JP2005292486A - Method for manufacturing toner, dispersion solution for manufactruring toner, and the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing toner, a fluid dispersion for manufacturing the toner, and the toner that can improve performance, such as charging characteristic and fixing characteristics by fully exhibiting a function of resin constituting the toner. <P>SOLUTION: In the method for manufacturing the toner, a liquid dispersion prepared by dispersing a 1st dispersoid, consisting principally of toluene-soluble 1st resin and a 2nd dispersoid containing toluene-insoluble 2nd resin is discharged in a particulate state from a discharge opening and then solidified to obtain granules. The 2nd dispersoid contains the 1st resin, in addition to the 2nd resin and the average grain size of the 2nd dispersoid is larger than the average grain size of the 1st dispersoid, thereby obtaining the granules having the 2nd resin unevenly distributed nearby surfaces, without being exposed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner production method, a toner production dispersion, 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 development process for developing the latent image with toner, a transfer process for transferring the toner image to a recording medium such as paper, and a process for fixing the toner image by heating, pressurizing, etc. using a fixing roller. doing.
Toners used in such electrophotography require characteristics such as predetermined charging characteristics and fixing characteristics in order to obtain excellent images. Therefore, conventionally, toner base particles are configured by combining resins having various characteristics (see, for example, Patent Document 1).
However, in the method according to Patent Document 1, the characteristics of each resin cannot be exhibited sufficiently.

JP 2002-296839 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner production method, a toner production dispersion, and a toner that can fully improve the performance of charging characteristics and fixing characteristics by sufficiently exerting the function of the resin constituting the toner. There is.

Such an object is achieved by the present invention described below.
The toner manufacturing method according to the present invention includes a first dispersoid composed mainly of a first resin soluble in toluene and a second dispersion composed of a second resin insoluble in toluene. A method for producing a toner, in which a dispersion liquid in which the quality is dispersed is discharged into a fine particle form from a discharge port, and the fine particle dispersion liquid is solidified to obtain a granular material,
The second dispersoid includes the first resin in addition to the second resin, and the average particle size of the second dispersoid is the average particle size of the first dispersoid. Is bigger than
A granular material unevenly distributed in the vicinity of the surface is obtained so that the second resin is not exposed.

As a result, when the discharged dispersion contracts (aggregates) and solidifies as the moisture evaporates, the first dispersoid easily moves inward than the second dispersoid. The second dispersoid containing the material moves relatively outward. As a result, the obtained granular material has the second resin unevenly distributed in the vicinity of the outer periphery thereof.
Since the second resin has higher mechanical strength and lower water absorption than the first resin, such a granular body has excellent mechanical strength and relatively low water absorption. Therefore, toner breakage and filming in the developing device and the like can be prevented, and good development results can be obtained over a long period of time. In addition, a reduction in charge amount due to water absorption of the toner is prevented, and excellent charging characteristics can be obtained over a long period. Further, since the hydrophilicity of the toner surface is relatively low, the toner transfer efficiency can be improved.

In particular, since the second dispersoid contains the first resin and the second resin, in the granular body, the second resin is in a form surrounded by the first resin, Exposure to the surface of the granular material is prevented while being positioned in the vicinity of the surface of the granular material. As a result, separation of the second resin from the granular material is prevented, and the above-described effects can be maintained for a long time. In addition, since the second resin is prevented from detaching from the granular material, it is possible to prevent fogging and hollowing out and to obtain excellent OHP colorability.
In addition, since the average particle diameter of the second resin in the second dispersoid is smaller than the average particle diameter of the second dispersoid, the second resin is temporarily separated from the second dispersoid. However, during the above-described solidification, the second resin moves to the inside of the granular material, and the exposure of the second resin to the surface of the obtained granular material is prevented.

In the toner production method of the present invention, it is preferable that the second resin has a higher crosslink density than the first resin.
Thereby, the mechanical strength of the obtained granular material can be made particularly excellent. As a result, toner destruction and filming in the developing device and the like can be prevented more reliably.
In the method for producing a toner of the present invention, it is preferable that the second resin has a crystallinity higher than that of the first resin.
As a result, the second resin starts to melt quickly and oozes out on the toner surface during fixing, so that it is possible to improve the releasability of the toner with respect to the fixing roller and the permeability of the toner into the paper. It can be made excellent.

The toner manufacturing method of the present invention includes a first dispersoid composed mainly of a first resin having a difference between an outflow start temperature Tfb and an outflow end temperature Tend of 10 ° C. or more in a flow tester, A dispersion liquid in which a second dispersoid composed of a second resin having a difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester is less than 10 ° C. is dispersed from the discharge port in the form of fine particles. A method for producing a toner which is discharged into a solid and solidifies the fine particle dispersion to obtain a granular material,
The second dispersoid includes the first resin in addition to the second resin, and the average particle size of the second dispersoid is the average particle size of the first dispersoid. Is bigger than
A granular material unevenly distributed in the vicinity of the surface is obtained so that the second resin is not exposed.
As a result, when the discharged dispersion contracts (aggregates) and solidifies as the moisture evaporates, the first dispersoid easily moves inward than the second dispersoid. The second dispersoid containing the material moves relatively outward. As a result, the obtained granular material has the second resin unevenly distributed in the vicinity of the outer periphery thereof.

  Since the second resin has higher mechanical strength and lower water absorption than the first resin, such a granular body has excellent mechanical strength and relatively low water absorption. Therefore, toner breakage and filming in the developing device and the like are prevented, and good development results can be obtained over a long period of time. In addition, a reduction in charge amount due to water absorption of the toner is prevented, and excellent charging characteristics can be obtained over a long period of time. Further, since the hydrophilicity of the toner surface is relatively low, the toner transfer efficiency can be improved.

In particular, since the second dispersoid contains the first resin and the second resin, in the granular body, the second resin is in a form surrounded by the first resin, Exposure to the surface of the granular material is prevented while being positioned in the vicinity of the surface of the granular material. As a result, separation of the second resin from the granular material is prevented, and the above-described effects can be maintained for a long time. In addition, since the second resin is prevented from detaching from the granular material, it is possible to prevent fogging and hollowing out and to obtain excellent OHP colorability.
In addition, since the average particle size of the second resin in the second dispersoid is smaller than the average particle size of the second dispersoid, the second resin is temporarily separated from the second dispersoid. However, during the above-described solidification, the second resin moves to the inside of the granular body, and the exposure of the second resin in the obtained granular body is prevented.

In the toner manufacturing method of the present invention, the melting point of the second resin is preferably lower than the softening point of the first resin.
As a result, since the second resin starts to melt more rapidly and oozes out on the toner surface at the time of fixing, it is possible to more surely improve the releasability of the toner with respect to the fixing roller and the permeability of the toner into the paper. And fixing properties can be made particularly excellent.

In the method for producing a toner of the present invention, the dispersion liquid is mixed by mixing the first dispersion liquid in which the first dispersoid is dispersed with the second dispersion liquid in which the second dispersoid is dispersed. It is preferable to obtain.
Thereby, since the variation in the particle diameter between the particles of the first dispersoid and the second dispersoid in the dispersion liquid can be made smaller, the second resin can be more reliably disposed near the surface of the granular material. It can be unevenly distributed.

In the toner production method of the present invention, the first resin is dissolved in toluene to form a first resin solution, the first resin solution is emulsified and dispersed in water to obtain a first emulsified dispersion, It is preferable to obtain the first dispersion by removing the toluene from one emulsified dispersion.
Thereby, the circularity of the first dispersoid can be made higher, and as a result, the circularity of the obtained granular material can be made higher.

In the method for producing a toner of the present invention, the first resin and the second resin are kneaded to obtain a kneaded product, and the kneaded product is mixed with toluene to obtain a second resin solution. The second resin solution is emulsified and dispersed in water so as to have an average particle size larger than the average particle size of the second resin to form a second emulsified dispersion, and the toluene is added from the second emulsified dispersion. It is preferable to obtain the second dispersion by removing.
Thereby, by adjusting the particle size of the second resin by kneading, it is possible to easily adjust the particle size of the second dispersoid in the dispersion, and by emulsifying and dispersing the kneaded product, A second dispersoid containing the first resin and the second resin can be easily obtained.

In the toner production method of the present invention, the average particle size of the total dispersoid in the second emulsified dispersion is 2 to 5 times the average particle size of the second resin in the kneaded product. preferable.
Thereby, the second resin can be more reliably contained in the second dispersoid during emulsification dispersion.
In the toner manufacturing method of the present invention, the second dispersoid is configured such that the second resin is in the form of particles, and the first resin covers the second resin. Is preferred.
Thereby, exposure of the 2nd resin to the granular material surface is prevented more reliably, and as a result, separation of the 2nd resin from the granular material is prevented more reliably.

In the toner production method of the present invention, the average particle size of the second resin in the second dispersoid is 1/5 to 1/2 times the average particle size of all the dispersoids in the dispersion. Preferably there is.
Thereby, exposure of the 2nd resin to the granular material surface is prevented more reliably, and as a result, separation of the 2nd resin from the granular material is prevented more reliably.

In the method for producing a toner of the present invention, it is preferable that the average particle size of the second dispersoid is larger than the average particle size of all the dispersoids in the dispersion.
Thereby, the second resin can be unevenly distributed in the vicinity of the surface of the granular body while preventing the second resin from being exposed to the surface of the granular body.
In the toner production method of the present invention, the average particle size of the second dispersoid is preferably 2 to 5 times the average particle size of all the dispersoids in the dispersion.
Thereby, the second resin can be unevenly distributed in the vicinity of the surface of the granular body while preventing the second resin from being exposed to the surface of the granular body.

In the toner production method of the present invention, it is preferable that the average particle size of the second dispersoid is 2 to 5 times the average particle size of the first dispersoid.
Thereby, the second resin can be unevenly distributed in the vicinity of the surface of the granular body while preventing the second resin from being exposed to the surface of the granular body.
The dispersion for toner production according to the present invention is a dispersion obtained by dispersing a dispersoid composed mainly of a resin in a fine particle form from a discharge port, and solidifying the fine particle dispersion to form a granular material. A dispersion used in a method for producing a toner obtained,
A first dispersoid composed mainly of a first resin soluble in toluene and a second dispersoid composed of a second resin insoluble in toluene are dispersed;
The second dispersoid includes the first resin in addition to the second resin,
The average particle size of the second dispersoid is larger than the average particle size of the first dispersoid.

Thereby, it is possible to obtain a granular material having excellent mechanical strength and relatively low water absorption. Therefore, toner breakage and filming in the developing device and the like can be prevented, and good development results can be obtained over a long period of time. In addition, a reduction in charge amount due to water absorption of the toner is prevented, and excellent charging characteristics can be obtained over a long period. Further, since the hydrophilicity of the toner surface can be made relatively low, the toner transfer efficiency can be improved over a long period of time.
In addition, since the second resin can be prevented from detaching from the granular material, it is possible to prevent fogging and hollowing out and to obtain excellent OHP colorability.

The toner of the present invention is manufactured using the method of the present invention.
Thereby, it is possible to obtain a granular material having excellent mechanical strength and relatively low water absorption. Therefore, toner breakage and filming in the developing device and the like can be prevented, and good development results can be obtained over a long period of time. In addition, a reduction in charge amount due to water absorption of the toner is prevented, and excellent charging characteristics can be obtained over a long period. Further, since the hydrophilicity of the toner surface is relatively low, the toner transfer efficiency can be improved over a long period of time.
In addition, since the second resin is prevented from detaching from the granular material, it is possible to prevent fogging and hollowing out and to obtain excellent OHP colorability.

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.
First, prior to the description of the toner manufacturing method, a preferred embodiment of the toner of the present invention will be described.
[Toner particles]
FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the toner (toner particles) of the present invention.
The toner particles 100 are composed of a granular body 9 formed by melting and joining a plurality of resin fine particles and an external additive (not shown).

<Granular body 9>
The granular material 9 is formed by melt-bonding a plurality of resin fine particles having different sizes. As shown in FIG. 1, the first resin portion 91 and the second unevenly distributed in the vicinity of the surface of the granular material 9. The resin part 92 is provided.
Since the granular material 9 is formed by melting and joining a plurality of resin fine particles, 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 external additive can be reliably supported in the vicinity of the surface of the toner base particles (granular body 9), the function of the external additive can be exhibited more effectively, and the characteristics and reliability of the toner as a whole can be achieved. Also improves. In addition, since a plurality of resin fine particles are melt-bonded, the mechanical stability of the toner particles 100 is improved, and even if the toner particles 100 have a relatively small particle size, it is easy and reliable. The circularity can be made relatively small. In particular, in the present embodiment, the granular material 9 is obtained by melting and integrating a plurality of resin fine particles, and there is substantially no boundary (interface) between the resin fine particles. Thereby, the above effects become more remarkable.

The first resin portion 91 is composed of a first resin soluble in toluene as a main material, and the second resin portion 92 is composed of a second resin insoluble in toluene as a main material.
The second resin insoluble in toluene has properties such as high mechanical strength and low water absorption compared to the first resin soluble in toluene. That is, the second resin portion 92 composed of the second resin as a main material has higher mechanical strength and water absorption than the first resin portion 91 composed of the first resin as a main material. Is low. Here, examples of the resin insoluble in toluene include a crosslinking component, a multibranched component, a linear high molecular weight component in the case of an amorphous resin, and a crystalline component in the case of a crystalline resin. In addition, the resin insoluble in toluene refers to a resin that does not substantially dissolve in toluene. For example, when 5 mg of toluene-insoluble resin is mixed in 5 g of toluene to obtain a mixed solution, the mixture is sufficiently heated with stirring and then passed through a membrane filter having a pore size of 0.2 μm. Resin that remains as a membrane filter.

Therefore, since the second resin portion 92 is unevenly distributed in the vicinity of the surface of the granular body 9, the granular body 9 sufficiently exhibits the characteristics of the second resin, and as a result, improves the mechanical strength of the toner. At the same time, the water absorption of the toner can be suppressed, and the toner has excellent characteristics such as charging characteristics and fixing characteristics.
In particular, the second resin portion 92 is configured to be surrounded by the first resin existing on the outermost surface of the granular material 9, and is not exposed to the surface of the granular material 9. Located near the surface. In other words, the second resin portions 92 that are aggregates of the second resin scattered are covered with the first resin so as not to be exposed on the surface of the granular material 9 as much as possible.

  Therefore, the second resin (second resin portion 92) is prevented from being detached from the granular material 9, and the above-described excellent characteristics can be maintained for a long time. In addition, since the second resin (second resin portion 92) is prevented from detaching from the granular material 9, it is possible to prevent fogging and hollowing out over a long period of time and to obtain excellent OHP coloring properties. . Here, the ratio of the area of the second resin portion 92 on the surface of the granular body 9 to the degree of exposure of the second resin portion 92 to the surface of the granular body 9, that is, the total surface area of the granular body 9 is 50%. Is preferably 20% or less, and more preferably 10% or less. Thereby, the separation of the second resin (second resin portion 92) from the granular body 9 is more reliably prevented, and the above-described effects can be obtained more effectively.

Each of the first resin and the second resin is a binder resin (binder resin). That is, each of the first resin portion 91 and the second resin portion 92 is composed of a binder resin as a main material. The 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.
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 acid ester copolymer, styrene-vinyl methyl ether copolymer Union or 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 A coalescence, a xylene resin, a polyvinyl butyral resin, a terpene resin, a phenol resin, an aliphatic or alicyclic hydrocarbon resin, and the like can be given, and one or more of these can be used in combination.

  Also, 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 of crystallizing)) By using a combination of different components, etc., the advantages of each component can be obtained, and various properties required for the 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.

  As described above, a resin soluble in toluene (hereinafter also referred to as a toluene-soluble resin) can be appropriately selected as the first resin from the binder resins as described above, and is insoluble in toluene. A resin (hereinafter also referred to as a toluene insoluble resin) can be appropriately selected as the second resin. Further, from the binder resins as described above, those having excellent mechanical strength can be appropriately selected as the second resin, and those having inferior mechanical strength can be appropriately selected as the first resin. Can do. Furthermore, among the binder resins as described above, one having high water absorption can be appropriately selected as the second resin, and one having low water absorption can be appropriately selected as the first resin. it can.

In particular, a crystalline polyester resin can be used as the second resin.
As the acid component of the crystalline polyester resin, aliphatic polycarboxylic acids such as succinic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid and the like can be used. In particular, it is preferable to use decamethylene dicarboxylic acid, whereby a crystalline polyester resin having very high crystallinity can be obtained.

  The polyol component of the crystalline polyester resin includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentadiol, 1,6-hexanenediol, neopentyl glycol. In addition, aliphatic polyols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol can be used. In particular, it is preferable to use 1,6-hexanediol, whereby a crystalline polyester resin having very high crystallinity can be obtained.

  When polymerizing a crystalline polyester resin using decamethylene carboxylic acid, it is difficult to remove reaction by-products during polymerization due to the high viscosity and boiling point of decamethylene dicarboxylic acid. The obtained crystalline polyester resin tends to have a low degree of polymerization and a small molecular weight. Therefore, for example, in the case of polymerizing a crystalline polyester resin composed of decamethylene dicarboxylic acid and 1,6-hexanediol, other than the above monomers, to the extent that the crystallinity of the crystalline polyester resin by the aforementioned monomers is not significantly impaired. By adding a small amount of dicarboxylic acid or polyol, etc., different from the above monomer, it is possible to effectively remove reaction by-products during the polymerization, thereby increasing the degree of polymerization and obtaining a crystalline polyester resin having a large molecular weight. Can do. By using such a crystalline resin having a large molecular weight as the second resin, the glass transition temperature of the amorphous resin during mixing of the crystalline resin and the amorphous resin (first resin) can be reduced. It is possible to prevent a decrease and, in turn, a decrease in toner storage stability and durability. At this time, the monomer added in a small amount preferably has a boiling point as low as possible.

  The second resin preferably has a higher crosslink density than the first resin. Thereby, the mechanical strength of the granular material 9 obtained can be made more excellent. As a result, toner destruction and filming in the developing device and the like can be prevented more reliably. Here, the crosslink density refers to the ratio of the number of cross-linked structural units (crosslinking points) to the structural units of the entire resin.

The crosslink density of the second resin is preferably 0.5 to 1, and more preferably 0.8 to 1. Thereby, the mechanical strength of the granular material 9 obtained can be further improved.
The second resin preferably has a higher crystallinity than the first resin. As a result, the second resin starts to melt quickly and oozes out on the toner surface during fixing, so that it is possible to improve the releasability of the toner with respect to the fixing roller and the permeability of the toner into the paper. It can be made excellent. Here, the degree of crystallinity refers to the ratio of crystal parts to the total mass of the resin.

The crystallinity of the second resin is preferably 0.5 to 1, and more preferably 0.8 to 1. Thereby, the fixing characteristics can be further improved.
The melting point of the second resin is preferably lower than the softening point of the first resin. As a result, the crystalline resin starts to melt more rapidly at the time of fixing and oozes out on the toner surface, so that the releasability of the toner to the fixing roller and the permeability of the toner to the paper can be improved more reliably. The fixing property can be particularly excellent.

The “binder resin” used in the production of the toner described later may be the “binder resin” itself constituting the finally obtained toner, or a precursor (for example, a corresponding binder resin). Monomer, dimer, trimer, oligomer, prepolymer, etc.).
Further, as described above, the granular material 9 (toner mother particles) may be any material as long as it is mainly composed of a binder resin. However, toner constituents other than the binder resin (for example, Colorants, waxes, charge control agents, and the like). As described above, when the resin fine particles 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 resin fine particles contain a colorant, the dispersibility of the colorant in the toner particles 100 can be made particularly easy. Further, when the resin fine particles contain a colorant, it is possible to effectively prevent the colorant from exuding to the outside of the toner particles 100 (unintentional colorant exudation). 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.

  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.

  Further, if the 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 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.

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-hydroxystearic acid amide, stearic acid amide, phthalic anhydride amide waxes, 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

  In addition, the constituent components of the toner other than the binder resin such as the colorant, the wax, and the charge control agent may not be included in the resin fine particles. For example, when the toner particle 100 (granular body 9) has fine particles other than 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 resin fine particles are included, it is preferable that the boundary (interface) between the fine particles does not substantially exist as described above.

  Moreover, it is preferable that the average particle diameter D of the granular material 9 is 2-20 micrometers, and it is more preferable that it is 3-8 micrometers. When the average particle diameter D of the granular material 9 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 residual toner and a decrease in transfer efficiency. In addition, it becomes difficult to manufacture the granular material 9 (toner particles 100). On the other hand, if the average particle diameter D of the granular material 9 exceeds the above upper limit value, the average particle diameter of the toner particles 100 also increases, so that the contour portion of an image formed using toner, particularly the development of character images and light patterns is developed. 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 9 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 9 is 1.6 μm or less, variations in charging characteristics, fixing characteristics and the like are particularly reduced, and the reliability of the entire toner is further improved.
The granular material 9 may have a configuration (configuration not shown) other than the first resin portion 91 and the second resin portion 92. The granular material 9 may be provided with fine particles other than resin fine particles, for example. More specifically, the granular material 9 may include, for example, a colorant fine particle mainly composed of a colorant, a wax fine particle mainly composed of wax, and the like as a configuration not shown.

<External additive>
In the present embodiment, the toner particle 100 has an external additive (not shown) in addition to the granular material 9. That is, the toner particles 100 are obtained by adding an external additive to the vicinity of the surface of the granular material 9 constituted by the first resin portion 91 and the second resin portion 92. 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.
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 difficult to embed in the mother particle (granular material 9) 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 this range, the rutile-anatase type titanium oxide can sufficiently perform the functions described above, and is embedded in the toner base particles (granular material). Difficult to release 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, at least a part of the components used as the external additive may be contained in the toner particles in the finally obtained toner.
The toner particles 100 have a coverage of the external additive (the ratio of the area covered by the external additive in the surface area of the granule 9, 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 coated with fine 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.

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 decrease. 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. Further, it becomes difficult to manufacture the toner particles 100 (granular bodies 9). On the other hand, when the average particle diameter D ″ of the toner particles 100 exceeds the upper limit, the reproducibility in developing the contour portion of an image formed using toner, particularly a character image or a 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.
Further, the toner (toner particle 100) may contain components other than the binder resin, the colorant, the wax, and the 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.), resin 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. 2 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 preparing a dispersion, and FIG. 3 is a toner production used for producing the toner of the present invention. FIG. 4 is a cross-sectional view showing a preferred embodiment of a nozzle that ejects droplets (liquid) for producing granules as fine particles. In the following description, the left side in FIG. 2 is referred to as “base end”, the right side is referred to as “tip”, the upper side in FIG. 3 is referred to as “tip”, and the lower side is referred to as “base end”.

  The toner production method of the present invention includes a first dispersoid composed mainly of a first resin soluble in toluene and a second dispersion composed of a second resin insoluble in toluene. A step of obtaining a granular material by discharging a dispersion obtained by dispersing the fine particles into fine particles and solidifying the particles, wherein the second dispersoid is a material other than the second resin. The first resin is included, and the average particle size (volume average particle size) is larger than the average particle size (volume average particle size) of the first dispersoid.

  As a result, when the discharged dispersion contracts and solidifies as the water evaporates, the first dispersoid is more easily moved inward than the second dispersoid. Move outward. As a result, the toner (toner particles) having the structure shown in FIG. 1 as described above, that is, the second resin portion 92 composed mainly of the second resin is not exposed on the surface of the granular material 9. The toner particles 100 unevenly distributed in the vicinity of the outer peripheral portion of the granular material 9 can be preferably manufactured.

As described above, the second resin having higher mechanical strength and lower water absorption than the first resin is unevenly distributed in the vicinity of the surface of the toner, thereby improving the mechanical strength of the toner and improving the water absorption of the toner. Therefore, a toner excellent in characteristics such as charging characteristics and fixing characteristics can be manufactured.
In particular, since the second resin is prevented from being exposed to the surface of the toner, the above characteristics can be achieved over a long period of time. In addition, the second resin is prevented from being detached, and as a result, the obtained toner prevents fogging and voids and has excellent OHP colorability.

  The toner production method of the present embodiment includes a step of preparing a dispersion (suspension) using a kneaded material obtained by kneading a material containing a binder resin (dispersion preparation step), and finely dispersing the dispersion. A process of obtaining a granular material in which a plurality of resin fine particles are melt-bonded by being ejected as finely-divided (micronized) droplets and solidified (including semi-solidified) while being transported in the solidified part (granular material production) Step) and a step of applying an external additive to the obtained granule (external additive applying step). The dispersion liquid in the present embodiment only needs to contain at least a binder resin. In the following description, a case where a dispersion liquid containing a binder resin is mainly used as a constituent component will be described. Examples of the dispersion include an emulsion (emulsion) and a suspension (suspension). Among these, it is preferable to use a suspension. 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.

<Dispersion adjustment process>
As described above, the toner particles 100 can be manufactured using the dispersion liquid (suspension) 6. Hereinafter, the configuration of the dispersion liquid 6 and the method for preparing the dispersion liquid 6 will be described.
<Composition of dispersion>
First, the configuration of the dispersion 6 will be described.
The dispersion 6 has a configuration in which a dispersoid (dispersed phase) 61 is finely dispersed in a dispersion medium 62. Then, the dispersion liquid 6 includes, as the dispersoid 61, a first dispersoid 611 composed of the first resin as a main material, and a second dispersion composed of the first resin and the second resin. Quality 612. Here, the second dispersoid 612 has an average particle size larger than that of the first dispersoid 612.

1. Dispersion Medium The dispersion medium 62 may be any material as long as it can disperse the dispersoid 61 described below, but is mainly a material generally used as a solvent (hereinafter referred to as “solvent material”). It is preferable that it is comprised by these.
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, ethyl benzoate, amine solvents such as trimethylamine, hexylamine, triethylamine, aniline, nitrile solvents such as acrylonitrile, 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 dispersion medium 62 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)). It is preferable that Thereby, for example, the dispersibility of the dispersoid 61 in the dispersion medium 62 can be improved, and the dispersoid 61 in the dispersion liquid 6 has a relatively small particle size and small variation in size. be able to. As a result, the obtained granular material 9 (toner mother particles) has a small variation in size and shape among the particles, and a relatively high circularity. In particular, when the dispersion medium 62 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 dispersion medium 62, the constituent material of the dispersion medium 62 is an azeotropic mixture (lowest boiling azeotrope mixture) between at least two kinds of components constituting the mixture. ) Is preferably used. As a result, the dispersion medium 62 can be efficiently removed in a solidifying section or the like of the toner manufacturing apparatus described later. In addition, it becomes possible to remove the dispersion medium 62 at a relatively low temperature in a solidifying section or the like of a toner manufacturing apparatus to be described later, and it is possible to more effectively prevent deterioration of characteristics of the obtained granular material 9 (toner base particles). . 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.

Further, the boiling point of the dispersion medium 62 (dispersion medium 62 to be removed in the subsequent step) is not particularly limited, but is preferably 180 ° C. or less, more preferably 150 ° C. or less, and 35 to 130 ° C. More preferably. As described above, when the boiling point of the dispersion medium 62 is relatively low, the dispersion medium 62 can be removed relatively easily in a solidifying section or the like of the toner manufacturing apparatus described later. Moreover, by using such a material as the dispersion medium 62, the residual amount of the dispersion medium 62 in the obtained granular material 9 can be made particularly small. As a result, the reliability as a toner is further increased.
The dispersion medium 62 may contain components other than the materials described above. For example, in the dispersion medium 62, some constituents of the dispersoid 61, inorganic fine powders such as silica, titanium oxide, and iron oxide, organic fine powders such as fatty acids, fatty acid metal salts, and polymerized fine powders are used. Various additives such as powder may be included.

2. Dispersoid Dispersion liquid 6 includes, as dispersoid 61, at least a first dispersoid 611 composed of a first resin as a main material, a second resin composed of a first resin and a second resin. The dispersoid 612 is included.
2-1. First Dispersoid The first dispersoid 611 includes a toluene-soluble resin selected from the binder resin (binder resin) described above as a first resin.

  Although content of binder resin (1st resin) in the 1st dispersoid 611 is not specifically limited, It is preferable that it is 50-99 wt%, and it is more preferable that it is 60-90 wt%. When the content of the binder resin in the first dispersoid 611 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, if the content of the binder resin in the first dispersoid 611 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.

Moreover, when the raw material K5 containing a colorant is used for the preparation of the kneaded material K7 described later, the colorant is preferably contained in the first dispersoid 611 in the dispersion liquid 6.
The content of the colorant in the dispersion 6 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.

Moreover, when the raw material K5 containing a wax is used for the preparation of the kneaded material K7 described later, the wax is preferably contained in the first dispersoid 611 in the dispersion liquid 6.
The wax content in the dispersion 6 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 611 dispersed in the dispersion medium 62 may have, for example, substantially the same composition among the particles or may have different compositions. .
The average particle diameter d ₁ of the first dispersoid 611 in the dispersion 6 is not particularly limited, but is preferably 0.04 to 1.0 μm, and more preferably 0.10 to 0.80 μm. . When the average particle diameter d1 of the _first dispersoid 611 is a value in such a range, the finally obtained granular material 9 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 d ₁ of the first dispersoid 611 in the dispersion liquid 6 is too small, the particle diameter of the obtained granular material 9 (toner mother particles) becomes too small, or the flow of the dispersion liquid 6 It may be difficult to eject the dispersion 6 as droplets of a sufficiently uniform size in the granular material manufacturing process described later. On the other hand, if the average particle diameter d ₁ of the first dispersoid 611 in the dispersion 6 is too large, the particle size of the obtained granular material 9 (toner base particle) becomes too large, or the granular material 9 (toner base particle). ) May be difficult to sufficiently increase the circularity.

Further, when the average particle diameter of the first dispersoid 611 in the dispersion 6 is d ₁ [μm] and the average particle diameter of the granular material 9 is D [μm], a relationship of 2 ≦ D / d ₁ ≦ 200 Is more preferable, 3 ≦ D / d ₁ ≦ 150 is more preferable, and 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 9). 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 9, so that the fluidity tends to be deteriorated. Therefore, the thin layer on the developing roller tends to be non-uniform. On the other hand, when D / d ₁ exceeds the upper limit, the irregularities on the surface of the granular material 9 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 611 in the dispersion 6 is not particularly limited, but is preferably 2 to 70 wt%, more preferably 5 to 60 wt%, and 10 to 50 wt%. Further preferred. When the content of the first dispersoid 611 is less than the lower limit value, the circularity of the obtained granular material 9 (toner mother particles) 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 611 exceeds the upper limit, depending on the composition of the dispersion medium 62 and the like, the viscosity of the dispersion 6 increases, and the shape of the obtained granular material 9 (toner base particles), It shows a tendency that the variation in size becomes large. Further, if the content of the first dispersoid 611 exceeds the upper limit, it may be difficult to sufficiently atomize and eject the droplets of the dispersion 6 in the granular material manufacturing process described later. .

2-2. Second Dispersoid The second dispersoid 612 includes a toluene-soluble resin (first resin) and a toluene-insoluble resin (second resin) selected from the binder resin (binder resin) described above. .
The second dispersoid 612 is preferably configured so that the second resin is in the form of particles and the first resin covers the second resin. Thereby, the exposure of the second resin to the surface of the granular material 9 is more reliably prevented, and as a result, the separation of the second resin from the granular material 9 is more reliably prevented.

  The content of the first resin in the second dispersoid 612 is not particularly limited, but is preferably 2 to 70 wt%, more preferably 5 to 60 wt%, and 10 to 50 wt%. Is more preferable. As a result, the obtained granular material has the second resin unevenly distributed in the vicinity of the surface of the granular material 9, while the second resin is exposed to the surface of the granular material 9 and the second resin is detached from the granular material 9. Can be prevented more reliably.

  In addition, the content of the second resin in the second dispersoid 612 is not particularly limited, but is preferably 20 to 70 wt%, more preferably 30 to 60 wt%, and 10 to 50 wt%. More preferably. As a result, the obtained granular material has characteristics such as better charging characteristics and fixing characteristics while preventing the second resin from being exposed to the surface of the granular body 9 and detachment of the second resin from the granular body 9. Can be demonstrated.

  The average particle size of the second resin in the second dispersoid 612 is the total dispersoid in the dispersion 6 (including the other dispersoids of the first dispersoid 611 and the second dispersoid 612). The average particle diameter is preferably 1/5 to 1/2 times, more preferably 1/3 to 1/2. Thereby, the exposure of the second resin to the surface of the granular material 9 is more reliably prevented, and as a result, the separation of the second resin from the granular material 9 is more reliably prevented.

  Further, the average particle size of the second dispersoid 612 is preferably 2 to 5 times, more preferably 2 to 3 times the average particle size of the first dispersoid 611. Thereby, the 2nd dispersoid 612 can be unevenly distributed in the surface vicinity of the granular material 9 more reliably in the below-mentioned granular material manufacturing process. Further, the first resin and the second resin derived from the second dispersoid 612 can be uniformly dispersed on the surface of the granular material 9 (toner base particles), and a higher quality toner can be obtained.

Further, the average particle size of the second dispersoid 612 is preferably 2 to 5 times, more preferably 2 to 3 times the average particle size of all dispersoids in the dispersion 6. Thereby, the second dispersoid 612 can be more unevenly distributed in the vicinity of the surface of the granular material 9 in the granular material manufacturing process described later. Further, the first resin and the second resin derived from the second dispersoid 612 can be more uniformly dispersed on the surface of the granular material 9 (toner mother particles), and a higher quality toner can be obtained. .
The average particle size of the second dispersoid 612 is larger than the average particle size of all the dispersoids in the dispersion liquid 6 (including other dispersoids of the first dispersoid 611 and the second dispersoid 612). Is preferred. Thereby, the 2nd dispersoid 612 can be unevenly distributed in the surface vicinity of the granular material 9 more reliably in the below-mentioned granular material manufacturing process.

The average particle diameter d2 of the _second dispersoid 612 in the dispersion 6 is not particularly limited, but is preferably 0.10 to 3.0 [mu] m, and more preferably 0.50 to 1.50 [mu] m. . When the average particle diameter d2 of the _second dispersoid 612 is a value in such a range, the finally obtained granular material 9 has an appropriate circularity and has characteristics and shapes between the particles. It can be obtained as having excellent uniformity and particularly excellent mechanical stability. On the other hand, if the average particle diameter d2 of the _second dispersoid 612 in the dispersion 6 is too small, a granular material described later depends on the average particle diameter of the first dispersoid 611 and the viscosity of the dispersion medium 62. It may be difficult to dispose the second dispersoid 612 near the surface of the granular material 9 in the manufacturing process. On the other hand, if the average particle diameter d2 of the _second dispersoid 612 in the dispersion 6 is too large, the degree of circularity may be reduced depending on the particle diameter of the granular material 9 finally obtained. There is a risk of variations in characteristics and shapes.

  The content of the second dispersoid 612 in the dispersion 6 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 second dispersoid 612 is less than the lower limit value, the circularity of the obtained granular material 9 (toner mother particles) tends to decrease. Further, when solidifying, a large amount of heat energy may be required. On the other hand, when the content of the second dispersoid 612 exceeds the upper limit, depending on the composition of the dispersion medium 62 and the like, the viscosity of the dispersion 6 increases, and the shape of the obtained granular material 9 (toner base particles), It shows a tendency that the variation in size becomes large. In addition, if the content of the second dispersoid 612 exceeds the upper limit, it may be difficult to sufficiently atomize and eject the droplets of the dispersion 6 in the granular material manufacturing process described later. .

Note that the second dispersoid 612 dispersed in the dispersion medium 62 may have, for example, substantially the same composition or different composition among the particles. .
Further, the dispersion 6 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 61 in the dispersion 6 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 dispersion 6 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. When the dispersion 6 contains a dispersant, the content of the dispersion aid in the dispersion 6 is not particularly limited, but is preferably 2.0 wt% or less, and is 0.005 to 0.5 wt%. Is more preferable.

Further, the dispersion 6 may contain an emulsifier and the like. In particular, when the dispersion (suspension) 6 is prepared via an emulsion as described later, the emulsifier used in the preparation of the emulsion may be contained in the dispersion 6 ( It may remain). For example, when the dispersion (suspension) 6 is prepared via an emulsion as described below, the dispersion 6 (particularly in the dispersoid 61) contains the solvent used for the preparation of the emulsion. May remain.
In addition, components other than the dispersoid 61 may be dispersed in the dispersion 6 as insoluble matters. For example, in the dispersion 6, 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 adjusting dispersion>
In the present embodiment, a first dispersion in which the first dispersoid 611 is dispersed and a second dispersion in which the second dispersoid 612 is dispersed are manufactured, and these dispersions are mixed. A dispersion liquid in which the first dispersoid 611 and the second dispersoid 612 are dispersed is obtained. Hereinafter, the production of the first dispersion, the production of the second dispersion, and the mixing of the first dispersion and the second dispersion will be sequentially described.

(Production of first dispersion)
<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. In the present embodiment, the raw material K5 includes a first resin that is soluble in toluene as a binder resin.
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. If 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 around 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. When 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 increased, 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 61 in the dispersion 6 described later can be made particularly excellent. As a result, even in the finally obtained toner, variations in composition and characteristics among the toner particles can be particularly 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.
Note that the pulverization step may be omitted.

<< Preparation process (first dispersion) >>
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 dispersoid (dispersed particles) containing the binder resin is dispersed in the aqueous dispersion medium by gradually adding the binder resin liquid to the stirred aqueous liquid while dropping. An emulsified liquid (emulsion) is obtained. At this time, the particle size of the dispersoid (particularly, the dispersoid constituted of the first resin) in the emulsion is adjusted according to the degree of stirring.

  Thereafter, the solvent is removed from the obtained emulsion to obtain a suspension in which the constituents of the kneaded product are dispersed as a dispersoid. Specifically, a suspension obtained by dispersing the first dispersoid 611 composed mainly of the toluene-soluble resin in the kneaded product K7 is obtained. At this time, the particle size of the first dispersoid 611 is substantially determined by the degree of the above-described emulsification dispersion, and is approximately the same as the particle size of the toluene-soluble resin in the above-mentioned emulsion dispersion.

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 611 can be further increased. As a result, the granular material 9 (toner mother particles) 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 611) 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 toluene-soluble resin in the kneaded product K7, but can be easily removed in the solvent removal step. Preferably there is.

The solvent is preferably a solvent having low compatibility with the dispersion medium 62 described above (for example, a solvent having a solubility in 100 g of the 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 first dispersoid 611 can be finely dispersed in a stable state in the first dispersoid (dispersion 6). it can.
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 dispersion medium 62, 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 nitriles such as acrylonitrile and acetonitrile. Organic solvents such as tolyl solvents, nitro solvents such as nitromethane and nitroethane, 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 compound 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 solvent removal in the solvent removal step is insufficient, the dispersion 6 Inside, the first dispersoid 611 can be finely dispersed in a stable state.

Moreover, when preparing the suspension as a 1st dispersion liquid by the above methods, it is preferable to satisfy the following conditions. That is, the boiling point under atmospheric pressure of the solvent used for preparing the suspension (solvent capable of dissolving the toluene-soluble resin in the kneaded product K7) is T _bp (sol) [° C.], and the dispersion containing the kneaded product is used. Satisfies the relationship of | T _bp (dm) −T _bp (sol) | ≦ 40, where T _bp (dm) [° C.] is the boiling point of the liquid used as a dispersion medium of the liquid (emulsion) under atmospheric pressure. It is preferable to do this. By satisfying such a relationship, the solvent removal step of preparing the suspension from the emulsion can be performed smoothly, and more reliably preventing the solvent from remaining in the resulting suspension. Can do. 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, the solvent removal step is performed sufficiently smoothly so that the solvent does not substantially remain in the resulting suspension. Rapid vaporization (boiling) can be reliably prevented, and irregularly shaped dispersoids can be effectively prevented from occurring in the kneaded product suspension obtained.
When the method as described above is adopted, the first dispersion liquid in which the dispersion of the size of the first dispersoid 611 is extremely small can be easily and reliably prepared.

The first dispersion can be prepared by the following method in addition to the above.
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 K7 is gradually added into the stirred aqueous liquid to obtain a suspension in which the dispersoid containing the binder resin is dispersed in the aqueous dispersion medium. .
In addition, when the kneaded material is added, for example, an aqueous liquid may be heated. Thereby, the particle size of the first dispersoid 611 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.

  When the first dispersion is prepared by such a method, the first dispersion can be prepared without substantially using an organic solvent or using a very 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.

(Production of second dispersion)
<Kneaded material>
In the present embodiment, first, a kneaded product is obtained using a raw material including at least a binder resin among the above-described toner constituent materials. In the present embodiment, the raw material includes a first resin that is soluble in toluene and a second resin that is insoluble in toluene as the binder resin.

As the kneaded raw material, that is, the kneaded product, the degree of kneading increases, the average particle size of the second resin in the kneaded product decreases. Therefore, by adjusting the degree of kneading, the average particle diameter of the second resin in the kneaded product can be adjusted to a desired one. Further, even if the first resin and the second resin are not easily bonded to each other, the kneading can increase the bonding strength between the first resin and the second resin.
This kneaded material can be manufactured using, for example, an apparatus as shown in FIG. 2 in the same manner as the kneaded material K7 described above. That is, also in the production of the second dispersion, the kneaded product can be obtained by performing the kneading step, the extrusion step, the cooling step, and the pulverization step in the same manner as in the production of the first dispersion.

<< Preparation process (second dispersion) >>
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 solution containing the kneaded product is prepared. By using, for example, a solvent capable of dissolving at least a part of the constituent material (particularly, the first resin) of the kneaded material containing the first resin and the second resin described above as the binder resin liquid. Can be prepared.
Next, the dispersoid (dispersed particles) containing the binder resin is dispersed in the aqueous dispersion medium by gradually adding the binder resin liquid to the stirred aqueous liquid while dropping. The obtained emulsion (emulsion, second emulsion dispersion) is obtained.

At this time, the particle size of the dispersoid (second dispersoid 612 including the first resin and the second resin) in the emulsion is adjusted according to the degree of stirring.
The degree of stirring is preferably performed so that the particle size of the dispersoid in the emulsion is larger than the particle size of the second resin in the kneaded product. Thereby, the dispersoid in an emulsion liquid can be easily formed as what contains 1st resin (toluene soluble resin) and 2nd resin (toluene insoluble resin).

The average particle size of the total dispersoid in the emulsion, that is, in the second emulsion dispersion is preferably 2 to 5 times the average particle size of the second resin in the kneaded product. It is more preferable to be 3 times. Thereby, the second resin can be more reliably contained in the second dispersoid during emulsification dispersion.
Thereafter, the solvent is removed from the obtained emulsion to obtain a suspension in which the components of the kneaded product are dispersed as a dispersoid. Specifically, a suspension obtained by dispersing the second dispersoid 612 composed of the toluene-soluble resin and the toluene-insoluble resin in the kneaded product is obtained. At this time, the particle size of the second dispersoid 612 is substantially determined by the degree of stirring during the aforementioned emulsification dispersion, and is approximately the same as the particle size of the toluene-soluble resin in the aforementioned emulsified dispersion.

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 second dispersoid 612 can be further increased. As a result, the granular material 9 (toner mother particles) 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. Further, when such a method is used, the particle size of the dispersoid (second dispersoid 612) 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 toluene-soluble resin in the kneaded product, and is the same as that used in the preparation of the first dispersion described above. Can be used.

The second dispersion can be prepared by the following method in addition to those described above.
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 binder resin solution containing the first resin and a second resin pulverized into a powder or granular form by freeze pulverization or the like are 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 (particularly, the first resin) of the raw material containing the first resin as described above. it can.
Next, the above-mentioned binder resin solution and the second resin are mixed, and this is gradually put into the stirred aqueous liquid. Thereby, a suspension in which the dispersoid containing the first resin and the second resin is dispersed in the aqueous dispersion medium is obtained.

(Mixing of the first dispersion and the second dispersion)
The first dispersion obtained as described above and the second dispersion are mixed. Thereby, the dispersion liquid 6 which disperse | distributes the 1st dispersoid 611 and the 2nd dispersoid 612 can be obtained.
In this way, the first dispersion liquid 611 and the second dispersion liquid 612 are relatively easily dispersed by manufacturing the first dispersion liquid and the second dispersion liquid separately and mixing them. A dispersion 6 can be obtained. In addition, when the dispersion liquid 6 is obtained in this way, the dispersion of the particle diameters between the particles of the first dispersoid 611 and the second dispersoid 612 in the dispersion liquid 6 can be reduced, which will be described later. In the granular body manufacturing process, the second resin can be reliably distributed near the surface of the granular body 9.

<Granule production process and granule (toner base particle)>
Next, a plurality of the dispersions 6 derived from the dispersoid 61 (the first dispersoid 611 and the second dispersoid 612) are obtained by subjecting the dispersion 6 to the granular material production process described in detail below. A granular material 9 formed by melting and joining resin fine particles is obtained.
Thus, by obtaining the granular material 9 as a granular material 9 in which a plurality of resin fine particles derived from the dispersoid 61 are melt-bonded, the obtained granular material 9 is obtained between each particle, Variations in shape, size, composition, etc. are particularly small. In other words, as described above, when the granular material 9 is obtained as an aggregate (junction) of a plurality of dispersoids 61, the dispersoid 61 constituting the dispersion 6 has a (( Even if the variation in shape, size, composition, etc. (between individual dispersoid particles) is relatively large, the obtained granular material 9 has variations in shape, size, composition, etc. among the particles. It will be 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. In addition, even when a classification process, a thermal spheronization process, a mechanical surface modification process, or the like is performed after the granule manufacturing process, such a process can be simplified or performed under mild conditions. .

  In particular, the granular material 9 obtained in this step is excellent in mechanical strength because the second resin portion 92 having a relatively high strength is located near the surface of the granular material 9, and a relatively large external force is applied. Even in such a case, unintentional collapse (particularly, collapse near the unjoined portion of the crevasse-like shape) hardly occurs. In addition, since the second resin has a relatively low water absorption, the granular material 9 has a low water absorption, and a decrease in chargeability due to water absorption is prevented. Furthermore, since the granular body 9 has a form in which the second resin is covered with the first resin, the exposure of the second resin from the surface of the granular body 9 and the second resin from the granular body 9 are performed. Is prevented from falling off.

<Toner production equipment>
A toner manufacturing apparatus 1 used in the toner manufacturing method of the present invention includes a head unit 2 that discharges the dispersion liquid 6 as described above, a dispersion liquid supply unit 4 that supplies the dispersion liquid 6 to the head unit 2, and a head unit 2. The solidification part 3 in which the dispersion liquid 6 discharged from is conveyed, and the collection | recovery part 5 which collect | recovers the manufactured granular material 9 are provided.

The dispersion liquid supply unit 4 stores the dispersion liquid 6 as described above, and the dispersion liquid 6 is fed into the head unit 2.
The dispersion liquid supply unit 4 may have any function as long as it has a function of supplying the dispersion liquid 6 to the head unit 2. Alternatively, the dispersion liquid supply unit 4 may have stirring means 41 for stirring the dispersion liquid 6 as illustrated. Thereby, for example, even if the dispersoid 61 is difficult to disperse in the dispersion medium, the dispersion 6 in which the dispersoid 61 is sufficiently uniformly dispersed can be supplied into the head portion 2.

As shown in FIG. 4, the head unit 2 includes a dispersion liquid storage unit 21, a piezoelectric element 22, and a discharge unit 23.
The dispersion liquid storage section 21 stores the dispersion liquid 6 as described above.
The dispersion liquid 6 stored in the dispersion liquid storage unit 21 is discharged from the discharge unit 23 to the solidifying unit 3 by the pressure pulse of the piezoelectric element 22.

  In the present embodiment, as shown in FIG. 4, an acoustic lens (concave lens) 25 is installed in the dispersion liquid storage unit 21. By installing such an acoustic lens 25, for example, the pressure pulse (vibration energy) generated by the piezoelectric element 22 can be converged by the pressure pulse converging unit 26 in the vicinity of the ejection unit 23. As a result, vibration energy generated by the piezoelectric element 22 can be efficiently used as energy for discharging the dispersion liquid 6. Therefore, even if the dispersion liquid 6 stored in the dispersion liquid storage unit 21 has a relatively high viscosity, it can be reliably discharged from the discharge unit 23. In addition, even if the dispersion 6 stored in the dispersion storage unit 21 has a relatively large cohesive force (surface tension), it can be discharged as fine droplets. The particle diameter of the toner particles 100 can be controlled to a relatively small value.

Further, in the present embodiment, as shown in FIG. 4, a diaphragm member 13 having a converging shape is disposed between the acoustic lens 25 and the ejection unit 23 toward the ejection unit 23. Thereby, convergence of the pressure pulse (vibration energy) generated by the piezoelectric element 22 can be assisted, and the pressure pulse generated by the piezoelectric element 22 can be used more efficiently.
In addition, although this embodiment demonstrated the structure which used the concave lens as an acoustic lens, an acoustic lens is not limited to this. For example, a Fresnel lens, an electronic scanning lens, or the like may be used as the acoustic lens.
Although the shape of the discharge part 23 is not specifically limited, It is preferable that it is a substantially circular shape. Thereby, the sphericity of the discharged dispersion 6 and the formed granular material 9 can be increased.

  When the discharge part 23 is a substantially circular shape, the diameter (nozzle diameter) is, for example, preferably 5 to 500 μm, and more preferably 10 to 200 μm. When the diameter of the discharge part 23 is less than the lower limit value, clogging is likely to occur, and the dispersion of the size of the discharged dispersion liquid 6 may increase. On the other hand, when the diameter of the discharge part 23 exceeds the upper limit, the discharged dispersion liquid 6 may entrap bubbles depending on the force relationship between the negative pressure of the dispersion liquid storage part 21 and the surface tension of the nozzle. There is sex.

As shown in FIG. 4, the piezoelectric element 22 includes a lower electrode (first electrode) 221, a piezoelectric body 222, and an upper electrode (second electrode) 223 that are stacked in this order. In other words, the piezoelectric element 22 has a configuration in which the piezoelectric body 222 is interposed between the upper electrode 223 and the lower electrode 221.
The piezoelectric element 22 functions as a vibration source, and the diaphragm 24 vibrates due to the vibration of the piezoelectric element (vibration source) 22 and has a function of instantaneously increasing the internal pressure of the dispersion liquid storage unit 21. It is.

  The head unit 2 is in a state where a predetermined ejection signal is not input from a piezoelectric element driving circuit (not shown), that is, a state where no voltage is applied between the lower electrode 221 and the upper electrode 223 of the piezoelectric element 22. Then, the piezoelectric body 222 is not deformed. For this reason, the diaphragm 24 is not deformed and the volume of the dispersion liquid storage unit 21 is not changed. Therefore, the dispersion 6 is not discharged from the discharge unit 23.

  On the other hand, in a state where a predetermined ejection signal is input from the piezoelectric element driving circuit, that is, in a state where a predetermined voltage is applied between the lower electrode 221 and the upper electrode 223 of the piezoelectric element 22, the piezoelectric body 222 is deformed. Arise. As a result, the diaphragm 24 is greatly deflected (bends downward in FIG. 2), and the volume of the dispersion liquid storage unit 21 is reduced (changed). At this time, the pressure in the dispersion liquid storage unit 21 increases instantaneously, and the granular dispersion liquid 6 is discharged from the discharge unit 23.

  When one discharge of the dispersion liquid 6 is completed, the piezoelectric element driving circuit stops applying the voltage between the lower electrode 221 and the upper electrode 223. Thereby, the piezoelectric body 222 returns almost to its original shape, and the volume of the dispersion liquid storage unit 21 increases. At this time, a pressure (pressure in the positive direction) acting from the dispersion liquid supply unit 4 to the discharge unit 23 acts on the dispersion liquid 6. For this reason, air is prevented from entering the dispersion liquid storage part 21 from the discharge part 23, and an amount of the dispersion liquid 6 corresponding to the discharge amount of the dispersion liquid 6 is supplied from the dispersion liquid supply part 4 to the dispersion liquid storage part 21. The

By applying the voltage as described above at a predetermined cycle, the piezoelectric element 22 vibrates and the granular dispersion liquid 6 is repeatedly discharged.
As described above, in the present exemplary embodiment, the fluid dispersion liquid is ejected in a granular form by the vibration of the piezoelectric body, and the toner is obtained by solidifying the liquid dispersion.
As a result, the shape of the discharged dispersion liquid is stabilized, and as a result, a toner having a stable shape can be obtained, and the manufactured toner particles have a high sphericity (geometrically perfect spherical shape). Can be made relatively easy.

  Also, the vibration frequency of the piezoelectric body, the opening area (nozzle diameter) of the discharge part, the temperature / viscosity of the dispersion, the discharge amount of one drop of the dispersion, the content of the dispersoid in the dispersion, the dispersion in the dispersion The particle size of the quality can be controlled relatively accurately, and the toner to be manufactured can be easily controlled to a desired shape and size. Further, by controlling these conditions and the like, for example, the production amount of toner and the like can be easily and reliably managed.

Further, since the vibration of the piezoelectric body is used, the dispersion liquid can be discharged at a predetermined interval. Therefore, it is possible to effectively prevent the discharged granular dispersions from colliding with each other and agglomerating, and it is difficult to form irregularly shaped powders or the like as compared with the case of using the conventional spray drying method. .
In the head unit 2 as described above, the initial velocity of the dispersion 6 discharged from the head unit 2 to the solidifying unit 3 is preferably, for example, 0.1 to 10 m / second, and 2 to 8 m / second. More preferably. When the initial speed of the dispersion liquid 6 is less than the lower limit, the productivity of the toner decreases. On the other hand, when the initial velocity of the dispersion liquid 6 exceeds the upper limit, the sphericity of the obtained granular material 9 tends to decrease.

  In addition, the viscosity of the dispersion 6 discharged from the head unit 2 is not particularly limited, but is preferably 5 to 3000 cps, and more preferably 10 to 1000 cps, for example. When the viscosity of the dispersion liquid 6 is less than the lower limit, it is difficult to sufficiently control the size of the discharged particles (granular dispersion liquid 6), and the dispersion of the obtained granular material 9 may increase. is there. On the other hand, when the viscosity of the dispersion 6 exceeds the upper limit, the diameter of the formed particles increases, the discharge speed of the dispersion 6 decreases, and the amount of energy required for discharging the dispersion 6 tends to increase. Show. In addition, when the viscosity of the dispersion liquid 6 is particularly large, the dispersion liquid 6 cannot be discharged as droplets.

  Further, the dispersion 6 discharged from the head unit 2 may be preheated. By heating the dispersion 6 in this manner, for example, even if the dispersoid 61 is in a solid state (or a relatively high viscosity state) at room temperature, the dispersoid is in a molten state (or in discharge). The viscosity is relatively low). As a result, in the solidified part 3 to be described later, the dispersoid 61 contained in the granular dispersion 6 is smoothly aggregated (fused), and the resulting granular material 9 has a particularly high circularity.

Further, the discharge amount of one drop of the dispersion 6 is slightly different depending on the content of the dispersoid 61 in the dispersion 6, but is preferably 0.05 to 500 pl, and more preferably 0.5 to 5 pl. Is more preferable. By setting the discharge amount of one drop of the dispersion 6 to a value in such a range, the granular material 9 can have an appropriate particle size.
Incidentally, the granular dispersion liquid 6 discharged from the head unit 2 is generally sufficiently larger than the dispersoid 61 in the dispersion liquid 6. That is, a large number of dispersoids 61 are dispersed in the granular dispersion liquid 6. For this reason, even if the dispersion of the particle size of the dispersoid 61 is relatively large, the ratio of the dispersoid 61 in the discharged granular dispersion liquid 6 is almost uniform for each droplet. Therefore, even when the particle size variation of the dispersoid 61 is relatively large, the granular material 9 has a small particle size variation by making the discharge amount of the dispersion 6 substantially uniform. Such a tendency becomes more remarkable. For example, when the average particle size of the discharged dispersion 6 is Dd [μm] and the average particle size of the dispersoid 61 in the dispersion 6 is Dm [μm], the relationship of Dm / Dd <0.5 is satisfied. It is preferable to satisfy the relationship of Dm / Dd <0.2.

  Further, when the average particle size of the discharged dispersion 6 is Dd [μm] and the average particle size of the manufactured toner particles is Dt [μm], a relationship of 0.05 ≦ Dt / Dd ≦ 1.0 is established. It is preferable to satisfy, and it is more preferable to satisfy the relationship of 0.1 ≦ Dt / Dd ≦ 0.8. By satisfying such a relationship, it is possible to relatively easily obtain a granular material 9 that is sufficiently fine, has a high degree of circularity, and has a sharp particle size distribution.

  The frequency of the piezoelectric element 22 is not particularly limited, but is preferably 10 kHz to 500 MHz, and more preferably 20 kHz to 200 MHz. When the vibration frequency of the piezoelectric element 22 is less than the lower limit value, toner productivity decreases. On the other hand, when the vibration frequency of the piezoelectric element 22 exceeds the upper limit, the discharge of the granular dispersion liquid 6 cannot follow, and there is a possibility that the dispersion of the size of one drop of the dispersion liquid 6 becomes large.

The toner manufacturing apparatus 1 having the illustrated configuration has a plurality of head portions 2. Then, a granular dispersion 6 is discharged from each of these head units 2 to the solidifying unit 3.
Each head unit 2 may discharge the dispersion 6 almost simultaneously, but it is preferable that at least two adjacent head units are controlled so that the discharge timing of the dispersion 6 is different. . Thereby, before the granular dispersion liquid 6 discharged from the adjacent head part 2 solidifies, it can prevent more effectively that a granular dispersion liquid collides and aggregates.

  Further, as shown in FIG. 2, the toner manufacturing apparatus 1 includes a gas flow supply unit 10, and the gas supplied from the gas flow supply unit 10 passes through the duct 101 to the head unit 2 -head. From each gas injection port 7 provided between the parts 2, it becomes the structure injected by a substantially uniform pressure. Thereby, the dispersion liquid 6 can be conveyed and solidified, maintaining the interval of the granular dispersion liquid 6 intermittently discharged from the discharge unit 23. As a result, collision and aggregation between the discharged granular dispersions 6 are more effectively prevented.

In addition, by injecting the gas supplied from the gas flow supply means 10 from the gas injection port 7, it is possible to form a gas flow that flows in substantially one direction (downward in the figure) in the solidifying unit 3. If such a gas flow is formed, the granular dispersion 6 (granular body 9) in the solidification part 3 can be conveyed more efficiently.
In addition, an air current curtain is formed between particles ejected from each head unit 2 by ejecting gas from the gas ejection port 7, for example, a collision between particles ejected from adjacent head units, Aggregation can be prevented more effectively.

A heat exchanger 11 is attached to the gas flow supply means 10. Thereby, the temperature of the gas injected from the gas injection port 7 can be set to a preferable value, and the granular dispersion 6 discharged to the solidifying unit 3 can be solidified efficiently.
Further, when such a gas flow supply means 10 is provided, the solidification speed of the dispersion 6 discharged from the discharge unit 23 can be easily controlled by adjusting the supply amount of the gas flow. .

  Although the temperature of the gas injected from the gas injection port 7 varies depending on the composition of the dispersoid 61 and the dispersion medium 62 contained in the dispersion 6, it is usually preferably 100 to 250 ° C., and 150 to 200 ° C. It is more preferable that When the temperature of the gas injected from the gas injection port 7 is in such a range, the dispersion medium 62 contained in the dispersion 6 is efficiently removed while maintaining the uniformity of the shape of the obtained granular material 9. The toner productivity can be particularly improved.

  The humidity of the gas injected from the gas injection port 7 is, for example, preferably 50% RH or less, more preferably 30% RH or less, and further preferably 20% RH or less. When the humidity of the gas ejected from the gas ejection port 7 is 50% RH or less, the solidifying unit 3 described later can efficiently remove the dispersion medium 62 contained in the dispersion 6, and toner productivity. Is further improved.

The granular dispersion 6 discharged from the head unit 2 becomes a granular body 9 by being solidified while being transported through the solidifying unit 3.
The granular material 9 is obtained, for example, by removing the dispersion medium 62 from the discharged granular dispersion 6. In such a case, the dispersoid 61 (the first dispersoid 611 and the second dispersoid 612) contained in the dispersion 6 is removed as the dispersion medium 62 in the discharged dispersion 6 is removed. Aggregate. At this time, since the particle size of the first dispersoid 611 in the dispersion liquid 6 is smaller than that of the second dispersoid 612, the first dispersoid 611 is likely to move inward, so that the second dispersoid 611 is relatively second. The dispersoid 612 moves to the outside. As a result, the granular material 9 is obtained as an aggregate of the dispersoid 61 in which the second dispersoid 612 is unevenly distributed outward. In addition, when the above-mentioned solvent is contained in the dispersoid 61, the said solvent is also normally removed in the solidification part 3. FIG.

The particle size of the dispersoid 61 contained in the dispersion liquid 6 is normally sufficiently smaller than the obtained granular material 9 (the granular dispersion liquid 6 to be discharged). Therefore, the granular material 9 obtained as an aggregate of the dispersoid 61 has a sufficiently large circularity.
Further, when the granular medium 9 is obtained by removing the dispersion medium 61, the obtained toner particles 100 are usually smaller than the dispersion liquid 6 ejected from the ejection unit 23. For this reason, even if the area (opening area) of the discharge part 23 is relatively large, the size of the obtained granular material 9 can be made relatively small. Therefore, even if the head portion 2 is not obtained by performing special precision processing (even if it can be manufactured relatively easily), a sufficiently fine granular material 9 can be obtained.

Further, as described above, since the area of the discharge section 23 does not need to be extremely small, the particle size distribution of the dispersion 6 discharged from each head section 2 is made sufficiently sharp. be able to. As a result, the granular material 9 also has a small particle size variation, that is, a sharp particle size distribution.
As described above, by using the dispersion liquid as the discharge liquid, even if the granular material 9 to be produced has a sufficiently small particle diameter, the circularity is easily made sufficiently high, and the particle diameter The distribution can be sharp. As a result, the obtained toner has a uniform charge between the particles, and the toner thin layer formed on the developing roller is leveled and densified when the toner is used for printing. Become. 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 9 are uniform, the bulk density of the entire toner (aggregate of granular material 9) 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.

In particular, the obtained granular material 9 has excellent mechanical strength because the second dispersoid 612 composed mainly of toluene insoluble resin forms the second resin portion 92 in the vicinity of the surface thereof. , The water absorption is low. As a result, adhesion to the developing roller and reduction in chargeability due to water absorption can be prevented, and the charging characteristics and fixing characteristics are excellent.
The solidified portion 3 is configured by a cylindrical housing 31.

During the production of the toner, the inside of the housing 31 is preferably maintained at a temperature within a predetermined range. As a result, variations in characteristics among the granular materials 9 due to differences in manufacturing conditions can be reduced, and the reliability of the entire toner is improved.
As described above, for the purpose of keeping the temperature in the housing 31 within a predetermined range, for example, a heat source or a cooling source is installed inside or outside the housing 31, or a flow path for the heat medium or the cooling medium is formed in the housing 31. It is good also as a made jacket.

  In the illustrated configuration, the pressure in the housing 31 is adjusted by the pressure adjusting means 12. As described above, by adjusting the pressure in the housing 31, the dispersion medium 62 in the discharged dispersion liquid 6 can be efficiently removed, and the toner productivity is improved. In the configuration shown in the figure, the pressure adjusting means 12 is connected to the housing 31 by a connecting pipe 121. Further, an enlarged diameter portion 122 having an enlarged inner diameter is formed in the vicinity of the end portion of the connection pipe 121 connected to the housing 31, and a filter 123 for preventing suction of the granular material 9 and the like is further provided. ing.

The pressure in the housing 31 is not particularly limited, but is preferably 0.15 MPa or less, more preferably 0.005 to 0.15 MPa, and even more preferably 0.109 to 0.110 MPa.
In the above description, the dispersoid 61 in the granular dispersion liquid 6 is aggregated (fused) by removing the dispersion medium 62 from the dispersion liquid 6 in the solidification unit 3, and the granular material 9 is obtained. However, the toner particles are not limited to those obtained in this way. For example, when a precursor of a resin material (for example, a monomer, a dimer, an oligomer, or the like corresponding to the resin material) is included in the dispersoid 61, the granular material 9 is obtained by causing the polymerization reaction to proceed in the solidified portion 3. Such a method may be used.

The housing 31 is connected to voltage applying means 8 for applying a voltage. By applying a voltage having the same polarity as that of the granular dispersion 6 (granular body 9) to the inner surface side of the housing 31 by the voltage applying means 8, the following effects are obtained.
Usually, the toner particles are positively or negatively charged. For this reason, when there is a charged substance charged with a polarity different from that of the toner particles, a phenomenon occurs in which the toner particles are electrostatically attracted and attached to the charged substance. On the other hand, if there is a charged material charged with the same polarity as the toner particles, the charged material and the toner particles repel each other, and the phenomenon that the toner adheres to the surface of the charged material can be effectively prevented. Therefore, by applying a voltage having the same polarity as that of the granular dispersion liquid 6 (granular body 9) to the inner surface side of the housing 31, it is effective that the dispersion liquid 6 (granular body 9) adheres to the inner surface of the housing 31. Can be prevented. Thereby, the generation of irregularly shaped toner powder can be more effectively prevented, and the recovery efficiency of the granular material 9 is also improved.

  The housing 31 has a reduced diameter portion 311 in the vicinity of the collection portion 5 that decreases in inner diameter in the downward direction in FIG. By forming such a reduced diameter portion 311, it is possible to efficiently recover the granular material 9. As described above, the dispersion 6 discharged from the discharge unit 23 is solidified in the solidification unit 3, but such solidification is almost completely completed in the vicinity of the recovery unit 5, and the reduced diameter portion. In the vicinity of 311, problems such as agglomeration hardly occur even if each particle contacts.

The granular material 9 obtained by solidifying the granular dispersion 6 is recovered by the recovery unit 5.
The toner obtained as described above may be subjected to classification treatment or the like as necessary.
For the classification treatment, for example, a sieve, an airflow classifier or the like can be used.
The toner of the present invention produced as described above has a uniform shape and a sharp particle size distribution (small width).

  In the above-described embodiment, the dispersion liquid is intermittently ejected from the head portion by the piezoelectric pulse. However, other methods can be used as the dispersion liquid ejection method (injection method). For example, as a method for discharging (injecting) the dispersion liquid, a method such as a spray drying method or a so-called bubble jet (“Bubble Jet” is a registered trademark) method is used, and “the dispersion liquid is pressed against a smooth surface with a gas flow. A method of injecting a dispersion liquid in the form of droplets (fine particles) using a nozzle that draws the thin layer flow into a thin laminar flow and ejects the thin laminar flow as fine particles away from the smooth surface (Japanese Patent Application No. 2002-321889) A method as described in the specification) ”or the like may be used. The spray drying method is a method of obtaining liquid droplets by spraying (spraying) a liquid (dispersion) using a high-pressure gas. 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, as a method for ejecting (injecting) the dispersion liquid, a “method for intermittently ejecting the dispersion liquid from the head portion by a change in gas volume” can be applied.

<External addition process (external addition process)>
The granular material 9 obtained as described above is subjected to an external addition treatment for applying an external additive. Thereby, a toner (toner particle 100) is obtained.
As described above, since the granular body 9 is formed by melting and joining a plurality of resin fine particles, usually, fine irregularities exist on the surface of the granular body 9. 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 9 (toner base particles) and the external additive using a Henschel mixer or the like. Alternatively, the external additive may be jetted and / or convected into the solidifying unit 3 and attached to the liquid dispersion 6 or the granular material 9 (toner base particles).
As the external additive, for example, those described above can be used.

Further, in the toner, substantially all of the external additive may be attached to the granular material 9, or a part of the external additive may be released from the surface of the granular material 9. That is, the toner may contain an external additive released from the granular material 9. Thus, when the external additive released from the granular material 9 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 9. It can function as a microcarrier that is charged to polarity.
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 first resin, the difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester is 10 ° C. or more, and the second resin is the difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester. If the difference is less than 10 ° C., the effect of the present invention can be obtained. That is, if the difference between the outflow start temperature Tfb and the outflow end temperature Tend in the first resin and the second resin has the relationship as described above, the strength of the obtained granular material can be improved. , Water absorption can be suppressed. Further, the second resin is melted quickly at the time of fixing, and offset can be prevented. Here, the difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester is less than 10 ° C. includes the case where no outflow occurs.

In this case, the second resin may have a difference between the outflow start temperature Tfb and the outflow end temperature Tend of less than 10 ° C., but is preferably less than 5 ° C. As a result, the second resin melts more agilely, so that even if the maximum peak temperature Tm of the heat of dissolution is relatively low, such as 60 to 85 ° C., the fixing characteristics are reduced without deteriorating the storage stability of the toner. It can be improved further.
The effect of the present invention can also be obtained by using a resin showing only the glass transition point Tg as the first resin and a resin showing both the glass transition point Tg and the melting point Tm as the second resin. . In this case, in the differential scanning calorimeter (DSC) measurement, the first resin shows only an endothermic peak corresponding to Tg, and the second resin shows two endothermic peaks corresponding to Tg and Tm.

  In the above-described embodiment, the kneaded product is used for preparing the dispersion. However, the method for preparing the dispersion is not limited to this. For example, it may be prepared through a step of adding each component such as a binder resin and a colorant into a liquid medium (liquid). Further, the first dispersoid and the second dispersion in the dispersion may be formed by a method such as an emulsion polymerization method, for example.

In the above-described embodiment, the dispersion 6 is manufactured by mixing the first dispersion in which the first dispersoid is dispersed and the second dispersion in which the second dispersoid is dispersed. It is not limited to this.
Moreover, although embodiment mentioned above demonstrated the structure which uses a suspension liquid as a dispersion liquid, you may use an emulsion as a dispersion liquid, for example.

In the above-described embodiment, the toner particles are described as being composed of the granular body including the first resin portion and the second resin portion, and the external additive. However, the toner particles (toner) May not have an external additive. 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 dispersion liquid 6 is jetted downward has been described, but the jetting direction of the dispersion liquid may be any direction such as vertically upward and horizontal.

  In the above-described embodiment, the toluene-soluble resin is contained in the first dispersoid (first resin part), and the toluene-insoluble resin is contained in the second dispersoid (second resin part). Although described as a thing, a part of toluene insoluble resin may be contained in the 1st dispersoid (1st resin part). In such a case, it is sufficient that the amount of the second resin in the second dispersoid is larger than that of the second resin in the first dispersoid.

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, intermediates such as placing the granule (toner base particles) obtained by removing the dispersion medium from the dispersion and the toner particles to which the external additive has been added to the granule under reduced pressure or heating. Processing and post-processing 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 and spheroidizes the powder obtained by removing a dispersion medium from a dispersion liquid. 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.

Further, in the above-described embodiment, the colorant, the wax, and the like are described as the constituents of the dispersoid in the dispersion, but these components are included in the dispersion as the constituents of the dispersion medium. There may be.
Further, in the above-described embodiment, the granular material 9 has been described as one in which a plurality of resin fine particles are fused and integrated, and the boundary (interface) between the resin fine particles does not substantially exist. It may have a clear interface (boundary surface) between the fine particles.

(Example 1)
<Adjustment of dispersion>
First, a resin soluble in toluene by synthesizing trimetic anhydride, terephthalic acid, isophthalic acid, polyoxyethylene (2,4) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol by a conventional method A polyester resin (hereinafter referred to as polyester resin 1) containing a component (first resin) and an insoluble resin component (second resin) was obtained.

  This polyester resin 1 has a gel content (crosslinking component, second resin): 10% by weight, oxidation: 8 mgKOH / g, softening point Tf1 / 2: 160 ° C., glass transition point Tg: 64 ° C., weight average molecular weight Mw: It was 110000 and the number average molecular weight Mn: 3600. The crosslink density of the toluene soluble resin (first resin) of the polyester resin 1 was 0, and the crosslink density of the toluene insoluble resin (second resin, crosslink component) of the polyester resin 1 was 1. . Moreover, the difference of the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester of the polyester resin 1 was 45 degreeC.

In addition, the measurement of oxidation was performed according to JIS K0070 using the polyester resin 1 weighed according to the expected oxidation as a sample.
Further, the softening point Tf1 / 2 was measured by pressure-molding a polyester resin 1: 1.0 g to obtain a pellet-like sample, and this was performed using a flow tester (manufactured by Shimadzu Corporation, CFT-500D). . Further, this measurement was performed under the conditions of a temperature rising rate: 5 ° C./min, a cylinder pressure: 2.0 MPa, a die hole diameter: 1.0 mm, a die hole length: 1.0 mm, and a softening point calculation method: 1/2 method. went.

  The glass transition point was measured by packing a polyester resin (1:10 mg) in an aluminum cell and using a differential scanning calorimeter (DSC-220C / EXSTRA6000PC station, manufactured by Seiko Instruments Inc.). Moreover, this measurement was performed on the conditions of measurement temperature: 0-200 degreeC, temperature increase rate: 5 degreeC / min, Tg: second run method. Here, read from the DSC curve at the time of the second temperature increase, the endothermic peak of the DSC curve or the endothermic start temperature of the endothermic shoulder (the temperature at the intersection of the tangent line before the endotherm and the tangent line after the endotherm) was defined as Tg. .

  The molecular weight distribution was measured by dissolving polyester resin 1: 5 mg in tetrahydrofuran (hereinafter referred to as THF): 5 g to obtain a solution, and passing this solution through a membrane filter having a pore size of 0.2 μm. Impurities were removed to obtain a THF-soluble component, which was used as a sample, and a gel permeation chromatogram (manufactured by Tosoh Corporation, HLC-8220) was used. Moreover, this measurement uses three TSKgel SuperHZ4000s manufactured by Tosoh Corporation as a column, THF as a solvent, an RI detector as a detector, a monodisperse polystyrene standard sample (weight average molecular weight: 580 to 3.9 million) as a standard sample, The column temperature was 25 ° C. and the flow rate was 0.5 ml / min.

The obtained polyester resin 1 is mixed with toluene to form a resin solution, and the resin solution is further separated into a toluene-soluble resin and a toluene-insoluble resin (gel content) by a centrifuge to dissolve the resin. The toluene insoluble resin was taken out from the liquid.
Thereafter, the resin solution containing a toluene-soluble resin was divided into 1: 4 to obtain a first resin solution and a second resin solution (first resin solution: second resin solution = 1: 4. ).

The taken out toluene-insoluble resin was freeze-pulverized to obtain fine particles having an average particle diameter of 0.2 μm.
The toluene-insoluble resin fine particles are mixed into the first resin solution to form a resin solution, and then the resin solution is quickly dropped into water and stirred to obtain an emulsified dispersion (second emulsification). Dispersion) was obtained.

By removing toluene from the obtained emulsified dispersion (second emulsified dispersion), the dispersoid (second dispersoid) composed of the toluene-soluble resin and the toluene-insoluble resin of the polyester resin 1 is dispersed in water. Suspension (second dispersion) was obtained. The average particle size of the dispersoid (second dispersoid) in this suspension was 1.5 μm.
On the other hand, toluene-soluble resin is obtained by removing toluene from the above-mentioned second resin solution. This toluene-soluble resin: 79.2 parts by weight, copper phthalocyanine pigment: (Toner Cyan BG manufactured by Client): 5 weights Part, charge control agent (Copy Charge N4P manufactured by Clariant): 1 part by weight, synthetic ester wax (WEP-5 manufactured by NOF Corporation): 4 parts by weight using a twin screw extruder (TEM41SS manufactured by Toshiba Machine Co., Ltd.) And kneaded to obtain a kneaded product.

The obtained kneaded material was dissolved in toluene to obtain a resin solution, and this resin solution was dropped into water and stirred to obtain an emulsified dispersion (first emulsified dispersion).
By removing toluene from the obtained emulsified dispersion (first emulsified dispersion), fine particles made of a toluene-soluble resin were dispersed in water as a dispersoid (first dispersoid) (first suspension). 1 dispersion). The average particle size of the dispersoid in this suspension was 0.13 μm.

Then, the first suspension and the second suspension were mixed to obtain a dispersion (suspension). The mixing ratio of the first dispersion and the second dispersion was adjusted so that the ratio of the toluene-soluble resin and the toluene-insoluble resin in the dispersion was the same as that of the polyester resin 1.
At this time, in the dispersion, a first dispersoid composed mainly of a toluene-soluble resin and a second dispersoid composed mainly of a toluene-soluble resin and a toluene insoluble resin, respectively. It was dispersed.
And the average particle diameter of all the dispersoids in the obtained dispersion liquid was 0.3 micrometer. The average particle diameter d1 of the _first dispersoid in the dispersion was 0.13 μm, and the average particle diameter d2 of the _second dispersoid was 1.5 μm.

<Manufacture of granular material>
The obtained dispersion was discharged in the form of particles using an apparatus as shown in FIG. 6 and solidified to obtain granules (toner mother particles). The average particle diameter D of this granular material was 6.0 μm.
In addition, the discharge part of each head part shall have a circular shape with a diameter of 8 μm.
At the time of discharging the dispersion, the temperature of the dispersion in the head is 25 ° C., the frequency of the piezoelectric body is 28 kHz, and the initial speed of the dispersion discharged from each head is 6.4 m / sec. The discharge amount of one drop of the dispersion was 0.25 pl. The average particle diameter D ′ of the ejected droplets was 7.0 μm. Further, the dispersion liquid was discharged so that the discharge timing of the dispersion liquid was shifted between adjacent head parts among the plurality of head parts.

  Further, the pressure in the housing (atmospheric pressure) was adjusted to 100 to 105 kPa when discharging the dispersion. Moreover, the temperature (atmosphere temperature) in a housing was adjusted so that it might be set to 60-70 degreeC. Further, a voltage was applied to the housing of the solidified portion so that the potential on the inner surface side was −200 V, thereby preventing the granular material 9 (toner base particles) from adhering to the inner wall.

<External processing>
The obtained granular material: 100 parts by weight, hydrophobic silica (TG811F manufactured by Cabot): 1 part by weight, hydrophobic silica (RX50 manufactured by Nippon Aerosil Co., Ltd.): 1 part by weight, hydrophobic rutile / anatase complex titania (titanium industry) A toner was obtained by externally adding 0.5 part by weight of STT-30s manufactured by the company. The average particle diameter D ″ of this toner was 6.1 μm.
The average particle size (volume average particle size) of the granular material and toner particles was measured using a Coulter Counter (manufactured by Beckman Coulter, Inc., Multiplier III type), and a 100 μm aperture tube attached thereto.

(Examples 2 and 3)
Except that the average particle size of the fine particles obtained by freeze-pulverizing the toluene-insoluble resin (average particle size of the toluene-insoluble resin in the second dispersoid) is as shown in Table 1, it is the same as in Example 1. A toner was manufactured.
Example 4
Terephthalic acid, isophthalic acid, polyoxypropylene (2,4) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,4) -2,2-bis (4-hydroxyphenyl) propane, Ethylene glycol was synthesized by a conventional method to obtain a polyester resin (hereinafter referred to as polyester resin 2) containing only a gel component (first resin) soluble in toluene.

  This polyester resin 2 has a gel content (crosslinking component, second resin): 0% by weight, oxidation: 7 mg KOH / g, softening point Tf1 / 2: 110 ° C., glass transition point Tg: 54 ° C., weight average molecular weight Mw: It was 5700, number average molecular weight Mn: 2100. These measurements were performed in the same manner as the measurement with the polyester resin 1 described above. The crystallinity of the polyester resin 2 (first resin) was 0. Moreover, the difference of the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester of the polyester resin 2 was 30 degreeC.

On the other hand, decamethylene carboxylic acid and 1,6-hexanediol were synthesized by a conventional method to obtain a crystalline resin.
This crystalline resin had an oxidation of 8.6 mg KOH / g, a crystal melting point: 70 ° C., a weight average molecular weight Mw: 6500, and a number average molecular weight Mn: 35600. The crystallinity of the crystalline resin (second resin) was 1. The difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester of the crystalline resin was 8 ° C.

  The molecular weight distribution of the crystalline resin was measured by adding crystalline resin to a solution in which sodium trifluoroacetate (CF8COONa) was added to hexafluoroisopropanol (hereinafter referred to as HFIP) to a concentration of 0.005 M [mol / l]. Dissolve to a concentration of 0.06% [wt / vol] to make a solution, and pass this solution through a pore size: 0.45 μm filter (Millipore-Millex-LH). Chromatogram (Waters, GPC-7) was used. This measurement uses two Shodex HFIP-806M manufactured by Showa Denko KK as the column, a differential refractive index detector as the detector, and a monodisperse polymethyl methacrylate standard sample (manufactured by Showa Denko KK) as the standard sample, and the column temperature: The measurement was performed at 23 ° C., a flow rate of 0.5 ml / min, and an inflow rate of 300 μl.

  Further, the melting point of the crystalline resin was measured by packing 10 mg of the crystalline resin in an aluminum cell and using a differential scanning calorimeter (Seiko Instruments, DSC-220C / EXTRA6000PC station). This measurement was performed under the conditions of measurement temperature: 0 to 200 ° C., rate of temperature increase: 5 ° C./min, Tg: second run method. Here, the maximum endothermic temperature of the endothermic peak of the DSC curve is defined as Tg, which is read from the DSC curve at the second temperature increase.

Then, the obtained polyester resin 2:70 parts by weight and the obtained crystalline resin: 20 parts by weight were kneaded using a twin screw extruder (TEM41SS manufactured by Toshiba Machine Co., Ltd.) to obtain a kneaded product. .
This kneading was performed so that the average particle size of the resin component insoluble in toluene in the kneaded product was 0.2 μm. In measuring the average particle size, the kneaded material: 1 part by weight is dissolved in 100 parts by weight of toluene, and this is filtered through a funnel uniformly spread with a filter aid (Radiolite manufactured by Showa Chemical Industry Co., Ltd.) The residue is washed by passing hot water of 90 ° C. through the funnel after filtration, the residue after washing and the filter aid and ion-exchanged water are mixed, and this is centrifuged to obtain a filter aid, pigment, etc. Toluene-insoluble components other than the gel component are settled and removed, the fine particles comprising the gel component are separated, and this is dispersed in ion-exchanged water to obtain a measurement sample. Measured with Microtrac UPA).

The obtained kneaded material was mixed with toluene to form a resin solution, and this resin solution was dropped into water and stirred to obtain an emulsified dispersion (second emulsified dispersion).
By removing toluene from the obtained emulsified dispersion (second emulsified dispersion), the dispersoid (second dispersoid) composed of the toluene-soluble resin and the toluene-insoluble resin of the polyester resin 1 is dispersed in water. Suspension (second dispersion) was obtained. The average particle size of the dispersoid (second dispersoid) in this suspension was 1.5 μm.

On the other hand, polyester resin 2: 50 parts by weight, copper phthalocyanine pigment: (Client Toner Cyan BG): 5 parts by weight, charge control agent (Clariant Copy Charge N4P): 1 part by weight, twin screw extruder ( A kneaded product was obtained by kneading using TEM41SS manufactured by Toshiba Machine Co., Ltd.
The obtained kneaded material was dissolved in toluene to obtain a resin solution, and this resin solution was dropped into water and stirred to obtain an emulsified dispersion (first emulsified dispersion).

By removing toluene from the obtained emulsified dispersion (first emulsified dispersion), fine particles made of a toluene-soluble resin were dispersed in water as a dispersoid (first dispersoid) (first suspension). 1 dispersion). The average particle size of the dispersoid in this suspension was 0.13 μm.
Then, the first suspension and the second suspension were mixed to obtain a dispersion (suspension). In addition, the first dispersion liquid and the second dispersion liquid are adjusted so that the ratio of the toluene-soluble resin (polyester resin 2) and the toluene-insoluble resin (crystalline resin) in the dispersion liquid is 70:20. The mixing ratio was adjusted.

At this time, the dispersion includes a first dispersoid composed mainly of a toluene-soluble resin and a second dispersoid composed mainly of a toluene-soluble resin and a toluene-insoluble resin component. Each was dispersed.
And the average particle diameter of all the dispersoids in the obtained dispersion liquid was 0.3 micrometer. The average particle diameter d1 of the _first dispersoid in the dispersion was 0.13 μm, and the average particle diameter d2 of the _second dispersoid was 1.5 μm.
Using the obtained dispersion liquid, a granular material was manufactured and externally added in the same manner as in Example 1 to obtain a toner.

(Examples 5 and 6)
The same as in Example 4 except that the average particle size of gel in the kneaded product (average particle size of toluene insoluble resin in the second dispersoid) was changed as shown in Table 1 by changing the kneading conditions. Thus, a toner was produced.
(Example 7)
Except that the dispersion was discharged at a hot air temperature of 80 ° C. using a disk-type spray dryer (manufactured by Sakamoto Giken Co., Ltd., DCTRS-3N type) during the production of the granular material, the same as in Example 1. A toner was manufactured.

(Comparative Example 1)
Polyester resin obtained in Example 1 1:90 parts by weight, copper phthalocyanine pigment: (Toner Cyan BG manufactured by Client): 5 parts by weight, charge control agent (Copy Charge N4P manufactured by Clariant): 1 part by weight, synthetic ester Wax (Nippon Yushi Co., Ltd. WEP-5): 4 parts by weight were kneaded using a twin screw extruder (Toshiba Machine Co., Ltd. TEM41SS) to obtain a kneaded product.

This kneading was performed so that the average particle size of the resin component insoluble in toluene in the kneaded product was 2.0 μm.
The obtained kneaded material: 30 parts by weight was dissolved in 100 parts by weight of toluene to obtain a resin solution, and this resin solution was dropped into water and stirred to obtain an emulsified dispersion.
By removing toluene from the obtained emulsified dispersion, a dispersion (suspension) in which fine particles made of polyester resin 1 were dispersed in water as a dispersoid was obtained.
At this time, the polyester resin 1 is almost separated into a toluene-soluble resin component and a toluene-insoluble resin component (gel content) in the dispersion, and the toluene-soluble resin component is mainly used. The first dispersoid constituted as a material and the second dispersoid constituted mainly from a resin component insoluble in toluene were dispersed.

And the average particle diameter of all the dispersoids in the obtained dispersion liquid was 0.3 micrometer. The average particle diameter d1 of the _first dispersoid in the dispersion was 0.10 μm, and the average particle diameter d2 of the _second dispersoid was 2 μm.
Using the obtained dispersion liquid, a granular material was manufactured and externally added in the same manner as in Example 1 to obtain a toner.

(Comparative Example 2)
The toner was prepared in the same manner as in Comparative Example 1 except that the average particle size of gel in the kneaded product (average particle size of the second dispersoid) was changed as shown in Table 1 by changing the kneading conditions. Manufactured.
(Comparative Example 3)
Polyester resin obtained in Example 4: 70 parts by weight, crystalline resin obtained in Example 4: 20 parts by weight, copper phthalocyanine pigment: (Toner Cyan BG manufactured by Client): 5 parts by weight, charge control agent (Clariant Co. Copy Charge N4P): 1 part by weight was kneaded using a twin screw extruder (Toshiba Machine Co., Ltd. TEM41SS) to obtain a kneaded product. This kneading was performed so that the average particle size of the gel content (crystalline resin) in the kneaded product was 2 μm.
Using the obtained kneaded material, a toner was obtained in the same manner as in Comparative Example 1 described above.

(Comparative Example 4)
The toner was prepared in the same manner as in Comparative Example 3, except that the average particle size of gel in the kneaded product (average particle size of the second dispersoid) was changed as shown in Table 1 by changing the kneading conditions. Manufactured.
(Comparative Example 5)
The polyester resin 1 obtained in Example 1 was dissolved in toluene to obtain a resin solution, which was further separated into a toluene-soluble resin component and an insoluble resin component by a centrifuge. The difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester of the toluene-soluble resin (first resin) of the polyester resin 1 is 40 ° C., and the toluene-insoluble resin (second resin) of the polyester resin 1 Of the resin) did not flow out in the flow tester, and the outflow start temperature Tfb and the outflow end temperature Tend could not be measured.

Separated toluene soluble resin: 81 parts by weight, copper phthalocyanine pigment: (Toner Cyan BG manufactured by Client): 5 parts by weight, charge control agent (Copy Charge N4P manufactured by Clariant): 1 part by weight, synthetic ester wax (Japan) Oil and fat WEP-5): 4 parts by weight were kneaded using a twin screw extruder (Toshiki Kikai TEM41SS) to obtain a kneaded product.
Using the obtained kneaded material, a dispersion liquid in which the first dispersoid mainly composed of a toluene-soluble resin was dispersed was obtained in the same manner as in Example 1. By removing the solvent of this dispersion, fine particles derived from the first dispersoid mainly composed of a toluene-soluble resin were obtained. The average particle diameter of the fine particles was 0.31 μm.

On the other hand, the separated toluene-insoluble resin was freeze-pulverized to obtain fine particles having an average particle diameter of 0.2 μm.
And the fine particle which has a toluene soluble resin as a main component, and the fine particle which has a toluene insoluble resin as a main component are mixed, and it is set as a mixture, and this mixture is made into a thermal spheronizer (Nippon Pneumatic Industry Co., Ltd. product, SFS-3). Was used to obtain toner base particles in which a toluene-insoluble resin was fixed on the surface of fine particles mainly composed of a toluene-soluble resin.
The obtained toner base particles were externally added in the same manner as in Example 1 to obtain a toner.

(Comparative Example 6)
Polyester resin 2: 70 parts by weight obtained in Example 4, copper phthalocyanine pigment: (Toner Cyan BG manufactured by Client): 5 parts by weight, charge control agent (Copy Charge N4P manufactured by Clariant): 1 part by weight Using a screw extruder (TEM41SS manufactured by Toshiba Machine Co., Ltd.), kneading was performed to obtain a kneaded product.

Using the obtained kneaded material, a dispersion liquid in which the first dispersoid mainly composed of a toluene-soluble resin was dispersed was obtained in the same manner as in Example 1. By removing the solvent of the dispersion, fine particles containing a toluene-soluble resin as a main component were obtained.
On the other hand, the crystalline resin obtained in Example 4 was dropped and stirred in water in a heated and melted state to obtain a dispersion in which fine particles having an average particle diameter of 0.2 μm were dispersed.

To the obtained dispersion, fine particles containing the aforementioned toluene-soluble resin as a main component are added, and a dispersion (suspension of a blending ratio of crystalline resin: 20 parts by weight with respect to 76 parts by weight of toluene-soluble resin) )
This dispersion was spray-dried at a hot air temperature of 80 ° C. using a disk-type spray dryer (manufactured by Sakamoto Giken Co., Ltd., DCTRS-3N type) to obtain granules (toner base particles).
The obtained toner base particles were externally added in the same manner as in Example 1 to obtain a toner.

(Observation)
About the granular material and toner particle which were obtained in the said Examples 1-7 and the said Comparative Examples 1-6, these internal structures were observed using the transmission electron microscope (TEM).
In the granular materials and toner particles of Examples 1 to 7, it was confirmed that the second resin portion mainly composed of toluene insoluble resin was unevenly distributed to the outside and was uniformly dispersed. Further, the second resin portion was not exposed on the surface of the granular body, and was located slightly inside the surface of the granular body. On the other hand, the granular materials and toner particles of Comparative Examples 1 to 6 did not have such a configuration.

  Further, the granular materials and toner particles of Examples 1 to 7 and Comparative Examples 1 to 4 and 6 have moderate irregularities uniformly distributed on the surface, and the toner particles are outside the concave portions of the granular materials. It was confirmed that the additive was distributed and distributed uniformly. On the other hand, the particles and toner particles of Comparative Example 5 had unevenness on the surface, but their distribution was non-uniform, and the toner particles also had non-uniform distribution of external additives. When the hot air temperature of the thermal spheronizer was increased so that the unevenness distribution in the granular material of Comparative Example 5 was uniform, sufficient characteristics (particularly chargeability and durability) as a toner were obtained. I couldn't. This is because the resin constituting the granule is modified (generation of low molecular weight components due to thermal decomposition) and the wax oozes out to the surface of the granule, resulting in an increase in toner cohesion and a decrease in fluidity. It is inferred that the film becomes non-uniform or filming occurs in the developing device.

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 droplets, the first constituting the dispersion). The average particle diameter d ₁ of the dispersoid, the average particle diameter d ₂ of the second dispersoid, the constituent material of the second dispersoid, the average particle diameter of the second resin, etc. are shown in Table 1.

[2] Evaluation Each toner obtained as described above was evaluated for durability, storability, transfer efficiency, good fixing area, fogging, void, and OHP (overhead projector) color development.
[2.1] Durability The toner in the cartridge (ET cartridge cyan) of the laser printer (manufactured by Seiko Epson Corporation, LP-9000C) is replaced with the toner obtained in each of the above Examples and Comparative Examples. A cartridge was set in the printer, and the developing device in the cartridge was continuously driven so as to correspond to printing 6000 sheets of A4 size paper with no image data (printing rate 0%).

  At that time, when the A4 size paper is equivalent to 1000 sheets, when it is equivalent to 2000 sheets, when it is equivalent to 3000 sheets, when it is equivalent to 4000 sheets, when it is equivalent to 5000 sheets, and when it is equivalent to 6000 sheets, the cartridge is taken out from the printer, After the toner was sucked with a vacuum cleaner, the formation state of the toner fixed on the developing roller (filming) was visually observed and evaluated according to the following four criteria.

A: Filming does not occur up to 6000 sheets.
○: Filming has occurred within a period of up to 6000 sheets, but even if image formation is performed in this state, image defects (streaky image unevenness in the paper transport method) due to filming are completely recognized visually. Cannot be used, and there is no problem in practical use.
Δ: Filming occurs within a period of 4000 to 6000 sheets, and when image formation is performed in that state, image defects caused by filming can be easily confirmed visually, and there are limitations in practical use. is there.
×: Filming occurs within a period of up to 3000 sheets, and when image formation is performed in this state, image defects caused by filming can be easily confirmed visually and cannot be used practically. .

[2.2] Preservability The toner in the cartridge (ET cartridge cyan) of the laser printer (Seiko Epson, LP-9000C) is replaced with the toner obtained in each of the examples and comparative examples. The cartridge was left for 12 hours in an environment of a temperature of 35 ° C. and a relative humidity of 65% RH.
After that, the cartridge is set in the printer, 10 solid black images (printing rate 100%) are printed on A3 size paper, and the main scanning direction (perpendicular to the paper transport direction) at intervals of one turn of the developing roller on A3 size paper. The direction of formation of band-like image unevenness (banding) in the direction was visually observed and evaluated according to the following four criteria.

A: Banding does not occur.
○: Banding occurs in the initial stage, but it is difficult to visually confirm, and when 10 solid black images are printed on A size paper, the banding cannot be visually confirmed. there is no problem.
Δ: Banding that can be visually confirmed in the initial stage occurs, and when 10 solid black images are printed on A-size paper, the banding is reduced to the extent that visual confirmation is difficult, and there is a limit in practical use. .
×: Banding that can be easily visually confirmed in the initial stage occurs, and even if 10 solid black images are printed on A size paper, the banding can be reduced only to the extent that it can be visually confirmed. I can't stand up.

[2.3] Transfer efficiency The toner in the cartridge (ET cartridge cyan) of the laser printer (manufactured by Seiko Epson, LP-9000C) is replaced with the toner obtained in each of the examples and comparative examples. A simple cartridge was set in the printer, and this printer was used for evaluation as follows.

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.

[2.4] Good fixing area The toner in the cartridge (ET cartridge cyan) of the laser printer (Seiko Epson, LP-9000C) is replaced with the toner obtained in each of the above Examples and Comparative Examples. Such a cartridge was set in the printer, and evaluation was performed as follows using this printer.

In the evaluation of the good fixing area, the voltage applied to the developing roller and the voltage applied to the halogen lamp of the fixing device are modified so that they can be controlled from the outside rather than the printer body, and the amount of toner adhered on the paper The surface temperature of the fixing roller can be controlled to a predetermined value.
Also, A4 size paper (Fuji Xerox Co., Ltd., J paper) was used as an evaluation paper, a solid black image (toner adhesion amount) with a 10 mm margin at the leading edge of the paper and a toner uniformly attached to a 20 mm square area behind it. 0.75 mg / cm ² ) was used as an evaluation image.

  Then, the evaluation image is fixed while the surface temperature of the fixing roller is changed stepwise, and while the evaluation image passes through the fixing device, the toner of the evaluation image on the paper is transferred to the fixing roller and then again on the paper. It was visually observed whether or not it shifted to (offset). Here, the toner having a toner transfer from the fixing roller to the paper is regarded as having an offset, and the toner having no toner transition is regarded as having no offset. Of the temperatures at which no offset occurs, the lowest fixing roller surface temperature is defined as an offset lower limit temperature, and the highest fixing roller surface temperature is defined as an offset upper limit temperature.

  After visually observing the offset, the image after fixing was judged to have no offset, and the evaluation image after fixing was rubbed 5 times with a 1 kg load with an eraser (manufactured by Lion Business Machine Co., Ltd., ECR-502R for ink ballpoint pen), and the residual ratio of the image density Was measured with an optical densitometer (X-Rite model 404, manufactured by X-Rite). Here, the temperature region where the residual ratio of the image density is 90% or more was defined as a region where the fixing strength was good. Of the temperatures in the region where the fixing strength is good, the lowest fixing roller surface temperature is set as the lower limit fixing temperature, and the highest fixing roller surface temperature is set as the upper fixing temperature. The residual ratio of image density was determined as (image density residual ratio) = (image density after rubbing with an eraser) × 100 / (image density before rubbing with an eraser).

And it evaluated in accordance with the following four steps of criteria.
A: The temperature range of the fixing strength good range (difference between the fixing upper limit temperature and the fixing lower limit temperature) is 60 ° C. or more.
○: The temperature range of the fixing strength good region is 40 ° C. or more and less than 60 ° C., and there is no problem in actual use.
(Triangle | delta): The temperature range of fixing strength favorable range is less than 40 degreeC, and there exists a restriction | limiting on actual use.
X: There is no temperature range in the region where the fixing strength is good, and it cannot withstand actual use.

[2.5] Fog The toner in the cartridge (ET cartridge cyan) of a laser printer (manufactured by Seiko Epson, LP-9000C) is replaced with the toner obtained in each of the above examples and comparative examples. The cartridge was set in the printer, and 6000 sheets of A4 size paper were continuously printed on halftone images (printing rate 5%).

Thereafter, a white image with a printing rate of 0% is printed on A4 size paper, and the image density on the paper is visually observed and measured using an optical densitometer (X-Rite model 404, manufactured by X-Rite). Evaluation was made according to the following four-stage criteria.
A: Fog (toner adhesion in non-image area) cannot be visually confirmed, and the image density is less than 0.15.
○: It is difficult to visually confirm the fogging, and the image density is 0.15 or more and 0.00.
It is less than 2 and there is no problem in actual use.
(Triangle | delta): A fog can be confirmed slightly visually and image density is 0.20 or more and 0.00.
It is less than 3, and there is a limit in practical use.
X: The fogging can be clearly confirmed visually, and the image density is 0.30 or more, so that it cannot withstand actual use.

[2.6] Clogging The toner in the cartridge (ET cartridge cyan) of the laser printer (Seiko Epson, LP-9000C) was replaced with the toner obtained in each of the above Examples and Comparative Examples. A simple cartridge was set in the printer, and a halftone image (printing rate 5%) was continuously printed on 6000 sheets of A4 size paper.

Thereafter, a line image having a width of 2 dots (2 dots width in the main scanning direction × 20 mm length in the paper conveyance direction) is printed on A4 size paper, and the toner missing state (blank) in the center of the line image on the paper is visually checked. Observed and evaluated according to the following four-stage criteria.
A: No void occurs.
○: Slightly hollowed out, but the length of the hollowed out is less than 30% of the line image,
There is no problem in actual use.
Δ: Obviously a void has occurred and the length of the void is 30% or more of the line image,
There are restrictions on practical use.
X: Since fogging is severe, evaluation of hollows is impossible.

[2.7] OHP coloring property The toner in the cartridge (ET cartridge cyan) of the laser printer (manufactured by Seiko Epson Corporation, LP-9000C) is replaced with the toner obtained in each of the above Examples and Comparative Examples. Such a cartridge was set in the printer, and an evaluation image was printed on a transparent film (LP-9000C OHP sheet LPCOHPS1). At this time, a solid image (toner adhesion amount 0.75 mg / cm ² ) in which toner was uniformly adhered was formed on a 20 mm square area on a transparent film, and this was used as an evaluation image.

In this evaluation, the printer was remodeled so that the voltage applied to the developing roller could be controlled from the outside rather than the printer main body, and the toner adhesion amount on the transparent film could be controlled to a predetermined value.
And it evaluated in accordance with the following four steps of criteria.
A: A very clear cyan projection image is observed.
○: A projection image that can be clearly identified as cyan is observed, and there is no problem in actual use.
Δ: Can be cyan, but an opaque projection image is observed, and there is a limit in practical use.
X: Light is hardly transmitted and a black projection image is observed.
These results are summarized in Table 2.

As is clear from Table 2, the toners of the examples of the present invention obtained excellent results in all of durability, storage stability, transfer efficiency, good fixing area, fogging, voiding, and OHP light emission. .
On the other hand, with the toner of the comparative example, sufficient characteristics could not be obtained.
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 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 1st liquid (dispersion), and a cooler. 1 is a longitudinal sectional view schematically showing a first embodiment of a toner manufacturing apparatus used for manufacturing a toner of the present invention. FIG. 4 is an enlarged cross-sectional view of the vicinity of the head portion of the toner manufacturing apparatus shown in FIG. 3.

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 1 ... Toner manufacturing apparatus 2 ... Head 21 ... Dispersion storage part 22 ... Piezoelectric element 221 ... Lower electrode 222 ... Piezoelectric body 223 ... Upper electrode 23 ... Discharge part 24 ... Vibration Plate 25 …… Acoustic lens 26 …… Pressure pulse converging part 3 …… Solidifying part 31 …… Housing 311 …… Reducing diameter part 4 …… Dispersed liquid supply part 41 …… Agitation means 5 …… Recovery unit 6 …… Dispersion 61 …… Dispersoid 611 …… First dispersoid 612 …… Second dispersoid 62 …… Dispersion medium 7 …… Gas injection port 8 …… Voltage applying means 9 …… Granules (toner mother particles) 91 …… First resin portion 92 …… Second resin portion 10 …… Gas supply means 11 …… Heat exchanger 12 …… Pressure adjustment means 121 …… Connection pipe 122 …… Expansion Diameter 123 ... Filter 13 ... Drawing member 100 ... Toner particle 101 ... Duct

Claims (16)

Dispersion formed by dispersing a first dispersoid composed mainly of a first resin soluble in toluene and a second dispersoid composed of a second resin insoluble in toluene Is a method for producing a toner by discharging particles from a discharge port and solidifying the fine particle dispersion to obtain granules.
The second dispersoid includes the first resin in addition to the second resin, and the average particle size of the second dispersoid is the average particle size of the first dispersoid. Is bigger than
A method for producing a toner, characterized in that a granular material unevenly distributed in the vicinity of the surface is obtained so that the second resin is not exposed.   The toner production method according to claim 1, wherein the second resin has a higher crosslink density than the first resin.   The toner production method according to claim 1, wherein the second resin has a higher crystallinity than the first resin. A first dispersoid composed mainly of a first resin whose difference between the outflow start temperature Tfb and the outflow end temperature Tend in the flow tester is 10 ° C. or more, and the outflow start temperature Tfb and the outflow end temperature in the flow tester A dispersion liquid in which a second dispersoid composed of a second resin having a difference from Tend of less than 10 ° C. is dispersed is discharged into a fine particle form from a discharge port, and the fine particle dispersion liquid is discharged. A method for producing a toner that solidifies to obtain a granular material,
The second dispersoid includes the first resin in addition to the second resin, and the average particle size of the second dispersoid is the average particle size of the first dispersoid. Is bigger than
A method for producing a toner, characterized in that a granular material unevenly distributed in the vicinity of the surface is obtained so that the second resin is not exposed.   The toner manufacturing method according to claim 1, wherein a melting point of the second resin is lower than a softening point of the first resin.   6. The dispersion liquid according to claim 1, wherein the dispersion liquid is obtained by mixing the first dispersion liquid in which the first dispersoid is dispersed and the second dispersion liquid in which the second dispersoid is dispersed. 2. A method for producing the toner according to 1.   The first resin is dissolved in toluene to form a first resin solution, the first resin solution is emulsified and dispersed in water to form a first emulsified dispersion, and the toluene is removed from the first emulsified dispersion. The toner production method according to claim 6, wherein the first dispersion is obtained by removing the first dispersion.   The first resin and the second resin are kneaded to obtain a kneaded product, and the kneaded product is mixed with toluene to form a second resin solution. From the average particle diameter of the second resin in the kneaded product The second resin solution is emulsified and dispersed in water so as to have a larger average particle size to obtain a second emulsified dispersion, and the toluene is removed from the second emulsified dispersion, whereby the second The method for producing a toner according to claim 6 or 7, wherein a dispersion is obtained.   The method for producing a toner according to claim 8, wherein the average particle size of all dispersoids in the second emulsified dispersion is 2 to 5 times the average particle size of the second resin in the kneaded product.   The second dispersoid is configured such that the second resin is in the form of particles and the first resin covers the second resin. Toner production method.   11. The toner according to claim 10, wherein an average particle diameter of the second resin in the second dispersoid is 1/5 to 1/2 times an average particle diameter of all dispersoids in the dispersion. Production method.   12. The toner manufacturing method according to claim 1, wherein an average particle size of the second dispersoid is larger than an average particle size of all dispersoids in the dispersion.   The method for producing a toner according to any one of claims 1 to 12, wherein an average particle diameter of the second dispersoid is 2 to 5 times an average particle diameter of all dispersoids in the dispersion.   14. The toner manufacturing method according to claim 1, wherein an average particle diameter of the second dispersoid is 2 to 5 times an average particle diameter of the first dispersoid. A dispersion used in a method for producing a toner, in which a dispersion formed by dispersing a dispersoid composed mainly of a resin is discharged in a fine particle form from a discharge port, and the fine particle dispersion is solidified to obtain a granular material. There,
A first dispersoid composed mainly of a first resin soluble in toluene and a second dispersoid composed of a second resin insoluble in toluene are dispersed;
The second dispersoid includes the first resin in addition to the second resin,
A dispersion for toner production, wherein an average particle diameter of the second dispersoid is larger than an average particle diameter of the first dispersoid. A toner manufactured using the method according to claim 1.

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