JP5644367B2 - Toner, method for producing the same, and developer - Google Patents

Description

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

  In the developing process, toner used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed. In the transfer step, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper, the toner is melted and fixed on the paper surface in a heat fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, or a one-component developer that does not require a carrier (magnetic toner, non-magnetic toner) Magnetic toner) is known.

Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, etc., so-called pulverized toners, in which a toner binder such as a styrene resin or a polyester resin is melt-kneaded together with a colorant and pulverized, are widely used. It is used.
However, in recent years, there has been a tendency for the toner to have a small particle size in order to obtain a high-quality image. In the above pulverization method, if the particle size is 6 μm or less, the pulverization efficiency decreases and the loss due to classification increases, resulting in increased productivity. It was a problem in that the cost would be low.

Recently, a so-called polymerization type toner such as a suspension polymerization method and an emulsion polymerization aggregation method and a method with volume shrinkage called a polymer dissolution suspension method have been proposed and put into practical use (see Patent Document 1). These toners are excellent in terms of producing a toner having a small particle diameter.
However, since it is assumed that the dispersant is used in an aqueous medium, the dispersant that impairs the charging characteristics of the toner remains on the surface of the toner, causing problems such as loss of environmental stability and removal of this. It is known that a very large amount of washing water is required to achieve this, and this is a problem in that it is not always satisfactory as a production method.

As an alternative method for producing toner, a method has been proposed in which fine droplets are formed from fine nozzles using piezoelectric pulses, and then dried and solidified to form toner (see Patent Document 2). In addition, a method has been proposed in which fine droplets are formed by utilizing thermal expansion in the nozzle, and this is dried and solidified into a toner (see Patent Document 3). Furthermore, a method has been proposed in which minute droplets are formed using an acoustic lens and dried to solidify into toner (see Patent Document 4).
However, with these methods, it is easy to reduce the particle size of the toner, but there is a problem in that the number of droplets that can be ejected from one nozzle per unit time is small and productivity is low. This is a problem in that the spread of the particle size distribution due to coalescence cannot be avoided and a toner having a uniform particle diameter cannot be obtained, and there is a case where loss due to classification may occur.

Recently, in order to save energy, a toner that melts at a low temperature is used to reduce energy generated in the fixing process. Therefore, it has been proposed to use a crystalline resin that can be melted at a low temperature for the toner (see, for example, Patent Documents 5 to 8).
However, when these crystalline resins are prepared by a toner manufacturing method by forming microdroplets, the crystalline resin is difficult to dissolve in the solvent, so it is used as a dispersion, and the crystalline resin is clogged in the discharge holes. It was a problem.

  Therefore, when discharging the toner composition liquid, the toner composition liquid can be stably discharged for a long time without clogging the discharge hole, and a toner having a narrow particle size distribution, uniform and small particle diameter, and fixing at a low temperature is obtained. There is a need to provide a toner manufacturing method, a toner having a narrow particle size distribution, a uniform and small particle size, excellent low-temperature fixability, and capable of forming an image with low power consumption, and a developer containing the toner. This is the current situation.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, according to the present invention, when discharging the toner composition liquid, the toner composition liquid can be stably discharged for a long time without clogging the discharge hole, and the particle size distribution is narrow, uniform, small particle diameter, and can be fixed at a low temperature. Production method of toner capable of obtaining toner, toner having narrow particle size distribution, uniform and small particle size, excellent low-temperature fixability, and capable of forming an image with low power consumption, and developer containing the toner The purpose is to provide.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, the toner production method of the present invention comprises a toner composition liquid preparation step of preparing a toner composition liquid in which a toner composition containing at least a binder resin and a release agent is dissolved or dispersed in an organic solvent, and at least one A droplet forming step of discharging the toner composition liquid from the discharge holes to form droplets; and a drying step of solidifying the organic solvent in the toner composition liquid formed into droplets to form particles. The binder resin contains at least a crystalline polyester resin, and the crystalline polyester resin is dissolved in the toner composition liquid before being formed into droplets. The inventors have found that a toner composition liquid can be stably ejected for a long time without clogging the pores, and a toner having a narrow particle size distribution, a uniform, small particle size, and fixable at a low temperature can be obtained. It was.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner composition liquid preparation step of preparing a toner composition liquid in which a toner composition containing at least a binder resin and a release agent is dissolved or dispersed in an organic solvent; and the toner composition liquid from at least one ejection hole. A droplet forming step of discharging into droplets, and a drying step of drying and solidifying the organic solvent in the dropletized toner composition liquid, wherein the binder resin is at least a crystalline polyester resin And the crystalline polyester resin is dissolved in the toner composition liquid before being formed into droplets.
<2> The droplet forming step applies vibration to the toner composition liquid in the liquid column resonance liquid chamber in which at least one ejection hole is formed to form a standing wave by liquid column resonance, and the antinode of the standing wave The method for producing a toner according to <1>, wherein the toner composition liquid is ejected from the ejection holes formed in a region to form droplets.
<3> A droplet forming step is a step in which a vibration is applied to a thin film in which a plurality of discharge holes having the same opening diameter is formed, and a toner composition liquid is discharged from the discharge holes to form droplets. The method for producing a toner according to <1>.
<4> The crystalline polyester resin contains at least a divalent alcohol component and a divalent acid component, and at least one of the divalent alcohol component and the divalent acid component contains at least two monomers. The toner production method according to any one of <1> to <3>.
<5> The toner production method according to any one of <1> to <4>, wherein the crystalline polyester resin has a weight average molecular weight of 1,000 to 100,000.
<6> The toner production method according to any one of <1> to <5>, wherein the binder resin contains 3% by mass to 50% by mass of a crystalline polyester resin.
<7> The toner production method according to any one of <1> to <6>, wherein the content of the release agent in the toner particles is 3% by mass to 20% by mass.
<8> The binder resin according to any one of <1> to <7>, wherein the binder resin contains a resin other than the crystalline polyester resin, and Tg of the resin other than the crystalline polyester resin is 50 ° C to 70 ° C. A toner manufacturing method.
<9> Obtained by the method for producing a toner according to any one of <1> to <8>, having a weight average particle diameter of 1 μm to 10 μm and a particle size distribution (weight average particle diameter / number average particle diameter). , 1 to 1.15.
<10> A developer comprising at least the toner according to <9> and a carrier.

<11> The divalent alcohol component is at least selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol. The method for producing a toner according to any one of <4> to <8>, wherein the toner is one type.
<12> Divalent acid components are fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, and 1,12- The method for producing a toner according to any one of <4> to <8> and <11>, wherein the toner is at least one selected from dodecanedioic acid.
<13> Any one of <1> to <8> and <11> to <12>, wherein the organic solvent is at least one selected from tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, and toluene A method for producing the toner according to claim 1.

  According to the present invention, the above-described problems can be solved and the object can be achieved, and when the toner composition liquid is discharged, the toner composition liquid can be discharged stably for a long time without clogging the discharge holes. A toner manufacturing method capable of obtaining a toner having a narrow particle size distribution, uniform, small particle size, and fixing at low temperature, and having a narrow particle size distribution, uniform, small particle size, and excellent low temperature fixing property Further, a toner capable of forming an image with low power consumption and a developer containing the toner can be provided.

FIG. 1 is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation of a liquid column resonance standing wave. FIG. 2A is a schematic cross-sectional view showing an example of a liquid column resonance liquid chamber. FIG. 2B is an example of a discharge hole in the liquid column resonance liquid chamber, and is a schematic cross-sectional view enlarging FIG. 2A. FIG. 2C is an example of a discharge hole in the liquid column resonance liquid chamber, and is a schematic cross-sectional view enlarging FIG. 2A. FIG. 2D is an example of a discharge hole in the liquid column resonance liquid chamber, and is a schematic cross-sectional view enlarging FIG. 2A. FIG. 2E is an example of a discharge hole in the liquid column resonance liquid chamber, and is an enlarged schematic cross-sectional view of FIG. 2A. FIG. 2F is a schematic diagram illustrating an example of the structure of the discharge holes of FIGS. FIG. 3 is an example of a cross-sectional view showing an entire toner manufacturing apparatus for carrying out the toner manufacturing method according to the embodiment of the present invention. 4A is a cross-sectional view showing an example of a droplet discharge head in the droplet formation unit of FIG. 4B is a cross-sectional view taken along line A-A ′ showing the droplet forming unit of FIG. 3. FIG. 5A is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 1. FIG. 5B is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 2. FIG. 5C is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 2. FIG. 5D is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 3. FIG. 5E is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 4. FIG. 5F is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 4. FIG. 5G is a schematic diagram illustrating an example of a standing wave of velocity and pressure fluctuation when N = 5. FIG. 6A is a schematic diagram illustrating an example of a state of a liquid column resonance phenomenon that occurs in a liquid column resonance channel in a droplet discharge head in a droplet forming unit. FIG. 6B is a schematic diagram illustrating an example of a liquid column resonance phenomenon that occurs in the liquid column resonance flow path in the droplet discharge head in the droplet forming unit. FIG. 6C is a schematic diagram illustrating an example of a liquid column resonance phenomenon that occurs in the liquid column resonance flow path in the droplet discharge head in the droplet forming unit. FIG. 6D is a schematic diagram illustrating an example of a liquid column resonance phenomenon that occurs in the liquid column resonance flow path in the droplet discharge head in the droplet forming unit. FIG. 6E is a schematic diagram illustrating an example of a liquid column resonance phenomenon that occurs in the liquid column resonance flow path in the droplet discharge head in the droplet forming unit. FIG. 7 is a graph showing a droplet discharge principle of a film vibration type (indirect vibration type and direct vibration type) discharge means for carrying out the toner manufacturing method of the present invention. FIG. 8A is a schematic view showing an example of the structure of a film vibration type (indirect vibration type) discharge means for carrying out the toner manufacturing method of the present invention. FIG. 8B is a schematic view showing an example of a structure of a film vibration type (indirect vibration type) discharge means for carrying out the toner manufacturing method of the present invention viewed from below. FIG. 9A is a schematic view showing an example of the structure of a film vibration type (direct vibration type) discharge means for carrying out the toner manufacturing method of the present invention. FIG. 9B is a schematic view showing an example of a structure of a film vibration type (direct vibration type) discharge means for carrying out the toner manufacturing method of the present invention viewed from below. FIG. 10A is an example of a cross-sectional view showing an entire toner manufacturing apparatus for carrying out the toner manufacturing method according to the embodiment of the present invention. FIG. 10B is a diagram illustrating an example of an embodiment of a toner manufacturing method according to the present invention. FIG. 11 is a schematic view showing an example of the structure of a droplet discharge unit that discharges droplets in order to carry out the toner manufacturing method of the present invention. FIG. 12 is a diagram illustrating a conventional toner manufacturing method and a drop state of droplets when there is no conveyance airflow. FIG. 13 is a diagram illustrating an example of a toner particle size distribution obtained by the toner manufacturing method of the present invention. FIG. 14 is a diagram illustrating an example of a toner particle size distribution obtained by a conventional toner manufacturing method.

(Toner and toner production method)
The toner production method of the present invention includes at least a toner composition liquid preparation step, a droplet formation step, and a drying step, and further includes other steps as necessary.
The toner of the present invention contains at least a binder resin and a release agent, and further contains other components as necessary. The toner of the present invention is manufactured by the toner manufacturing method of the present invention.
Hereinafter, the toner of the present invention will be described in detail together with the description of the method for producing the toner of the present invention.

<Toner production method>
<< Toner Composition Solution Preparation Process >>
The toner composition liquid preparation step is a step of preparing a toner composition liquid in which a toner composition is dissolved or dispersed in an organic solvent.

-Toner composition-
The toner composition contains at least a binder resin and a release agent, and further contains other components as necessary.

--Binder resin--
The binder resin contains at least a crystalline polyester resin, and further contains other components such as a binder resin other than the crystalline polyester resin as necessary.

--- Crystalline polyester resin ---
A general crystalline polyester resin is difficult to dissolve in an organic solvent, so the crystalline polyester resin is finely dispersed in the organic solvent. (Hereinafter, sometimes referred to as “nozzle”) tends to be clogged.
On the other hand, in the present invention, the crystalline polyester resin is dissolved in an organic solvent. Thereby, clogging of the discharge holes can be prevented, and it is advantageous in that the toner composition liquid can be stably discharged for a long time when the toner composition liquid is discharged.
Therefore, in order to dissolve the crystalline polyester resin, it can be dissolved by appropriately combining the type of the crystalline polyester resin, the type of the organic solvent, and the solvent temperature.
Further, when the crystalline polyester is contained in the toner composition, it is advantageous in that the toner produced using the toner composition can be fixed at a low temperature.

  There is no restriction | limiting in particular as said crystalline polyester resin, Although it can select suitably according to the objective, A divalent alcohol (diol) component and a divalent acid (dicarboxylic acid) component are synthesize | combined as a main component. The linear resin to be used is preferable in that crystallinity is easily obtained.

There is no restriction | limiting in particular as said dihydric alcohol, According to the objective, it can select suitably according to the objective, For example, a C2-C12 saturated aliphatic diol compound etc. are mentioned. These may be used alone or in combination of two or more.
Specific examples of the divalent alcohol include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, or derivatives thereof. Etc.

Further, by adding a monovalent alcohol component, the end of the crystalline polyester resin molecule is capped, the molecular weight of the crystalline polyester resin can be reduced, and the solubility of the crystalline polyester resin in the organic solvent is increased. It is preferable in that it becomes higher.
There is no restriction | limiting in particular as said monohydric alcohol component, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol Hexanol, cyclohexanol, heptanol and the like. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said divalent acid, According to the objective, it can select suitably according to the objective, For example, C2-C12 dicarboxylic acid which has a double bond (C = C bond) And saturated dicarboxylic acids having 2 to 12 carbon atoms. These may be used alone or in combination of two or more.
Specific examples of the divalent acid include fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12- Examples include dodecanedioic acid or derivatives thereof.

Further, the addition of a monovalent acid component is preferable in that the end of the crystalline polyester resin molecule is capped, the molecular weight of the crystalline polyester resin can be reduced, and the solubility in an organic solvent is increased.
The monovalent acid component is not particularly limited and may be appropriately selected depending on the purpose. For example, for example, saturated fatty acids such as formic acid, acetic acid, propionic acid, stearic acid, oleic acid, linoleic acid, Saturated fatty acids, benzoic acid, pyruvic acid. Etc. These may be used alone or in combination of two or more.

  Moreover, by using two or more types of divalent alcohol components or two or more types of divalent acid components for either one or both of the divalent alcohol component and the divalent acid component, The regularity between molecules is disturbed, and the crystallinity is lowered. This is preferable in that the crystalline polyester resin is easily loosened and the solubility in an organic solvent is increased.

  The method for synthesizing the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of subjecting the alcohol component and the acid component to a polycondensation reaction under an appropriate catalyst. Etc.

The weight average molecular weight of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, 15,000 to 20,000 is particularly preferred. It is preferable that the number average molecular weight is within the preferable range in that the solubility of the crystalline polyester resin in an organic solvent is increased.
The molecular weight distribution of the crystalline polyester resin can be measured by gel permeation chromatography (GPC) using THF as a solvent.

  There is no restriction | limiting in particular as glass transition temperature (Tg) of the said crystalline polyester resin, Although it can select suitably according to the objective, 50 to 130 degreeC is preferable and 50 to 100 degreeC is more preferable. When the Tg of the crystalline polyester resin is less than 50 ° C., the storage stability of the toner may be deteriorated, and when it exceeds 130 ° C., fixing may be impossible at a low temperature.

The Tg can be measured by, for example, differential scanning calorimetry (DSC).
Specifically, about 10 mg of a sample is placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. First, the sample was heated from room temperature to 150 ° C. at a temperature increase rate of 10 ° C./min, then left at 150 ° C. for 10 minutes, cooled to room temperature, left for 10 minutes, and then again heated to 150 ° C. in a nitrogen atmosphere. The DSC is measured by heating at 10 ° C./min. Tg can be calculated from the contact point between the tangent line and the base line of the endothermic curve in the vicinity of Tg using the analysis system of the differential scanning calorimeter.
The crystalline polyester resin has a crystal structure in which molecules are regularly arranged to a certain degree below the melting point temperature, and when the melting point temperature is exceeded, the crystal structure collapses, takes a random structure, and is in a molten state. Therefore, in differential scanning calorimetry (DSC), it indicates a clear endothermic peak, not a step-like change in endothermic amount.

  There is no restriction | limiting in particular as an acid value of the said crystalline polyester resin, Although it can select suitably according to the objective, 0 mgKOH / g-70 mgKOH / g are preferable, and 1.0 mgKOH / g-50 mgKOH / g are more preferable. . When the acid value exceeds 70 mgKOH / g, the environmental fluctuation of charging may increase.

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

The method for determining whether or not the crystalline polyester resin is dissolved in the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the transparency is confirmed visually. Examples thereof include a method, a method for measuring turbidity, a method for measuring light scattering, and a method for measuring transmittance.
In the present invention, the crystalline polyester resin is dissolved when the crystalline polyester is dissolved in an organic solvent. In the case of insolubility, the crystalline polyester remains undissolved or becomes cloudy and cloudy.

  There is no restriction | limiting in particular as content of the said crystalline polyester resin in the said binder resin, Although it can select suitably according to the objective, 3 mass%-50 mass% are preferable, and 5 mass%-30 mass. % Is more preferable. When the content of the crystalline polyester resin is less than 3% by mass, the amount of the crystalline polyester resin is too small, and the effect of low-temperature fixing may not be sufficiently obtained. When the content exceeds 50% by mass, When the amount of crystalline polyester is too large, the melt viscosity of the toner is too low at the time of fixing, and hot offset tends to occur.

--Binder resin other than crystalline polyester resin ---
The binder resin other than the crystalline polyester resin (hereinafter sometimes referred to as “other binder resin”) is not particularly limited and may be appropriately selected depending on the intended purpose. Since the polyester resin is used by being dissolved in an organic solvent, the crystalline polyester resin and the other binder resin are mixed well so that the other binder resin can also be dissolved in the organic solvent. It is preferable in that it can be fixed at a lower temperature as compared with the case of using a dispersion type crystalline polyester resin.

  Such other binder resins are not particularly limited and may be appropriately selected depending on the purpose. For example, vinyl resins such as styrene monomers, acrylic monomers, and methacrylic monomers may be used. Copolymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, polymers Examples include malon indene resin, polycarbonate resin, and petroleum resin. These may be used alone or in combination of two or more.

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-. Amyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene Styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid. Examples include 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, and esters thereof.

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

When the other binder resin is a styrene-acrylic resin, a molecular weight distribution by GPC soluble in tetrahydrofuran (THF) as a resin component and a molecular weight of 3,000 to 50,000 (in terms of number average molecular weight) There is at least one peak. In addition, a resin having at least one peak in a region of 100,000 or more is preferable in terms of fixability, offset property, and storage stability.
The THF-soluble component is preferably a resin in which a component having a number average molecular weight distribution of 100,000 or less is 50% to 90%. A resin having a main peak in the region of 5,000 to 20,000 is particularly preferable.

Examples of other monomers that form the vinyl polymer or copolymer include the following (1) to (18).
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. Unsaturated (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; (16) Monomers having a carboxyl group such as anhydrides of α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monoesters thereof; (17) 2- Acrylic acid or methacrylic acid hydroxyalkyl esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy- Monomers having a hydroxy group such as 1-methylhexyl) styrene.

The vinyl polymer or copolymer of the other binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
There is no restriction | limiting in particular as a crosslinking agent used in this case, According to the objective, it can select suitably, For example, aromatic divinyl compounds, such as divinylbenzene and divinylnaphthalene; Ethylene glycol diacrylate, 1, 3- butylene Such as glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylate of these compounds with methacrylate Diacrylate compounds linked by alkyl chain; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol Call # 600 diacrylate, dipropylene glycol diacrylate, and diacrylate compounds connected with an alkyl chain containing an ether bond, such as those of acrylates of these compounds is replaced with methacrylate and the like.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  The polyfunctional crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligo Examples include ester acrylates or those obtained by replacing acrylates of the above compounds with methacrylate, triallyl cyanurate, triallyl trimellitate, and the like.

  Among these, as the other binder resin, from the viewpoint of fixability and offset resistance, an aromatic divinyl compound (particularly divinylbenzene), a divalent chain bonded with a bond chain containing one aromatic group and an ether bond. Acrylate compounds are preferable, and a combination of monomers such as a styrene copolymer or a styrene-acrylic copolymer is particularly preferable.

  These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, and more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of other monomer components.

  There is no restriction | limiting in particular as a polymerization initiator used for manufacture of the said vinyl polymer or copolymer, According to the objective, it can select suitably, For example, 2,2'- azobisisobutyronitrile, 2 , 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), Dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2, 4,4-trimethylpentane), 2-phenylazo-2 ′, 4′-dimethyl-4′-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone Ketone peroxides such as oxide, acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide Oxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxide Xidicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl -3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylper Oxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, To amyl peroxy-2-ethyl hexanoate, di -tert- butyl peroxy the hexa hydro terephthalate, and the like are tert- butylperoxy azelate. These may be used alone or in combination of two or more.

  The polyester polymer can be synthesized from, for example, an alcohol component and an acid component. There is no restriction | limiting in particular as a monomer which forms the said polyester polymer, According to the objective, it can select suitably, For example, the following are mentioned.

  The divalent alcohol component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or bisphenol A with ethylene oxide And diols obtained by polymerizing cyclic ethers such as propylene oxide. These may be used alone or in combination of two or more.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
The trihydric or higher polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, penta Erythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol , Trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene and the like. These may be used alone or in combination of two or more.

  The acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; succinic acid, adipic acid and sebacin. Alkyl dicarboxylic acids such as acid and azelaic acid or anhydrides thereof; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, And unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride. These may be used alone or in combination of two or more.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher acid together.
The trivalent or higher polyvalent carboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimetic acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2 , 5-Benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3 -Dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, or anhydrides thereof, partially lower alkyl esters Etc. These may be used alone or in combination of two or more.

When the other binder resin is a polyester-based resin, the molecular weight of the polyester-based resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, the number average molecular weight is 3,000 to 50,000. A crystalline polyester resin having at least one peak in the region is preferable in terms of toner fixing properties and offset resistance.
The THF-soluble component is preferably a crystalline polyester resin in which the component having a number average molecular weight of 100,000 or less is 60% to 100%, and the number average molecular weight is in the range of 5,000 to 20,000. A polyester resin in which at least one peak exists is more preferable.
The molecular weight distribution can be measured by gel permeation chromatography (GPC) using THF as a solvent.

  When the other binder resin is a polyester resin, the acid value is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 mgKOH / g to 100 mgKOH / g, preferably 0.1 mgKOH / G to 70 mgKOH / g is more preferable, and 0.1 mgKOH / g to 50 mgKOH / g is particularly preferable.

Further, when the polyester polymer, the vinyl polymer, and the other resin are used in combination, the acid value of the other binder resin as a whole is not particularly limited and may be appropriately selected according to the purpose. However, what has 60 mass% or more of resin which has 0.1 mgKOH / g-50 mgKOH / g is preferable.
The acid value can be measured, for example, by the same method as described above in accordance with JIS K-0070 for basic operation.

The glass transition temperature (Tg) of the other binder resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 35 ° C. to 80 ° C. from the viewpoint of toner storage stability, and 50 C. to 70.degree. C. is more preferable. If the Tg of the other binder resin is less than 35 ° C., the toner is likely to be deteriorated in a high temperature atmosphere, and offset tends to occur during fixing. There are things to do.
The Tg can be measured by, for example, a differential scanning calorimetry (DSC) apparatus.

--- Mold release agent--
There is no restriction | limiting in particular as said mold release agent, Although it can select suitably according to the objective, Waxes are preferable.
The waxes are not particularly limited, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax Aliphatic hydrocarbon waxes such as: Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; Animal waxes such as lanolin, whale wax, etc .; mineral waxes such as ozokerite, ceresin, and petrolatum; waxes based on fatty acid esters such as montanate ester wax and castor wax; fatty acids such as deoxidized carnauba wax ester Such as those deoxidizing a part or the whole thereof.

  Examples of the waxes further include saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid, or straight chain alkyl carboxylic acids having a straight chain alkyl group; prundic acid, eleostearic acid, valinaline Unsaturated fatty acids such as acids; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesilyl alcohol, or long-chain alkyl alcohols; saturated alcohols such as sorbitol; linoleic acid amides, olefins Fatty acid amides such as acid amides and lauric acid amides; Saturated fatty acid bisamides such as methylene biscapric acid amides, ethylene bislauric acid amides and hexamethylene bisstearic acid amides; Ethylene bisoleic acid amides and hexamethylene vinyls Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasic acid amide; m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Aromatic bisamides such as amides; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid Wax; partial ester compound of fatty acid such as behenic acid monoglyceride and polyhydric alcohol; methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  More preferable examples of the waxes include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and catalysts such as Ziegler catalysts and metallocene catalysts under low pressures. Polymerized polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by pyrolyzing high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, Synthetic hydrocarbon waxes synthesized by the Age method, synthetic waxes using a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and functional groups Mixture of hydrocarbon wax having a styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, and graft modified wax with vinyl monomers such as maleic anhydride.

Further, those waxes having a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method are also included. Also, low molecular weight solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, and other impurities are preferably used.
These release agents may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 140 degreeC is preferable at the point which balances fixing property and offset resistance, and 60 to 120 ° C. is more preferable. When the melting point of the mold release agent is less than 50 ° C., the blocking resistance may be lowered, and when it exceeds 140 ° C., the anti-offset effect may be hardly exhibited.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, It contains 3 mass%-20 mass% in the toner solidified in the drying process mentioned later. Preferably, 4 to 15% by mass is contained. When the content of the release agent is less than 3% by mass, the fixing roller may not easily release the toner during fixing, and offset may occur easily. When the content exceeds 20% by mass, The toner strength may be weakened and durability may be lost.

-Other ingredients-
The other components in the toner composition are not particularly limited, and can be appropriately selected according to the purpose such as the same as the conventional electrophotographic toner material. For example, a colorant, a dispersant, a charge control agent. , Etc. These may be used alone or in combination of two or more.

--- Colorant ---
The colorant is generally added to toner and used for color development on paper or an image carrier. However, for the purpose of imparting gloss to an image and protecting the image, there is a toner that does not contain a colorant, such as a clear toner. In the present invention, since a colorant may or may not be added, it can be applied to both a clear toner and a general color toner.

  There is no restriction | limiting in particular as said coloring agent, Resin normally used can be selected suitably, and can be used, for example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G ), Cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi -Red, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Kina Redon Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said colorant, Although it can select suitably according to the objective, It contains so that it may become 1 mass%-15 mass% in the toner solidified in the drying process mentioned later. It is preferable to contain it so that it may become 3 mass%-10 mass%.

The colorant can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the master batch or the master batch, the same resin as the binder resin can be used. In addition, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyl toluene and the like. And styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Copolymer, styrene-α-chloromethyl methacrylate Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, Styrene copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl Examples include butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The masterbatch can be obtained by mixing and kneading a coloring agent and a binder resin for the masterbatch with a high shear force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the binder resin. Also used is a so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded together with a binder resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. it can. This method is preferably used in that the wet cake of the colorant can be used as it is and does not need to be dried. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

  There is no restriction | limiting in particular as the usage-amount of the said masterbatch, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of binder resin.

The acid value of the binder resin for the masterbatch when the colorant is dispersed is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 mgKOH / g or less, and 20 mgKOH / g The following is more preferable. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, or the pigment dispersibility may be insufficient.
The acid value can be measured, for example, according to JIS K0070.

There is no restriction | limiting in particular as an amine value of the binder resin for the said masterbatch at the time of disperse | distributing the said coloring agent, Although it can select suitably according to the objective, 1-100 are preferable and 10-50 are preferable. More preferred. When the amine value is less than 1 or more than 100, pigment dispersibility may be insufficient.
The amine value can be measured according to, for example, JIS K7237.

-Dispersant-
There is no restriction | limiting in particular as said dispersing agent, Although it can select suitably according to the objective, It is preferable that compatibility with binder resin is high at the point of pigment dispersibility.
Specific examples of the dispersant include trade names of “Ajisper PB821”, “Ajisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by BYK Chemie Corp.), “EFKA-4010” (Manufactured by EFKA). These may be used alone or in combination of two or more.

  The weight average molecular weight of the dispersant is not particularly limited and may be appropriately selected depending on the intended purpose, but is the maximum molecular weight of the main peak in terms of styrene equivalent weight in gel permeation chromatography, 100,000 is preferable, and from the viewpoint of pigment dispersibility, 3,000 to 100,000 is more preferable, 5,000 to 50,000 is further preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the weight average molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant increases. May decrease.

  There is no restriction | limiting in particular as the usage-amount of the said dispersing agent, Although it can select suitably according to the objective, 1 mass part-200 mass parts are preferable with respect to 100 mass parts of said coloring agents, and 5 mass parts- 80 parts by mass is more preferable. When the amount of the dispersant used is less than 1 part by mass, the dispersibility may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, and molybdate chelate pigments. , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and salicylic acid Examples thereof include metal salts of derivatives. These may be used alone or in combination of two or more.

  Specific examples of the charge control agent include trade names such as Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, and oxynaphthoic acid metal complex E. -82, E-84 of salicylic acid metal complex, E-89 of phenol condensate (above, manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, retained Tsuchiya Chemical Industry Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst) , LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.) Manufactured by a chemical company), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  The amount of the charge control agent used is not particularly limited and can be appropriately selected according to the type of the binder resin, the presence or absence of additives used as necessary, the toner production method including the dispersion method, and the like. However, with respect to 100 parts by mass of the binder resin, 0.1 parts by mass to 10 parts by mass are preferable, and 0.2 parts by mass to 5 parts by mass are more preferable. If the amount of the charge control agent used exceeds 10 parts by mass, the chargeability of the toner may be too high, leading to a decrease in image density.

-Organic solvent-
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. However, an organic solvent capable of dissolving the binder resin, stably dispersing the dispersion, and easily drying is preferably selected. .
Examples of such organic solvents include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), methoxyethanol, dimethoxyethane, dioxane, dioxolane, and anisole; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and the like. Ketones; esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate; hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, toluene; methanol , Alcohols such as ethanol, n-propanol, i-propanol, and butanol. These may be used alone or in combination of two or more.
Among these, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene and the like are particularly preferable as the organic solvent in view of high solubility of the crystalline polyester.

-Preparation method of toner composition liquid-
The method for preparing the toner composition liquid is not particularly limited as long as the toner composition can be dissolved or dispersed in the organic solvent, and can be appropriately selected according to the purpose. The method of mixing the organic solvent with a homomixer, a bead mill or the like can make the components in the toner composition sufficiently fine with respect to the opening diameter of the discharge hole, and clog the discharge hole. It is preferable at the point which can prevent.
The release agent and other components as necessary in the toner composition may be melt-kneaded together with the binder resin, or may be added when dissolved or dispersed in an organic solvent.
The toner composition and the organic solvent may be hot melt kneaded, and a solution obtained by dissolving or dispersing the obtained kneaded material once in various solvents may be used as the toner composition liquid.

  The temperature of the toner composition liquid is not particularly limited and may be appropriately selected depending on the type of the organic solvent. The temperature is preferably from the freezing point to the boiling point of the organic solvent. When the temperature of the toner composition liquid is high, the toner composition liquid is easily dried and the discharge holes of the toner composition liquid are easily clogged. For this reason, it is necessary to prevent drying by applying an organic solvent vapor in the vicinity of the discharge hole of the toner composition liquid. On the other hand, when the temperature of the toner composition liquid is low, the crystalline polyester may not dissolve.

  There is no restriction | limiting in particular as solid content of the said toner composition liquid, Although it can select suitably according to the objective, 5 mass%-40 mass% are preferable. When the solid content is less than 5% by mass, the productivity is lowered, and the dispersion of other components such as the release agent and the colorant is liable to cause sedimentation and aggregation. Tends to be non-uniform and toner quality may be reduced. If the solid content exceeds 40% by mass, a toner having a small particle size may not be obtained.

<< Droplet formation process >>
The droplet forming step is a step of forming droplets by discharging the toner composition liquid from at least one discharge hole. In the droplet formation step, the method of forming droplets by discharging the toner composition liquid is not particularly limited as long as it can obtain droplets with a narrow particle size distribution and ensure toner productivity. However, it can be appropriately selected from known methods according to the purpose.
As a method for ensuring the productivity of the toner with a narrow droplet size distribution, for example, (1) vibration is applied to the toner composition liquid in the liquid column resonance liquid chamber in which at least one ejection hole is formed. In this manner, a standing wave is formed by liquid column resonance, and the toner composition liquid is discharged from the discharge hole formed in the antinode of the standing wave to form droplets (hereinafter referred to as “liquid column resonance”). (2) A vibration is applied to a thin film in which a plurality of ejection holes having the same opening diameter is formed by a vibrating means, and a toner composition liquid is ejected from the ejection holes to form droplets. The embodiment (hereinafter, sometimes referred to as “membrane vibration system”) is preferable. (3) Pressurizing a reservoir for storing the toner composition liquid, discharging the toner composition liquid from a through-hole of the reservoir to form a liquid column, and vibrating the liquid column by a vibrating means. In which Rayleigh splitting is induced in the liquid column. As a mode for inducing Rayleigh splitting in the liquid column (hereinafter, sometimes referred to as “Rayleigh splitting method”), for example, a method described in JP 2007-199463 A can be used.

-Liquid column resonance method-
In the liquid column resonance method, in the liquid droplet forming step, vibration is applied to the toner composition liquid in the liquid column resonance liquid chamber in which the ejection holes are formed to form a pressure standing wave by liquid column resonance. In the droplet forming method, it is essential to discharge the toner composition liquid in the form of droplets from the discharge hole formed in the region where the pressure standing wave becomes antinode.

  The discharge hole is not particularly limited as long as it is formed in a region that becomes the antinode of the pressure standing wave, and can be appropriately selected according to the purpose. It is preferable that a plurality of regions be formed for at least one of the regions, and that a plurality of regions be formed in one liquid column resonance liquid chamber.

The “region that becomes the antinode of the pressure standing wave” is a region where the amplitude in the pressure wave of the liquid column resonance standing wave is large and the pressure fluctuation is large, and is large enough to eject a droplet. This is a region having pressure fluctuation. There is no restriction | limiting in particular as an area | region used as such antinode of a pressure standing wave, Although it can select suitably according to the objective, as shown to FIG.1 and FIG.2A, the amplitude of the said pressure standing wave is A wavelength of ± 1/3 is preferable from a position where the peak is reached (a node as a velocity standing wave) to a position where the peak is minimized, and a wavelength of ± 1/4 is more preferable.
When the discharge hole is formed in a region that becomes the antinode of the pressure standing wave, even if a plurality of discharge holes are opened, a substantially uniform droplet can be formed from each discharge hole. Furthermore, it is preferable in that the droplets can be efficiently discharged and the discharge holes are not easily clogged.

  There is no particular limitation on the number of discharge holes formed for at least one of the regions that become the antinodes of the pressure standing wave, and it can be appropriately selected according to the purpose. Is preferable, 4 to 15 is more preferable, and 4 to 10 is particularly preferable. The productivity increases as the number of the ejection holes increases, but when the number exceeds 20, the ejection holes become too dense and the ejected droplets may coalesce into coarse particles, which may adversely affect image quality. .

  The number of discharge holes formed in the one liquid column resonance liquid chamber is not particularly limited and may be appropriately selected according to the purpose. In view of the above, 2 to 100 are more preferable, 4 to 60 are still more preferable, and 4 to 20 are particularly preferable. If the number of ejection holes exceeds 100, it is necessary to set a high voltage to the vibration means when forming droplets of a desired toner composition liquid from the 100 ejection holes. May become unstable. In the case of 4 to 20, the standing wave is stable and productivity is maintained.

There is no restriction | limiting in particular as an opening diameter of the said discharge hole, Although it can select suitably according to the objective, 1 micrometer-40 micrometers are preferable, 2 micrometers-15 micrometers are more preferable, and 6 micrometers-12 micrometers are especially preferable. If the opening diameter is less than 1 μm, the formed droplets are very small, and toner may not be obtained. Further, when solid fine particles such as a pigment are contained as a component of the toner composition liquid, there is a possibility that the ejection holes are frequently blocked and the productivity is lowered. Further, when the opening diameter exceeds 40 μm, the diameter of the toner droplet is large, and when this is dried and solidified to obtain a desired toner particle diameter of 1 μm to 8 μm, the toner composition is made very dilute with an organic solvent. In some cases, it is necessary to dilute, and a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient. On the other hand, when the opening diameter is 6 μm to 12 μm, when manufacturing a member in which the discharge holes are opened, it is possible to keep small variations in the diameters of the many discharge holes, and the discharge holes are concentrated to increase productivity. This is advantageous because it can be maintained.
When there are a plurality of discharge holes, all of the discharge holes may have the same opening diameter or may be different in at least one discharge hole, but all preferably have the same opening diameter. Here, “same” means that the opening diameter is within a range of ± 5%.
The opening diameter of the discharge hole means a diameter if it is a perfect circle, and an average diameter if it is a polygon such as an ellipse, a quadrangle, a hexagon, an octagon, or a regular polygon.

In addition, when a plurality of discharge holes are formed, the pitch between the discharge holes in one of the regions that become the antinodes of the pressure standing wave (the shortest distance between the central portions of the adjacent discharge holes) is not particularly limited. However, it is preferably 20 μm or more and not more than the length of the liquid column resonance liquid chamber, more preferably 20 μm to 200 μm, further preferably 40 μm to 135 μm, and more preferably 40 μm to 80 μm. Particularly preferred. When the pitch between the ejection holes is less than 20 μm, there is a high probability that droplets discharged from adjacent ejection holes collide with each other to form large droplets, which may lead to deterioration in toner particle size distribution. .
The pitch between the discharge holes may be all at equal intervals between the plurality of discharge holes, or at least one pitch may be different. It is preferable in that it can be obtained.

The shape of the opening of the discharge hole is not particularly limited and may be appropriately selected depending on the purpose. The shape of the opening may be the same as that of the liquid contact surface, and the cross-sectional shape may be appropriately selected. It may be changed.
For example, cross-sectional shapes as shown in FIGS. 2A is an example of a schematic cross-sectional view of the liquid column resonance liquid chamber, and the discharge holes 19 in FIG. 2A may have shapes as shown in FIGS.
FIG. 2B shows a shape in which the opening diameter becomes narrow while having a round shape from the liquid contact surface of the discharge hole 19 toward the discharge port, and the liquid near the outlet of the discharge hole 19 when vibration occurs. Is the most preferable shape for stabilizing the discharge.
FIG. 2C has a shape in which the opening diameter becomes narrow at a certain angle from the liquid contact surface of the discharge hole 19 toward the discharge port, and from the liquid contact surface in the cross section of the discharge hole to the discharge port. The heading angle (hereinafter sometimes referred to as “the angle of the discharge hole”) 44 can be changed as appropriate. As in FIG. 2C, the pressure applied to the liquid can be increased near the outlet of the discharge hole 19 when vibration occurs depending on the angle of the discharge hole. There is no restriction | limiting in particular as the range, Although it can select suitably according to the objective, 60 degrees-90 degrees are preferable. If it is less than 60 °, it is difficult to apply pressure to the liquid and it is difficult to process it, which is not preferable.
When the angle of the discharge hole is 90 °, FIG. 2D corresponds, but since it is difficult for pressure to be applied to the outlet of the discharge hole 19, 90 ° is the maximum value. When the angle exceeds 90 °, no pressure is applied to the outlet of the discharge hole 19, so that the droplet discharge becomes very unstable.
FIG. 2E has a shape that combines FIG. 2B and FIG. 2C. In this way, the shape may be changed step by step.

Moreover, an example of the figure which looked at the opening of the discharge hole of FIG. 2B-E from the bottom (opening side of a discharge hole) is shown to FIG. 2F. There is no restriction | limiting in particular as an opening arrangement position of a discharge hole, According to the objective, it can select suitably.
For example, the arrangement shown in FIG. 2F may be used, and the arrangement may be regularly arranged continuously in the width direction and the longitudinal direction of the liquid column resonance liquid chamber.

  The liquid column resonance liquid chamber is a liquid chamber capable of forming a stationary pressure wave by vibration applied by the vibration means in accordance with the principle of the liquid column resonance phenomenon described later, and becomes an antinode of the pressure standing wave. A discharge hole is formed in the region, and has a communication port for supplying the toner composition liquid (at the longitudinal end of the liquid column resonance liquid chamber), and if necessary, the longitudinal direction of the liquid column resonance liquid chamber A reflection wall surface (perpendicular to the longitudinal axis) is provided at least at one end or both ends. The liquid column resonance liquid chamber preferably has a vibration means disposed on one of the walls parallel to the longitudinal direction of the liquid column resonance liquid chamber, and the wall facing the wall on which the vibration means is disposed is provided. It is preferable that a discharge hole is formed.

  The shape of the liquid column resonance liquid chamber is not particularly limited as long as a pressure standing wave can be formed by the vibration, and can be selected as appropriate. For example, a quadrangular column (a rectangular parallelepiped), a cylinder, a truncated cone, etc. Can be mentioned.

  It is preferable that a reflection wall surface is provided on at least a part of both ends in the longitudinal direction of the liquid column resonance liquid chamber. Here, the “reflective wall surface” refers to a wall surface formed by a member that is hard enough to reflect a sound wave of a liquid, such as a metal member such as aluminum or stainless steel, or a member such as silicone.

As shown in FIG. 4A, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber is not particularly limited and can be appropriately selected according to the purpose. It is preferable to be determined based on a proper liquid column resonance principle.
Further, as shown in FIG. 4B, the width W of the liquid column resonance liquid chamber is not particularly limited and can be appropriately selected according to the purpose, but does not give an extra frequency to the liquid column resonance. It is preferable that the length is less than one half of the length L of the liquid column resonance liquid chamber.

  Further, when the distance between the end portion on the liquid common supply path side and the center portion of the discharge hole 19 closest to the end portion is Le, the distance ratio (Le / L) between L and Le is as follows: There is no restriction | limiting in particular, Although it can select suitably according to the objective, It is preferable that it is larger than 0.6.

  Further, the liquid column resonance liquid chamber is formed by joining frames formed of a material having high rigidity that does not affect the resonance frequency of the toner composition liquid at the vibration drive frequency. Preferably, examples of such a material include metal, ceramics, and silicone.

  It is preferable that a plurality of the liquid column resonance liquid chambers are arranged with respect to one droplet discharge means in order to dramatically improve productivity. The number of liquid column resonance liquid chambers installed for one droplet discharge means is not particularly limited and can be appropriately selected according to the purpose. However, in terms of achieving both operability and productivity, 100 to 2,000 are preferable, 100 to 1,000 are more preferable, and 100 to 400 are particularly preferable. If the number of liquid column resonance liquid chambers is one droplet forming unit provided in the above preferred range, it is advantageous in that both operability and productivity can be achieved.

The vibration means is not particularly limited as long as it can be driven at a predetermined frequency and imparts vibration to the toner composition liquid in the liquid column resonance liquid chamber, and can be appropriately selected according to the purpose. , Piezoelectric bodies, ultrasonic vibrators, and the like.
The piezoelectric body is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include piezoelectric ceramics such as lead zirconate titanate (PZT), piezoelectric polymers such as polyvinylidene fluoride (PVDF), and crystals. , A piezoelectric body formed of a material such as single crystal such as LiNbO ₃ , LiTaO ₃ , KNbO _3, or the like.
There is no restriction | limiting in particular as said ultrasonic vibration body, According to the objective, it can select suitably, For example, a magnetostriction element etc. are mentioned.

It is preferable that the vibration means is bonded to an elastic plate, and the elastic plate preferably forms part of the wall of the liquid column resonance liquid chamber so that the vibration means does not come into contact with the liquid.
Furthermore, it is preferable that the vibration means is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, it is preferable to arrange vibration means such as a block-like piezoelectric body via an elastic plate in accordance with the arrangement of the liquid column resonance liquid chambers, from the viewpoint that each liquid column resonance liquid chamber can be individually controlled.

  The frequency of the vibration is not particularly limited and can be appropriately selected according to the purpose. The liquid column resonance frequency varies depending on the opening arrangement of the discharge holes. Is preferable, but high-frequency vibration of 300 kHz or more is preferable, and 300 kHz to 1,000 kHz is more preferable.

--- Mechanism of droplet formation ---
Next, the mechanism of droplet formation according to the present embodiment will be described.
FIG. 4A is a cross-sectional view showing an example of a droplet discharge head in the droplet formation unit. In FIG. 4A, the droplet discharge head 11 includes a liquid column resonance resonance liquid chamber 18 that stores the toner composition liquid 14 therein, and a liquid common supply path 17. A discharge hole 19 is provided on one wall surface of the liquid column resonance liquid chamber, and a vibration means 20 is provided on the wall surface opposite to the discharge hole 19.
First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the droplet discharge head 11 of FIG. 4A will be described. When the sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c and the drive frequency applied to the toner composition liquid as the medium from the vibration means 20 is f, the wavelength λ at which the liquid resonance occurs is Are in a relationship.
λ = c / f (Formula 1)

Further, in the liquid column resonance liquid chamber 18 of FIG. 4A, the length from the end of the frame on the fixed end side to the end on the common liquid supply path 17 side is L, and further, the end of the frame on the common liquid supply path 17 side Let h1 be the height of h, and let the height of the communication port be h2.
In the case of a both-side fixed end that is assumed to be equivalent to a closed fixed end on the liquid common supply path 17 side, resonance occurs when the length L matches an even multiple of a quarter of the wavelength λ. Most efficiently formed. That is, it is expressed by the following formula 2.
L = (N / 4) λ (Expression 2)
(However, N represents an even number.)
The case where it is equivalent to the fixed end is a case where it can be considered that there is no pressure relief portion at a certain end. For example, the height of the reflection wall surface at a certain end is the communication for supplying the toner composition liquid. This refers to the case where the height of the mouth is twice or more, and the case where the area of the reflection wall surface at a certain end is twice or more the area of the opening of the communication port for supplying the toner composition liquid.
In FIG. 4A, the length from the end of the frame on the fixed end side of the liquid column resonance liquid chamber 18 to the end on the liquid common supply path 17 side corresponds to the length L. Further, the height h1 (= about 80 μm) of the end of the frame on the liquid common supply path 17 side is about twice the height h2 (= about 40 μm) of the communication port, and the both ends are closed. It can be considered equivalent.

Further, the above formula 2 is also established in the case of a double-sided open end where both ends are completely open or equivalent to a double-sided open end.
Similarly, when one side is equivalent to an open end having a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length L is the wavelength λ. Resonance is most efficiently formed when it matches an odd multiple of a quarter. That is, N in Expression 2 is expressed as an odd number. In the case of the open ends on both sides, L corresponds to an even multiple of a quarter of the wavelength, and in the case of one side fixed end, L corresponds to an odd multiple of a quarter of the wavelength.

The most efficient driving frequency f is derived from the following equation 3 from the above equations 1 and 2.
f = N × c / (4L) (Formula 3)
(L: length of liquid column resonance liquid chamber in longitudinal direction, c: velocity of sound wave of toner composition liquid, N: integer)
Therefore, in the toner manufacturing method of the present invention, it is preferable to apply a vibration having a frequency f at which the above formula 1 holds to the toner composition liquid. However, in reality, since the liquid has a viscosity that attenuates the resonance, the vibration is not amplified infinitely, and has a Q value. Resonance also occurs at frequencies near the highly efficient drive frequency f.

5A to 5G show the shape of the standing wave of the velocity and pressure fluctuation (resonance mode) when N = 1, 2, 3, 4, 5. FIG. Although it is originally a sparse / dense wave (longitudinal wave), it is generally expressed as shown in FIGS. The solid line is the velocity standing wave, and the dotted line is the pressure standing wave.
For example, as can be seen from FIG. 5A showing the case of one-side fixed end with N = 1, in the case of velocity distribution, the amplitude of the velocity distribution becomes zero at the closed end, and the amplitude becomes maximum at the open end.
When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, the wavelength at which the liquid resonates is λ, and the standing wave is most efficiently generated when the integer N is 1 to 5. . In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening of the supply side.
In acoustics, the open end is an end at which the moving speed of the medium (liquid) in the longitudinal direction becomes zero, and conversely, the pressure becomes maximum. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or open, a resonant standing wave of the form shown in FIGS. 5A to G is generated by superposition of waves, but the standing wave also depends on the number of discharge holes and the opening position of the discharge holes. The pattern fluctuates and a resonance frequency appears at a position deviated from the position obtained from the above equation 3. However, a stable ejection condition can be created by appropriately adjusting the driving frequency.

For example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, wall surfaces exist at both ends, and N = 2 resonance that is completely equivalent to the fixed ends on both sides. When the mode is used, the resonance frequency with the highest efficiency is derived as 324 kHz from Equation 2 above.
In another example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, and the same conditions as described above are used. When the equivalent N = 4 resonance mode is used, the most efficient resonance frequency is derived from the above equation 2 as 648 kHz. Even in the liquid column resonance liquid chamber having the same structure, higher-order resonance is obtained. Can be used.

  It should be noted that the liquid column resonance liquid chamber 18 in the droplet discharge head 11 of the droplet forming unit 10 of the present embodiment shown in FIGS. 3 and 4A is equivalent to the closed end state or the opening of the discharge hole 19 is open. In order to increase the frequency, an end portion that can be described as an acoustically soft wall is preferable due to the influence of the above. The influence of the opening of the discharge hole 19 here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, forming wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 as shown in FIG. 5B and FIG. 5E means that the resonance mode at both fixed ends and all the resonances at the one-side open end that the discharge hole side is regarded as an opening. The mode is preferred because it is available.

Further, the numerical aperture of the discharge holes 19, the opening arrangement position, and the cross-sectional shape of the discharge holes are factors that determine the drive frequency, and the drive frequency can be appropriately determined according to this.
For example, when the number of the discharge holes 19 (numerical aperture) is increased, the restriction at the tip of the liquid column resonance liquid chamber 18 which has been a fixed end gradually becomes loose, and a resonance standing wave almost close to the open end is generated and driven. The frequency increases. Furthermore, the opening position of the discharge hole 19 existing closest to the liquid common supply path 17 is a starting point, and a loose constraint condition is established. The cross-sectional shape of the discharge hole 19 is round or the volume of the discharge hole due to the thickness of the frame is large. The actual standing wave fluctuates or has a short wavelength, which is higher than the driving frequency. When a voltage is applied to the vibration means at the drive frequency determined in this way, the vibration means 20 is deformed, and a resonant standing wave is generated most efficiently at the drive frequency. Further, the liquid column resonance standing wave is generated even at a frequency in the vicinity of the drive frequency at which the resonance standing wave is generated most efficiently. That is, when the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, and the distance to the discharge hole 19 closest to the end on the liquid common supply path 17 side is Le, the length of both L and Le Then, the vibration means is vibrated using a drive waveform whose main component is a drive frequency f in a range determined by the following formulas 4 and 5, and a liquid column resonance is induced to eject a droplet from the ejection hole. It is possible.

N × c / (4L) ≦ f ≦ N × c / (4Le) (Formula 4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (Formula 5)
(L: length in the longitudinal direction of the liquid column resonance liquid chamber, Le: distance to the discharge hole closest to the end on the liquid supply path side, c: velocity of sound wave of the toner composition liquid, N: integer)

  Using the principle of the liquid column resonance phenomenon described above, a liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 4A, and the discharge hole 19 disposed in a part of the liquid column resonance liquid chamber 18. In this case, droplet discharge occurs continuously. Note that it is preferable to dispose the discharge hole 19 at a position where the pressure of the standing wave fluctuates the most, since the discharge efficiency is increased and the driving can be performed with a low voltage.

Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit will be described with reference to FIGS.
6A to 6E, the solid line written in the liquid column resonance liquid chamber is a velocity obtained by plotting the velocity at each arbitrary measurement position from the fixed end side to the end of the liquid common supply path side in the liquid column resonance liquid chamber. The distribution is shown, and the direction from the liquid common supply path side to the liquid column resonance liquid chamber is +, and the opposite direction is-.
In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is + with respect to the atmospheric pressure, and the negative pressure is-.
Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure.
6A to 6E, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other (the height h2 shown in FIG. 4A). ), The height of the frame serving as the fixed end (height h1 shown in FIG. 4A) is preferably about twice or more, so that the liquid column resonance liquid chamber 18 is approximately the fixed end on both sides. Each change over time of the velocity distribution and the pressure distribution under the condition is shown.

  FIG. 6A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 at the time of droplet discharge. In FIG. 6B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 6A and 6B, the pressure in the flow path provided with the discharge hole 19 in the liquid column resonance liquid chamber 18 is maximum. Thereafter, as shown in FIG. 6C, the positive pressure in the vicinity of the discharge hole 19 decreases, and the liquid droplet 21 is discharged in a negative pressure direction.

  And as shown to FIG. 6D, the pressure of the discharge hole 19 vicinity becomes the minimum. From this time, the filling of the toner composition liquid 14 into the liquid column resonance liquid chamber 18 starts. Thereafter, as shown in FIG. 6E, the negative pressure in the vicinity of the discharge hole 19 decreases, and shifts to the positive pressure direction. At this time, the filling of the toner composition liquid 14 is completed. Then, as shown in FIG. 6A again, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber 18 becomes maximum, and the droplet 21 is discharged from the discharge hole 19. As described above, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration means, and corresponds to an antinode of standing wave due to liquid column resonance at a position where the pressure fluctuates most. Since the discharge hole 19 is disposed in the droplet discharge region, the toner droplet 21 is continuously discharged from the discharge hole 19 in accordance with the antinode period.

  Hereinafter, an embodiment of a droplet forming process using the liquid column resonance method of the toner manufacturing method of the present invention will be described in detail with reference to the drawings. The droplet forming process in the toner manufacturing method of the present invention includes: It is not limited to this.

  FIG. 3 is an example of a cross-sectional view showing an entire toner manufacturing apparatus for carrying out the toner manufacturing method according to the embodiment of the present invention. 4A is a cross-sectional view showing an example of a droplet discharge head in the droplet formation unit of FIG. 4B is a cross-sectional view taken along line A-A ′ showing the droplet forming unit of FIG. 3.

The toner manufacturing apparatus 1 in which the droplet forming process shown in FIG. 3 is performed by liquid column resonance mainly includes a droplet forming unit 10 (droplet forming unit) and a dry collection unit 30 (particle forming unit). .
In the toner manufacturing apparatus 1, the droplet forming unit 10 is a liquid chamber having a liquid discharge region communicating with the outside through a discharge hole, and a liquid column resonance liquid chamber in which a liquid column resonance standing wave is generated under conditions described later. A plurality of droplet discharge heads 11 are arranged as droplet forming means for discharging the toner composition liquid as droplets from the discharge holes.
On both sides of each droplet discharge head 11, there is an air flow generated by an air flow generating means (not shown) so that the droplets of the toner composition liquid discharged from the droplet discharge head 11 flow out to the dry collection unit 30 side. An airflow passage 12 is provided through.
Further, the droplet forming unit 10 includes a raw material container 13 that stores a toner composition liquid 14 that is a toner raw material, and a toner discharge liquid that is stored in the raw material container 13 through a liquid supply pipe 16. And a liquid circulation pump 15 that pumps the toner composition liquid 14 in the liquid supply pipe 16 to be supplied to the liquid common supply path 17 (described later) in the liquid supply pipe 11 and returned to the raw material container 13 through the liquid return pipe 22. .

As shown in FIG. 4A, the droplet discharge head 11 includes a liquid common supply path 17 and a liquid column resonance liquid chamber 18.
The liquid column resonance liquid chamber 18 communicates with a liquid common supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. The liquid column resonance liquid chamber 18 is provided on a wall surface facing the discharge hole 19 and a discharge hole 19 that discharges the toner droplet 21 to one wall surface of the wall surfaces connected to both ends. And vibration means 20 for generating high-frequency vibration to form a standing wave. Note that a high-frequency power source (not shown) is connected to the vibration means 20.
In addition, for each liquid column resonance liquid chamber, a flow path for supplying liquid is connected from the common liquid supply path 17, and the common liquid supply path 17 communicates with a plurality of liquid column resonance liquid chambers 18. .
One discharge hole 19 may be provided in the liquid column resonance liquid chamber 18, but the discharge hole 19 is provided in the width direction in the liquid column resonance liquid chamber 18 as shown in FIG. A large number of openings can be provided, which is preferable because production efficiency is increased.

  The vibrating means 20 in the droplet discharge head 11 is not particularly limited as long as it can be driven at a predetermined frequency, and can be appropriately selected according to the purpose. However, the piezoelectric body is attached to an elastic plate. A combined form is preferred. The elastic plate forms a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the elastic body.

The dry collection unit 30 shown in FIG. 3 includes a chamber 31 and a toner collection unit 32.
In the chamber 31, a large descending airflow is formed by combining the airflow generated by the airflow generating means (not shown) and the descending airflow 33. The toner droplet 21 ejected from the droplet ejection head 11 of the droplet forming unit 10 is transported downward not only by gravity but also by a descending airflow 33, so that the ejected toner droplet 21 is air. It can suppress decelerating by resistance. Accordingly, when the toner droplets 21 are continuously ejected, the toner droplets 21 ejected before are decelerated by the air resistance, and the toner droplets 21 ejected later are the toner droplets 21 ejected before. By catching up with the toner droplets 21, it is possible to prevent the toner droplets 21 from being joined and integrated to increase the particle size of the toner droplets 21.
As the air flow generation means, either a method of providing a blower in the upstream portion and pressurizing, or a method of suctioning from the toner collecting means 32 and reducing the pressure can be employed.
The toner collecting means 32 is provided with a rotating airflow generator (not shown) that generates a rotating airflow that rotates around an axis parallel to the vertical direction. Further, the toner collecting means 32 has a toner storing means 35 for storing dried and solidified toner particles that have passed through a toner collecting tube 34 communicating with the chamber 31.

Next, the droplet formation by the liquid column resonance method will be outlined.
The toner composition liquid 14 accommodated in the raw material container 13 shown in FIG. 3 passes through the liquid supply pipe 16 by a liquid circulation pump 15 for circulating the toner composition liquid 14, and the droplet forming unit shown in FIG. 4B. 10 flows into the common liquid supply path 17 and is supplied to the liquid column resonance liquid chamber 18 of the droplet discharge head 11 shown in FIG. 4A.
In the liquid column resonance liquid chamber 18 filled with the toner composition liquid 14, a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration unit 20. Then, the toner droplet 21 is ejected from the ejection hole 19 arranged in a region where the amplitude of the liquid column resonance standing wave has a large amplitude and the pressure fluctuation is large and becomes the antinode of the standing wave.

  The toner composition liquid 14 that has passed through the common liquid supply path 17 flows through the liquid return pipe 22 and is returned to the raw material container 13. When the amount of the toner composition liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the ejection of the toner droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common The flow rate of the toner composition liquid 14 supplied from the supply path 17 increases, and the toner composition liquid 14 is replenished into the liquid column resonance liquid chamber 18. Then, when the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18, the flow rate of the toner composition liquid 14 passing through the liquid common supply path 17 is restored to the original, and the liquid supply pipe 16 and the liquid return pipe 22 are supplied. The flow of the toner composition liquid 14 circulating in the apparatus is again formed.

-Membrane vibration method-
In the film vibration method, in the liquid droplet forming step, vibration is applied to a thin film having a plurality of discharge holes having the same opening diameter by vibration means, and the toner composition liquid is discharged from the discharge holes to form liquid droplets. This is a droplet forming method that must be performed.
Examples of the vibration means in the membrane vibration system include indirect vibration type discharge means that indirectly applies vibration to the thin film and direct vibration type discharge means that directly applies vibration to the thin film.

The thin film is a member formed by discharging a solution or dispersion of the toner composition into droplets.
There is no restriction | limiting in particular as thickness of the said thin film, Although it can select suitably according to the objective, 5 micrometers-500 micrometers are preferable.
There is no restriction | limiting in particular as a shape of the said discharge structure, Although it can select suitably according to the objective, Circular is preferable at the point which vibrates uniformly.

There is no restriction | limiting in particular as a material of the said thin film, According to the objective, it can select suitably, For example, a metal etc. are mentioned.
The thin film may have an insulating liquid repellent film, which will be described later, formed on the entire exposed surface.
There is no restriction | limiting in particular as said thin film, Although it can select suitably according to the objective, When it is made to vibrate, it is preferable that it is provided so that bending may generate | occur | produce in the said thin film. There is no restriction | limiting in particular as a method to generate | occur | produce a deflection | deviation in the said thin film, According to the objective, it can select suitably, For example, it joins and fixes via the flame | frame provided in the outermost periphery part of the said thin film, and a junction part. The method etc. are mentioned.

The elastic modulus of the joint member is not particularly limited and can be selected according to the purpose. However, a concentric uniform vibration state in the discharge hole is obtained, and the droplet discharge state is stabilized and uniform. 10 ⁸ Pa or more is preferable in that a toner having a uniform particle size distribution can be obtained.
Use of a material having a high elastic modulus as the member of the joining portion is advantageous in that the outermost peripheral portion of the thin film and the thin film can be firmly fixed. Thereby, vibration is efficiently propagated to the thin film. In particular, it is preferable in that vibration is efficiently propagated when the thin film is circular (film).
The elastic modulus can be measured by, for example, an ultrasonic method.

  It is preferable that the thin film and the frame, and / or the thin film and the vibration generating means are electrically insulated by a liquid repellent film of the insulator or a bonding agent of the insulator.

The material used for the liquid repellent film or the bonding agent is not particularly limited as long as it is an insulator, and can be appropriately selected according to the purpose. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene -Fluorocarbon resins such as perfluoroalkyl vinyl ether copolymer (PFA), fluorinated ethylene propylene (FEP), and polyvinylidene fluoride; epoxy resins such as bisphenol A and bisphenol F; SiO _{2 and the} like. These may be used alone or in combination of two or more. Further, described in JP-A-2010-107904, it has a perfluoroalkyl group on the SiO ₂ film, and liquid-repellent film made of a compound having a siloxane bond group at the terminal can also be suitably used.

In the membrane vibration system, the plurality of ejection holes have the same opening diameter. If they do not have the same opening diameter, it is not preferable in that a toner having a uniform particle diameter cannot be obtained. Here, “same” means that the opening diameter is within a range of ± 5%.
The opening diameter of the discharge hole means a diameter if it is a perfect circle, and an average diameter if it is a polygon such as an ellipse, a quadrangle, a hexagon, an octagon, or a regular polygon.

  There is no restriction | limiting in particular as the numerical aperture of the several discharge hole in the said thin film, Although it can select suitably according to the objective, Two to 3,000 are preferable.

The pitch between the discharge holes of the plurality of discharge holes (the shortest distance between the central portions of the adjacent discharge holes) is not particularly limited and may be appropriately selected depending on the intended purpose. The length is preferably not more than the length of the liquid chamber, more preferably 20 μm to 200 μm, still more preferably 40 μm to 135 μm, and particularly preferably 40 μm to 80 μm. When the pitch between the ejection holes is less than 20 μm, there is a high probability that droplets discharged from adjacent ejection holes collide with each other to form large droplets, leading to deterioration of the toner particle size distribution. is there.
The pitch between the discharge holes may be all at equal intervals among the plurality of discharge holes, or at least one pitch may be different. However, the equal intervals may obtain a toner having a uniform particle diameter. It is preferable in that it can be performed.

  There is no restriction | limiting in particular as a cross-sectional shape of the opening part of a discharge hole, According to the objective, it can select suitably, For example, the shape similar to the shape of the discharge hole described by the said liquid column resonance etc. are mentioned.

--- Indirect vibration type discharge means ---
The indirect vibration type discharge means is means for applying longitudinal vibration to the thin film having a plurality of discharge holes having the same opening diameter.

The indirect vibration type discharge means is not particularly limited as long as it can give a certain longitudinal vibration to the thin film at a constant frequency, and can be appropriately selected according to the purpose. For example, the liquid column Examples thereof include a piezoelectric body, an ultrasonic vibration body, and the like similar to the resonance type vibration means.
Among these, the indirect vibration type discharge means is preferably a piezoelectric body that excites bimorph type flexural vibration in the thin film.
The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, by applying a voltage, flexural vibration is excited and the thin film can be vibrated.
There is no restriction | limiting in particular as a material of the said piezoelectric material, Although it can select suitably according to the objective, For example, the thing similar to the vibration means of the said liquid column resonance system etc. are mentioned.

  As shown in FIG. 7, the bending vibration has a cross-sectional shape in which the displacement ΔL is maximum (ΔLmax) at the center of the thin film and the vibration displacement ΔL is minimum (ΔLmin) at the outermost discharge hole, and periodically in the vibration direction. Vibrates up and down. As the film periodically vibrates, droplets are periodically discharged from the discharge holes.

  The arrangement of the indirect vibration type discharge means is not particularly limited as long as it can vibrate in the vertical direction with respect to the thin film, and can be appropriately selected according to the purpose. However, the vibration surface and the thin film are parallel to each other. Preferably they are arranged. Thereby, the thin film is efficiently imparted with the longitudinal vibration by the indirect vibration type discharge means.

--- Direct vibration type discharge means ---
The direct-type discharge means is means for applying vibration to the thin film having a plurality of discharge holes having the same opening diameter.
There is no restriction | limiting in particular as arrangement | positioning of the said direct type | mold discharge means, Although it can select suitably according to the objective, It is preferable to provide in the circumference | surroundings of a thin film, and it is more preferable to provide in an annular | circular shape.

The direct vibration type discharge means is not particularly limited as long as it can vibrate the thin film at a constant frequency, and can be appropriately selected according to the purpose. For example, the indirect vibration type discharge means Examples thereof include a piezoelectric body and an ultrasonic vibration body.
Among these, the indirect vibration type discharge means is preferably a piezoelectric body that excites bimorph type flexural vibration in the thin film. There is no restriction | limiting in particular also as the material of the said piezoelectric material, According to the objective, it can select suitably, For example, the thing similar to the said indirect vibration type discharge means etc. are mentioned.

  As shown in FIG. 7, the bending vibration is a cross section in which the displacement ΔL is maximum (ΔLmax) at the center of the thin film and the vibration displacement ΔL is minimum (ΔLmin) at the outermost discharge hole, as shown in FIG. It becomes a shape and bends and vibrates periodically in the vibration direction. As the film periodically bends and vibrates, droplets are periodically discharged from the discharge holes.

--- Mechanism of droplet formation ---
Next, the mechanism of droplet formation by the indirect vibration type discharge means and the direct vibration type discharge means will be described.
As shown in FIGS. 8A and 9A, these droplet discharge means cause the thin film 310 to periodically propagate by causing the thin film 310 having a plurality of discharge holes 314 facing the liquid flow path 311 to propagate the vibration generated by the vibration means. The plurality of discharge holes 314 are arranged in a relatively large area, and droplets can be periodically formed and discharged stably from the plurality of discharge holes 314.

Due to the vibration of the thin film, a sound pressure Pac proportional to the vibration speed Vm of the thin film is generated in the liquid in the vicinity of the nozzles provided in various places of the thin film. It is known that the sound pressure is generated as a reaction of the radiation impedance Zr of the medium (toner composition liquid), and the sound pressure is expressed by the product of the radiation impedance and the vibration velocity Vm of the thin film using the following equation (6). The
Pac (r, t) = Zr · Vm (r, t) (6)
Since the vibration velocity Vm of the thin film periodically varies with time, it is a function of time (t). For example, various periodic variations such as a sine waveform and a rectangular waveform can be formed.
Further, as shown in FIG. 7, the vibration displacement in the vibration direction is different in each part of the thin film, and Vm is also a function of position coordinates on the film. As described above, the vibration mode of the thin film used in the present invention is an axial object. Therefore, it is substantially a function of the radius (r) coordinate.

As described above, a sound pressure proportional to the vibration displacement speed of the thin film having the distribution is generated, and the toner composition liquid is supplied to the outside (gas phase) of the discharge hole in response to the periodic change of the sound pressure. Is discharged.
The toner composition liquid periodically discharged to the outside of the discharge hole forms a sphere due to the difference in surface tension between the inside of the discharge hole (liquid phase) and the outside of the discharge hole (gas phase), so that the liquid droplets are periodically formed. Will occur.

The speed range of the thin film that can eject droplets has a relationship as shown in FIG. 7, and the area range that can be ejected is limited. Therefore, it is desirable to form ejection holes in this area range. The discharge hole 314 is disposed at the center of the thin film 310 as shown in FIGS. 8B and 9B.
8B and 9B, the plurality of ejection holes are arranged in a concentric regular hexagonal shape, but this arrangement is not particularly limited and can be appropriately selected depending on the purpose.
8B and 9B, the thin film 310 is shown as a circular thin film, but the shape of the thin film 310 is not particularly limited and can be appropriately selected according to the purpose.

There is no restriction | limiting in particular as the vibration frequency of the film | membrane which enables droplet formation, Although it can select suitably according to the objective, 20kHz-2.0MHz are preferable and 50kHz-500kHz are more preferable. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid.
Furthermore, when the displacement amount of the sound pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.

  Hereinafter, an embodiment of a droplet forming process using the membrane vibration method of the toner manufacturing method of the present invention will be described in detail with reference to the drawings. The droplet forming process in the toner manufacturing method of the present invention is described below. It is not limited to.

FIG. 10A is an example of a cross-sectional view illustrating an entire toner manufacturing apparatus for carrying out a toner manufacturing method using a membrane vibration method.
First, with reference to FIG. 10A, an example of a liquid feeding form of the toner composition liquid 14 to the droplet forming unit 104 that discharges droplets by the indirect vibration type discharge unit or the direct vibration type discharge unit will be described.

  In the toner manufacturing apparatus 210 shown in FIG. 10A, the toner composition liquid 14 is stored in a raw material container 201 and connected to the droplet forming unit 104 by a liquid supply pipe 202. As the driving force for liquid feeding, the liquid feeding means 203 may be used, gravity may be used, or the liquid suction force by the discharge unit itself may be used. Since the liquid feeding of the toner composition liquid 14 to the droplet forming unit 104 has an adverse effect on the ejection if there is a pulsation, the liquid feeding means 203 is preferably one that does not pulsate due to gravity or the suction force of the ejection unit. . As the other liquid feeding means 203, various pumps can be used. As described above, for example, a gear pump is preferably used as a pump that does not cause pulsation.

In FIG. 10A, the toner composition liquid 14 supplied to the droplet forming unit 104 is shown to be circulated and returned to the raw material container 201, but is not necessarily circulated. The toner composition liquid may be supplied only.
When the toner composition liquid 14 is circulated, the amount of liquid can be controlled by a valve 204 provided in the middle of the liquid supply pipe 202. There is no restriction | limiting in particular as a kind of valve | bulb, According to the objective, it can select suitably from well-known things.
Further, in the liquid droplet forming unit 104 shown on the right side of the chamber 206 shown in FIG. 10A, the liquid supply path of the toner composition liquid 14 is described, but in the liquid droplet forming unit 104 shown on the left side, Although it has exactly the same liquid supply path, the description is omitted.

  The liquid feeding pressure to the droplet forming unit 104 and the pressure in the chamber 206 are managed by pressure gauges P1 and P2. At this time, if the relationship of P1> P2, the toner composition liquid 14 may ooze out from the discharge hole, and if P1 <P2, there is a possibility that gas enters the discharge means and the discharge stops, so P1 ≈P2 is desirable.

  As described above, the toner composition liquid 14 fed to the droplet forming unit 104 is discharged by the following indirect vibration means or linear vibration means.

--- Indirect vibration type discharge means ---
FIG. 8A is a schematic diagram illustrating an example of the structure of an indirect vibration type ejection unit. FIG. 8B is a schematic diagram illustrating an example of a structure of the indirect vibration type ejection unit viewed from below.
The indirect vibration type discharge unit 300 includes a thin film 310 having a plurality of discharge holes 314 having the same opening diameter, and a vibration unit (mechanical) that applies vibration to the thin film 310 by converting electricity into mechanical vibration. (Vibrating means) 305 and a frame 308 that forms a liquid flow path 311 for supplying the toner composition liquid 14 between the thin film 310 and the vibrating means 305. The toner composition liquid 14 is supplied from the toner composition liquid supply port 309, passes through the liquid flow path 311, and is discharged from the toner composition liquid discharge port 315.

The thin film 310 having the plurality of discharge holes 314 is installed in parallel to the vibration surface 313 of the vibration unit 305, and a part of the thin film 310 is bonded and fixed to the frame 308. Is a substantially vertical positional relationship. That is, the thin film 310 is given longitudinal vibration by the vibration means 305.
A circuit 306 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 303 of the vibration means 305, and the signal from the drive signal generating source 307 can be converted into mechanical vibration.
As a circuit for supplying an electric signal, a lead wire having an insulating coating on the surface is suitable. For the vibration means 305, it is preferable to use an element having a large vibration amplitude, such as various horn type vibrators and bolted Langevin type vibrators described later, for efficient and stable toner production.

  The vibration unit 305 includes a vibration generation unit 303 that generates vibrations, and a vibration amplification unit 304 that amplifies the vibrations generated by the vibration generation unit 303. A drive voltage (drive signal) having a required frequency is supplied from the drive signal generation source 307. ) Is applied between the electrodes 302 of the vibration generating means 303, and vibration is excited in the vibration generating means 303. This vibration is amplified by the vibration amplifying means 304, and the vibration surface 313 arranged parallel to the thin film 310 is formed. The thin film 310 vibrates at a required frequency due to periodic vibration, and the periodic pressure generated by the vibration of the vibration surface 313.

In the example shown in FIG. 8A, a horn type vibrator is used as the vibration means 305 having the vibration generation means 303 and the vibration amplification means 304, and this horn type vibrator has the amplitude of the vibration generation means 303 such as a piezoelectric element. Since the vibration can be amplified by the vibration amplifying means 304, the vibration generating means 303 itself for generating mechanical vibration may be small vibration, which is preferable in terms of extending the life of the production apparatus because the mechanical load is reduced.
There is no restriction | limiting in particular as a shape of a horn type | mold vibrator, According to the objective, it can select suitably from well-known typical horn shapes.

Further, the vibration generating means 303 is not limited to the horn type vibrator, and a particularly high-strength bolted Langevin type vibrator can also be used.
This bolted Langevin type vibrator is preferable in that piezoelectric ceramics are mechanically coupled and are not damaged during high amplitude excitation.

  The size of the vibration means 305 that generates mechanical vibration is generally increased as the oscillation frequency decreases, and according to the required frequency, the vibration means is appropriately directly drilled to provide a reservoir. be able to. It is also possible to vibrate the entire storage part efficiently.

--- Direct vibration type discharge means ---
FIG. 9A is a schematic diagram illustrating an example of the structure of a direct vibration type ejection unit. FIG. 9B is a schematic diagram illustrating an example of a structure in which the direct vibration type ejection unit is viewed from below.
The direct vibration type discharge unit 400 includes a thin film 310 having discharge holes 314 having at least the same opening diameter for discharging the toner droplets 21, an annular vibration generating unit 403 for vibrating the thin film 310, and the toner composition liquid 14. A frame 308 provided with a liquid flow path 311 for supplying the liquid is provided. The toner composition liquid 14 is supplied from the toner composition liquid supply port 309, passes through the liquid flow path 311, and is discharged from the toner composition liquid discharge port 315.

The outer periphery of the thin film 310 is bonded and fixed to the frame 308. The annular vibration generating means 403 is disposed around the area of the thin film 310 where the discharge holes 314 are provided.
The annular vibration generating means 403 includes an annular piezoelectric body 401 and an electrode 402, and a drive voltage (drive signal) having a required frequency is applied to the electrode 402 from the drive signal generation source 307 through the circuit 306. For example, bending vibration is generated.

  The cross-sectional shape of the discharge hole 314 is described as a shape whose size does not change between the opening of the discharge hole 314 and the liquid contact surface in FIGS. 8A and 9A, but the cross-sectional shape can be changed as appropriate. For example, the cross-sectional shapes as shown in FIGS.

<< Drying process >>
The drying step is a step of solidifying toner particles by drying the organic solvent in the toner composition liquid formed into droplets in the droplet forming step.
The method for solidifying the droplets is not particularly limited as long as the droplets can be solidified into particles, and a known method can be appropriately selected according to the purpose. For example, the organic solvent contained in the droplets is dried. Examples include a method of evaporating into a gas and performing shrinkage solidification by drying.

  Hereinafter, an embodiment of the drying process of the toner production method of the present invention will be described in detail with reference to the drawings. However, the drying process in the toner production method of the present invention is not limited to this.

-Liquid column resonance method-
When the droplet forming process is performed by a liquid column resonance method, as shown in FIG. 3, the toner droplet 21 ejected from the droplet ejection head 11 of the droplet ejection unit 10 is not only caused by gravity, The air flow generated by the air flow generating means (not shown) is conveyed downward by the descending air flow 33 formed through the air flow passage 12. Next, a spiral airflow is formed along the conical inner wall surface forming the toner collecting means 32 by the rotating airflow and the descending airflow 33 generated by a rotating airflow generator (not shown) in the toner collecting means 32, The toner particles are dried and solidified in a laminar flow state on the spiral airflow. The dried and solidified toner particles are stored in the toner storing means 35 through the toner collecting tube 34.

-Membrane vibration method-
Next, a drying process when the droplet forming process is performed by a membrane vibration method will be described.
FIG. 11 is a schematic view showing an example of the structure of a droplet discharge unit that discharges droplets by the film vibration method in the toner manufacturing method of the present invention.
In FIG. 11, the toner composition liquid 14 stored in the raw material container 201 in the droplet forming step is conveyed from the raw material container 201 to the droplet forming unit 104 through the liquid supply pipe 202. The droplet forming unit 104 has an ejection hole 314 provided in the droplet ejection head 312, and the toner droplet 21 is ejected from the ejection hole 314.

  The toner droplet 21 ejected from the ejection hole 314 in the droplet forming step is transported not only by gravity but also along the primary transport airflow 207 that flows in the same direction as the ejection direction. It can suppress that the discharged toner droplet 21 is decelerated by air resistance. Accordingly, when the toner droplets 21 are continuously ejected, the toner droplets 21 ejected before are decelerated by the air resistance, and the toner droplets 21 ejected later are the toner droplets 21 ejected before. By catching up with the toner droplets 21, it is possible to prevent the toner droplets 21 from being joined and integrated to increase the particle size of the toner droplets 21.

There is no restriction | limiting in particular as a kind of gas used as the primary conveyance airflow 207, According to the objective, it can select suitably, For example, nonflammable gas, such as air and nitrogen, etc. are mentioned.
Further, in order to prevent the droplet discharge stop due to the discharge hole 314 being closed by the toner composition liquid 14 being dried around and at the discharge hole 314 disposed in the droplet forming unit 104, A vapor of the same or similar material as the solvent used may be included.

There is no restriction | limiting in particular as the temperature of the primary conveyance airflow 207, Although it can select suitably according to the objective, It is desirable that there is no fluctuation | variation at the time of production.
There is no restriction | limiting in particular as airflow speed H of a primary conveyance airflow, Although it can select suitably according to the objective, It is preferable that it is the same as that of a droplet discharge speed, or it is faster than it, but it needs to be significantly quicker. Absent. More preferably, it is in the range of 1.0 to 1.5 times the droplet discharge speed.

The primary transport airflow 207 is designed so that the shroud airflow 105 is created by supplying gas from the shroud airflow outlet 103, and the airflow direction is the same as the droplet discharge direction by the shroud cover 108.
The flow velocity of the shroud air flow 105 is adjusted in order to determine the air flow velocity at the portion that has passed through the droplet discharge head 312 of the droplet forming unit 104, that is, the primary conveyance air flow velocity. If the air flow velocity in the vicinity of the droplet discharge head 312 is not uniform, the toner droplets 21 are coalesced. Therefore, it is necessary to precisely supply the gas to the shroud outlet.

  The shape of the shroud cover 108 is not particularly limited as long as the airflow direction is the same as the droplet discharge direction, and can be appropriately selected according to the purpose. As shown in FIG. The flow velocity may be controlled by narrowing the opening in the vicinity of the liquid droplet ejection head 312, or the diaphragm may not be provided.

The droplet forming unit 104 is provided with a secondary transport airflow 208 that is faster than the free fall speed of the toner droplet 21 and has an angle with respect to the ejection direction of the toner droplet 21.
The toner droplet 21 transported by the primary transport airflow 207 is then placed on the airflow that is faster than the free fall speed of the toner droplet 21 and that is angled with respect to the ejection direction of the toner droplet 21. The toner droplet 21 is bent in the direction in which the secondary transport airflow 208 flows, and the coalescence probability of particles ejected from the same ejection hole 314 is extremely lowered as shown in FIG.
The angle of the secondary transport airflow 208 is preferably less than 120 ° with respect to the primary transport airflow 207.

  In FIG. 11, the secondary transport airflow 208 is illustrated as having an angle of 90 ° with respect to the primary transport airflow 207 in the droplet forming unit 104, but is not limited to 90 °. Is preferably 45 ° or more and less than 100 °, and particularly preferably 60 ° or more and 90 ° or less. When the angle is 120 ° or more, the ejected droplet 21 returns to the ejection unit side by the secondary transport airflow 208, so that the toner droplet 21 is likely to adhere to the droplet ejection head 312. Since the adhered droplets block the discharge holes 314, the discharge may stop. Also, if the angle is less than 45 °, the effect of reducing the coalescence establishment that occurs when the ejection direction of the toner droplet 21 is forcibly bent is small.

  The air flow velocity V of the secondary conveyance air flow 208 is not particularly limited and can be appropriately selected according to the purpose. However, V / H with respect to the air flow velocity H of the primary conveyance air flow 207 is a toner droplet. In terms of preventing 21 coalescence, 0.5 to 3.0 is preferable, 0.75 to 2.0 is more preferable, and 1.0 to 1.5 is even more preferable. If V / H is less than 0.5, the effect of forcibly bending the discharge direction by the secondary conveyance airflow inlet 209 may be weak and the effect of preventing coalescence may be small. Since the ejection trajectory of the toner droplet 21 ejected on the surface is excessively bent in the direction in which the secondary transport airflow flows, the prevention efficiency of coalescence may be reduced.

There is no restriction | limiting in particular as a kind of gas used as the secondary conveyance airflow 208, According to the objective, it can select suitably, For example, nonflammable gas, such as air and nitrogen, etc. are mentioned.
Further, in order to prevent coalescence by drying the droplets 21, it is preferable to have conditions that can promote drying of the droplets. For this reason, it is desirable that the solvent vapor contained in the toner composition liquid is not included. The dried droplets are advantageous in that coalescence can be suppressed because the solidification of the surface has already progressed even if the particles come into contact with the droplets in a scattered state.
There is no restriction | limiting in particular as the temperature of the secondary conveyance airflow 208, Although it can select suitably according to the objective, It can adjust suitably and it is desirable that there is no fluctuation | variation at the time of production.

  In this way, the discharged toner droplets 21 are dried while maintaining a low probability of coalescence, and become dry particles 22. The generated dry particles 22 are collected by a collector (not shown) and sent to a toner storage unit (not shown).

  The particle size distribution of the toner collected in this way is, for example, as shown in FIG. This is an example of the collected toner, but it can be seen that there are almost only toner particles having a single particle size. This is obtained when the toner droplets 21 discharged as described above are obtained by drying without coalescence.

On the other hand, in the conventional toner manufacturing method, the drop state of droplets when there is no transport airflow will be described with reference to FIG. FIG. 12 is the same as FIG. 11 except that the primary transport airflow 207 and the secondary transport airflow 208 are not used.
The toner droplets 21 discharged from the droplet forming unit 104 are subjected to air resistance, the discharge speed rapidly decreases, and starts to fall naturally. When the discharge speed is reduced, the distance between the droplets is shortened, and eventually the droplets are coalesced. In addition, the coalesced particles have increased air resistance and delayed drying, causing coalescence with other droplets, and several droplets may coalesce. Later, dried particles 24 are produced and the resulting toner particle size distribution is broadened.

The particle size distribution of the collected toner is as shown in FIG.
This is an example of the collected toner, but the dry particles forming the peak indicated by the basic particle diameter in the figure are the liquid droplets 21 that have not been coalesced and dried and solidified as they are. The dry particles forming the peak described as double are those obtained by drying and solidifying after the droplets 21 are coalesced after ejection. Similarly, it can be inferred from the particle size distribution measurement results that the coalescence of 3 times, 4 times, or more is proceeding.

  A toner manufacturing apparatus 210 shown in FIG. 10A has a dry collection unit 220 and a chamber 206 as a space for discharging toner, and the droplet forming unit 104 shown in FIG. Yes. Although details of the droplet forming unit 104 are as shown in FIG. 11 and are not shown in detail, the droplet forming unit 104 is equipped with a droplet discharge means and a shroud for generating a primary conveying airflow 207.

  In the chamber 206, the secondary transport airflow 208 flows from the upper secondary transport airflow inlet 209 to the guide pipe 212 communicating with the chamber 206.

The droplet forming unit 104 is attached to the side wall of the chamber 206 at an angle such that the primary conveying airflow 207 in the droplet forming unit 104 flows perpendicularly to the secondary conveying airflow 208. There may be a plurality of discharge units attached in the chamber 206.
FIG. 10A shows a state where two discharge units are arranged. FIG. 10A shows a state where the secondary transport airflow 208 flows downward from above, but if the secondary transport airflow 208 has an angle of less than 120 ° C. with respect to the direction of the primary transport airflow 207, the secondary transport airflow 208 is shown. There is no particular limitation on the flow direction of the liquid, and it can be set as appropriate. preferable.

Droplets (not shown) from the droplet forming unit 104 are ejected in the direction of the primary transport airflow 207, and then the direction is forcibly bent by the secondary transport airflow 208, resulting in a locus as indicated by reference numeral 500. It is possible to prevent the coalescence of the droplets, and the organic solvent contained in the droplets volatilizes during the conveyance with the primary conveyance airflow 207 and the secondary conveyance airflow 208. Dry particles with a narrow particle size distribution can be prevented during transport in the chamber 206.
Dry particles (not shown) pass through the guide tube 212 by the secondary conveying airflow 208, are collected by the toner collecting unit 213, and are stored in the toner storing unit 214. As the toner collecting means 213, a general apparatus can be used, and a cyclone collecting machine is preferably used.

FIG. 10B is a schematic view of the arrangement of the droplet forming unit 104 attached to the chamber 206 as seen from above. Here, although the toner composition liquid supply device to the discharge unit is actually attached, it is not shown for simplicity of explanation.
Here, four examples of the number of discharge units arranged in the chamber 206 are shown, but there is no particular limitation and the number can be increased in accordance with the production amount. A plurality may be arranged in the vertical direction.

In the chamber 206 (a), four droplet forming units 104 are arranged in the chamber 206, all ejecting toward the center of the chamber 206, and all the trajectories 500 of the ejected toner droplets are directed toward the center of the chamber 206. The droplets are conveyed downward by a secondary air flow not shown while moving toward the center.
In the chamber 206 (b), four droplet forming units 104 are arranged in the chamber 206, but are arranged at an angle with respect to the center. By providing an angle, it is not necessary to consider the coalescence with the droplets discharged from the opposing discharge unit, and the volume of the chamber 206 can be used efficiently, which is suitable when a plurality of discharge units are arranged. is there. The angle with respect to the center of the droplet forming unit 104 can be arbitrarily adjusted.

<< Other processes >>
The other steps are not particularly limited and may be appropriately selected depending on the purpose. If necessary, the particles dried by the drying collection unit in the drying step may be further fluidized bed dried or vacuum dried. It is preferable to have a secondary drying step.
If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixability, and charging characteristics will change over time, but the organic solvent will volatilize during fixing by heating, which will adversely affect users and peripheral devices. It is preferable to carry out sufficient drying.

<Toner>
The toner of the present invention is a toner produced by the toner production method of the present invention, and contains at least a binder resin containing a crystalline polyester resin and a release agent, and further contains other resins as necessary. Contains ingredients.
The binder resin and the release agent are the same as the components in the toner composition.

<< Other ingredients >>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, etc. are mentioned. These may be used alone or in combination of two or more.

-Fluidity improver-
The fluidity improver is preferable in that it can be added to the toner surface to improve the fluidity of the toner (become easy to flow).

The fluidity improver is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fluororesin powders such as carbon black, vinylidene fluoride fine powder, and polytetrafluoroethylene fine powder; Fine powder silica such as silica and dry process silica; fine powder unoxidized titanium, fine powder unalumina, treated silica, surface treated with silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, etc. Is mentioned. These may be used alone or in combination of two or more.
Among these, the fluidity improver is preferably fine powdered silica, finely powdered titanium oxide, or finely powdered non-alumina, and more preferably treated silica obtained by surface treatment with a silane coupling agent or silicone oil.

  The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.

  Specific examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, trade names such as AEROSIL-130, AEROSIL-300, AEROSIL-380, AEROSIL-TT600, AEROSIL-MOX170, AEROSIL. -MOX80, AEROSIL-COK84 (Nippon Aerosil Co., Ltd.); Ca-O-SiL-M-5, Ca-O-SiL-MS-7, Ca-O-SiL-MS-75, Ca-O- SiL-HS-5, Ca-O-SiL-EH-5 (above, manufactured by CABOT); Wacker HDK-N20 V15, Wacker HDK-N20E, Wacker HDK-T30, Wacker HDK-T40 (above, WAKER-CHEMIE) Manufactured); D-CFine Si1ica (manufactured by Dow Corning); Franco1 (manufactured by Franci1), and the like.

  Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. There is no restriction | limiting in particular as a hydrophobization degree measured by the methanol titration test in the said processing silica fine powder, Although it can select suitably according to the objective, Silica fine powder shows a value of 30%-80%. What processed the body is especially preferable. The hydrophobized treated silica fine powder is applied by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with the silica fine powder. As a preferred method, a method of treating a silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

  There is no restriction | limiting in particular as an organosilicon compound, According to the objective, it can select suitably, For example, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, Vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyl Dimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β Chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule Examples thereof include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si in the unit located at the end. Furthermore, silicone oils such as dimethyl silicone oil are also included. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The particle size of the fluidity improver is not particularly limited and may be appropriately selected depending on the intended purpose. The average primary particle size is preferably 0.001 μm to 2 μm, preferably 0.002 μm to 0.2 μm. More preferred.
The number average particle size of the fluidity improver is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 nm to 100 nm, and more preferably 5 nm to 50 nm.
The particle size can be measured, for example, with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like.

The fluidity improving agent, the specific surface area by measuring nitrogen adsorption by the BET method is not particularly limited and may be appropriately selected depending on the intended purpose, preferably at least ^{30m 2 / g, 60m 2 /} g~ 400 m ² / g is more preferable. As the surface-treated fine powder is preferably not less than ^{20m 2 / g, 40m 2 /} g~300m 2 / g is more preferable.

  There is no restriction | limiting in particular as the usage-amount of these fluidity improvers, Although it can select suitably according to the objective, 0.03 mass part-8 mass parts are preferable with respect to 100 mass parts of toner particles.

-Cleaning improver-
The cleaning property improving agent is preferable in that it can improve the removability of the toner remaining on the electrostatic latent image carrier and the primary transfer medium after the toner is transferred onto a recording paper or the like.
The cleaning property improver is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid; polymethyl methacrylate fine particles, polystyrene fine particles and the like. Examples thereof include fine polymer particles produced by soap-free emulsion polymerization. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a weight average particle diameter of the said polymer fine particle, Although it can select suitably according to the objective, A thing with a comparatively narrow particle size distribution is preferable, and a thing of 0.01 micrometer-1 micrometer is more preferable.

The other components such as the fluidity improver and the cleaning property improver are used by adhering to or fixing on the surface of the toner, and are also called external additives.
A method for externally adding the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method using various powder mixers.
The powder mixer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the powder mixer used in the case of immobilization include a hybridizer, mechanofusion, and Q mixer.

<< Weight average particle diameter of toner >>
There is no restriction | limiting in particular as a weight average particle diameter of the said toner, Although it can select suitably according to the objective, 1 micrometer-10 micrometers are preferable, and 3 micrometers-6 micrometers are more preferable. When the toner has a weight average particle size of less than 1 μm, the cohesive force and power of the toner become too high, it becomes difficult to copy sufficient toner on paper or an image carrier, May result in a light image. On the other hand, if it exceeds 10 μm, the toner may be too large to produce a high-definition image.

<< Toner particle size distribution >>
The particle size distribution of the toner can be compared by the ratio of the volume average particle diameter (Dv) and the number average particle diameter (Dn), and can be expressed as Dv / Dn.
A general pulverized toner has Dv / Dn of about 1.15 to 1.25. In general, the polymerized toner has Dv / Dn = 1.10 to 1.15. However, in an electrophotographic system, a narrow particle size distribution is required for the development process, the transfer process, and the fixing process. Such a broadening of the particle size distribution is undesirable.
On the other hand, the Dv / Dn of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose. However, it is possible to maintain a stable image over a long period of time and improve the print quality. .15 is preferable, 1-1.12 is more preferable, and 1-1.09 is particularly preferable.
In addition, when Dv / Dn is 1, it shows that all the particle sizes are the same, and it shows that a particle size distribution is so wide that Dv / Dn is large.
The particle size can be analyzed using a flow particle image analyzer (Sysmex Corporation FPIA-2000).

(Developer)
The developer of the present invention contains at least a toner and a carrier, and further contains other components as necessary. The two-component developer is advantageous in that it can improve the service life when used in a high-speed printer or the like that can improve the information processing speed.
Since the toner contained in the developer is the toner of the present invention, detailed description thereof is omitted.

<Career>
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose. However, a resin-coated carrier having carrier core particles and a coating layer obtained by coating (coating) the carrier core particles with a coating material is preferable.

<< carrier core particles >>
The material for the carrier core particles is not particularly limited and can be appropriately selected from known materials according to the purpose. Examples thereof include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide. And magnetic materials such as metals such as iron, cobalt and nickel, or alloys thereof.
The element contained in the magnetic material is not particularly limited and can be appropriately selected according to the purpose. For example, iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, Bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium and the like can be mentioned. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components; manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are particularly preferable.

<< Coating layer >>
The material for the coating layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers. Acrylic resins such as acrylic acid ester copolymers and methacrylic acid ester copolymers; fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer and polyvinylidene fluoride; silicone resins, polyester resins, polyamide resins, Preferable examples include polyvinyl butyral and aminoacrylate resin. In addition, an ionomer resin, a polyphenylene sulfide resin, etc. are also mentioned. These may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

  In the resin-coated carrier, the method for coating at least the surface of the carrier core with the resin coating agent is not particularly limited and can be appropriately selected depending on the purpose. For example, the resin is dissolved or suspended in a solvent. And a method of adhering to the coated carrier core, or a method of simply mixing in a powder state.

  There is no restriction | limiting in particular as a usage-ratio of the said coating | covering material with respect to the said resin coat carrier, Although it can select suitably according to the objective, 0.01 mass part-5 mass parts with respect to 100 mass parts of resin coat carriers Is preferable, and 0.1 part by mass to 1 part by mass is more preferable.

  There is no restriction | limiting in particular as a usage example which coat | covers carrier core particle | grains (magnetic body) with the coating | coated (coat) material of 2 or more types of mixtures, According to the objective, it can select suitably, For example, (1) Titanium oxide Treated with 12 parts by mass of a mixture of di, methyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5) with respect to 100 parts by mass of fine powder, (2) Dimethyldichlorosilane with respect to 100 parts by mass of silica fine powder And those treated with 20 parts by mass of a mixture of dimethyl silicone oil and a dimethyl silicone oil (mass ratio 1: 5). Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.

  The mixture of the fluororesin and the styrene copolymer is not particularly limited and may be appropriately selected depending on the purpose. For example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, Mixture of polytetrafluoroethylene and styrene-methyl methacrylate copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10) and styrene-2-ethylhexyl acrylate copolymer Mixture (copolymer mass ratio 10: 90-90: 10) and styrene-acrylic acid 2-ethylhexyl-methyl methacrylate copolymer (copolymer mass ratio 20-60: 5-30: 10: 50) Etc.

  The silicone resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a modified resin produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with the silicone resin. Examples include silicone resins.

The volume resistance value of the carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm. Examples of the method for adjusting the volume resistance value include a method for adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated.

  There is no restriction | limiting in particular as a particle size of the said carrier, Although it can select suitably according to the objective, 4 micrometers-200 micrometers are preferable, 10 micrometers-150 micrometers are more preferable, 20 micrometers-100 micrometers are still more preferable. Among these, it is particularly preferable that the carrier has a 50% particle size of 20 μm to 70 μm.

  The mixing ratio of the toner and the carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 part by mass to 200 parts by mass of the toner with respect to 100 parts by mass of the carrier. The toner is more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the carrier.

  In the developing method using the toner of the present invention, any electrostatic latent image carrier used in the conventional electrophotographic method can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

(Synthesis Example 1: Synthesis of crystalline polyester resin A)
1,6-hexanediol 0.8 mol and 1,5-pentanediol 0.2 mol as the alcohol component, fumaric acid 1 mol as the carboxylic acid component, tin octylate as the esterification catalyst, nitrogen introduction tube, dehydration Placed in a 5 liter four-necked flask equipped with a tube, a stirrer, and a thermocouple, subjected to a condensation polymerization reaction at 170 ° C. for 4 hours in a nitrogen atmosphere, then heated to 200 ° C. and allowed to react for 1 hour, Furthermore, the crystalline polyester resin A was synthesize | combined by making it react at 8 kPa for 1 hour. The compounds used for the synthesis of the crystalline polyester resin A are summarized in Table 1 below.

(Synthesis Example 2: Synthesis of crystalline polyester resin B)
In Synthesis Example 1, the alcohol component was changed to 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and instead of 0.1 mol of 1,5-pentanediol, 1,4-butane Crystalline polyester resin B was synthesized in the same manner as in Synthesis Example 1, except that 0.9 mol of diol was used and 1 mol of 1,8-octanedicarboxylic acid was used instead of 1 mol of fumaric acid. . The compounds used for the synthesis of the crystalline polyester resin B are summarized in Table 1 below.

(Synthesis Example 3: Synthesis of crystalline polyester resin C)
Synthesis Example 1 except that the amount of 1,6-hexanediol, which is an alcohol component, was changed from 0.8 mol to 1 mol and 0.2 mol of 1,5-pentanediol was not added in Synthesis Example 1. A crystalline polyester resin C was synthesized in the same manner as in Example 1. The compounds used for the synthesis of the crystalline polyester resin C are summarized in Table 1 below.

(Synthesis Example 4: Synthesis of crystalline polyester resin D)
In Synthesis Example 1, the alcohol component was replaced with 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and 1 mol of 1,4-butanediol was used. A crystalline polyester resin D was synthesized in the same manner as in Synthesis Example 1, except that 1 mol of 1,8 octanedicarboxylic acid was used instead of 1 mol of acid. The compounds used for the synthesis of the crystalline polyester resin D are summarized in Table 1 below.

(Synthesis Example 5: Synthesis of crystalline polyester resin E)
In Synthesis Example 1, the alcohol component was replaced with 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and 1 mol of 1,6-hexanediol was used. A crystalline polyester resin E was synthesized in the same manner as in Synthesis Example 1 except that 0.9 mol of fumaric acid and 0.1 mol of 1,8 octanedicarboxylic acid were used instead of 1 mol of acid. The compounds used for the synthesis of the crystalline polyester resin E are summarized in Table 1 below.

(Synthesis example 6: Polyester resin F)
In Synthesis Example 1, the alcohol component was replaced with 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and 0.7 mol of BPA-PO and 0.3 mol of BPA-EO were used. Polyester resin E was synthesized in the same manner as in Synthesis Example 1 except that 0.9 mol of terephthalic acid and 0.07 mol of trimetic anhydride were used instead of 1 mol of fumaric acid. The compounds used for the synthesis of the polyester resin E are summarized in Table 1 below.

<Confirmation of physical properties>
Number average molecular weight (Mn) of crystalline polyester resin A, crystalline polyester resin B, crystalline polyester resin C, crystalline polyester resin D, crystalline polyester resin E, and polyester resin F synthesized in Synthesis Examples 1-6, The weight average molecular weight (Mw), the flow tester T1 / 2, and the glass transition point (Tg) were measured by the following methods.
The solubility of crystalline polyester resin A, crystalline polyester resin B, crystalline polyester resin C, crystalline polyester resin D, crystalline polyester resin E, and polyester resin F synthesized in Synthesis Examples 1 to 6 in ethyl acetate Were also tested.

-Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw)-
Each resin synthesized in Synthesis Examples 1 to 6 was added to hexafluoroisopropanol (HFIP) [concentration 0.005 M (mol / L) -CF ₃ COONa / HFIP] to which sodium trifluoroacetate (CF ₃ COONa) was added. After dissolving at 0.06% (wt / vol), the solution was filtered through a 0.45 μm-Millex-LH (Millipore) filter to prepare a GPC sample. The sample thus prepared was measured using GPC under the following conditions. The results are shown in Table 2 below.
[GPC measurement conditions]
Apparatus: Gel permeation chromatograph GPC-7 (manufactured by Waters)
Column: Shodex HFIP-806M (inner diameter 8.0 mm / length 30 cm) × 2 (manufactured by Showa Denko KK)
Flow rate: 0.5 mL / min Temperature: 23 ° C
Injection volume: 300 μL
Detector: Differential refractive index detector R-401 (manufactured by Waters)
Molecular weight calibration: Monodisperse polymethyl methacrylate (PMMA) standard sample (manufactured by Showa Denko KK)

-Measurement of flow tester T1 / 2-
The flow tester T1 / 2 is the melting temperature in the 1/2 method.
A pellet-shaped sample is produced by pressure molding using 1.0 g of each of the resins synthesized in Synthesis Examples 1 to 6, and softened using a flow tester (elevated flow tester CFT500 type, manufactured by Shimadzu Corporation). The point (Tf1 / 2), the difference (Tend−Tfb) between the outflow start temperature (Tfb) and the outflow end temperature (Tend) was measured under the following conditions. The results are shown in Table 2 below.
[Flow tester measurement conditions]
Load: 30 kg / cm ²
Temperature increase rate: 3.0 ° C./min Die diameter: 0.50 mm,
Die length: 1.0mm
Tf1 / 2 calculation method: 1/2 method

-Measurement of glass transition point (Tg)-
Each of the resins synthesized in Synthesis Examples 1 to 6 was used in an amount of 10 mg, packed in an aluminum cell, and using a differential scanning calorimeter (DSC) (automatic differential scanning calorimeter DSC-60A, manufactured by Shimadzu Corporation), the following: It measured on condition of this. Note that Tg was the endothermic peak of the DSC curve at the second temperature rise or the endothermic start temperature of the endothermic shoulder (the temperature of the tangent before the endothermic start and the intersection after the endotherm). The results are shown in Table 2 below.
[Differential scanning calorimeter measurement conditions]
Measurement temperature: 0 ° C to 200 ° C
Temperature increase rate: 10 ° C / min

-Solubility in ethyl acetate-
Each resin synthesized in Synthesis Examples 1 to 6 was dissolved in 30 ° C. ethyl acetate according to the concentration, and it was judged whether or not it was visually dissolved, and what was left undissolved or turbid was produced. “X” means that all dissolved and became transparent, “◯”. The results are shown in Table 3 below.

It was confirmed that the crystalline polyester resin A, the crystalline polyester resin B, the crystalline polyester E, and the polyester resin F were dissolved in ethyl acetate.

(Preparation Example 1: Preparation of colorant dispersion)
20 parts by mass of carbon black (Regal 400, manufactured by Cabot) and 2 parts by mass of a pigment dispersant (Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd.) are primarily dispersed in 78 parts by mass of ethyl acetate using a mixer having stirring blades. I let you. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Further, a carbon black dispersion liquid was prepared by passing through a filter (manufactured by PTFE) having pores of 0.45 μm and dispersing to a submicron region.

(Preparation Example 2: Preparation of wax dispersion (release agent))
A container equipped with a stirring blade and a thermometer is charged with 20 parts by mass of carnauba wax and 80 parts by mass of ethyl acetate, heated to 85 ° C. and stirred for 20 minutes to dissolve the carnauba wax, and then rapidly cooled to obtain fine particles of carnauba wax. Precipitated. This dispersion was further finely dispersed by a strong shearing force using a bead mill (LMZ06, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm.
It was 0.56 micrometer when the weight average particle diameter of wax was measured using the laser diffraction / scattering type particle size distribution measuring apparatus (LA-950, Horiba, Ltd. make).

(Preparation Example 3: Preparation of crystalline polyester resin A solution)
10 parts by mass of the crystalline polyester resin A synthesized in Synthesis Example 1 and 90 parts by mass of ethyl acetate were charged, and the crystalline polyester resin A was completely dissolved at 30 ° C. This solution was kept at 30 ° C.

(Preparation Example 4: Preparation of solution of crystalline polyester resin B)
10 parts by mass of the crystalline polyester resin B synthesized in Synthesis Example 2 and 90 parts by mass of ethyl acetate were charged, and the crystalline polyester resin A was completely dissolved at 30 ° C. This solution was kept at 30 ° C.

(Preparation Example 5: Preparation of dispersion of crystalline polyester resin C)
In a container in which a stirring blade and a thermometer are set, 20 parts by mass of the crystalline polyester resin C synthesized in Synthesis Example 3 and 80 parts by mass of ethyl acetate are charged, heated to 85 ° C. and stirred for 20 minutes to dissolve the crystalline polyester resin C. Then, it was cooled rapidly to precipitate fine particles of crystalline polyester resin C. This dispersion was further finely dispersed by a strong shearing force using a bead mill (manufactured by Ashizawa Finetech Co., Ltd., LMZ06) filled with zirconia beads having a diameter of 0.3 mm to obtain a dispersion of crystalline polyester resin C. .
It was 0.73 micrometer when the weight average particle diameter of the dispersion liquid of the crystalline polyester resin C was measured by the method similar to the preparation example 2.

(Preparation Example 6: Preparation of dispersion of crystalline polyester resin D)
In Preparation Example 5, a crystalline polyester resin D dispersion was prepared in the same manner as in Preparation Example 5, except that the crystalline polyester resin D synthesized in Synthesis Example 4 was used instead of the crystalline polyester resin C. did.
It was 0.67 micrometer when the weight average particle diameter of the dispersion liquid of the crystalline polyester resin D was measured by the method similar to the preparation example 2.

(Preparation Example 7: Preparation of solution of crystalline polyester resin E)
10 parts by mass of the crystalline polyester resin B synthesized in Synthesis Example 2 and 90 parts by mass of ethyl acetate were charged, and the crystalline polyester resin A was completely dissolved at 30 ° C. This solution was kept at 30 ° C.

(Preparation Example 8: Preparation of polyester resin F solution)
20 parts by mass of polyester resin F and 80 parts by mass of ethyl acetate were charged, and polyester resin F was completely dissolved. This solution was kept at 30 ° C.

(Preparation Example 8: Preparation of toner composition liquid)
A solution of crystalline polyester resin A (Preparation Example 3), a solution of crystalline polyester resin B (Preparation Example 4), and a dispersion of crystalline polyester resin C so as to have the composition and addition amount shown in Table 4 below (Preparation Example 5), at least one of a dispersion of crystalline polyester resin D (Preparation Example 6), a dispersion of crystalline polyester resin E (Preparation Example 7), and a solution of polyester resin F (Preparation Example 8) The colorant dispersion (Preparation Example 1), the wax dispersion (Preparation Example 2) and ethyl acetate were mixed to obtain a toner composition liquid having a solid content of 10%. In order to remove coarse particles in each toner composition liquid, toner composition liquids 1 to 9 were obtained by passing through a filter (SBP-010, manufactured by Loki Techno Co., Ltd.) having an opening of 1 μm. The toner composition liquid had a liquid temperature of 25 ° C.

(Example 1-1)
<Preparation of toner base particles 1-1>
Liquid droplets were ejected from the toner composition liquid using the toner production apparatus shown in FIGS. 1 to 3 under the following conditions by a liquid droplet ejection head using the liquid column resonance principle shown in FIG. Thereafter, the liquid droplets were dried and solidified, collected by a cyclone, and then secondarily dried at 35 ° C. for 48 hours, whereby toner base particles 1-1 were produced.
[Liquid column resonance conditions]
Resonance mode: N = 2
Length between both ends in the longitudinal direction of the liquid column resonance liquid chamber: L = 1.8 mm
Height of end of frame on liquid common supply path side of liquid column resonance liquid chamber: h1 = 80 μm
The height of the communication port of the liquid column resonance liquid chamber: h2 = 40 μm
[Toner base particle preparation conditions]
Dispersion specific gravity: ρ = 1.1 g / cm ³
Discharge hole shape: perfect circle Discharge hole diameter: 7.5 μm
Number of discharge holes: 4 per liquid column resonance liquid chamber Minimum distance between adjacent discharge hole centers: 130 μm (all equally spaced)
Dry air temperature: 40 ° C
Applied voltage: 10.0V
Drive frequency: 395 kHz

<Preparation of Toner 1-1>
To 100 parts by mass of the toner base particles 1-1, 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) as a fluidity improver and titanium oxide (SMT-150AI, manufactured by Teika Co., Ltd.) 1 0.0 part by mass was subjected to an external addition process using a Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.) to obtain toner 1-1.

(Example 1-2)
<Preparation of toner base particles 1-2>
The toner composition liquid was converted to toner using the toner production apparatus shown in FIGS. 10A, 9A, and 9B. That is, droplets were ejected by vibrating a thin film having ejection holes under the following toner base particle production conditions. Thereafter, the liquid droplets were dried and solidified, collected by a cyclone, and then secondary dried at 35 ° C. for 48 hours to prepare toner base particles 1-2.
[Toner base particle preparation conditions]
Dispersion specific gravity: ρ = 1.1 g / cm ³
Discharge hole shape: perfect circle Discharge hole diameter: 7.5 μm
Number of discharge holes: 19 Shortest distance between adjacent discharge hole centers: 200 μm (all at equal intervals)
Dry air temperature: 40 ° C
Applied voltage: 45.0V
Drive frequency: 80 kHz

<Preparation of Toner 1-2>
To 100 parts by mass of the toner base particles 1-2, 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) as a fluidity improver and titanium oxide (SMT-150AI, manufactured by Teika Co., Ltd.) 1 0.0 part by mass was subjected to an external addition process using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain toner 1-2.

(Examples 2-1, 3-1, 4-1, 5-1, 6-1, 7-1, Comparative Examples 1-1, 2-1, 3-1)
In Example 1-1, Examples 2-1 and 3-1 were performed in the same manner as Example 1-1 except that the toner composition liquid shown in Table 5 below was used instead of toner composition liquid 1. 4-1, 5-1, 6-1 and 7-1 and toners 2-1, 3-1, 4-1, 5- in Comparative Examples 1-1, 2-1, and 3-1. 1, 6-1, 7-1, 8-1, 9-1 and 10-1 were produced.

(Examples 2-2, 3-2, 4-2, 5-2, 6-2, 7-2, Comparative Examples 1-2, 2-2, 3-2)
In Example 1-2, Examples 2-2 and 3-2 were performed in the same manner as Example 1-2 except that the toner composition liquid shown in Table 5 below was used instead of toner composition liquid 1. 4-2, 5-2, 6-2, and 7-2, and the toners 2-2, 3-2, 4-2, and 5- of Comparative Examples 1-2, 2-2, and 3-2 2, 6-2, 7-2, 8-2, 9-2, and 10-2 were prepared.

-Evaluation of particle size distribution-
The weight average particle diameter (Dw) and the number average particle diameter (Dn) of the toners 1-1 to 10-2 were measured with a particle size measuring device (Multisizer III, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. Analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10 mass% surfactant (alkylbenzene sulfonate Neogen SC-A, Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass beaker (100 mL volume). Next, 0.5 g of each toner was added, and after stirring with microspatel, 80 mL of ion-exchanged water was added. Subsequently, the dispersion process was carried out for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.).
This dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner dispersion was dropped so that the concentration indicated by Multisizer III was 8 ± 2%. The target particle size was 2.001 μm or more and 20.1874 μ or less.

After measuring the volume and number of toner particles or toner, the volume distribution and number distribution were calculated. From the obtained distribution, the weight average particle diameter (Dw) and number average particle diameter (Dn) of the toner were determined. The results are shown in Table 6.
As an index of the particle size distribution, Dw / Dn obtained by dividing the weight average particle diameter (Dw) of the toner by the number average particle diameter (Dn) was used. If it is completely monodispersed, Dw / Dn = 1, and the larger this value, the wider the distribution.

<Creation of carrier>
The following composition was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming liquid was coated on the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 40 μm using a fluid bed type coating apparatus to obtain a magnetic carrier.
[composition]
Silicone resin (organostraight silicone) 100 parts by mass Toluene 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by mass Carbon black 10 parts by mass

<Production of developer>
For each of toner 1-1 to toner 10-2, 4 parts by mass of black toner and 96 parts by mass of the magnetic carrier were mixed by a ball mill to prepare a two-component developer.
Each two-component developer was evaluated for the minimum fixing temperature and the hot offset property by the following method.

-Evaluation of minimum fixing temperature-
Each of the produced two-component developers is put in a commercially available copying machine (Imagiono 455, manufactured by Ricoh Co., Ltd.), and the fixing temperature is increased every 100 degrees to 10 degrees, and the image is printed on paper (type 6000 paper, manufactured by Ricoh Co., Ltd.). Was output. The output image was rubbed by hand, and the temperature at which the toner could not be peeled was evaluated as the minimum fixing temperature. The results are shown in Table 6 below.

-Evaluation of hot offset property-
Each of the produced two-component developers is put in a commercially available copying machine (Imagiono 455, manufactured by Ricoh Co., Ltd.), and an image is printed on paper (type 6000 paper, manufactured by Ricoh Co., Ltd.) while changing the fixing temperature from low temperature to high temperature. Output. The temperature at which the glossiness of the output image decreased or the temperature at which the offset image was recognized in the image was defined as the offset generation temperature, and the hot offset property was evaluated based on the following evaluation criteria. The results are shown in Table 6 below.
[Evaluation criteria]
○: Offset generation temperature is 200 ° C or more ×: Offset generation temperature is less than 200 ° C

-Evaluation of clogging of discharge holes-
When the toner base particles were produced, the droplet discharge head was observed with a CCD camera, and it was confirmed whether or not the discharged droplets were ejected from the discharge port, and the clogging of the discharge port was evaluated. The results are shown in Table 6 below.
[Evaluation criteria]
○: Continuous droplet formation was possible without clogging the discharge holes for 3 hours. Δ: Clogging occurred in less than 50% of the discharge holes in 1 hour. ×: Clogging occurred in 50% or more of the discharge holes in 1 hour.

-Evaluation of manufacturability-
In the toners 1-1 to 7-2 of Examples 1-1 to 7-2, the toner could be suitably formed into droplets without clogging the ejection holes in the continuous droplet formation for 3 hours.
On the other hand, in the toners 8-1 to 10-2 of Comparative Example 1-1 to Comparative Example 2-2, some of the ejection holes were clogged when the toner droplets were formed, and the toner could not be dropletized.
In Comparative Example 1-1, about 60% of the ejection holes were clogged in one hour, and the toner could not be formed into droplets. In Comparative Example 1-2, about 40% of the ejection holes were clogged in one hour, and the toner could not be formed into droplets. When the clogged discharge holes were analyzed, the crystalline polyester resin C was the main component.
In Comparative Example 2-1, about 70% of the ejection holes were clogged in one hour, and the toner could not be formed into droplets. In Comparative Example 2-2, about 50% of the ejection holes were clogged in one hour, and the toner could not be formed into droplets. Analysis of these clogged discharge holes revealed that crystalline polyester D was the main component.
In Comparative Examples 3-1 and 3-2, the toners 10-1 and 10-2 were able to form toner droplets without clogging the ejection holes in continuous droplet formation for 3 hours.

  The crystalline polyester resin in the ejection hole was analyzed by a microscopic laser Raman spectroscope and identified by comparing with each toner component.

From the results of Table 6 and the evaluation of manufacturability, the toners 1-1 to 7-2 of Examples 1-1 to 7-2 have good manufacturability, and the particle size distribution is Dw / Dn of 1.15 or less. A toner having a narrow small particle diameter was obtained, and it could be fixed at a low temperature and had good hot offset property.
On the other hand, although the toners 8-1 to 9-2 of Comparative Examples 1-1 to 2-2 had good hot offset properties, the discharge holes were clogged and there was a problem in productivity. In addition, the toners 10-1 and 10-2 of Comparative Examples 3-1 and 3-2 were good in manufacturability and hot offset property, but a toner having a low fixing minimum temperature of 150 ° C. and capable of being fixed at low temperature. Couldn't get.

The toner manufacturing method of the present invention is capable of stably discharging the toner composition liquid for a long time without clogging the discharge holes when discharging the toner composition liquid, so that it is excellent in toner productivity and has a narrow particle size distribution, A toner having a uniform and small particle size, excellent low-temperature fixability, and capable of forming an image with low power consumption, and a developer containing the toner can be obtained.
The toner and developer of the present invention can be suitably used for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing and the like.

1,210 Toner manufacturing apparatus 10, 104 Droplet forming unit (droplet forming means)
DESCRIPTION OF SYMBOLS 11, 312 Droplet discharge head 12 Air flow path 13, 201 Raw material container 14 Toner composition liquid 15 Liquid circulation pump 16, 202 Liquid supply pipe 17 Liquid common supply path 18 Liquid column resonance liquid chamber 19, 314 Discharge hole 20, 305 Vibration Means 21 Toner droplet 22 Liquid return tube 23 Unattached particles 24 Adhered particles 30 Dry collection unit (particle formation means)
31, 206 Chamber 32, 213 Toner collecting means 33 Downstream air 34 Toner collecting tube 35, 214 Toner storage means 44 Angle from liquid contact surface to discharge outlet in cross section of discharge hole 103 Shroud airflow outlet 104 Droplet forming unit 203 Liquid feed means 204 Valve 205 Shroud airflow 207 Primary transport airflow 208 Secondary transport airflow 209 Secondary transport airflow inlet 212 Guide pipe 300 Indirect vibration type discharge means 301 Piezoelectric body 302, 402 Electrode 303 Vibration generating means 304 Vibration amplifying means 306 Circuit 307 Drive signal generation source 308 Frame 309 Toner composition liquid supply port 310 Thin film 311 Liquid flow path 313 Vibration surface 315 Toner composition liquid discharge port 400 Direct vibration type discharge means 401 Annular piezoelectric body 403 Annular vibration generation means 500 Trajectory L liquid Both pillars The length from the end of the frame on the fixed end side to the end on the liquid common supply path 17 side in the liquid chamber 18 W The width of the liquid column resonance liquid chamber 18 h1 The height of the end of the frame on the liquid common supply path 17 side h1
h2 Height of communication port on liquid common supply path 17 side PG1, PG2, P1, P2 Pressure gauge

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 05-045929 A JP 11-249339 A JP 2001-117268 A JP 2001-222138 A

Claims (8)

A toner composition liquid preparation step for preparing a toner composition liquid in which a toner composition containing at least a binder resin and a release agent is dissolved or dispersed in an organic solvent;
A droplet forming step of discharging the toner composition liquid from at least one discharge hole to form droplets;
A drying step of drying and solidifying the organic solvent in the dropletized toner composition liquid,
The binder resin contains at least a crystalline polyester resin, and the crystalline polyester resin is dissolved in the toner composition liquid before being formed into droplets;
The weight average molecular weight of the crystalline polyester resin is a 15,000-20,000, and the glass transition temperature of the crystalline polyester resin is, Ri 50 ℃ ~67.3 ℃ der,
The crystalline polyester resin satisfies at least one of the following conditions (1) and (2) (provided that the crystalline polyester resin is composed of a crystalline part and an amorphous part, and the crystalline part is a polyurethane resin) excluding.) the toner manufacturing method, characterized in that.
(1) It contains two or more divalent alcohol components, and two of the divalent alcohol components are 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Two types to be selected.
(2) Two or more divalent acid components are contained, and two of the divalent acid components are fumaric acid and 1,8-octanedicarboxylic acid.   The droplet forming step imparts vibration to the toner composition liquid in the liquid column resonance liquid chamber in which at least one ejection hole is formed to form a standing wave by liquid column resonance, and the amplitude of the standing wave is maximum. The method for producing toner according to claim 1, wherein the toner composition liquid is ejected from the ejection holes formed at a wavelength of ± 1/3 from a position to a minimum position to form droplets.   The droplet forming step is a step of forming a droplet by applying vibration to a thin film in which a plurality of discharge holes having the same opening diameter is formed by vibration means, and discharging a toner composition liquid from the discharge holes. 2. The method for producing a toner according to 1. The method for producing a toner according to claim 1, wherein the binder resin contains 3% by mass to 50% by mass of a crystalline polyester resin. The toner production method according to claim 1, wherein the content of the release agent in the toner particles is 3% by mass to 20% by mass. The toner manufacturing method according to claim 2, wherein reflection wall surfaces are provided on at least a part of both ends in the longitudinal direction of the liquid column resonance liquid chamber. The toner manufacturing method according to claim 2, wherein, in the droplet forming step, a vibration having a frequency f that satisfies the following formula (3) is applied to the toner composition liquid.
f = N × c / (4L) (3) (where L is the length of the liquid column resonance liquid chamber in the longitudinal direction, c is the velocity of the sound wave of the toner composition liquid, and N is , Each representing an integer.) The toner production method according to claim 1, wherein the binder resin contains a resin other than the crystalline polyester resin, and the Tg of the resin other than the crystalline polyester resin is 50 ° C. to 70 ° C. 8.