finally obtained toner has a particularly small variation in shape, size, composition, etc. among the respective toner particles 100 (granular bodies 4). As a result, the toner The overall characteristics are particularly excellent, and the reliability is improved. On the other hand, when D / d ₁ is less than the lower limit, the surface irregularities are relatively large with respect to the average particle diameter D of the granular material 4, and thus the fluidity tends to deteriorate. Therefore, the thin layer on the developing roller tends to be non-uniform. On the other hand, if D / d ₁ exceeds the upper limit, the irregularities on the surface of the granular material 4 become too small, and the effect of improving the transfer efficiency is lowered and the cleaning property tends to be lowered.

  The content of the first dispersoid 311A in the first dispersion 3A is not particularly limited, but is preferably 2 to 70 wt%, more preferably 5 to 60 wt%, and 10 to 50 wt%. More preferably. When the content of the first dispersoid 311A is less than the lower limit value, the circularity of the obtained granular material 4 (toner base particles 4A) tends to decrease. Further, when solidifying, a large amount of heat energy may be required. On the other hand, when the content of the first dispersoid 311A exceeds the upper limit, depending on the composition of the first dispersion medium 32A and the like, the viscosity of the first dispersion 3A increases, and the resulting granular material 4 (toner There is a tendency that variations in the shape and size of the mother particles 4A) increase. Further, if the content of the first dispersoid 311A exceeds the upper limit, it may be difficult to sufficiently atomize and eject the droplets of the first dispersion 3A in the granular material manufacturing process described later. There is sex.

2-2. Dispersoid (adhesive resin)
The dispersoid 312A is made of a material containing at least an adhesive resin. Thus, in the present embodiment, the adhesive resin is included as a constituent material of the dispersoid 31A. Thus, in the first dispersion 3A, the adhesive resin is mainly contained in a phase other than the first dispersoid 311A (a phase other than the phase mainly composed of the binder resin). preferable. As a result, the toner particles 100 having the above-described configuration can be easily and reliably manufactured. In particular, when the adhesive resin is included as a constituent material of the dispersoid 31A (dispersoid 312A) of the first dispersion 3A, the unjoined portion of the joined body 40 can be more reliably bonded. The mechanical strength of the toner particles 100 is particularly excellent.

The average particle size _{d 2} of the dispersoid 312A in the first dispersion 3A is not particularly limited, but is preferably 0.04～1.0Myuemu, more preferably from 0.10~0.80μm . When the dispersoid average particle size d ₂ of 312A is within this range, the granulate 4 finally obtained, the unbonded portion as described above, can be efficiently formed adhesive resin phase 42 it can. Moreover, the granular material 4 finally obtained can be obtained as having an appropriate circularity, excellent properties and uniformity in shape among the particles, and having particularly excellent mechanical stability. it can. In contrast, if the average particle size d ₂ of the dispersoid 312A in the first dispersion 3A is too small, depending on the content or the like of the dispersoid 312A in the first dispersion 3A, the unbonded portion, the adhesive It may be difficult to efficiently form the resin phase 42, and the proportion of voids (holes) in the granular material 4 may increase. If the average particle size d ₂ of the dispersoid 312A in the first dispersion 3A is too large, the content and the like of the dispersoid 312A in the first dispersion 3A, efficiently binder resin fine particles It becomes difficult to melt-bond, and the mechanical stability of the granular material 4 (toner particles 100) tends to be reduced.

  The content of the dispersoid 312A in the first dispersion 3A is not particularly limited, but is preferably 2 to 80 wt%, more preferably 10 to 60 wt%, and 20 to 40 wt%. Further preferred. When the content of the dispersoid 312A is less than the lower limit, the circularity of the obtained granular material 4 (toner base particles 4A) tends to be reduced. Further, when solidifying, a large amount of heat energy may be required. On the other hand, when the content of the dispersoid 312A exceeds the upper limit, depending on the composition of the first dispersion medium 32A and the like, the viscosity of the first dispersion 3A increases, and the resulting granular material 4 (toner base particles 4A). ) Shows a tendency for variations in shape and size to increase. Further, if the content of the dispersoid 312A exceeds the upper limit, it may be difficult to sufficiently atomize and eject the droplets of the first dispersion 3A in the granule manufacturing process described later. .

The dispersoid 312A dispersed in the first dispersion medium 32A may have, for example, substantially the same composition or different composition among the particles. .
Moreover, components other than the above may be contained in the first dispersion 3A. Examples of such components include a dispersant and a dispersion aid. Among these, when a dispersant and a dispersion aid are used, for example, the dispersibility of the dispersoid 31A in the first dispersion 3A (droplet 9A) can be improved.

  Examples of the dispersant include inorganic dispersants such as tricalcium phosphate, nonionic organic dispersants such as polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, polyethylene glycol lauric acid diester, and metal tristearate (for example, aluminum salt). Etc.), distearic acid metal salts (eg, aluminum salts, barium salts, etc.), stearic acid metal salts (eg, calcium salts, lead salts, zinc salts, etc.), linolenic acid metal salts (eg, cobalt salts, manganese salts, lead) Salts, zinc salts, etc.), octanoic acid metal salts (eg, aluminum salts, calcium salts, cobalt salts, etc.), oleic acid metal salts (eg, calcium salts, cobalt salts, etc.), palmitic acid metal salts (eg, zinc salts, etc.) ), Naphthenic acid metal salts (eg calcium salts, cobalt salts, man Salts, lead salts, zinc salts, etc.), resinate metal salts (eg, calcium salts, cobalt salts, manganese salts, lead salts, zinc salts, etc.), polyacrylic acid metal salts (eg, sodium salts), polymethacryl Acid metal salt (for example, sodium salt), polymaleic acid metal salt (for example, sodium salt), acrylic acid-maleic acid copolymer metal salt (for example, sodium salt), polystyrene sulfonic acid metal salt (for example, sodium) Anionic organic dispersants such as salts) and cationic organic dispersants such as quaternary ammonium salts. Among these, nonionic organic dispersants or anionic organic dispersants are particularly preferable.

The content of the dispersant in the first dispersion 3A is not particularly limited, but is preferably 3.0 wt% or less, and more preferably 0.01 to 1.0 wt%.
Examples of the dispersion aid include anions, cations, and nonionic surfactants.
The dispersing aid may be used alone without being used in combination with the dispersing agent, but is preferably used in combination with the dispersing agent. In the case where the first dispersion 3A contains a dispersant, the content of the dispersion aid in the first dispersion 3A is not particularly limited, but is preferably 2.0 wt% or less, 0.005 to More preferably, it is 0.5 wt%.

In addition, the first dispersion 3A may contain an emulsifier and the like. In particular, when the first dispersion (suspension) 3A is prepared via an emulsion as described later, the emulsifier used during the preparation of the emulsion is contained in the first dispersion 3A. It may be contained (may remain). Further, for example, when the first dispersion (suspension) 3A is prepared via an emulsion as described later, the emulsion is contained in the first dispersion 3A (particularly in the dispersoid 31A). A part of the solvent used for the preparation of may remain.
Further, in the first dispersion 3A, components other than the dispersoid 31A may be dispersed as an insoluble matter. For example, in the first dispersion 3A, inorganic fine powders such as silica, titanium oxide, and iron oxide, organic fine powders such as fatty acids and fatty acid metal salts, and the like may be dispersed.

<< Method for Preparing First Dispersion (First Dispersion Preparation Step) >>
The first dispersion 3A as described above can be prepared, for example, as follows (can be prepared through the following dispersion preparation step).
First, a kneaded product K7 pulverized in powder or granular form and a powdery or granular adhesive resin are added to water or a water-soluble liquid to obtain a dispersion preparation liquid (crushed product-containing liquid) 2. The average particle diameter of the kneaded material K7 in the liquid 2 for preparing a dispersion is preferably 0.1 μm to 5 mm, more preferably 1 μm to 2 mm, and further preferably 10 μm to 1 mm. Moreover, the average particle diameter of the adhesive resin in the liquid 2 for preparing a dispersion is preferably 0.1 μm to 5 mm, more preferably 1 μm to 2 mm, and further preferably 10 μm to 1 mm.
Thereafter, the dispersion preparation liquid 2 obtained as described above is ejected from a plurality of nozzles, and the dispersion preparation liquid 2 ejected from each nozzle is caused to collide with each other. The kneaded material K7 and the adhesive resin contained therein are atomized, and the atomized kneaded material (first dispersoid 311A) and the atomized adhesive resin (dispersoid 312A) are converted into the liquid (first dispersion medium 32A). ) A first dispersion 3A dispersed therein is obtained (atomization step).
More specifically, the first dispersion 3A can be obtained using an apparatus (atomization apparatus) as shown in FIG.

  As shown in FIG. 4, the atomization apparatus B1 includes nozzles B21 and B22 for injecting the dispersion preparation liquid 2 as described above, and a dispersion preparation liquid supply unit B3 for supplying the dispersion preparation liquid 2. , Housing part B5 having chamber part B4 for colliding liquid preparation liquid 2 ejected from nozzle B21 and nozzle B22, atomized kneaded material K7 (first dispersoid 311A) and atomized adhesive And a recovery unit B6 that recovers the first dispersion 3A (dispersion liquid 2) containing the resin (dispersoid 312A). Further, as shown in FIG. 4, the atomization apparatus B1 is supplied from the dispersion preparation liquid supply unit B3 between the dispersion preparation liquid supply unit B3 and each nozzle (nozzle B21, nozzle B22). An ultra-high pressure generating pump B7 that pressurizes (accelerates) the dispersion-preparing liquid 2 and a branch B8 that branches the dispersion-preparing liquid 2 pressurized (accelerated) by the ultrahigh-pressure generating pump B7 to each nozzle. Have.

  The dispersion preparation liquid supply unit B3 may have any function as long as it has a function of supplying the dispersion preparation liquid 2 to the ultrahigh pressure generation pump B7, but as illustrated, stirring for stirring the dispersion preparation liquid 2 It may have means B31. Thereby, for example, even if the kneaded material K7 and the adhesive resin are difficult to disperse in the first dispersion medium 32A, the dispersion liquid in which the powdery or granular kneaded material K7 and the adhesive resin are sufficiently uniformly dispersed The preparation liquid 2 can be supplied to the ultrahigh pressure generation pump B7.

  Further, as shown in FIG. 5, the nozzle B21 and the nozzle B22 are arranged so that the dispersion liquid preparation liquid 2 ejected from each nozzle collides at a predetermined angle θ on the central axis of the chamber B4. Yes. Although this collision angle (theta) is not specifically limited, It is preferable that it is 90-180 degrees, and it is more preferable that it is 120-180 degrees. By making the collision angle θ within such a range, when two jets collide, the kinetic energy of the jets is reduced to the energy that atomizes the kneaded material K7 and the adhesive resin with as little loss as possible ( Collision energy), and the kneaded material K7 and the adhesive resin can be efficiently atomized. On the other hand, if the collision angle θ is less than the lower limit, the loss of kinetic energy of the jet flow becomes large, and the kneaded material K7 and the adhesive resin may not be sufficiently atomized. Note that the collision angle indicates an angle formed by two straight lines as shown in FIG. 5 and is 180 ° or less.

The kneaded material K7 and the adhesive resin in the dispersion liquid 2 are atomized as follows by the atomizer B1.
The dispersion preparation liquid 2 supplied from the dispersion preparation liquid supply section B3 into the atomization apparatus B1 is pressurized (accelerated) by the ultrahigh pressure generation pump B7 and branched by the branch section B8. Each of the branched liquid preparation liquids 2 is transported to the nozzle B21 and the nozzle B22, sprayed from the tip of each nozzle, and collides. The kneaded material K7 and the adhesive resin in the dispersion preparing liquid 2 are atomized by collision to obtain the first dispersion 3A. The first dispersion 3A descends in the housing part B5 and is recovered by the recovery part B6.

  The pressure (injection pressure) for injecting the dispersion preparation liquid 2 from the nozzle B21 and the nozzle B22 is preferably 50 to 300 MPa, and more preferably 70 to 250 MPa. By setting the injection pressure within such a range, the first dispersion 3A including the dispersoid 31A (first dispersoid 311A, dispersoid 312A) having an appropriate particle diameter can be efficiently obtained. On the other hand, if the injection pressure is too low, the kneaded material K7 and the adhesive resin are not sufficiently atomized, and it is difficult to sufficiently reduce the size of the dispersoid 31A in the obtained first dispersion 3A. In some cases, the first dispersion 3A may not be obtained (the kneaded product K7 and the adhesive resin cannot be dispersed in the liquid). On the other hand, if the injection pressure is too high, the kneaded material K7 and the constituent materials of the adhesive resin may be deteriorated and deteriorated. In addition, the injection pressure in the nozzle B21 and the nozzle B22 may be the same or different.

In such a atomization step, for example, the dispersion liquid 2 may be heated (heated). As a result, the circularity of the dispersoid 31A in the obtained first dispersion 3A can be made moderate, and as a result, the circularity of the finally obtained toner particles can be made relatively high. Can do. That is, by heating in this way, the kneaded product K7 in the dispersion-preparing liquid 2 and the atomized kneaded product K7 (first dispersoid 311A), adhesive, while performing the atomization treatment of the adhesive resin, A thermal spheronization treatment can be performed on the resin (dispersoid 312A).
Moreover, it is preferable that it is 20-200 degreeC, and, as for the temperature of the liquid 2 for dispersion preparation injected from each nozzle, it is more preferable that it is 40-160 degreeC. Thereby, the above-mentioned effect becomes more remarkable.

  In addition, the atomization apparatus B1 is such that at least a part of the first dispersion 3A (or the kneaded product K7 and the adhesive resin) is pulverized from the recovery unit B6 to the dispersion preparation liquid supply unit (dispersion supply unit) B3 It has means for transporting the dispersion preparation liquid 2). That is, as shown in FIG. 4, the first dispersion 3A (or kneaded product K7, dispersion preparation liquid 2 in which at least a part of the adhesive resin is crushed) is transported by the transport pump B9. It is conveyed to the liquid supply part B3 for preparing a dispersion via the pipe B10.

  Thus, it is preferable that the atomization process is repeatedly performed. Thereby, it is possible to efficiently form the dispersoid 31A having a small variation in shape among the particles and a small width of the particle size distribution. This repetition is preferably performed until the average particle diameter of the obtained dispersoid 31A (first dispersoid 311A, dispersoid 312A) becomes a value within the above range. Thereby, the above-mentioned effect becomes more remarkable.

  When the first dispersion 3A is prepared by the method as described above, the first dispersion 3A can be prepared without substantially using an organic solvent or using an extremely small amount of an organic solvent. it can. For this reason, it is possible to substantially prevent the organic solvent from being volatilized in a solidifying section or the like of a toner manufacturing apparatus as will be described later. As a result, the toner can be manufactured by a method that hardly causes adverse effects on the environment.

Although the preferred embodiment of the kneaded material K7 in the dispersion preparation liquid 2 and the apparatus for atomizing the adhesive resin (atomization apparatus B1) has been described above, the configuration of the atomization apparatus is not limited to this. For example, each part constituting the atomization apparatus can be replaced with an arbitrary one that exhibits the same function, or another structure can be added.
For example, in the above-described embodiment, an apparatus using two nozzles has been described. However, the present invention is not limited to this, and three or more nozzles may be used. When three or more nozzles are used in this way, the collision angle θ of the dispersion-preparing liquid 2 ejected from the two nozzles whose tip ends are the farthest is in the above-described range. Is preferred.

  As described above, the method as described above causes the dispersion preparation liquid 2 obtained as described above to be ejected from two or more nozzles, and the dispersion preparation liquids 2 ejected from the respective nozzles are combined. It has the atomization process of making it knead | mix and knead | mixed the kneaded material K7 and adhesive resin. As a result, the finally obtained toner has a small variation in shape among the toner particles and a particularly small width of the particle size distribution. In addition, by performing atomization in this way, the kneaded product K7 can be atomized while more suitably maintaining the dispersion state of the additives such as wax in the kneaded product K7. As a result, the obtained toner has excellent properties such as durability, storage stability, and charging characteristics.

Further, in the above description, the dispersion liquid preparation liquid 2 has been described as including an adhesive resin, but the dispersion liquid preparation liquid 2 may not include an adhesive resin. More specifically, the liquid preparation liquid 2 that does not contain an adhesive resin is subjected to the same treatment as described above, and then a powdery (fine powder) adhesive resin is applied to the treated liquid. The first dispersion 3A may be prepared by adding. Further, for example, the dispersion preparation liquid 2 containing the kneaded material K7 and not containing the adhesive resin is subjected to the same treatment as described above to obtain the first liquid (binder resin suspension) and bonding. The dispersion preparation liquid 2 containing the resin and not containing the kneaded material K7 is subjected to the same treatment as above to obtain a second liquid (adhesive resin suspension), and then the first liquid (condensation). The intended first dispersion 3A can be obtained by mixing the (resin suspension) and the second liquid (adhesive resin suspension). Thereby, each of the kneaded material K7 and the adhesive resin can be atomized under optimum conditions, and as a result, both the first dispersoid 311A and the dispersoid 312A have an optimum particle size distribution, and The first dispersion 3A with little modification and deterioration of the constituent materials can be obtained easily and reliably. In the above description, the adhesive resin is described as constituting the dispersoid. However, the adhesive resin may constitute the dispersion medium. In addition, when the adhesive resin is a constituent material of the dispersion medium as described above, for example, the same treatment as described above is performed on the dispersion liquid 2 that does not include the adhesive resin, and then the above-described treatment is performed. The first dispersion 3A can be prepared by adding an adhesive resin to the liquid. Thereby, for the preparation of the first dispersion 3A, an adhesive resin having a relatively large particle diameter can be used, the handling of the adhesive resin is facilitated, and the modification of the adhesive resin due to the collision energy as described above, Deterioration and the like can be prevented.
The first dispersion 3A can also be prepared by the following method. In this method, as described below, a kneaded product suspension (binder resin suspension) in which a kneaded product is dispersed as a dispersoid and an adhesive resin suspension in which an adhesive resin is dispersed as a dispersoid are mixed. As a result, the intended first dispersion 3A is obtained.

First, preparation of a kneaded product suspension (binder resin suspension) will be described.
First, an aqueous liquid in which a dispersant and / or a dispersion aid is added to water or a water-soluble (excellent water compatibility) liquid as necessary is prepared.
On the other hand, a binder resin liquid containing the kneaded material K7 is prepared. The binder resin liquid can be prepared, for example, by using a solvent capable of dissolving at least a part of the constituent material of the kneaded material K7 (particularly, the binder resin).
Next, the binder resin liquid is gradually added dropwise to the stirred aqueous liquid, whereby the first dispersoid (dispersed particles) containing the binder resin in the aqueous dispersion medium is added. ) Is dispersed in an emulsion (emulsion).

  Thereafter, the solvent is removed from the obtained emulsion to obtain a kneaded product suspension (binder resin suspension) in which the kneaded product is dispersed as the first dispersoid. The removal of the solvent can be performed, for example, by heating the emulsion or placing it in a reduced pressure atmosphere (solvent removal step). By using such a method, the circularity of the first dispersoid 311A in the first dispersion 3A (droplet 9A) can be further increased. As a result, the granular material 4 (toner base particles 4A) can be obtained with a sufficiently high circularity and a particularly small variation in shape among the particles. In addition, when dripping the binder resin liquid, the aqueous liquid and / or the binder resin liquid may be heated. Moreover, when such a method is used, the particle size of the dispersoid (first dispersoid 311A in the first dispersion 3A) in the kneaded product suspension can be controlled to an appropriate size.

The solvent may be any solvent as long as it can dissolve at least a part of the constituent material (particularly the binder resin) of the kneaded product K7, but can be easily removed in the solvent removal step. It is preferred that
The solvent is preferably a solvent having low compatibility with the above-described first dispersion medium 32A (for example, a solvent having a solubility in 100 g of dispersion medium at 25 ° C. of 30 g or less). Thereby, even if the solvent removal in the solvent removal step is insufficient, the first dispersoid 311A is finely dispersed in a stable state in the first dispersion 3A (droplet 9A). Can do.

  The composition of the solvent can be appropriately selected according to, for example, the composition of the binder resin described above, the composition of the colorant, the composition of the first dispersion medium 32A, and the like. Examples of the solvent include inorganic solvents such as water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, and 3-heptanone. , Ketone solvents such as 4-heptanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, t-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, Alcohol solvents such as n-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol, 2-methoxyethanol, allyl alcohol, furfuryl alcohol, phenol, diethyl ether, dipropyl ether, diisopropyl Ether solvents such as pyr ether, dibutyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), 2-methoxyethanol Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, methylcyclohexane, octane, didecane, methylcyclohexene, isoprene, toluene, xylene, benzene, ethylbenzene , Aromatic hydrocarbon solvents such as naphthalene, pyridine, pyrazine, furan, pyrrole, thiophene, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine Aromatic heterocyclic compound solvents such as furfuryl alcohol, amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dichloromethane, chloroform, 1,2-dichloroethane, trichlorethylene, Halogenated solvents such as chlorobenzene and carbon tetrachloride, acetylacetone, ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, isopentyl acetate, ethyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, ethyl formate, Ester solvents such as isobutyl formate, ethyl acrylate, methyl methacrylate and ethyl benzoate; amine solvents such as trimethylamine, hexylamine, triethylamine and aniline; and nitric acids such as acrylonitrile and acetonitrile. Organic solvents such as tolyl solvents, nitro solvents such as nitromethane and nitroethane, and aldehyde solvents such as acetaldehyde, propionaldehyde, butyraldehyde, pentanal, and acrylic aldehyde, and the like, one or more selected from these Can be used. Among these, those containing an organic solvent are preferable, ketone solvents (more preferably, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), etc.), ether solvents, cellosolve solvents are preferable. , Aliphatic hydrocarbon solvents (more preferably cyclohexane etc.), aromatic hydrocarbon solvents (more preferably toluene, ethylbenzene etc.), aromatic heterocyclic compounds solvents, amide solvents, halogen compound solvents ( More preferably, from chloroform, trichloroethylene, carbon tetrachloride, etc.), ester solvents (more preferably, ethyl acetate, propyl acetate, butyl acetate, etc.), amine solvents, nitrile solvents, nitro solvents, aldehyde solvents, etc. Contains one or more selected Than it is. By using such a solvent, it is possible to remove the solvent in the solvent removal step relatively easily, and even if the removal of the solvent in the solvent removal step is insufficient, the first In the dispersion liquid 3A (droplet 9A), the first dispersoid 311A can be finely dispersed in a stable state.

Next, preparation of the adhesive resin suspension will be described.
First, in the same manner as described above, an aqueous liquid is prepared by adding a dispersant and / or a dispersion aid as necessary to water or a water-soluble (excellent compatibility with water) liquid.
On the other hand, an adhesive resin liquid containing an adhesive resin is prepared. The adhesive resin liquid can be prepared, for example, by using a solvent capable of dissolving at least a part of the adhesive resin.
Next, the adhesive resin liquid is added to the stirred aqueous liquid while gradually dropping, thereby emulsifying the dispersoid (dispersed particles) containing the adhesive resin in the aqueous dispersion medium. A liquid (emulsion) is obtained.

  Thereafter, by removing the solvent from the obtained emulsion, an adhesive resin suspension in which the adhesive resin is dispersed as a dispersoid is obtained. The removal of the solvent can be performed, for example, by heating the emulsion or placing it in a reduced pressure atmosphere (solvent removal step). By using such a method, the circularity of the dispersoid 312A in the first dispersion 3A (droplet 9A) can be further increased. When dropping the adhesive resin liquid, the aqueous liquid and / or the adhesive resin liquid may be heated. Moreover, when such a method is used, the particle size of the dispersoid in the adhesive resin suspension (the dispersoid 312A in the first dispersion 3A) can be controlled to an appropriate size.

The solvent may be any solvent as long as it can dissolve at least a part of the adhesive resin, but is preferably easily removed in the solvent removal step.
The solvent is preferably a solvent having low compatibility with the above-described first dispersion medium 32A (for example, a solvent having a solubility in 100 g of dispersion medium at 25 ° C. of 30 g or less). Thereby, even if the removal of the solvent in the solvent removal step is insufficient, the dispersoid 312A can be finely dispersed in a stable state in the first dispersion 3A (droplet 9A).

Further, the composition of the solvent can be appropriately selected according to, for example, the composition of the adhesive resin described above, the composition of the first dispersion medium 32A, and the like. What was illustrated as a solvent used at the time of preparation of (binder resin suspension) can be used. By using such a solvent, the removal of the solvent in the solvent removal step can be performed relatively easily, and even if the removal of the solvent in the solvent removal step is insufficient, In the dispersion liquid 3A (droplet 9A), the dispersoid 312A can be finely dispersed in a stable state.
Thereafter, the first dispersion 3A is obtained by mixing the kneaded material suspension (binder resin suspension) obtained as described above and the adhesive resin suspension.

Moreover, when preparing the suspension as 1st dispersion liquid 3A by the above methods, it is preferable to satisfy the following conditions. That is, the boiling point of the solvent (solvent capable of dissolving at least a part of the constituent material of the kneaded material K7) used for the preparation of the kneaded material suspension (binder resin suspension) under atmospheric pressure is T _bp ( sol) [° C.], where T _bp (dm) [° C.] is the boiling point under atmospheric pressure of the liquid used as the dispersion medium of the dispersion (emulsion) containing the kneaded product, | T _bp (dm) −T _It is preferable to satisfy the relationship of _bp (sol) | ≦ 40. By satisfying such a relationship, the solvent removal step of preparing the kneaded product suspension from the emulsified liquid can be performed smoothly, and the solvent remains more reliably in the obtained kneaded product suspension. Can be prevented. Further, it is more preferable that the relationship of −30 <T _bp (dm) −T _bp (sol) <40 is satisfied between T _bp (sol) and T _bp (dm), and −20 <T _bp ( dm) −T _bp (sol) <40 is more preferable, and it is most preferable that the relationship 0 ≦ T _bp (dm) −T _bp (sol) <40 is satisfied. By satisfying such a relationship, from the inside of the dispersoid in the solvent removal step, etc., while performing the solvent removal step sufficiently smoothly so that the solvent does not substantially remain in the kneaded product suspension obtained. It is possible to reliably prevent the solvent from being rapidly vaporized (boiled), and to effectively prevent the formation of an irregularly shaped dispersoid in the kneaded product suspension obtained.
When the method as described above is employed, the first dispersion 3A having a very small variation in size of the dispersoid 31A (first dispersoid 311A, dispersoid 312A) can be easily and reliably prepared.
The first dispersion 3A can also be prepared by the following method. In this method, similarly to the method described above, a kneaded product suspension (binder resin suspension) in which the kneaded product is dispersed as a dispersoid, and an adhesive resin suspension in which an adhesive resin is dispersed as a dispersoid. By mixing, the intended first dispersion 3A is obtained.

First, preparation of a kneaded product suspension (binder resin suspension) will be described.
First, an aqueous liquid in which a dispersant and / or a dispersion aid is added to water or a water-soluble liquid as necessary is prepared.
On the other hand, a kneaded material K7 pulverized into a powder or granule is prepared.

Next, the kneaded product is gradually added into an agitated aqueous liquid, whereby a kneaded material suspension in which the dispersoid containing the binder resin is dispersed in the aqueous dispersion medium (condensation). (Resin suspension) is obtained.
In addition, when the kneaded material is added, for example, an aqueous liquid may be heated. Thereby, the particle size of the first dispersoid 311A in the first dispersion 3A can be controlled to an appropriate size. The average particle size of the kneaded material put into the aqueous liquid is preferably 0.1 μm to 5 mm, more preferably 0.15 to 10 μm, and still more preferably 0.2 to 2 μm.

Next, preparation of the adhesive resin suspension will be described.
First, an aqueous liquid in which a dispersant and / or a dispersion aid is added to water or a water-soluble liquid as necessary is prepared.
On the other hand, a powdery or granular adhesive resin is prepared.
Next, an adhesive resin suspension in which a dispersoid containing the adhesive resin is dispersed in an aqueous dispersion medium is obtained by gradually introducing the adhesive resin into a stirred aqueous liquid. .

  In addition, when the adhesive resin is added, for example, an aqueous liquid may be heated. Thereby, the particle size of the dispersoid 312A in the first dispersion 3A can be controlled to an appropriate size. The average particle size of the adhesive resin put into the aqueous liquid is preferably 0.1 μm to 5 mm, more preferably 0.15 to 10 μm, and further preferably 0.2 to 2 μm.

  After that, the first dispersion 3A is obtained by mixing the kneaded material suspension (binder resin suspension) obtained as described above and the adhesive resin suspension. When the first dispersion 3A is prepared by such a method, the first dispersion 3A can be prepared without substantially using an organic solvent or using an extremely small amount of an organic solvent. . For this reason, it is possible to substantially prevent the organic solvent from being volatilized in a solidifying section or the like of a toner manufacturing apparatus as will be described later. As a result, the toner can be manufactured by a method that hardly causes adverse effects on the environment.

The first dispersion 3A can also be prepared by the following method.
First, a binder resin dispersion (binder resin suspension) obtained by dispersing a kneaded product K7 containing at least a binder resin, and a colorant dispersion (colorant suspension) obtained by dispersing at least a colorant. And an adhesive resin dispersion (adhesive resin suspension) obtained by dispersing the adhesive resin. The binder resin dispersion, the colorant dispersion, and the adhesive resin dispersion can be suitably prepared by applying the method described above.

  Next, the binder resin dispersion, the colorant dispersion, and the adhesive resin dispersion are mixed and stirred. Thus, the first dispersoid 311A composed of a material containing a binder resin, the dispersoid (dispersoid for adhesion) 312A composed of a material containing an adhesive resin, and a material containing a colorant are included. A first dispersion 3A containing the dispersoid (dispersoid for coloring) obtained is obtained. As described above, the first dispersion 3A may include a dispersoid other than the first dispersoid 311A and the dispersoid 312A. Further, when such a method is used, the particle size of the dispersoid 31A (the first dispersoid 311A, the dispersoid 312A for adhesion, and the dispersoid for coloring) in the first dispersion 3A is appropriately set. The size can be controlled.

  In such a method, for example, first, the binder resin dispersion and the colorant dispersion may be mixed and stirred without adding the adhesive resin dispersion to obtain a new binder resin suspension. At this time, if necessary, an aggregating agent such as an inorganic metal salt may be added while stirring. Thereby, the aggregate which the kneaded material and the colorant aggregated to an appropriate size can be formed. Then, the first dispersion 3A can be obtained by adding the adhesive resin dispersion to the new binder resin suspension and further mixing and stirring. When such a method is used, the particle size of the dispersoid 31A (particularly, the first dispersoid 311A) in the first dispersion 3A can be controlled to an appropriate size by the aggregation.

<Second dispersion>
Next, the second dispersion 3B prepared using the resin fine particles as described above and a method for preparing the second dispersion 3B will be described.
<< Configuration of Second Dispersion >>
First, the configuration of the second dispersion 3B will be described.
The second dispersion 3B has a configuration in which the second dispersoid (dispersed phase) 31B is finely dispersed in the second dispersion medium 32B. The second dispersion 3B includes at least resin fine particles mainly composed of a fluorine-based resin as the second dispersoid 31B.

1. Second Dispersion Medium The second dispersion medium 32B may be any material as long as it can disperse the second dispersoid 31B described later, but the constituent material of the second dispersion medium 32B includes For example, the solvent materials exemplified as the constituent material of the first dispersion medium 32A can be used. In the case where the second dispersion medium 32B is composed of such a solvent material, it is preferable that the following conditions are satisfied.

  The second dispersion medium 32B is mainly composed of water and / or a water-soluble liquid (a liquid having excellent compatibility with water (for example, a liquid having a solubility in 100 g of water at 25 ° C. of 30 g or more)). Preferably there is. Thereby, for example, the dispersibility of the second dispersoid 31B in the second dispersion medium 32B can be improved, and the second dispersoid 31B in the second dispersion 3B has a relatively small particle size. In addition, it is possible to reduce the size variation. As a result, the resulting toner particles 100 are such that resin fine particles (external additive) 4B are uniformly dispersed in the vicinity of the surface of the toner base particles 4A, and the performance of the external additive 4B can be more fully exhibited. In particular, when the second dispersion medium 32B is composed of water, for example, in the toner manufacturing process, the organic solvent can be substantially prevented from volatilizing. As a result, the toner can be produced by a method that hardly causes adverse effects on the environment, that is, an environmentally friendly method.

  When a mixture of a plurality of components is used as the constituent material of the second dispersion medium 32B, the constituent material of the second dispersion medium 32B is an azeotropic mixture between at least two kinds of components constituting the mixture. It is preferable to use one that can form (the lowest boiling azeotrope). As a result, the second dispersion medium 32B can be efficiently removed in a solidifying part or the like of the toner manufacturing apparatus described later. In addition, it becomes possible to remove the second dispersion medium 32B at a relatively low temperature in a solidifying section or the like of a toner manufacturing apparatus described later, and it is possible to more effectively prevent deterioration of the characteristics of the obtained toner particles 100.

In addition, the boiling point of the second dispersion medium 32B (second dispersion medium 32B to be removed in a later step) is not particularly limited, but is preferably 180 ° C. or lower, more preferably 150 ° C. or lower. Preferably, it is 35-130 degreeC. As described above, when the boiling point of the second dispersion medium 32B is relatively low, the second dispersion medium 32B can be removed relatively easily in a solidifying section or the like of the toner manufacturing apparatus described later. . Further, by using such a material as the second dispersion medium 32B, the residual amount of the second dispersion medium 32B in the obtained toner particles 100 can be made particularly small. As a result, the reliability as a toner is further increased.
Further, the second dispersion medium 32B may contain components other than the materials described above. For example, in the second dispersion medium 32B, some of the constituents of the second dispersoid 31B, inorganic fine powders such as silica, titanium oxide, and iron oxide, fatty acids, fatty acid metal salts, polymer polymerization fines. Various additives such as organic fine powder such as powder may be included.

2. Second Dispersoid The second dispersoid 31B includes resin fine particles mainly composed of a fluororesin.
The average particle diameter _{d 3} of the second of the dispersoid 31B in the second dispersion 3B (resin fine particles) is not particularly limited, but is preferably 0.04~1.0μm, 0.10~0. More preferably, it is 80 μm. When the average particle diameter d ₃ of the second dispersoids 31B is within this range, can be deposited efficiently resin particles in a recess in the vicinity of the surface of the bonded body as described above. Moreover, the granular material 4 finally obtained can be obtained as having an appropriate circularity, excellent properties and uniformity in shape among the particles, and having particularly excellent mechanical stability. it can. In contrast, if the average particle diameter d ₃ of the second of the dispersoid 31B in the second dispersion 3B is too small, depending on the content or the like of the second of the dispersoid 31B in the second dispersion 3B, It becomes difficult to efficiently attach resin fine particles in the recesses near the surface of the joined body as described above. If the average particle diameter d ₃ of the second of the dispersoid 31B in the second dispersion 3B is too large, depending on the content or the like of the second of the dispersoid 31B in the second dispersion 3B, resinous Thus, it becomes difficult to efficiently melt and bond the fine particles to each other, and the mechanical stability of the granular material 4 (toner particles 100) tends to be lowered.

The content of the second dispersoid 31B in the second dispersion 3B is such that when the second dispersion 3B is ejected by a nozzle M2 ′, which will be described later, the ejected droplets 9B are converted into resin fine particles by toner base particles. If it has sufficient viscosity and the number of resin fine particles to adhere uniformly to the vicinity of the surface, there is no particular limitation.
The dispersoid 31B dispersed in the second dispersion medium 32B may have, for example, substantially the same composition or different composition between the particles. .

  The second dispersion 3B may contain components other than those described above. Examples of such components include a dispersant and a dispersion aid. Among these, when a dispersant and a dispersion aid are used, for example, the dispersibility of the dispersoid 31B in the second dispersion 3B can be improved. As the dispersant and the dispersion aid, for example, those exemplified above can be used.

The content of the dispersant in the second dispersion 3B is not particularly limited, but is preferably 3.0 wt% or less, and more preferably 0.01 to 1.0 wt%.
Examples of the dispersion aid include anions, cations, and nonionic surfactants.
The dispersing aid may be used alone without being used in combination with the dispersing agent, but is preferably used in combination with the dispersing agent. In the case where the second dispersion 3B contains a dispersant, the content of the dispersion aid in the second dispersion 3B is not particularly limited, but is preferably 2.0 wt% or less, 0.005 to More preferably, it is 0.5 wt%.

The second dispersion 3B may contain, for example, a dispersoid mainly composed of components other than the resin fine particles, that is, a dispersoid other than the dispersoid 31B.
Further, the second dispersion 3B may contain an emulsifier and the like. In particular, when the second dispersion (suspension) 3B is prepared via an emulsion as described later, the emulsifier used in preparing the emulsion is contained in the second dispersion 3B. It may be contained (may remain). In addition, for example, when the second dispersion (suspension) 3B is prepared via an emulsion as described later, in the second dispersion 3B (particularly in the second dispersoid 31B). A part of the solvent used for preparing the emulsion may remain.
In the second dispersion 3B, components other than the second dispersoid 31B may be dispersed as an insoluble matter. For example, in the second dispersion 3B, inorganic fine powders such as silica, titanium oxide, and iron oxide, organic fine powders such as fatty acids and fatty acid metal salts, and the like may be dispersed.

<< Method for Preparing Second Dispersion (Second Dispersion Preparation Step) >>
The second dispersion 3B as described above can be suitably prepared, for example, by applying the method for preparing the first dispersion 3A described above. For example, the second dispersion 3B can be suitably obtained by replacing the “kneaded material K7”, “binder resin”, and “adhesive resin” with “resin fine particles” in the above-described method.

<Granule production process and granule>
Next, the first dispersion liquid 3A and the second dispersion liquid 3B as described above are subjected to a granule manufacturing process as described in detail below, whereby a plurality of bindings derived from the first dispersoid 311A are obtained. Adhesive resin phase in the vicinity of the surface of toner base particles 4A having a joined body 40 formed by joining resin fine particles and an adhesive resin phase 42 composed of an adhesive resin derived from dispersoid 312A at an unjoined portion of the binder resin fine particles. A granular body 4 is obtained in which the resin fine particles 4B derived from the second dispersoid 31B are adhered (fixed or embedded) to 42.

  Thus, the granular material 4 obtained by obtaining the granular material 4 as the one having the bonded body 40 formed by bonding a plurality of binder resin fine particles derived from the first dispersoid 311A, Variations in shape, size, composition, etc. are particularly small. In other words, as described above, when the granular material 4 is obtained as an aggregate (joined body) of a plurality of first dispersoids 311A, the first dispersoid constituting the first dispersion 3A. Even when 311A has a relatively large variation in shape, size, composition, etc. among the individual particles (between individual dispersoid particles), the obtained granular material 4 has a shape between the particles. Variations in size, composition, etc. are small. As a result, the finally obtained toner has particularly small variations in shape, size, composition, and the like among the respective toner particles, has excellent properties as a whole toner, and improves reliability. Further, even when such a toner is manufactured, classification processing, thermal spheronization processing, mechanical surface modification, and the like are performed, such processing can be simplified or performed under mild conditions. it can. Further, the granular material 4 thus obtained has excellent mechanical strength and relatively large external force because the unbonded portion of the binder resin fine particles is bonded (adhered) by the adhesive resin phase 42 derived from the dispersoid 311A. Even if is added, unintentional collapse (particularly, collapse near the unjoined portion of the crevasse-like shape) hardly occurs. Further, in the granular material 4 thus obtained, the resin fine particles 4B do not exist so much in the toner base particles 4A but exist in the vicinity of the surface, so that the mechanical strength of the toner base particles 4A is increased by the resin fine particles 4B. Decrease can be prevented, and the resin fine particles 4B can sufficiently exhibit the performance required as an additive. In particular, since the fluororesin constituting the resin fine particles 4B has excellent releasability and chargeability, the obtained toner particles 100 have extremely excellent fixing characteristics and charging characteristics. Even though such resin fine particles 4B have excellent releasability, the toner base particles 4A are firmly bonded (fixed or embedded) to the toner base particles 4A (particularly, the adhesive resin phase 42). Is prevented from falling off. As a result, the toner particles 100 have excellent fixing characteristics and charging characteristics over a long period of time.

  On the other hand, when the granular material cannot be obtained as an aggregate (junction) of the dispersoid (first dispersoid) as described above, that is, each dispersoid particle is an independent granular material (toner). When the mother particles are formed, the finally obtained toner has a large variation in shape, size, composition, etc. among the toner particles. As a result, the characteristics of the toner as a whole are lowered and the reliability is low. In such a case, even if classification processing is performed after the toner production described later, it is difficult to sufficiently reduce the variation in size among the particles, and the yield of toner production is also as follows. Remarkably low. In order to suppress the variation in shape as described above, it is conceivable to perform a heat spheronization treatment at the time of forming the granular material or after the formation of the granular material. In such a case (particularly, formation of the granular material). If the conditions of the thermal spheronization treatment are not relatively severe, it is difficult to sufficiently reduce the variation in the shape of the obtained granular material. Deterioration and destruction of the compatibilized state and finely dispersed state of each component in the granular material are likely to occur, and it is difficult to exert sufficient characteristics in the finally obtained toner.

  Further, when the resin fine particles as described above are present in a large amount in the toner base particles, particularly in the joined body, the obtained granular material is inferior in mechanical strength. That is, when a large amount of resin fine particles are present inside the toner base particles, even when a plurality of binder resin fine particles are bonded to each other, when an external force is applied, the resin fine particles are releasable. As a result, the granular material tends to collapse (decompose) from the vicinity of the joint between the resin fine particles and the toner base particles. Therefore, the toner composed of such granular materials has a large variation in shape, size, characteristics and the like among the toner particles, and the reliability of the toner as a whole is low.

Further, when the resin fine particles as described above are present in a large amount in the toner base particles, particularly in the joined body, the obtained granular material cannot sufficiently exhibit the performance required for the resin fine particles as a toner. That is, in such a case, since the resin fine particles cannot directly exhibit charging characteristics and fixing characteristics outside the toner base particles, the obtained toner particles are inferior in charging characteristics and fixing characteristics.
The toner can be manufactured using, for example, a toner manufacturing apparatus M1 as shown in FIG.

<Toner production equipment>
As shown in FIG. 6, the toner manufacturing apparatus M1 includes a nozzle M2 that ejects the first dispersion 3A (droplet 9A) as described above, and a dispersion supply that supplies the first dispersion 3A to the nozzle M2. A part M4, a nozzle M2 ′ that ejects the second dispersion 3B (droplet 9B) as described above, a dispersion supply part M4 ′ that supplies the second dispersion 3B to the nozzle M2 ′, and a droplet 9A and the solidification part M3 which convects the droplet 9B, and the gas flow supply means M5 which produces a gas flow in the solidification part M3.

  The dispersion liquid supply unit M4 may have any function as long as it has a function of supplying the first dispersion liquid 3A to the nozzle M2. However, as shown in the drawing, the dispersion liquid supply section M4 includes a stirring unit M41 that stirs the first dispersion liquid 3A. There may be. Thereby, for example, even if the dispersoid 31A is difficult to disperse in the first dispersion medium 32A, the first dispersion 3A in which the dispersoid 31A is sufficiently uniformly dispersed is supplied to the nozzle M2. be able to.

The nozzle M2 has a function of ejecting the first dispersion 3A as fine droplets (fine particles) 9A. The nozzle M2 will be described in detail later.
The dispersion liquid supply unit M4 ′ only needs to have a function of supplying the second dispersion liquid 3B to the nozzle M2 ′, and can be configured in the same manner as the above-described dispersion liquid supply unit M4. In the present embodiment, the dispersion liquid supply unit M4 ′ has the same configuration as the dispersion liquid supply unit M4.
The nozzle M2 ′ has a function of ejecting the second dispersion 3B as fine droplets (fine particles) 9B, and can be configured similarly to the nozzle M2. In the present embodiment, the nozzle M2 ′ has the same configuration as the nozzle M2.

Further, as shown in FIG. 6, the toner manufacturing apparatus M1 has a gas flow supply means M10, and the gas supplied from the gas flow supply means M10 is supplied to the nozzles M2 and M2 ′ via a duct M101. And used for jetting the first dispersion 3A (droplet 9A) from the nozzle M2 and the jet of the second dispersion 3B (droplet 9B) from the nozzle M2 ′, which will be described in detail later.
A valve M11 is attached to the gas flow supply means M10. Thereby, the pressure of the gas used for jetting the first dispersion liquid 3A (droplet 9A) can be adjusted.

In the toner manufacturing apparatus M1 having the illustrated configuration, fine droplets 9A and 9B are ejected from the nozzles M2 and M2 ′ to the solidifying portion M3, respectively.
The droplets (fine particles) 9A ejected from the nozzle M2 are solidified while being transported through the solidified portion M3, whereby a bonded body 40 in which a plurality of binder resin fine particles are melt bonded and an adhesive resin phase 42 are formed. The resulting toner base particles 4A.

  When the first dispersion medium 32A includes the solvent material as described above, the solvent material is removed when the droplet (fine particle) 9A is conveyed through the solidified portion M3. In such a case, as the first dispersion medium 32A in the ejected droplet 9A is removed, the plurality of first dispersoids 311A (binder resin fine particles) contained in the droplet 9A are removed. Aggregate. As a result, the toner base particles 4A are aggregates (bonded bodies) of a plurality of binder resin fine particles (binder resin fine particles derived from the first dispersoid 311A), and are not bonded to the unbonded portions of the binder resin fine particles. The adhesive resin phase 42 is obtained.

  Further, in the case where the first dispersion medium 32A is substantially composed of a liquid adhesive resin without substantially containing a solvent material, the adhesive resin is used when the droplets (fine particles) 9A are conveyed through the solidified portion M3. Is cured or semi-cured. As a result, the toner base particles 4A are aggregates (bonded bodies) of a plurality of binder resin fine particles (binder resin fine particles derived from the first dispersoid 311A), and are not bonded to the unbonded portions of the binder resin fine particles. The toner base particles 4 </ b> A having the adhesive resin phase 42 are obtained.

  As described above, the toner base particles 4A are obtained as an aggregate (junction) of the binder resin fine particles derived from the first dispersoid 311A, but the binder resin fine particles are the first dispersion. Any material may be used as long as it contains at least a part of the components constituting the material 311A. For example, it may be composed of a material from which some of the components contained in the first dispersoid 311A are removed. .

  On the other hand, the droplets (fine particles) 9B ejected from the nozzle M2 ′ are applied to the vicinity of the surface of the toner base particles 4A while being convected (stirred) and solidified in the solidified portion M3, whereby the toner base particles 4A. The second dispersoid 31B in the droplet 9B is fixed or embedded in the adhesive resin phase 42. As a result, in the solidified portion M3, the granular body 4 is obtained in which the resin fine particles derived from the second dispersoid 31B are fixed or embedded in the adhesive resin phase 42 of the toner base particles 4A.

  The ejection of the droplet 9B from the nozzle M2 ′ may be at the same time as the ejection of the droplet 9A from the nozzle M2, but is preferably after the toner base particles 4A are formed in the solidified portion M3. . In other words, it is preferable to eject the droplet 9B from the nozzle M2 'after the droplet 9A is solidified or semi-solidified. Thereby, the resin fine particles can be reliably attached not to the inside of the toner base particles 4A but to the vicinity of the surface. In this case, the ejection of the droplet 9A from the nozzle M2 may be interrupted while the nozzle M2 'ejects the droplet 9B.

  When the droplet (fine particle) 9B is transported through the solidified portion M3, the solvent material contained in the second dispersion medium 32B is removed along with the transport, and the second material contained in the droplet 9B. Dispersoid 31B is applied in a state of being dispersed on the surface of toner base particles 4A. As a result, the granular body 4 is obtained as a resin particle fixed or embedded in the adhesive resin phase 42 of the toner base particle 4A.

  The solidification part M3 is comprised by the cylindrical housing M31. The lower part of the housing M31 is divided vertically by a dispersion plate M7 in which a plurality of openings M71 are formed, and further a gas flow supply means M5 for generating a gas air flow in the solidified portion M3 through the openings M71 of the dispersion plate M7. It is connected. As a result, a fluidized bed is formed on the dispersion plate M7 by the gas stream, and the droplets 9A and 9B, the toner base particles 4A, the granular material 4 and the like in the solidified portion M3 do not fall below the dispersion plate M7. The solidified portion M3 flows (flys) as indicated by the arrows in the figure.

During the production of the granular body 4 (from the discharge of the first dispersion liquid 3A and the second dispersion liquid 3B to the formation of the granular body 4), the inside of the housing M31 is preferably maintained at a temperature within a predetermined range. As a result, variations in characteristics among the granular bodies 4 due to differences in manufacturing conditions can be reduced, and the reliability of the entire toner is improved.
Thus, for the purpose of keeping the temperature in the housing M31 within a predetermined range, for example, a heat source or a cooling source is installed inside or outside the housing M31, or a flow path for the heat medium or the cooling medium is formed in the housing M31. It is good also as a made jacket.

  The temperature in the housing M31 (the temperature of the gas stream) is not particularly limited, but is preferably 40 to 200 ° C, more preferably 50 to 150 ° C, and further preferably 60 to 140 ° C. . When the temperature in the housing M31 is a value within the above range, for example, the first dispersion medium 32A is configured from the droplets 9A while sufficiently preventing the toner constituent material (particularly the binder resin) from being modified. The solvent material to be removed can be removed more smoothly. Further, when the temperature in the housing M31 is a value within the above range, the adhesive resin phase 42 can be efficiently formed.

  In the illustrated configuration, the pressure in the housing M31 is adjusted by the pressure adjusting means M12. Thus, by adjusting the pressure in the housing M31, for example, the solvent material constituting the first dispersion medium 32A can be efficiently removed from the ejected droplets 9A, and the toner productivity can be improved. Will improve. In the configuration shown in the figure, the pressure adjusting means M12 is connected to the housing M31 by a connecting pipe M121. Further, an enlarged diameter portion M122 having an enlarged inner diameter is formed in the vicinity of the end portion of the connection pipe M121 connected to the housing M31, and a filter M123 for preventing suction of the granular material 4 and the like is further provided. ing.

  The pressure in the housing M31 is not particularly limited, but is preferably 150 kPa or less, more preferably 100 kPa or less, and further preferably 0.1 to 50 kPa. When the pressure in the housing M31 is a value within the above range, for example, the solvent material that constitutes the first dispersion medium 32A from the droplets 9A while sufficiently preventing the generation of irregularly shaped particles 4 or the like, It can be removed more smoothly.

The particle size of the dispersoid 31A (particularly, the first dispersoid 311A) contained in the first dispersion 3A (droplet 9A) is usually larger than that of the toner base particles 4A (droplets 9A) obtained. It is small enough. Therefore, toner mother particles 4A obtained as an aggregate of dispersoid 31A (first dispersoid 311A) have a sufficiently large circularity.
In addition, when the first dispersion medium 32A includes the solvent material as described above, the toner base particles 4A obtained are usually smaller than the droplets 9A ejected from the nozzle M2. For this reason, even when the droplet 9A of the first dispersion 3A ejected from the nozzle (ejection unit) M2 is relatively large, the size of the obtained toner base particles 4A (granular body 4) is relatively large. It can be small. Therefore, in this embodiment, the granular material 4 with a particularly small average particle diameter can be easily obtained.
In this embodiment, as will be described in detail later, the droplets 9A ejected from the nozzle M2 can be made sufficiently small and the particle size distribution can be made sufficiently sharp. As a result, the granular material 4 also has a small variation in particle size, that is, a sharp particle size distribution.

  As described above, by using a dispersion liquid (particularly a suspension) as a jet liquid (discharge liquid), even when the particle size (toner base particles) to be produced is sufficiently small, The circularity can be made sufficiently high and the particle size distribution can be sharp. As a result, the obtained toner has a uniform charge between the toner particles, and a thin layer of toner formed on the developing roller when the toner is used for printing, which is leveled and densified. It becomes. As a result, defects such as fog are hardly generated and a sharper image can be formed. Further, since the shape and particle size of the granular material 4 are uniform, the bulk density of the entire toner (aggregate of granular material 4) can be increased. As a result, it is advantageous for increasing the amount of toner filled in the cartridge of the same volume and for reducing the size of the cartridge.

The housing M31 is connected to voltage application means M8 for applying a voltage. By applying a voltage having the same polarity as that of the droplet 9A (granular body 4) to the inner surface side of the housing M31 by the voltage applying means M8, the following effects can be obtained.
Usually, the toner base particles are positively or negatively charged. For this reason, if there is a charged substance charged with a polarity different from that of the toner base particles, a phenomenon occurs in which the toner base particles are electrostatically attracted and adhered to the charged substance. On the other hand, if there is a charged substance charged with the same polarity as the toner mother particles, the charged substance and the toner mother particles repel each other, effectively preventing the phenomenon that the toner adheres to the surface of the charged object. it can. Therefore, by applying a voltage having the same polarity as the droplet 9A (toner mother particle 4A) to the inner surface side of the housing M31, it is effective that the droplet 9A (toner mother particle 4A) adheres to the inner surface of the housing M31. Can be prevented. Thereby, generation | occurrence | production of the toner powder of irregular shape can be prevented more effectively, and the collection | recovery efficiency of the granular material 4 also improves.

Further, the housing M31 is provided with a collection unit (not shown) in the vicinity of the upper side of the dispersion plate M7 so that almost completely solidified granular material can be taken out by the collection unit.
As a result, the droplets 9A are solidified into the toner base particles 4A, and the particulates 4 obtained by applying the resin fine particles 4B in the droplets 9B to the vicinity of the surface of the toner base particles 4A are used in the recovery unit. To be recovered.

<Nozzle M2>
Next, the nozzle M2 that ejects the granular first dispersion 3A (droplet 9A) will be described in detail. The nozzle M2 ′ has the same configuration as that of the nozzle M2, and therefore the description thereof is omitted.
In the present embodiment, the first dispersion 3A is ejected as fine particles (droplets 9A) in a unique state. That is, in this embodiment, as shown in FIG. 7, the first dispersion 3 </ b> A sent to the inclined surface 7 is thinly stretched into a thin laminar flow 8 by the gas flow flowing along the inclined surface 7. The laminar flow 8 flowing along the inclined surface 7 is too thin when leaving the inclined surface 7 and cannot be in a layered state (film state), and is broken into pieces by the surface tension to form fine particle droplets 9A. . In particular, since the laminar flow 8 is composed of a dispersion (a suspension containing a solid dispersoid) 3A, a uniform liquid (for example, a liquid or a solution substantially consisting of a pure substance) is used. Compared to the case, the droplet 9A is easily subdivided from the thin laminar flow 8. Therefore, in the present embodiment, the fine particle-like first dispersion liquid 3A (droplet 9A) can be ejected particularly efficiently. Further, it is possible to prevent the droplet from forming a projection by pulling the tail. In the present embodiment, the first dispersion 3A is jetted as fine laminar flow 8 as fine particles (droplets 9A) with a gas flow. Therefore, there is a feature that the droplets 9A of the first dispersion 3A can be formed into circular ultrafine particles. Thereby, clogging of the supply port 5 of the first dispersion 3A can be prevented more reliably, and the processing of the supply port 5 can be easily performed.

Furthermore, as shown in FIG. 7, when a sharp edge 7A is provided at the tip of the inclined surface 7, and the atomizing gas and the spreading gas are caused to collide with the edge 7A, air (gas) can be vibrated vigorously. The air vibration has the effect of making the first dispersion 3A further fine.
Further, the nozzle M2 used in the present embodiment has a ring-shaped edge 7A at the tip of the inclined surface 7, and the first dispersion 3A (droplet 9A) is formed into fine particles in a hollow cone state from the edge 7A. Can be jetted. Thereby, for example, the solvent material constituting the first dispersion medium 32A can be efficiently removed from the droplet 9A ejected by the holocon.

The nozzle M2 that ejects the liquid shown in FIG. 7 in the form of fine particles includes a supply port 5 that discharges the first dispersion 3A (droplet 9A) in a ring shape, and a first dispersion that is discharged from the supply port 5. An inclined surface 7 for flowing 3A and a gas port 10 for injecting pressurized gas onto the inclined surface 7 are provided.
The nozzle M <b> 2 shown in this figure includes an inner ring (cylinder) 11, an intermediate ring (cylinder) 12, and an outer ring (cylinder) 13. A supply port 5 is provided between the inner ring 11 and the intermediate ring 12, an atomizing gas flow path 14 is provided at the center of the inner ring 11, and a spreading gas supply path is provided between the intermediate ring 12 and the outer ring 13. 15.

The inner ring 11 has a cylindrical outer shape, and the intermediate ring 12 has a cylindrical inner shape. A slit-shaped supply port 5 having a predetermined width is provided between the inner ring 11 and the intermediate ring 12. ing. The supply port 5 is formed in a ring shape, and the slit width is designed such that the first dispersion liquid 3A is not clogged. In the nozzle of the present embodiment, it is not necessary to send out the first dispersion 3A from the supply port 5 as a thin film (thin layer). This is because the first dispersion 3A is thinly stretched on the inclined surface 7 and ejected as fine particles (droplets 9A). Therefore, the slit width of the supply port 5 takes into consideration the flow rate of the first dispersion 3A to be sent out, the length of the inclined surface 7, the flow velocity of the atomized gas injected onto the inclined surface 7, the inner diameter of the supply port 5, and the like. Designed for optimum value. For example, the slit width of the supply port 5 is designed to be 0.2 to 1.5 mm, preferably 0.4 to 1 mm, and optimally about 0.8 mm.
The diameter of the supply port 5 is designed to an optimum value in consideration of the flow rate of the dispersion liquid to be discharged (injected), the dimension of the slit width, and the like. The diameter of the supply port 5 is designed to be about 50 mmφ, for example, in a nozzle that ejects the first dispersion 3A (droplet 9A) of 1000 g / min. The diameter of the supply port 5 is designed to be large when the flow rate is large and small when the flow rate is small.

  The outer peripheral portion of the inner ring 11 and the tip surface of the intermediate ring 12 are cut into a tapered shape to form an inclined surface 7. The inclined surfaces 7 of the inner ring 11 and the intermediate ring 12 are flush with each other so that the gas flowing along and flowing along the inclined surface 7 of the inner ring 11 is not turbulent at the boundary between the inner ring 11 and the intermediate ring 12. Is formed. When the inclined surface 7 of the inner ring 11 and the intermediate ring 12 is the same plane, there is no step between the inclined surface 7 of the inner ring 11 and the intermediate ring 12 and the inclined surface 7 of the intermediate ring 12 from the inclined surface 7 of the inner ring 11. It means a state in which gas flows linearly. Thus, in order to process the inclined surface 7 of the inner ring 11 and the intermediate ring 12 into a tapered shape on the same plane, for example, the inner ring 11 and the intermediate ring 12 may be connected and tapered. Furthermore, the inclined surface 7 is a smooth surface along the flow direction of the first dispersion liquid 3A so that the first dispersion liquid 3A flowing along the surface does not become a turbulent flow. The inclined surface 7 of the nozzle shown in the figure is conical and has a smooth surface as a whole.

  By providing the inclined surface 7 on the inner ring 11 and the intermediate ring 12, the supply port 5 is opened in the middle of the inclined surface 7. The inclination angle α of the inclined surface 7 provided in the inner ring 11 and the intermediate ring 12 is not particularly limited, but is, for example, 100 to 170 degrees, preferably 120 so that the angle of the supply port 5 with respect to the inclined surface 7 becomes an obtuse angle. It is designed to be -160 degrees, more preferably 130-160 degrees, and most preferably about 150 degrees. The larger the inclination angle α, the more stable the liquid outflow. However, the optimum value of the inclination angle α varies depending on the slit width. The inclination angle α is preferably designed so that the opening width of the supply port 5 on the inclined surface 7 does not exceed 2 mm.

  A center ring 16 is disposed at the tip of the inner ring 11, and a gas port 10 is opened between the center ring 16 and the inner ring 11. Although not shown, the center ring 16 is fixed to the inner ring 11 and disposed at a predetermined position. The center ring 16 is processed into a tapered shape along the inclined surface 7 of the inner ring 11 on the outer peripheral surface. A gas port 10 formed between the center ring 16 and the inner ring 11 has a slit shape, from which a pressurized gas is injected into a laminar flow state and flows along the inclined surface 7.

The atomizing gas flow path 14 of the inner ring 11 is connected to a pressurized gas source F. The gas port 10 injects atomized gas that flows along the inclined surface 7. The pressurized gas source F is, for example, 3 to 20 kg / cm ² , preferably 4 to 15 kg / cm ² , more preferably 4 to 10 kg / cm ² , and most preferably about 6.5 kg / cm ^2. To supply. When the atomizing gas injection pressure is increased, the flow velocity of the gas flowing along the inclined surface 7 is increased, and the first dispersion 3A is thinned more effectively and the first dispersion 3A is made into fine droplets. (Fine particles) 9A. However, when the injection pressure is increased, a special compressor is required and the energy consumption increases. Therefore, the optimum value is designed in consideration of the required particle diameter of the fine particles and the energy consumption.

  Furthermore, the nozzle shown in FIG. 7 injects spreading gas to the outer periphery of the inclined surface 7 in addition to the atomizing gas. However, the spreading gas is not necessarily injected. This is because the first dispersion 3A can be injected as fine particles (droplets 9A) with atomizing gas without injecting spreading gas. The nozzle for injecting the atomizing gas and the spreading gas has the advantage that the atomizing gas and the spreading gas collide with each other at the edge 7A of the inclined surface 7 to make the droplet 9A smaller. Furthermore, the angle of the holocon can be adjusted with the spreading gas. Further, depending on the properties of the first dispersion 3A, separation at the edge 7A may be worsened, and there is a possibility of causing a liquid backflow to the spreading gas side. Occurrence can be prevented more reliably.

The spreading gas is injected from a spreading gas injection port 17 provided between the intermediate ring 12 and the outer ring 13. The spreading gas can be a low pressure gas compared to the atomizing gas. For example, when the atomizing gas is about 6.5 kg / cm ² , the spreading gas can be about 1 kg / cm ² . The spreading gas does not need to force the first dispersion 3A to be thinly stretched unlike the atomizing gas, and can be set in the range of 0.5 to ³ kg / cm ² , for example.

  In the nozzle for injecting both atomizing gas and spreading gas, the tip of the inclined surface 7 has a sharp edge 7A. The intermediate ring 12 forms an inclined surface 7 on the tip surface, and an outer periphery of the tip is processed into a cylindrical shape, thereby forming an edge 7A at the tip of the inclined surface 7. The intermediate ring 12 having this shape can form a sharp edge 7A having an angle of (180 degrees−inclination angle α) at the tip of the inclined surface 7. However, although the nozzle is not shown, the outer periphery of the intermediate ring 12 can be processed into a taper shape to adjust the angle of the edge 7A.

The nozzle shown in FIG. 7 can eject the first dispersion 3A as fine particles (droplets 9A) in the following state, for example.
(1) A pressurized atomizing gas is supplied to the atomizing gas flow path 14 provided in the center of the inner ring 11, and the spreading gas is supplied to the spreading gas injection port 17 between the intermediate ring 12 and the outer ring 13. Then, the first dispersion 3 </ b> A is sent out from the supply port 5 to the inclined surface 7.
(2) The first dispersion 3 </ b> A supplied to the inclined surface 7 is thinly stretched by an atomizing gas flowing along the inclined surface 7 to become a thin laminar flow 8. For example, the atomized gas is caused to flow along the inclined surface 7 at a flow rate of about Mach 1.5, the first dispersion 3A is sent to the supply port 5, and the flow rate at the tip of the thin laminar flow 8 is set to 1 of the atomized gas. If / 20, then 25.5 m / s. If the diameter of the edge 7A provided at the tip of the inclined surface 7 is about 50 mm, the first dispersion 3A is supplied at about 1 liter / min, and the membrane pressure of the thin laminar flow 8 is about 4 μm.
(3) The thin laminar flow 8 having a small film thickness as described above is too thin to pass through the edge 7A of the inclined surface 7 and cannot be in a film state, and is broken into pieces by the surface tension to form the fine droplet 9A. Become.
(4) The atomized droplet 9A collides with the atomizing gas and the spreading gas at the edge 7A, rubs and vibrates to make the droplet 9A smaller particles (droplet 9A).
(5) The fine particle droplets 9A are carried radially by the atomizing gas and the spreading gas. This state is called a holocorn. The cone angle of the hollow cone is determined by the angle of the inclined surface 7, but can also be adjusted by the injection pressure of the atomizing gas and the spreading gas.
The droplet 9 </ b> A ejected in the state of a hollow cone is solidified as described above, and becomes toner mother particles 4 </ b> A including the joined body 40 and the adhesive resin phase 42.

  FIG. 8 shows a nozzle in which liquid A and liquid B are mixed to form dispersion fine particles (droplets 9A). In the nozzle shown in this figure, the intermediate ring 12 of the nozzle shown in FIG. 7 has a double tube structure of an inner intermediate ring (cylinder) 12A and an outer intermediate ring (cylinder) 12B. A B liquid supply port 5 is provided between the inner intermediate ring 12A and the outer intermediate ring 12B. The ring-shaped inner intermediate ring 12A has tapered inclined surfaces 7 on the inner surface and the outer surface, and the tip thereof is a sharp edge 7A. The front end surface of the outer intermediate ring 12B is also tapered to form an inclined surface 7. The inclined surface 7 of the outer intermediate ring 12B is connected to the same plane as the inclined surface 7 of the inner intermediate ring 12A.

  The nozzle shown in FIG. 8 has inclined surfaces 7 on the inner side surface and the outer side surface of the inner intermediate ring 12A, the A liquid supply port 5 is provided on the inclined surface 7 provided on the inner side, and B is provided on the outer inclined surface 7 side. A liquid supply port 5 is provided. Both the gas port 10 of the inner ring 11 and the spreading gas injection port 17 between the outer intermediate ring 12B and the outer ring 13 so that both the A liquid and the B liquid can be thinly extended to the inclined surface 7 by atomizing gas. High-pressure atomized gas is injected from

By using the nozzle M2 having such a structure, a toner having high uniformity (dispersibility) can be obtained even when components having poor dispersibility and compatibility are used. Further, by using the nozzle M2 having such a structure, it has a multi-phase structure (a structure including a phase of a bonded body 40 formed by fusion-bonding a plurality of binder resin fine particles and an adhesive resin phase 42). The toner particles 100 can be obtained easily and reliably. In the present embodiment, the liquid A and the liquid B may have substantially the same composition or may have different compositions. It is assumed that the liquid B has substantially the same composition, that is, both the liquid A and the liquid B are the first dispersion 3A as described above. In addition, the case where A liquid and B liquid have a different composition is explained in full detail later.
When the A liquid and the B liquid have substantially the same composition, it is possible to more reliably reduce variations in the composition and characteristics of the obtained granular material. Further, by supplying the liquid (first dispersion 3A) having the same composition from the plurality of supply ports 5, the ejection conditions (conditions for ejecting the droplets 9A) of the first dispersion 3A are more reliably controlled. be able to.

  The nozzle shown in FIG. 8 has inclined surfaces 7 on both the inner and outer sides of the inner intermediate ring 12A, and can supply A liquid and B liquid to the inner and outer inclined surfaces 7, respectively. It is configured. The nozzle shown in FIG. 9 has four supply ports 5 in the middle of the inclined surface 7. In the nozzle having such a structure, the liquid (first dispersion 3A) can be supplied from the four supply ports 5 and discharged simultaneously. In the nozzle shown in FIG. 9 as well, a liquid (first dispersion 3A) having substantially the same composition may be supplied from all the supply ports 5 as described above. Thereby, the same effect as described above can be obtained.

  Further, FIGS. 10 and 11 show a nozzle that can eject the dispersion liquid as finer fine particles. In the nozzles shown in these drawings, the intermediate ring 12 has a double tube structure of an inner intermediate ring (cylindrical body) 12A and an outer intermediate ring (cylindrical body) 12B, as in the nozzle shown in FIG. A B liquid supply port 5 is provided between the inner intermediate ring 12A and the outer intermediate ring 12B. The ring-shaped inner intermediate ring 12A has tapered inclined surfaces 7 on both the inner side surface and the outer side surface, and the tip thereof is a sharp edge 7A. The front end surface of the outer intermediate ring 12B is also tapered to form an inclined surface 7. Further, a liquid A supply port 5 is provided between the inner intermediate ring 12 </ b> A and the inner ring 11.

  An enlarged view of the inclined surface is shown in FIG. As shown in this figure, the inclined surface 7 of the inner intermediate ring 12A is slightly stepped in the vicinity of the supply port 5 with respect to the extended line of the outer intermediate ring 12B and the inclined surface 7 of the inner ring 11 located on both sides thereof. It is provided and formed low (so that the angle formed by the inclined surface 7 of the inner intermediate ring 12A is smaller than the angle formed by the inclined surface 7 of the outer intermediate ring 12B). In the nozzle having the inclined surface having such a shape, the gas flow flowing along the inclined surface 7 as shown by the arrow smoothly discharges (discharges) the liquid (first dispersion 3 </ b> A) from the supply port 5. It has the feature that it can be. This is because the inclined surface 7 of the inner intermediate ring 12A does not protrude with respect to the inclined surface 7 on the outer peripheral side (outer intermediate ring 12B). Although not shown, when the inclined surface 7 of the inner intermediate ring 12A protrudes from the extended line of the inclined surface 7 (outer intermediate ring 12B) located on the outer peripheral side thereof, the gas collides with the protruding portion to smoothly liquid (first 1 dispersion 3A) becomes difficult to discharge.

Furthermore, in the nozzle shown in the enlarged view of FIG. 12, the inclined surface 7 of the inner intermediate ring 12A is curved so that the tip portion protrudes from an extension line of the adjacent inclined surface 7. In the inclined surface 7 of the inner intermediate ring 12A having such a shape, the gas flow that flows in the direction of the arrow along the inclined surface 7 is strongly pressed against the inclined surface 7 at the tip portion, and flows on the inclined surface 7. The thin laminar flow 8 of the liquid (first dispersion 3A) can be stretched more thinly. For this reason, the nozzle having such a structure has an advantage that the first dispersion 3A can be ejected as finer fine particles (droplets 9A).
In such a nozzle, if the angles of the outer intermediate ring 12B, the inner intermediate ring 12A, and the tip of the inner ring 11 are designed as shown in the figure, the first dispersion 3A can be injected with a holocone.

  In the nozzle shown in FIGS. 7, 8, and 10, the spreading gas injection port 17, and the distal end portions of the center ring 16 and the outer ring 13 constituting the gas port 10 are configured by a gas permeable member 18. The breathable member 18 has a breathability that allows the gas press-fitted into the gas port 10 to penetrate from the surface. The air permeable member 18 is made of, for example, a sintered metal made of stainless steel having an average particle diameter of about 1 μm. The air-permeable member 18 has an effect of preventing a mist from adhering to the surfaces of the center ring 16 and the tip of the outer ring 13 by injecting part of the gas injected from the gas port 10 from the surface.

  Furthermore, FIG. 13 shows a nozzle that can spray fine particles on both the holocone and the full cone. FIG. 14 shows an enlarged view of the main part of the tip of the nozzle in this figure. Also in this nozzle, as in the nozzle shown in FIG. 8, the intermediate ring 12 has a double tube structure of an inner intermediate ring 12A and an outer intermediate ring 12B. A B liquid supply port 5 is provided between the inner intermediate ring 12A and the outer intermediate ring 12B. The ring-shaped inner intermediate ring 12A has tapered inclined surfaces 7 on both the inner surface and the outer surface, and the tip thereof is a sharp edge 7A. The front end surface of the outer intermediate ring 12B is a straight inclined surface 7. Further, a liquid A supply port 5 is provided between the inner intermediate ring 12 </ b> A and the inner ring 11.

  FIG. 15 shows an enlarged view of the inclined surface 7 provided on the inner intermediate ring 12A. Also in the nozzle shown in this figure, the inclined surface 7 of the inner intermediate ring 12A is inclined between the outer intermediate ring 12B and the inner ring 11 located on both sides in the vicinity of the supply port 5, as in the nozzle shown in FIG. A level difference is provided with respect to the extended line of the surface 7 and is formed low (so that the angle formed by the inclined surface 7 of the inner intermediate ring 12A is smaller than the angle formed by the inclined surface 7 of the outer intermediate ring 12B). Yes. Even in the nozzle having the inclined surface 7 having such a shape, the gas flow flowing along the inclined surface 7 as shown by the arrow smoothly discharges the liquid (first dispersion 3A) from the supply port 5. Can do.

  Further, the nozzle shown in FIG. 15 is formed so that the inclination angle of the inclined surface 7 of the inner intermediate ring 12A changes toward the tip direction, and the tip portion protrudes from the extension line of the adjacent inclined surface 7. Has been. In the inclined surface 7 of the inner intermediate ring 12A having such a shape, the gas flow flowing in the direction of the arrow along the inclined surface 7 is strongly pressed against the inclined surface 7 at the tip portion, and flows on the inclined surface 7. The thin laminar flow 8 of the liquid (first dispersion 3A) can be stretched thinly. For this reason, the nozzle of this structure has the feature that the 1st dispersion liquid 3A can be ejected as finer fine particles (droplets 9A).

  Furthermore, in such a nozzle, the angle of the outer ring 13, the outer intermediate ring 12B, the inner intermediate ring 12A, and the inner ring 11 tip is designed to an angle as shown in the figure, and the first dispersion 3A is added. Can be injected with both a hollow cone and a full cone. For example, the atomizing gas injection pressure injected from the gas port 10 between the outer intermediate ring 12B and the outer ring 13 is used as the atomizing gas injection pressure injected from the gas port 10 between the center ring 16 and the inner ring 11. If it is larger than this, the first dispersion 3A can be jetted in the state of a holocone. On the contrary, the atomizing gas injection pressure injected from the gas port 10 between the outer intermediate ring 12 </ b> B and the outer ring 13 is the atomizing gas injection pressure injected from the gas port 10 between the center ring 16 and the inner ring 11. If it is stronger, the first dispersion 3A can be sprayed in a full cone state.

Similarly to the nozzle shown in FIG. 10, the nozzle shown in FIG. 13 has mist on the surfaces of the center ring 16 and the outer ring 13, with the tip portions of the center ring 16 and the outer ring 13 constituting the gas port 10 as the breathable members 18. Is prevented from adhering.
In addition, the nozzle shown in FIG. 16 has a unique structure that prevents mist adhesion without using a breathable member. The nozzle of this figure has a gas peeling recess 19 on the tip surface of the center ring 16 and has a gas peeling recess 19 inside the supply port 5 and on the tip surface of the nozzle. The gas peeling recess 19 is connected to the flow path 1 between the inner ring 11 and the center ring 16 through a through hole 20 provided in the center ring 16. As shown in FIG. 17, the through hole 20 opens in a direction in which the gas to be injected is rotated by the gas separation recess 19, that is, inclined from the radial direction to the tangential direction. The surface of the gas peeling recess 19 is a smooth surface that can flow in a laminar flow state without disturbing the gas flow. Further, the outer peripheral portion of the gas separation recess 19 is streamlined like an airplane wing and is smoothly curved toward the gas port 10.

  In the nozzle having such a structure, when pressurized gas is injected from the through hole 20 to the gas peeling recess 19 in the tangential direction, the gas collides with the inner surface of the taper gas peeling recess 19 and spreads thinly. It becomes a swirl flow. At this time, the ratio of the air flow toward the outlet direction (upward in the figure) of the gas peeling recess 19 can be changed by the taper angle (θ) of the gas peeling recess 19. When the taper angle (θ) is 15 degrees as shown in the figure, the swirling airflow toward the exit direction is about 70%, and the remaining about 30% becomes the swirling airflow toward the bottom of the gas separation recess 19, After reaching the bottom, decrease the wind speed and head toward the exit. And it is caught in the above-mentioned about 70% whirling airflow, and is discharged | emitted from the gas peeling recessed part 19.

  The swirling airflow of the gas flowing along the inner surface of the gas separation recess 19 moves along the inclined surface of the taper surface and the aerodynamic part of the airfoil, and flows along the airfoil surface when reaching the tip. The gas is drawn into the atomizing gas injected from the flow path 1 provided between the inner ring 11 and the center ring 16. Since the streamlined airfoil portion is smoothly curved toward the gas port 10, the gas flows along the surface, creating a gas layer that flows to the front of the central ring 16.

  Since almost the entire front surface of the center ring 16 is covered with this flowing gas layer, the mist (droplet 9A) of the first dispersion 3A is prevented from adhering. The number of through-holes 20 is preferably about six so that gas can be uniformly injected from the gas peeling recess 19. However, the number of through holes can be further increased. Further, when the through hole is formed in a slit shape and the lateral width is widened, the gas can be blown out uniformly from the gas peeling recess even when the number of the through holes is small.

  In the nozzle having such a structure, since the front surface of the nozzle is covered with the gas layer, the flying mist is prevented from adhering to the surface, and is blown off by the streamline air stream which is a flowing gas layer. Further, when the nozzle having such a structure is used, the same effect can be obtained with a smaller amount of gas than the method of preventing powder adhesion by the air permeable member 18 described above.

  Furthermore, the nozzle shown in FIG. 18 can supply gas and liquid (dispersed liquid) uniformly from the gas port 10 and the supply port 5. The nozzle shown in this figure has helical ribs 22 in the flow path 1 and the liquid flow path 21. In the flow path 1 and the liquid flow path 21, ribs are provided between the rings for centering when assembling the rings, that is, for precisely matching the centers of all the rings. By bringing the tips of the ribs into contact, each ring is centered and assembled accurately.

  The nozzle of FIG. 18 has a helical rib 22 that spins a gas flowing in the axial direction to rotate in a spiral manner in the flow path 1 that communicates with the gas ports 10 opened on both sides of the edge 7A. The gas injected from the gas ports 10 on both sides of the edge 7A is injected toward the edge 7A while rotating in opposite directions. In the nozzle having such a structure, the atomized gases flowing on both sides of the edge 7A are reversed to each other, and when the mist is formed at the tip of the edge 7A, the twisting action of both gases is added to increase the mist crushing effect. You can make mist.

  However, the nozzle for injecting the first dispersion 3A is not necessarily limited to the atomizing gas that flows on both sides of the edge as a reverse spin. For example, the atomizing gas on both sides of the edge is spun in the same direction. It may be. Further, in a nozzle having a plurality of gas ports, the gas ejected from all the gas ports may not be spun. Therefore, you may have a helical rib only in a specific flow path.

  Further, in the nozzle shown in FIG. 18, helical ribs 22 are also provided in the liquid flow path 21. Normally, the liquid (first dispersion 3A) has a slower flow rate than the gas, so in the illustrated nozzle, the inclination angle α of the helical rib 22 is increased to about 60 degrees. Inclination angle (alpha) can be made into the range of 30-70 degree, for example, Preferably it is 45-65 degree. Similarly to the helical rib 22 of the flow channel 1, the helical rib 22 of the liquid flow channel 21 has a strong spin when the inclination angle α is large, but on the other hand, the flow resistance of the liquid tends to increase. Indicates. For this reason, the inclination angle α of the helical rib 22 is appropriately selected in consideration of the flow resistance and spin of the liquid.

By using the nozzle M2 as described above, the following effects can be obtained.
-The dispersion can be ejected as extremely small fine particles, and can be continuously ejected for a long time while sufficiently effectively preventing clogging. Further, since the dispersion liquid is stretched into a thin laminar flow to form droplets of fine particles, the droplets can be ejected as extremely small fine particles at a flow rate of gas flowing along a smooth surface.
-It can be ejected as fine droplets by increasing the ejection amount per unit time.

  Further, the initial velocity of the first dispersion 3A (droplet 9A) ejected from the nozzle M2 to the solidifying part M3 is preferably, for example, 0.1 to 10 m / sec, and is 2 to 8 m / sec. Is more preferable. When the initial velocity of the first dispersion 3A (droplet 9A) is less than the lower limit, toner productivity is reduced. On the other hand, when the initial velocity of the first dispersion 3A (droplet 9A) exceeds the upper limit, the sphericity (circularity) of the obtained granular material 4 tends to decrease.

  Further, the viscosity of the first dispersion 3A ejected from the nozzle M2 is not particularly limited, but is preferably 5 to 3000 cps and more preferably 10 to 1000 cps at 25 ° C., for example. When the viscosity of the first dispersion 3A is less than the lower limit, it becomes difficult to sufficiently control the size of the ejected particles (droplets 9A), and the resulting dispersion of the granular material 4 increases. There is. On the other hand, when the viscosity of the first dispersion 3A exceeds the upper limit, the diameter of the formed droplets increases. In addition, when the viscosity of the first dispersion 3A is particularly large, adhesion to the nozzle tip becomes intense and continuous operation becomes difficult, and the first dispersion 3A becomes difficult to be supplied to the nozzle.

  The first dispersion 3A ejected from the nozzle M2 may be preheated (heated). By heating the first dispersion 3A in this way, for example, the viscosity of the first dispersion 3A is reduced, and clogging at the nozzle M2 can be more effectively prevented and sprayed. The size of the droplets (mist) 9 can be made sufficiently small, and the variation in size among the droplets 9A can be made particularly small. Further, by heating the first dispersion 3A, the solidification part M3 smoothly causes the aggregation (fusion) of the binder resin fine particles derived from the first dispersoid 311A to proceed smoothly, and the adhesive resin phase 42 is made efficient. It can be formed well. As a result, the finally obtained toner particles 100 have more excellent shape stability.

Further, the ejection amount of one drop of the first dispersion 3A (the volume of one droplet 9A) is slightly different depending on the content of the first dispersoid 311A in the first dispersion 3A. 0.05 to 500 pl is preferable, and 0.5 to 5 pl is more preferable. By setting the spray amount for one drop of the first dispersion 3A within such a range, the granular material 4 can be made to have an appropriate particle size.
In addition, the average particle diameter D ′ of the droplets 9A obtained by atomizing the first dispersion 3A is preferably 2.5 to 20 μm, and more preferably 4 to 15 μm. By setting the average particle diameter D ′ of the droplets 9A within such a range, the same effect as described above can be obtained.

Incidentally, the droplet 9A ejected from the nozzle M2 is generally sufficiently larger than the dispersoid 31A in the first dispersion 3A. That is, a large number of dispersoids 31A are dispersed in the droplet 9A. For this reason, even if the particle size variation of the dispersoid 31A (particularly, the first dispersoid 311A) is relatively large, the ratio of the dispersoid 31A in the ejected droplets 9A is the ratio of each droplet. It is almost uniform. Therefore, even when the dispersion of the particle size of the dispersoid 31A is relatively large, the toner mother is obtained by making the ejection amount of the first dispersion 3A (volume per droplet of the droplet 9A) substantially uniform. The particles 4A have a small variation in particle size. Such a tendency is more remarkable as the ratio of the average particle diameter of the dispersoid 31A (particularly, the first dispersoid 311A) to the average particle diameter of the first dispersion 3A (droplet 9A) to be ejected is smaller. It will be something. For example, the average particle diameter of the jetted first dispersion 3A (droplet 9A) is D ′ [μm], and the average particle diameter of the first dispersoid 311A in the first dispersion 3A is d ₁ [μm. when _a], it is preferable to satisfy the relation d 1 _/D'<0.5, more preferably satisfy the relation: _{d 1 /D'<0.2, d 1 / D} '<0. It is more preferable that the relationship 1 is satisfied.

  Further, when the average particle diameter of the first dispersion 3A (droplet 9A) to be ejected is D ′ [μm] and the average particle diameter of the finally obtained toner particles 100 is D ″ [μm], It is preferable that the relationship 0.05 ≦ D ″ /D′≦1.0 is satisfied, and it is more preferable that the relationship 0.1 ≦ D ″ /D′≦0.8 is satisfied. By satisfying such a relationship, it is possible to relatively easily obtain toner particles 100 that are sufficiently fine, have a high degree of circularity, and have a sharp particle size distribution.

  In the above description, one type of liquid (the first dispersion 3A) is discharged from the supply port 5 of the nozzle M2. However, in the nozzle M2 having the plurality of supply ports 5, for example, each supply Liquids having different compositions can be discharged from the mouth 5. More specifically, in the nozzle M2 as shown in FIG. 8 to FIG. 18, liquids having different compositions are discharged from the supply ports 5 and joined together, thereby including a binder resin and an adhesive resin. After the first dispersion 3A is formed, the first dispersion 3A can be sprayed toward the solidification part M3. For example, in the description of the method for preparing the first dispersion 3A described above, by mixing the dispersion (suspension) containing the binder resin and the dispersion (suspension) containing the adhesive resin, A plurality of methods for preparing the first dispersion 3A containing the binder resin and the adhesive resin have been described. Dispersions containing the binder resin (binder resin suspension) prepared by these methods, A dispersion liquid (adhesive resin suspension) containing an adhesive resin can be discharged from the plurality of supply ports 5 of the nozzle M2 as a first liquid and a second liquid, respectively. In the nozzle M2 having three or more supply ports 5 as shown in FIG. 9, for example, three or more kinds of liquids can be used in combination. More specifically, in the nozzle M2 configured as shown in FIG. 9, a dispersion liquid (binding resin suspension) containing a binding resin and a liquid containing an adhesive resin (adhesion) are respectively supplied from four supply ports 5. Resin suspension), a dispersion containing a colorant (colorant suspension), a dispersion containing a wax (wax suspension), and joining these in the vicinity of the inclined surface 7 and edge 7A, You may inject as 3 A of 1st dispersion liquids. Further, in the nozzle M2 configured as shown in FIG. 9, three types of liquids may be used. That is, liquids having different compositions are discharged from three of the four supply ports 5, and liquids having the same composition as any of these three liquids are discharged from the remaining one supply port 5. It may be discharged. Further, as described above, when a plurality of types of liquids are used, two or more of these include a dispersoid (first dispersoid) mainly composed of a binder resin and an adhesive resin. The content of the binder resin and the adhesive resin may be different from each other. Thus, the adhesive resin phase 42 can be selectively formed in the vicinity of the surface of the toner base particles 4A by using a combination of two or more kinds of liquids. That is, the toner base particles 4A can be obtained in the vicinity of the central portion thereof substantially consisting only of the constituent material of the binder resin fine particles and having the adhesive resin phase 42 in the unbonded portion near the surface. As a result, the properties of the binder resin can be more effectively exhibited in the finally obtained toner.

  In the above description, a nozzle (liquid (dispersion)) as shown in FIGS. 7 to 18 is pressed against a smooth surface by a gas flow to be thinned to form a thin laminar flow, and the thin laminar flow is separated from the smooth surface. The method of making the dispersion into droplets (fine particles) using a nozzle that sprays as dispersion fine particles has been described, but any method can be used as long as a droplet-like dispersion can be obtained. For example, a spray drying method, a so-called ink jet method, a bubble jet (“bubble jet” is a registered trademark) method, or the like may be used.

The spray drying method is a method of obtaining droplets by ejecting (spraying) a liquid (dispersion) using a high-pressure gas.
Moreover, as a method to which a so-called ink jet method is applied, a method described in Japanese Patent Application No. 2002-169349 can be cited. That is, in the present invention, as a method of forming a droplet-like dispersion, “a method in which a dispersion is intermittently ejected from a head portion by piezoelectric pulses and conveyed in a solidified portion by an air current and granulated” is applied. can do.

  Moreover, as a method to which a so-called bubble jet (“bubble jet” is a registered trademark) method is applied, a method described in the specification of Japanese Patent Application No. 2002-169348 can be cited. That is, in the present invention, as a method of forming a droplet-like dispersion, “a method of intermittently discharging the dispersion from the head portion by changing the volume of the gas and making it granular while being conveyed in the solidified portion by an air current” Can be applied.

In particular, in the present invention, when the nozzle as described above is used, the following advantages are obtained as compared with the case where a general spray drying method is applied.
That is, in the method using the nozzle as described above, it is possible to easily and accurately control the ejection condition (amount of ejected droplets) of the dispersion compared to a general spray drying method. For this reason, for example, a granular material (toner base particle) having a desired size and shape can be efficiently produced. In particular, in the method described above, the formed fine particles can have very small size variation (small particle size distribution width), and therefore, variation in the moving speed of each particle can also be reduced. . Therefore, collision and aggregation between the ejected particles can be effectively prevented before the ejected dispersion liquid (droplet) is solidified, and as a result, an irregularly shaped powder is hardly formed. Accordingly, variation in the shape and size of the obtained granular material (toner mother particles) is particularly small, and even in the final toner, variations in charging characteristics, fixing characteristics, etc. among the particles are small, and the entire toner As a result, the reliability is particularly high. In the above-described method, even when the size of the granular material (toner base particle) to be manufactured is relatively small, the particle size distribution of the granular material (toner base particle) can be sharpened.

In the toner manufacturing apparatus M1, a plurality of nozzles (ejection units) M2 and M2 ′ may be provided. When a plurality of nozzles (injection units) M2 are provided, gas injection means (not shown) may be provided between the nozzles (injection units) M2 and the nozzles (injection units) M2. Thereby, the 1st dispersion liquid 3A can be conveyed and solidified, maintaining the space | interval of the droplet 9A intermittently ejected from the nozzle M2. As a result, collision and aggregation of the ejected droplets 9A are more effectively prevented.
Further, by providing the gas ejecting means, an airflow curtain is formed between particles (droplets) ejected from each nozzle M2, for example, collision and aggregation between particles ejected from adjacent nozzles. Can be more effectively prevented.

When such a gas injection means is provided, it is preferable that a heat exchanger (not shown) having a function of setting the temperature of the injected gas to a preferable value is attached. Thereby, the droplet 9A ejected to the solidification part M3 can be solidified efficiently.
Further, when such a gas injection means is provided, the solidification speed and the like of the droplet 9A injected from the nozzle M2 can be easily controlled by adjusting the supply amount of the gas flow.

<External addition process (external addition process)>
The granular material 4 obtained as described above may be subjected to an external addition treatment in which an external additive is added in addition to the resin fine particles to obtain a toner (toner particle 100).
As described above, since the granular body 4 includes the bonded body 40 formed by melting and bonding a plurality of binder resin fine particles, fine irregularities are usually present on the surface of the granular body 4. As a result, the external additive can be reliably supported, and the function as the external additive can be exhibited more effectively.

The external addition process can be performed, for example, by mixing the granular material 4 and the external additive using a Henschel mixer or the like. Alternatively, the external additive may be jetted and / or convected so that the external additive adheres to the droplet 9A or the granular material 4 (toner base particle 4A).
As the external additive, for example, those described above can be used.

Further, substantially all of the external additive may be attached to the granular material 4 in the toner, or a part of the external additive may be released from the surface of the granular material 4. That is, the toner may contain an external additive released from the granular material 4. As described above, when the external additive released from the granular material 4 is contained in the toner in a predetermined ratio (relatively small amount), such a free external additive is, for example, opposite to the granular material 4. It can function as a microcarrier that is charged to polarity.
If necessary, the granule may be washed with water, solid-liquid separated, and dried under reduced pressure after the aforementioned granule production process and prior to the external addition treatment.
The toner obtained as described above may be subjected to classification treatment as necessary. The classification process may be performed before the external addition process.
For the classification treatment, for example, a sieve, an airflow classifier or the like can be used.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to this.
For example, in the above-described embodiment, the kneaded product is used for preparing the first dispersion, but the method for preparing the dispersion is not limited to this. For example, the first dispersion liquid may be prepared through a step of adding each component such as a binder resin, an adhesive resin, and a colorant into a liquid medium (liquid). Further, the first dispersoid and the second dispersion constituting the dispersion may be formed by a method such as an emulsion polymerization method, for example.

In the above-described embodiment, the first dispersion is described as being prepared using a kneaded material made of a material containing at least a binder resin and an adhesive resin, but instead of the adhesive resin, You may use the mixture of adhesive resin and another component.
In the above-described embodiment, the configuration in which the suspension is used as the first dispersion or the second dispersion has been described. For example, an emulsion may be used as these dispersions.
In the above-described embodiment, the toner particles are described as being composed of a granular material composed of toner base particles and resin fine particles and an external additive. However, the toner particles (toner) are composed of external additives. It may not have an agent. In other words, the granular material as described above may be used as toner particles as it is.

  In addition, each part of the toner manufacturing apparatus used for manufacturing the toner of the present invention can be replaced with an arbitrary one that exhibits the same function, or another configuration can be added. For example, in the above-described embodiment, the configuration in which the granular first dispersion 3A (droplet 9A) and the second dispersion 3B (droplet 9B) are ejected downward has been described. The injection direction may be any direction such as vertically upward or horizontal.

In the above-described embodiment, the binder resin is included in the binder resin fine particles (joined body) and the adhesive resin is included in the adhesive resin phase. However, a part of the adhesive resin is the binder resin. It may be contained in fine particles (conjugate). Similarly, a part of the binder resin may be included in the adhesive resin phase.
In the embodiment described above, the rutile-anatase type titanium oxide has been described as being added as an external additive. For example, by using the rutile-anatase-type titanium oxide as one component of the raw material provided for the kneading step. The toner may be contained in the toner.
Further, intermediate treatment and post-treatment such as placing the obtained granular material (toner mother particles) and toner particles to which an external additive has been applied to the granular material in a reduced pressure environment or a heated environment may be performed. Thereby, it is possible to more effectively prevent the dispersion medium and the like from remaining in the finally obtained toner particles.

  Moreover, you may perform the thermal spheronization process which heats the powder obtained by removing the 1st dispersion medium from a 1st dispersion liquid, and spheroidizes. Thereby, the circularity of the obtained granular material (toner base particles) can be further improved. The thermal spheronization treatment can be performed by spraying the powder obtained by removing the dispersion medium from the dispersion liquid (droplets) into a heated atmosphere using, for example, compressed air. Further, the thermal spheronization treatment may be performed in a liquid.

Moreover, although embodiment mentioned above demonstrated the structure which uses a continuous twin-screw extruder as a kneading machine, the kneading machine used for kneading | mixing a raw material is not limited to this. For kneading the raw materials, for example, various kneaders such as a kneader, a batch type triaxial roll, a continuous biaxial roll, a wheel mixer, and a blade type mixer can be used.
In the illustrated configuration, the kneader having two screws has been described. However, the number of screws may be one or three or more.

In the above-described embodiment, the configuration using the belt type as the cooler has been described. However, for example, a roll type (cooling roll type) cooler may be used. Moreover, the cooling of the kneaded material extruded from the extrusion port of the kneader is not limited to the one using the above-described cooling machine, and may be performed by air cooling or the like, for example.
In the above-described embodiment, the colorant, the wax, and the like are described as the constituents of the first dispersoid in the first dispersion, but these components are the constituents of the first dispersion medium. It may be contained in the first dispersion as a component.
In the above-described embodiment, the joined body 40 is described as a plurality of binder resin fine particles fused and integrated, and the boundary (interface) between the binder resin fine particles does not substantially exist. However, it may have a clear interface (boundary surface) between the binder resin fine particles.

[1] Production of Toner A toner was produced as follows.
(Example 1)
<Preparation of binder resin suspension (first dispersion)>
First, polyester resin as a binder resin (glass transition point Tg: 62 ° C., softening point Tf _1/2 : 108 ° C., weight average molecular weight Mw: 9800): 100 parts by weight, phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd.) Phthalocyanine blue): 5 parts by weight, Cr-salicylic acid complex as a charge control agent (Bontron E-81, manufactured by Orient Chemical Industries): 1 part by weight, carnauba wax as a wax: 3 parts by weight, tetrahydrofuran as a solvent (Wako Pure Chemicals) 300 parts by weight were prepared.
These components were mixed and dispersed in a ball mill for 10 hours to prepare a binder resin solution.
On the other hand, an aqueous solution in which 10 parts by weight of nonionic surfactant (manufactured by Sanyo Chemical Industries, Nonipol 85) as a dispersant was dissolved in 590 parts by weight of ion-exchanged water was prepared.

  Next, 600 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and a binder resin solution: 409 weights while stirring at a rotation speed of 4000 rpm using a TK homomixer (manufactured by Tokki Kako). The portion was gradually added dropwise over 10 minutes. At this time, the liquid temperature was kept at 70 ° C. The emulsion was further stirred for 10 minutes while maintaining the liquid temperature at 70 ° C. after the completion of the dropwise addition of the binder resin solution.

Next, the tetrahydrofuran in the emulsion (dispersoid) is volatilized and removed under conditions of temperature: 45 ° C. and atmospheric pressure: 150 to 80 mmHg, then cooled to room temperature, and further ion-exchanged water is added. Thus, a binder resin suspension (first dispersion) in which solid fine particles were dispersed was obtained. The solid content (dispersoid) concentration in the binder resin suspension was 30 wt%. The average particle size d ₁ of the dispersoid constituting the binder resin suspension was 0.24 .mu.m. The average particle size of the dispersoid was measured using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).

<Resin fine particle suspension (second dispersion)>
On the other hand, a dispersion (Daikin Industries, Lubron LDW-40) in which polytetrafluoroethylene (PTFE) was dispersed in water at 40 vol% was prepared.
By adding ion exchange water to this dispersion, a resin fine particle suspension having a solid content (dispersoid) concentration of 1.6 wt% was obtained as a second dispersion. The average particle diameter _{d 3} of the dispersed PTFE into this second dispersion (dispersoid) was 0.20 [mu] m. The average particle size of the dispersoid was measured using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).

<Manufacture of granular material>
The first dispersion liquid and the second dispersion liquid obtained as described above were put into the respective dispersion liquid supply sections of the toner manufacturing apparatus having the configuration shown in FIGS. While stirring the dispersion liquid in each dispersion liquid supply unit with the stirring means, each metering pump supplies each nozzle to the first dispersion liquid from one of the two nozzles, and the second dispersion liquid from the other nozzle. Each was sprayed to the solidified part. The temperature of the dispersion in each dispersion supply unit was adjusted to 25 ° C.

  The first dispersion liquid and the second dispersion liquid were jetted by jetting each dispersion liquid together with compressed air having a pressure of 0.55 MPa at an initial speed of 4.2 m / sec. The first dispersion liquid and the second dispersion liquid are sprayed at 20 mL per minute, and the average spray amount for one drop of the first dispersion liquid sprayed from the nozzle is 1.5 pl (particle diameter D ′: 7.2 μm). )Met. At this time, the spray amount of the first dispersion: the spray amount of the second dispersion was 95: 5 in terms of the solid content ratio.

The second dispersion was sprayed immediately after the first dispersion was finished. The spray time of the first dispersion and the spray time of the second dispersion were both 3 minutes.
Further, at the time of jetting the dispersion liquid, air at a temperature of 100 ° C., a humidity of 30% RH, and a flow rate of 0.9 m ³ / min is jetted vertically upward from the opening of the dispersion plate to generate a gas stream in the solidified portion, At this time, the pressure in the housing was adjusted to 1 to 5 kPa. In addition, a voltage was applied to the housing of the solidified portion so that the potential on the inner surface side became −200 V, thereby preventing the dispersion liquid (granular material (toner mother particles)) from adhering to the inner wall. .

  As described above, by spraying the first dispersion liquid, the dispersion medium is removed from the sprayed first dispersion liquid in the solidification portion, and a plurality of binder resin fine particles (contained from the first dispersoid). Toner mother particles composed mainly of a binder resin were obtained by melt bonding of the resin fine particles). After that, the toner base particles flowed (flyed) in the solidified portion by a gas stream, and the second dispersion was sprayed as described above, so that in the solidified portion, in the vicinity of the surface of the toner base particles. In addition, PTFE resin fine particles derived from the second dispersoid adhered to each other to obtain a granular material.

The granular material formed in the solidified part was recovered with a cyclone. The recovered granular material had an average circularity R of 0.978, a circularity standard deviation of 0.012, a volume-based average particle diameter D of 5.2 μm, and a volume-based particle diameter standard deviation of 1.1 μm. The circularity was measured in a water dispersion system using a flow particle image analyzer (manufactured by Toa Medical Electronics Co., Ltd., FPIA-2000). However, the circularity R is represented by the following formula (I).
R = L ₀ / L ₁ (I)
(Wherein, L ₁ [μm] is the circumference of the projected image of the particle to be measured, and L ₀ [μm] is the circumference of a perfect circle having an area equal to the area of the projected image of the particle to be measured. Represents.)

<External treatment (manufacture of toner)>
An external additive: 2 parts by weight was added to 100 parts by weight of the obtained granular material to obtain a cyan toner as a final toner (toner particles). The external additive was applied using a vertical high-speed mixer. As an external additive, hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., R-972) was used. The finally obtained toner (toner particles) has an average circularity R of 0.978, a circularity standard deviation of 0.010, a volume-based average particle diameter D ″ of 5.3 μm, and a volume-based particle diameter standard. The deviation was 1.0 μm.
Further, the coverage of the external additive in the obtained toner (toner particles) was 150%.

(Example 2)
<Preparation of binder resin suspension>
First, nonionic surfactant (Sanyo Chemical Industries, Nonipol 85): 15 parts by weight, anionic surfactant (Daiichi Kogyo Seiyaku, Neogen SC): 5 parts by weight, and ion-exchanged water: An aqueous solution prepared by mixing 600 parts by weight was prepared.

Next, while stirring this aqueous solution in a flask, 300 parts by weight of styrene (manufactured by Wako Pure Chemical Industries, Ltd.) as a binder resin binder and butyl acrylate (Wako Pure Chemical Industries, Ltd.) are added to the aqueous solution. Product): An emulsion was obtained by gradually adding a mixture of 100 parts by weight and acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.): 10 parts by weight.
Next, an aqueous solution obtained by mixing 2 parts by weight of ammonium persulfate (manufactured by Tokai Denka Co., Ltd.) and 50 parts by weight of ion-exchanged water was added to the emulsion.

Next, the inside of the flask was purged with nitrogen, and then the solution in the flask was heated under the conditions of 70 ° C. × 5 hours while stirring to carry out an emulsion polymerization reaction.
Thereafter, the reaction solution is cooled to room temperature, and then moisture is removed by heating in an oven at 80 ° C., which is composed of a styrene resin (glass transition point Tg: 55 ° C., softening point Tf _1/2 : 134 ° C.). Thus, a binder resin suspension in which a dispersoid having an average particle diameter d _{1 of} 0.37 μm was dispersed was obtained.

<Preparation of colorant suspension>
Phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 60 parts by weight, anionic surfactant (Sanyo Chemical Industries, Ionette D-2): 2 parts by weight, and ion-exchanged water: 300 By mixing the weight part with a homogenizer, a colorant suspension in which colorant particles are dispersed as a dispersoid having an average particle diameter of 0.18 μm was obtained.

<Preparation of wax suspension>
Carnauba wax as wax: 100 parts by weight, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 5 parts by weight, ion-exchanged water: 1000 parts by weight, using a homogenizer, 100 parts The mixture was heated to 0 ° C. and then cooled to obtain a wax suspension in which wax particles were dispersed as a dispersoid having an average particle size of 0.45 μm.

<Preparation of adhesive resin suspension>
First, an epoxy resin as an adhesive resin (glass transition point Tg: 58 ° C., softening point Tf _1/2 : 92 ° C., weight average molecular weight Mw: 8200): 100 parts by weight, tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.): 100 It melt | dissolved in the weight part and obtained the adhesive resin solution.
On the other hand, an aqueous solution prepared by dissolving 2 parts by weight of an anionic emulsifying dispersant (Sanyo Kasei Kogyo Co., Ltd., Ionette D-2) in 198 parts by weight of ion-exchanged water was prepared.

  Next, 200 parts by weight of this aqueous solution was placed in a 3 liter round bottom stainless steel container, and the adhesive resin solution: 200 parts by weight was stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. Was gradually added dropwise over 10 minutes. At this time, the liquid temperature was kept at 25 ° C. The emulsion was further stirred for 10 minutes while maintaining the liquid temperature at 25 ° C. after the completion of the dropwise addition of the binder resin solution.

Next, under the conditions of temperature: 50 ° C. and atmospheric pressure: 150-80 mmHg, the tetrahydrofuran in the emulsion (dispersoid) was removed, and then cooled to room temperature, whereby the solid fine particles (epoxy resin) were dispersed. An adhesive resin suspension was obtained. Thereafter, ion-exchanged water was further added so that the solid content (dispersoid) concentration was 30 wt% to obtain a final adhesive resin suspension. The average particle size _{d 2} of the dispersoid constituting the adhesive resin suspension was 0.21 [mu] m.

<Preparation of suspension for granule production (first dispersion)>
By stirring the binder resin suspension, the colorant suspension, the wax suspension, and the adhesive resin suspension are added to the binder resin suspension in this order, thereby mainly producing styrene. Suspensions for the production of granules comprising a dispersoid composed of a resin, a dispersoid composed mainly of an epoxy resin, a dispersoid composed mainly of a phthalocyanine pigment, and a dispersoid composed mainly of carnauba wax. A turbid liquid (suspension) was obtained. The mixing ratio of the binder resin suspension, the colorant suspension, the wax suspension, and the adhesive resin suspension was set to 65: 5: 5: 25 by weight. Further, the viscosity at 25 ° C. of the obtained suspension for producing a granular material (suspension) was 18 cps.

<Resin fine particle suspension (second dispersion)>
On the other hand, a dispersion liquid (Lublon LDW-40, manufactured by Daikin Industries, Ltd.) in which polytetrafluoroethylene (PTFE) was dispersed in water at 40% by volume was prepared.
By adding ion exchange water to this dispersion, a resin fine particle suspension having a solid content (dispersoid) concentration of 1.6 wt% was obtained as a second dispersion. The average particle diameter _{d 3} of the dispersed PTFE into this second dispersion was 0.20 [mu] m. The average particle size of the dispersoid was measured using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).

<Manufacture of granular material>
The first dispersion liquid and the second dispersion liquid obtained as described above were put into the respective dispersion liquid supply sections of the toner manufacturing apparatus having the configuration shown in FIGS. While stirring the dispersion liquid in each dispersion liquid supply unit with the stirring means, each metering pump supplies each nozzle to the first dispersion liquid from one of the two nozzles, and the second dispersion liquid from the other nozzle. Each was sprayed to the solidified part. The temperature of the dispersion in each dispersion supply unit was adjusted to 25 ° C.

  The first dispersion liquid and the second dispersion liquid were jetted by jetting each dispersion liquid together with compressed air having a pressure of 0.64 MPa at an initial speed of 4.2 m / sec. The first dispersion liquid and the second dispersion liquid are sprayed at 20 mL per minute, and the average spray amount for one drop of the first dispersion liquid sprayed from the nozzle is 1.5 pl (particle diameter D ′: 7.0 μm). )Met. At this time, the spray amount of the first dispersion: the spray amount of the second dispersion was 95: 5 in terms of the solid content ratio.

In addition, the second dispersion was sprayed immediately after the first dispersion was sprayed. The spray time of the first dispersion and the spray time of the second dispersion were both 3 minutes.
Further, at the time of jetting the dispersion liquid, air at a temperature of 100 ° C., a humidity of 30% RH, and a flow rate of 0.9 m ³ / min is jetted vertically upward from the opening of the dispersion plate to generate a gas stream in the solidified portion, At this time, the pressure in the housing was adjusted to 1 to 5 kPa. In addition, a voltage was applied to the housing of the solidified portion so that the potential on the inner surface side became −200 V, thereby preventing the dispersion liquid (granular material (toner mother particles)) from adhering to the inner wall. .

As described above, by spraying the first dispersion liquid, the dispersion medium is removed from the sprayed first dispersion liquid in the solidification portion, and a plurality of binder resin fine particles (contained from the first dispersoid). The adhesive resin in the first dispersion adhered the binder resin fine particles to obtain toner base particles mainly composed of the binder resin. At this time, the adhesive resin was present on the surface of the toner base particles and in the vicinity thereof. Thereafter, when the toner base particles flowed (flyed) in the solidified portion by a gas stream, the second dispersion liquid was sprayed as described above, so that in the solidified portion, in the vicinity of the surface of the toner base particles. In addition, PTFE resin fine particles derived from the second dispersoid adhered to each other to obtain a granular material. At this time, the resin fine particles were mainly fixed to the adhesive resin portion in the vicinity of the surface of the toner base particles.
The granular material formed in the solidified part was recovered with a cyclone. The recovered granular material had an average circularity R of 0.981, a circularity standard deviation of 0.010, a volume-based average particle diameter D of 5.0 μm, and a volume-based particle diameter standard deviation of 0.9 μm.

<External treatment (manufacture of toner)>
An external additive was applied to the obtained granular material in the same manner as in Example 1 to obtain a final toner (toner particle). The coverage of the external additive in the obtained toner (toner particles) was 150%.

(Example 3)
Granules were obtained in the same manner as in Example 2 except that the dispersoid of the second dispersion was tetrafluoroethylene / ethylene polymer (ETFE). Then, silica particles were externally added to the obtained granular material in the same manner as in Example 1 to obtain a final toner.
Example 4
A polyester resin as a binder resin, a phthalocyanine pigment as a colorant, a Cr salicylic acid complex as a charge control agent, and a carnauba wax as a wax are kneaded to obtain a kneaded product. Granules were obtained in the same manner as in Example 1 except that the surfactant was dispersed in an aqueous solution dissolved in ion-exchanged water to obtain the first dispersion. Then, silica particles were externally added to the obtained granular material in the same manner as in Example 1 to obtain a final toner.

(Comparative Example 1)
A granular material was obtained in the same manner as in Example 1 except that only the first dispersion liquid was injected into the solidified portion with a nozzle without using the resin fine particle suspension. Then, resin fine particles were mechanically embedded in the obtained granular material with a vertical high-speed mixer, and then silica particles were externally added in the same manner as in Example 1 to obtain a final toner.
(Comparative Example 2)
A granular material is obtained in the same manner as in Example 1 except that the first dispersion liquid and the second dispersion liquid are mixed to prepare a mixed liquid, and this mixed liquid is injected into the solidification portion with one nozzle. It was. Then, silica particles were externally added to the obtained granular material in the same manner as in Example 1 to obtain a final toner.

(Comparative Example 3)
A granular material was obtained in the same manner as in Example 2 except that only the first dispersion was sprayed into the solidified portion with a nozzle without using the resin fine particle suspension. Then, resin fine particles were mechanically embedded in the obtained granular material with a vertical high-speed mixer, and then silica particles were externally added in the same manner as in Example 1 to obtain a final toner.

(Comparative Example 4)
Granules were obtained in the same manner as in Example 1 except that a resin fine particle suspension of dimethylaminoethyl methacrylate polymer was used as the second dispersion. Then, silica particles were externally added to the obtained granular material in the same manner as in Example 1 to obtain a final toner.
In preparing the resin fine particle suspension, first, a resin solution in which 100 parts by weight of dimethylaminoethyl methacrylate polymer was dissolved in 100 parts by weight of polyvinyl alcohol was prepared.
Meanwhile, 200 parts by weight of an aqueous solution in which a nonionic surfactant (manufactured by Sanyo Chemical Industries, Nonipol 85) was dissolved in ion-exchanged water at the same mixing ratio as described above was prepared.

  Next, 200 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and TK homomixer (manufactured by Tokki Kako Co., Ltd.) is used to stir the resin solution: 110 parts by weight while stirring at a rotational speed of 4000 rpm. The solution was gradually added dropwise over 10 minutes. At this time, the liquid temperature was kept at 80 ° C. The emulsion was further stirred for 10 minutes while the liquid temperature was kept at 80 ° C. after completion of the dropping of the resin solution.

  Next, the polyvinyl alcohol in the emulsion (dispersoid) is volatilized and removed under conditions of temperature: 45 ° C. and atmospheric pressure: 150-80 mmHg, then cooled to room temperature, and further ion-exchanged water is added. As a result, a resin fine particle suspension (second dispersion) in which solid fine particles were dispersed was obtained. The solid content (dispersoid) concentration in the resin fine particle suspension was 1.6 wt%.

  The surface shapes of the granular materials and toner particles obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were observed using a scanning electron microscope (SEM). In the granular materials and toner particles of Examples 1 to 4 and Comparative Example 4, it was confirmed that a plurality of binder resin fine particles were melt-bonded and the resin fine particles were fixed or embedded on the surface of the binder resin fine particles. It was done. On the other hand, in the granular materials of Comparative Examples 1 and 3, a plurality of binder resin fine particles are melt-bonded, and the resin fine particles adhere to the surface of the fine particles, but the distribution is uneven and unevenly distributed. The appearance of the resin particles that had fallen off was confirmed. Further, in the granular material of Comparative Example 2, although a plurality of binder resin fine particles were melt-bonded, it was confirmed that the particle size was uneven or cracked, and the surface of the fine particles was The resin fine particles did not adhere much.

For each of the examples and comparative examples, the average circularity R, the circularity standard deviation, the volume-based average particle diameter D, the particle diameter standard deviation, and the average circularity R of the toner particles for the granular material (toner base particles). , Circularity standard deviation, volume-based average particle diameter D ″, and particle diameter standard deviation are the conditions of the dispersion used in the production of the toner (the average particle diameter D ′ of the droplet, the average particle of the first dispersoid The results are shown in Table 1 together with the diameter d ₁ ).

[2] Evaluation Each toner obtained as described above was evaluated for durability, transfer efficiency, image density, good fixing range, and charging characteristics.
[2.1] Durability The toner obtained in each of the above examples and comparative examples is packed in a cartridge of a laser printer (manufactured by Seiko Epson Corporation, LP-3000C), set in the printer, and developed without printing. The device was driven continuously. After 12 hours, the developing device was taken out from the printer, and the formation state of the toner thin layer on the developing roller was visually observed and evaluated according to the following four criteria.
A: No disturbance is observed in the thin layer.
○: Disturbance is hardly observed in the thin layer.
Δ: Some disturbance is observed in the thin layer.
X: Many streaky disturbances are clearly recognized in the thin layer.

[2.2] Transfer efficiency Evaluation was performed as follows using a laser printer (manufactured by Seiko Epson Corporation, LP-3000C).
The toner on the photoconductor immediately after the development process (before transfer) to the photoconductor (image carrier) and the toner on the photoconductor after transfer (after printing) are collected using separate tapes. The weight was measured. When the toner weight on the photoconductor before transfer is W _b [g] and the toner weight on the photoconductor after transfer is W _a [g], it is obtained as (W _b −W _a ) × 100 / W _b. The value was determined as transfer efficiency. It can be said that the larger the numerical value, the better the transfer efficiency.

[2.3] Image Density of the solid image portion of a print sample obtained using a laser printer (manufactured by Seiko Epson Corporation, LP-3000C) using the toner obtained in each of the above Examples and Comparative Examples. The print density and uniformity were visually observed and evaluated according to the following three criteria.
A: Image density is sufficient and uniform, and extremely excellent.
○: Image density is sufficient and uniform.
X: Insufficient image density or streaky unevenness.

[2.4] Good Fixing Area First, a laser printer equipped with a fixing device (manufactured by Seiko Epson Corporation, LP-3000C) was prepared. In this fixing device, the time Δt required for the toner to pass through the nip portion was set to 0.05 seconds.
Next, an unfixed image sample was collected using the above laser printer, and the following test was performed with the fixing device of the laser printer. The solid amount of the sample to be collected was adjusted to an adhesion amount of 0.40 to 0.50 mg / cm ² .

In the state where the surface temperature of the fixing roller of the fixing device constituting the laser printer is set to a predetermined temperature, the paper on which the unfixed toner image is transferred (Seiko Epson, high-quality plain paper) is introduced into the fixing device. As a result, the toner image was fixed on the paper, and the presence or absence of offset after fixing was visually confirmed.
Similarly, the set temperature of the surface of the fixing roller is sequentially changed within a range of 100 to 250 ° C., and the presence or absence of occurrence of an offset at each temperature is confirmed. It was determined as “range” and evaluated according to the following four-stage criteria.
(Double-circle): The width | variety of a favorable fixing area is 60 degreeC or more.
◯: The width of the fixing good region is 45 ° C. or more and less than 60 ° C.
(Triangle | delta): The width | variety of a favorable fixing area is 30 degreeC or more and less than 45 degreeC.
X: The width of the good fixing region is less than 30 ° C.

[2.5] Charging characteristics The following tests were carried out using a laser printer (manufactured by Seiko Epson Corporation, LP-3000C).
In a laser printer, stop the operation during printing, remove the cartridge, measure the charge distribution using the powder charge distribution measurement device (E-spart analyzer, manufactured by Hosokawa Micron), and determine the charge amount and The positive charge amount was determined as the reverse charge amount.
The charge amount was determined for the initial charge amount under room temperature conditions (25 ° C., humidity 45%) and the charge amount after printing 1,000 sheets (after 1K).

The amount of charge after printing 1,000 sheets (after 1K) was evaluated according to the following four criteria.
A: The amount of change (absolute value) from the initial charge amount is less than 1 μC / g.
A: The amount of change (absolute value) from the initial charge amount is 1 μC / g or more and less than 4 μC / g.
Δ: The amount of change (absolute value) from the initial charge amount is 4 μC / g or more and less than 8 μC / g.
X: The amount of change (absolute value) from the initial charge amount is 8 μC / g or more.
In addition, the reversely chargeable toner is obtained by the existence ratio with respect to the total toner amount. When the existence ratio of the reversely chargeable toner is less than 2 wt%, ◎, when it is 2 wt% or more and less than 3 wt%, ○ When the amount is less than 4 wt%, Δ, and when it is 4 wt% or more, ×.
These results are summarized in Table 2.

As is apparent from Table 2, the toner of the present invention gave excellent results in all of durability, transfer efficiency, image density, good fixing range, and charging characteristics.
On the other hand, with the toners of Comparative Examples 1 to 3, sufficient charging characteristics and durability could not be obtained. This is because, in Comparative Examples 1 and 3, regarding the charging characteristics, the distribution of the resin fine particles present on the surface of the toner base particles is non-uniform, and the resin fine particles are unevenly distributed on the surface of the toner base particles. In Comparative Example 2, it is presumed that the amount of resin fine particles near the surface of the toner base particles was small. In addition, regarding the durability, since the release property of the resin fine particles is high, the bond strength between the resin fine particles and the toner base particles is not sufficient. For example, in Comparative Examples 1 and 3, the resin fine particles are This is because the toner base particles dropped out, and in Comparative Example 2, it is presumed that the strength of the toner base particles was reduced by the resin fine particles.

Further, the toner of Comparative Example 2 was inferior to Examples 1 to 4 in terms of a good fixing region. This is presumably because there are many resin fine particles in the toner base particles.
The toner of Comparative Example 4 was excellent in durability, but was inferior in transfer efficiency, image density, good fixing range, and charging characteristics as compared with Examples 1 to 4. That is, it can be seen that PTFE and ETFE are superior to the dimethylaminoethyl methacrylate polymer as a constituent material of the resin fine particles.

  In addition, as a colorant, C.I. I. Pigment blue, carbon black, quinacridone (PR 122), pigment red 57: 1, C.I. I. Except that Pigment Yellow 93 was used, toners were prepared in the same manner as in the above Examples and Comparative Examples, and these toners were evaluated in the same manner as described above. As a result, the same results as those of the respective Examples and Comparative Examples were obtained.

FIG. 2 is a cross-sectional view schematically showing a preferred embodiment of the toner (toner particles) of the present invention. It is a flowchart for a softening point analysis. It is a longitudinal cross-sectional view which shows typically an example of a structure of the kneading machine for manufacturing the kneaded material used for preparation of a dispersion liquid, and a cooler. It is a longitudinal cross-sectional view which shows typically suitable embodiment of the apparatus for preparing a dispersion liquid. It is an expanded sectional view of the chamber vicinity of the apparatus shown in FIG. FIG. 3 is a longitudinal sectional view schematically showing a preferred embodiment of a toner production apparatus used for producing the toner of the present invention. It is sectional drawing which shows suitable embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles. It is sectional drawing which shows other embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles. It is sectional drawing which shows other embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles. It is sectional drawing which shows other embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles. It is a principal part expanded sectional view of the nozzle shown in FIG. It is an expanded sectional view which shows the inner side intermediate ring front-end | tip part of the nozzle shown in FIG. It is sectional drawing which shows other embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles. It is a principal part expanded sectional view of the nozzle shown in FIG. It is an expanded sectional view which shows the inner side intermediate ring front-end | tip part of the nozzle shown in FIG. It is sectional drawing which shows other embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles. It is a top view of the gas peeling recessed part shown in FIG. It is sectional drawing which shows other embodiment of the nozzle which injects a dispersion liquid as microparticles | fine-particles.

Explanation of symbols

  K1 …… Kneading machine K2 …… Process part K21 …… Barrel K22, K23 …… Screw K24 …… Fixing member K25 …… Deaeration port K3 …… Head K31 …… Internal space K32 …… Extrusion port K33 …… Transverse Area gradually decreasing part K4 ... Feeder K5 ... Raw material K6 ... Cooler K61, K62, K63, K64 ... Roll K611, K621, K631, K641 ... Rotating shaft K65, K66 ... Belt K67 ... Discharge part K7 ... ... Kneaded material B1 ... Atomizer B21, B22 ... Nozzle B3 ... Liquid supply part for dispersion preparation (dispersion supply part) B31 ... Agitating means B4 ... Chamber B5 ... Housing part B6 ... Recovery part B7 …… Ultra-high pressure generating pump B8 …… Branching part B9 …… Conveying pump B10 …… Conveying pipe M1 …… Toner manufacturing device M , M2 '... Nozzle M3 ... Solidification part M31 ... Housing M311 ... Reduced diameter part M4, M4' ... Dispersed liquid supply part M41, M41 '... Stirring means M5 ... Gas flow supply means M7 ... Dispersion Plate M71 …… Open M8 …… Voltage applying means M10 …… Gas flow supplying means M101 …… Duct M11 …… Valve M12 …… Pressure adjusting means M121 …… Connecting pipe M122 …… Expanded diameter part M123 …… Filter 1 …… Flow path 2 …… Liquid for preparing dispersion (liquid containing pulverized product) 3A …… First dispersion 3B …… Second dispersion 31A …… Dispersoid 31B …… Second dispersoid 311A …… First Dispersoid 312A …… Dispersoid 32A …… First dispersion medium 32B …… Second dispersion medium 4 …… Granular body 4A …… Toner base particle 40 …… Joint body 42 …… Adhesive resin phase 4B …… Resin Fine Particle 5 ... Supply port 7 ... Inclined surface 7A ... Edge 8 ... Thin laminar flow 9A, 9B ... Droplet 10 ... Gas port 11 ... Inner ring 12 ... Intermediate ring 12A ... Inner intermediate ring 12B …… Outer intermediate ring 13 …… Outer ring 14 …… Atomized gas flow path 15 …… Spreading gas supply path 16 …… Center ring 17 …… Spreading gas injection port 18 …… Breathable member 19 …… Gas Peeling recess 20 ... Through hole 21 ... Liquid flow path 22 ... Helical rib F ... Pressurized gas source P ... Pump 100 ... Toner particle

Claims (13)

A method for producing a toner in which resin fine particles mainly composed of a fluorine-based resin are added to toner base particles,
A first dispersion liquid in which the first dispersoid containing the binder resin is finely dispersed in the first dispersion medium, and a second dispersion material in which the second dispersoid containing the resin fine particles is finely dispersed in the second dispersion medium. 2 dispersion liquids are discharged from different nozzles into the solidified part where the gas stream is generated,
A method for producing a toner, comprising solidifying the first dispersion in the form of fine particles to form the toner base particles, and applying the resin fine particles to the toner base particles to obtain a granular material.   2. The granule is obtained by solidifying the first dispersion in the form of fine particles to form the toner base particles, and fixing or embedding the resin fine particles on or near the periphery of the toner base particles. Toner production method.   The toner manufacturing method according to claim 1, wherein the binder resin is a thermoplastic resin.   The method for producing a toner according to claim 1, wherein the resin fine particles have an average particle size of 0.04 to 1.0 μm.   The method for producing a toner according to claim 1, wherein the first dispersion medium and the second dispersion medium are aqueous dispersion media.   The toner manufacturing method according to claim 1, wherein the first dispersion contains an adhesive resin.   The toner manufacturing method according to claim 6, wherein the adhesive resin is an epoxy resin.   The method for producing a toner according to claim 1, wherein the temperature of the gas stream is 40 to 200 ° C.   A toner manufactured by the method for manufacturing a toner according to claim 1. A toner in which resin fine particles mainly composed of a fluorine-based resin are added to toner base particles,
The toner base particles are mainly composed of a binder resin, and at least a part of the outer periphery of the toner base particles or the vicinity thereof is composed of an adhesive resin.
The toner, wherein the resin fine particles are attached to the adhesive resin.   The toner according to claim 9 or 10, having an average particle diameter of 2 to 20 µm.   The toner according to claim 9, wherein the standard deviation of the particle diameter between the particles is 1.5 μm or less. The toner according to claim 9, wherein an average circularity R represented by the following formula (I) is 0.95 or more.
R = L ₀ / L ₁ (I)
(Where, L ₁ [μm] is the circumference of the projected image of the toner particles to be measured, and L ₀ [μm] is the circumference of a perfect circle having an area equal to the area of the projected image of the toner particles to be measured) Represents length)

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