JP2013218163A - Toner, method for producing the same, and developer - Google Patents

Abstract

A toner composition liquid can be stably discharged for a long time without clogging discharge holes, a toner having a narrow particle size distribution, a uniform and small particle size, and excellent in low-temperature fixability and heat-resistant storage stability can be obtained. Providing a toner manufacturing method.
A toner composition liquid preparing step of preparing a toner composition liquid in which a toner composition containing 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 forming droplets by discharging, a drying step of drying the organic solvent in the toner composition liquid that has formed the droplets, and particles obtained in the drying step have active hydrogen groups A collecting step of collecting in an aqueous medium containing the compound, wherein the binder resin contains two or more amorphous resins, and at least one of the amorphous resins is the active hydrogen group The toner is a non-crystalline resin having a site capable of reacting with a compound having at least one of the non-crystalline resins and an amorphous polyester resin.
[Selection figure] None

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 and the like are 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, it is required to use toner that melts at a low temperature 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 Patent Documents 5 to 8).
However, for further low-temperature fixing, it is necessary to lower the thermal characteristics of the binder resin, but the heat-resistant storage stability tends to deteriorate as the thermal characteristics of the binder resin decrease.

In order to solve the above-described problems at the same time, several proposals have been made so far. For example, in a method of granulating toner by discharging a toner composition liquid from discharge holes to form toner, the toner composition liquid It has been proposed to have a uniform particle size distribution and achieve both low-temperature fixability and heat-resistant storage stability by causing crosslinking or elongation reaction when the binder resin precursor therein is formed into droplets (patent) Reference 9-9).
However, in the above proposal, since the crosslinking or elongation reaction starts before the toner droplets are formed, it becomes difficult to form droplets due to an increase in the viscosity of the toner composition liquid, etc., resulting in clogging of the discharge portion. There is a problem that the toner cannot be produced stably for a long period of time. In order to solve the problem, the binder resin precursor and a compound that crosslinks or extends with the binder resin precursor are mixed immediately before droplet formation, and an apparatus for realizing the mixing is performed. This necessitates the production cost of toner. Furthermore, the proposal has a problem that it is difficult to form a toner having a structure in which the surface is covered with a layer whose strength is improved by the crosslinking or elongation reaction.

  Therefore, when discharging the toner composition liquid, the toner composition liquid can be stably discharged for a long time without clogging the discharge hole, the particle size distribution is narrow, uniform, small particle size, low temperature fixability and heat resistant storage stability. Toner manufacturing method capable of obtaining excellent toner, toner having narrow particle size distribution, uniform and small particle size, excellent low-temperature fixability and heat-resistant storage stability, and capable of forming an image with low power consumption, and At present, it is required to provide a developer containing toner.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can stably discharge the toner composition liquid for a long time without clogging the discharge holes, has a narrow particle size distribution, a uniform and small particle size, excellent low-temperature fixability and heat-resistant storage stability, and low power consumption. It is an object of the present invention to provide a toner manufacturing method capable of obtaining a toner capable of forming an image.

  As a result of intensive studies to achieve the above object, the present inventors have prepared a toner composition liquid in which a toner composition containing a binder resin and a release agent is dissolved or dispersed in an organic solvent. A preparation step, a droplet formation step of discharging the toner composition liquid from at least one discharge hole to form droplets, and drying for drying and solidifying the organic solvent in the toner composition liquid forming the droplets A step of collecting the particles obtained in the drying step in an aqueous medium containing a compound having an active hydrogen group, wherein the binder resin is an amorphous resin of two or more types Wherein at least one of the amorphous resins has a site capable of reacting with the compound having an active hydrogen group, and at least one of the amorphous resins is an amorphous polyester. In the manufacturing method of toner which is resin When the toner composition liquid is discharged, the toner composition liquid can be stably discharged for a long time without clogging the discharge hole, the particle size distribution is narrow, uniform and small particle size, and low temperature fixability and heat resistant storage stability. As a result, it was found that an excellent toner can be obtained, and the present invention has been completed.

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,
The toner production method of the present invention includes a toner composition liquid preparation step of preparing a toner composition liquid in which a toner composition containing a binder resin and a release agent is dissolved or dispersed in an organic solvent, and at least one ejection hole. A droplet forming step of discharging the toner composition liquid to form droplets, a drying step of drying the organic solvent in the toner composition liquid forming the droplets, and particles obtained in the drying step, A collection step of collecting in an aqueous medium containing a compound having an active hydrogen group, wherein the binder resin contains two or more types of amorphous resins, and at least one of the amorphous resins Is an amorphous resin having a site capable of reacting with the compound having an active hydrogen group, and at least one of the amorphous resins is an amorphous polyester resin.

  According to the present invention, it is possible to solve the above-described problems and achieve the above-mentioned object, stably discharge the toner composition liquid for a long time without clogging the discharge holes, narrow the particle size distribution, uniform and small. It is possible to provide a toner manufacturing method capable of obtaining a toner having an excellent particle size, low-temperature fixability and heat-resistant storage stability and capable of forming an image with low power consumption.

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. 10C is a view for explaining another example of the embodiment of the toner production method of the present invention. FIG. 11 is a schematic view showing an example of the structure of a droplet discharge unit that discharges droplets for carrying 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 production method)
The toner production method of the present invention includes a toner composition liquid preparation step, a droplet formation step, a drying step, and a collection step, and further includes other steps as necessary.
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 composition liquid 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 a binder resin and a release agent, and further contains other components as necessary.

-Binder resin-
The binder resin includes two or more kinds of amorphous resins, and may further include other resin components as necessary.
The binder resin other than the amorphous resin described later is not particularly limited, and can be appropriately selected from conventionally known binder resins for toner according to the purpose. For example, an epoxy resin having crystallinity. Resins, polyvinyl resins, polyester resins and the like can be mentioned.
Whether or not the resin has crystallinity, that is, whether or not it is amorphous can be confirmed, for example, by whether or not a peak exists in an X-ray diffraction pattern by a powder X-ray diffraction apparatus. As a specific example, in the case of a polyester resin, when the diffraction pattern has crystallinity when at least one diffraction peak exists at a position where 2θ is 19 ° to 25 °, and the diffraction peak does not exist. It can be confirmed that it is amorphous.
The powder X-ray diffraction measurement is performed using, for example, a powder X-ray diffractometer RINT1100 (manufactured by Rigaku Electric Co., Ltd.) using a wide-angle goniometer under conditions of Cu as a tube and tube voltage-current as 50 kV-30 mA. Can do.

--- Amorphous resin--
The amorphous resin is not particularly limited as long as it is two or more, at least one has a site capable of reacting with a compound having an active hydrogen group, and at least one is an amorphous polyester resin. It can be appropriately selected depending on the purpose, and examples thereof include amorphous polystyrene resin, (meth) acrylic resin, and polyester resin.

--- Amorphous resin (prepolymer) having a site capable of reacting with a compound having an active hydrogen group ---
The amorphous resin having a site capable of reacting with the compound having an active hydrogen group (hereinafter sometimes referred to as “prepolymer”) has a site capable of reacting with the compound having an active hydrogen group. If it is a thing, there will be no restriction | limiting in particular, It can select suitably from well-known resin, for example, a polyol resin, a polyacryl resin, a polyester resin, an epoxy resin, a butadiene resin, a styrene-butadiene resin, these derivative resins etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin having a functional group capable of being bonded with urethane or urea is preferable from the viewpoint of excellent low-temperature fixability of the toner, and a polyurethane-modified polyester resin (polyurethane-modified polyester resin) prepolymer is particularly preferable.

  The polyurethane-modified polyester resin is a polycondensate of a polyol and a polycarboxylic acid, and can be obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate. In this case, examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, an alcoholic hydroxyl group is preferable.

Examples of the polyol include a diol and a trivalent or higher polyol, and a diol alone or a mixture of a diol and a small amount of a polyol is preferable.
The diol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, Hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide) De, butylene oxide, etc.) adducts; alkylene oxide (ethylene oxide of the bisphenols, propylene oxide, and the like butylene oxide, etc.) adducts. These may be used individually by 1 type and may use 2 or more types together.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols, alkylene oxide adducts of the bisphenols and alkylene glycols having 2 to 12 carbon atoms, Is particularly preferable.

  The trivalent or higher polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a trihydric or higher polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Sorbitol, etc.); trivalent or higher phenols (trisphenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid include dicarboxylic acids and trivalent or higher polycarboxylic acids, and dicarboxylic acids alone and mixtures of dicarboxylic acids and a small amount of polycarboxylic acids are preferable.
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); Alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.) Aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), etc. Is mentioned.
In addition, as said polycarboxylic acid, you may make it react with a polyol (PO) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio between the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. The equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] In general, the ratio is 1/1 to 2/1, preferably 1/1 to 1.5 / 1, and more preferably 1.02 / 1 to 1.3 / 1.

  There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2, 6- diisocyanatomethyl caproate etc.); Alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.) Isocyanurates; those obtained by blocking the polyisocyanate with a phenol derivative, oxime, caprolactam or the like. These may be used individually by 1 type and may use 2 or more types together.

When obtaining a polyester-based prepolymer having an isocyanate group, the ratio of the polyisocyanate and the polyester-based resin having active hydrogen is not particularly limited and may be appropriately selected depending on the intended purpose. And the equivalent ratio [NCO] / [OH] of the hydroxyl group-containing polyester [OH] is usually 1/1 to 5/1, preferably 1.2 / 1 to 4/1, and 1.5 / 1 to 2.5 / 1 is more preferable.
There is no restriction | limiting in particular as content of the polyisocyanate (PIC) component in the prepolymer which has an isocyanate group at the terminal, Although it can select suitably according to the objective, Usually 0.5 mass%-40 mass% 1 mass% to 30 mass% is preferable, and 2 mass% to 20 mass% is more preferable.

  There is no restriction | limiting in particular as content in the said binder resin of the said prepolymer, Although it can select suitably according to the objective, 1 mass%-30 mass% are preferable, and 5 mass%-20 mass% are More preferably, 5% by mass to 18% by mass is even more preferable. When the content is less than 1% by mass, the reaction between the prepolymer and the compound having an active hydrogen group is not sufficient, and the effects of the present invention may not be obtained. When the content exceeds 30% by mass, May interfere with low-temperature fixability.

--- Compound having an active hydrogen group ---
The compound having an active hydrogen group (hereinafter also referred to as “active hydrogen group-containing compound”) is obtained by converting the prepolymer present in the toner outer shell portion into the active hydrogen in the collecting step in the toner production method of the present invention. It acts as an extender or a cross-linking agent when the group-containing compound is extended or cross-linked.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. Examples thereof include water and amines. Among these, amines are preferable in that they can be increased in molecular weight by elongation or cross-linking reaction with a prepolymer, and conventionally known amines can be suitably used.

  There is no restriction | limiting in particular as said amines, According to the objective, it can select suitably, For example, aliphatic diamines (C2-C18), aromatic diamines (C6-C20), etc. are mentioned, as needed. The polyamine more than trivalence used may be included.

As the aliphatic diamines (C2 to C18), for example,
[1] Aliphatic diamine (C2-C6 alkylene diamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) diamine [diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]);
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substitutes [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2, 5-hexamethylenediamine, methyliminobispropylamine, etc.];
[3] Aliphatic or heterocyclic-containing aliphatic diamine (alicyclic diamine (C4 to C15) [1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylenedicyclohexane diamine (hydrogenated methylene Dianiline), etc.], heterocyclic diamines (C4 to C15) [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4 bis (2-amino-2-methylpropyl) piperazine, 3, 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.];
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.);
Etc.

As aromatic diamines (C6-C20), for example,
[1]: unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine ), Diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylene Amines, etc.];
[2]: Aromatic diamine having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], for example, 2,4- and 2,6-tolylenediamine, Crudetolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl- 2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl- 2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′ , 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylsulfone, and the like, and isomers thereof Various proportions of mixtures;
[3]: Aromatic diamine [methylene bis-o-chloroaniline, 4-chloro-] having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group, etc.) o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5 -Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) Selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2- Fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.];
[4]: Aromatic diamine having a secondary amino group [a part or all of —NH 2 of the aromatic diamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group such as methyl Or a lower alkyl group such as ethyl)] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].
In addition to these, the diamine component is obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per 1 mol of acid) polyamine (alkylene diamine, polyalkylene polyamine etc.). And low molecular weight polyamide polyamines, etc.], polyether polyamines [hydride of cyanoethylated polyether polyols (polyalkylene glycols, etc.), etc.].

---- Amorphous polyester resin ---
The amorphous polyester resin is a polyester resin obtained by polyesterification of one or more polyols represented by the following general formula (1) and one or more polycarboxylic acids represented by the following general formula (2). It is amorphous.
A- (OH) _m ... General formula (1)
[In General Formula (1), A represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aromatic group that may have a substituent or a heterocyclic aromatic group, and m is an integer of 2 to 4. Represents. ]
B- (COOH) _n ... General formula (2)
[In General Formula (2), B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aromatic group that may have a substituent or a heterocyclic aromatic group, and n is an integer of 2 to 4 Represents. ]

  There is no restriction | limiting in particular as a polyol represented by the said General formula (1), According to the objective, it can select suitably, For example, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2- propylene glycol, 1, 3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

  There is no restriction | limiting in particular as polycarboxylic acid represented by the said General formula (2), According to the objective, it can select suitably, For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalate Acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid , N-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-di Ruboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empor trimer Examples include acids, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bis (trimellitic acid), and the like.

  There is no restriction | limiting in particular as an acid value of the said polyester resin, Although it can select suitably according to the objective, 10 mgKOH / g-50 mgKOH / g are preferable, and 15 mgKOH / g-40 mgKOH / g are more preferable. When the acid value is less than 10 mgKOH / g, the dispersion stabilizing effect during production may not be obtained, and when it exceeds 50 mgKOH / g, the environmental stability of the toner charging ability may be deteriorated. On the other hand, when the acid value is within the particularly preferable range, it is advantageous in terms of charging ability of the toner.

The acid value 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

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said polyester resin, Although it can select suitably according to the objective, 1,000-200,000 are preferable and 4,000-6,000 are more preferable. . When the weight average molecular weight is less than 1,000, the hot offset resistance may be lowered, and when it exceeds 200,000, the low-temperature fixing performance may be lowered. On the other hand, when the weight average molecular weight is in the more preferable range, it is advantageous in terms of low-temperature fixing and hot offset resistance.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) using THF as a solvent.

  There is no restriction | limiting in particular as content in the said binder resin of the said amorphous polyester resin, Although it can select suitably according to the objective, 50 mass%-100 mass% are preferable, 75 mass%-100 The mass% is more preferable. When the content is less than 50% by mass, the influence of other materials is increased, and the fixing characteristics may be deteriorated.

-Other resin components-
--- Crystalline polyester resin ---
There is no restriction | limiting in particular as said crystalline polyester resin, as long as it has crystallinity, According to the objective, it can select from well-known polyester resin suitably.
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. Therefore, the crystalline polyester resin used in the present invention is preferably one that dissolves 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.
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, by incorporating the crystalline polyester resin in the toner composition, it is advantageous in that further low-temperature fixing can be expected.

  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.
Examples of the divalent alcohol include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and derivatives thereof. It is done. These may be used alone or in combination of two or more.

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 according to the objective, 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.
Examples of the divalent acid include fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, and 1,12-dodecane. Examples thereof include diacids and derivatives thereof. These may be used alone or in combination of two or more.

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 acid, benzoic acid, pyruvic acid, etc. are mentioned. 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 glass transition temperature (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. The glass transition temperature (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 an analysis system of a 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. Therefore, in differential scanning calorimetry (DSC), it indicates a clear endothermic peak, not a stepwise 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 mgKOH / g-50 mgKOH / g are more preferable. When the acid value exceeds 70 mgKOH / g, the environmental fluctuation of charging may increase.
As described above, the acid value can be measured according to JIS K-0070.

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.

-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 usually used for toners can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sax. Aliphatic hydrocarbon waxes such as sol wax; 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 beeswax, lanolin, spermaceti; mineral waxes such as ozokerite, ceresin, and petrolatum; waxes based on fatty acid esters such as montanate ester wax and castor wax; deacidified carnauba wax, etc. Fatty acids Such as those deoxidizing part or all ester and the like.

  Examples of the waxes further include palmitic acid; stearic acid; montanic acid; saturated linear fatty acids such as linear alkyl carboxylic acids having a linear alkyl group; non-existent such as prandidic acid, eleostearic acid, and valinalic acid. Saturated fatty acids: Stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, long-chain alkyl alcohol and other saturated alcohols; polyhydric alcohols such as sorbitol; linoleic acid amide, olefinic acid amide, lauric acid Fatty acid amides such as amides; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, Unsaturated fatty acid amides such as' -dioleyl adipate amide and N, N'-dioleyl sepasin amide; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; wax grafted with aliphatic hydrocarbon wax using vinyl monomers such as styrene and acrylic acid; behenic acid monoglyceride, etc. Examples include partial ester compounds of fatty acids and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  More preferable examples of the waxes include, for example, polyolefins obtained by radical polymerization of olefins under high pressure; polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins; catalysts such as Ziegler catalysts and metallocene catalysts under low pressures. Polyolefins polymerized using radiation; polyolefins polymerized using radiation, electromagnetic waves or light; low molecular weight polyolefins obtained by thermally decomposing high molecular weight polyolefins; paraffin wax; microcrystalline wax; Fischer-Tropsch wax; Hydrocarbon wax synthesized by the method, the age method, etc .; a synthetic wax using a compound having one carbon atom as a monomer; a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group; a hydrocarbon wax Mixture of hydrocarbon wax having a functional group; styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, and graft modified wax with vinyl monomers such as maleic anhydride.

The above waxes having a sharp molecular weight distribution using a press sweating 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 preferably used. Further, those obtained by removing low molecular weight solid fatty acid, low molecular weight solid alcohol, low molecular weight solid compound and other impurities from the waxes are also 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 and the toner are difficult to release during fixing, and offset may be easily generated. When the content exceeds 20% by mass. , The strength of the toner may be weakened and the 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, there are toners that do not contain a colorant, such as clear toner, for the purpose of imparting gloss to the image and protecting the image. 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.

  The colorant is not particularly limited, and can be appropriately selected from those usually used in toners. 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 Fayce Red, Parachlor Ortho Nitroaniline Red, Risor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing 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 , Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid gree Nlake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said colorant, Although it can select suitably according to the objective, As content in the toner solidified in the drying process mentioned later, 1 mass%-15 mass% are preferable. 3 mass%-10 mass% are more preferable.

The colorant can also be used as a master batch combined with a binder resin.
As the binder resin used for the production of the masterbatch or kneaded with the masterbatch, the same resin as the binder resin can be used. Besides, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene Polymers of styrene such as styrene and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer Polymer, 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-chlorometac Methyl formate copolymer, Styrene-acrylonitrile copolymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid Styrene copolymers such as copolymers and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used alone or in combination of two or more.

  The masterbatch can be obtained by mixing and kneading a colorant and a binder resin for the masterbatch with a high shear force. At that 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 the mixing and kneading, a high shearing dispersion device such as a three-roll mill can be suitably 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, and the dispersibility of the colorant may be insufficient.
The acid value can be measured, for example, according to JIS K0070.

The amine 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 1 mgKOH / g to 100 mgKOH / g, 10 mgKOH / g to 50 mgKOH / g is more preferable. If the amine value is less than 1 mg KOH / g or more than 100 mg KOH / g, the dispersibility of the colorant 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, A thing with high compatibility with binder resin is preferable at the point of the dispersibility of a coloring agent.
Examples of the dispersant include, for example, “Azisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by Big Chemie Co., Ltd.), and “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 conversion mass in gel permeation chromatography, 500 to 100,000 is preferable, and from the viewpoint of dispersibility of the colorant, 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 content 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 content of the dispersant is less than 1 part by mass, the dispersibility may be lowered, and when it exceeds 200 parts by mass, the chargeability may be reduced.

---- 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.

  Examples of the charge control agent include commercially available product names such as bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, bontron S-34 of a metal-containing azo dye, and an oxynaphthoic acid metal complex. E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above , Manufactured by Hodogaya Chemical 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, Hoechst) LRA-901, LR-147 (Nippon Kaichi) Other examples include copper phthalocyanine; perylene; quinacridone; azo pigments; polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. .

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the type of binder resin, the presence or absence of an external additive used as necessary, the toner production method including a dispersion method, and the like. However, with respect to 100 parts by mass of the binder resin, 0.1 part by mass to 10 parts by mass is preferable, and 0.2 part by mass to 5 parts by mass is more preferable. If the content 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, the binder resin can be dissolved, and the dispersion containing the binder resin and the release agent can be stably dispersed. An organic solvent that can be dried 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, and toluene are preferable in terms of high solubility of the crystalline polyester.

<< Method for Preparing 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 contained as necessary in the toner composition may be melt-kneaded 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.
For example, (1) the toner composition liquid in the liquid column resonance liquid chamber in which at least one ejection hole is formed is vibrated by vibration means. A mode in which a standing wave due to liquid column resonance is applied to form a droplet by ejecting the toner composition liquid from the ejection hole formed in the antinode of the standing wave (hereinafter referred to as “liquid”). (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. (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 flying 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 colorant are contained as a component of the toner composition liquid, there is a possibility that the discharge 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, leading to deterioration of the toner particle size distribution. is there.
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.
Specifically, 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 hole 19 formed in the wall 41 of the liquid column resonance liquid chamber in FIG. 2A may have a shape as shown in FIGS. Good.
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 of the discharge hole 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. There is no restriction | limiting in particular as an opening arrangement position of the discharge hole formed in the wall 41 of a liquid column resonance liquid chamber, 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 the sound wave of the liquid, for example, a metal member such as aluminum or stainless steel, a member such as silicone, or the like.

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, such materials include metals, ceramics, silicones and the like.

  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 controlled individually 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 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 with 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. As shown in equations 4 and 5, which will be described later, 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, or 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 having a form as shown in FIGS. 5A to G is generated by superposition of waves. 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 ejection hole 19 decreases, and the toner droplet 21 is ejected 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 toner 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 step shown in FIG. 3 is performed by liquid column resonance mainly includes a droplet forming unit 10 (droplet forming means) and a drying collection unit 30 (particle forming means). Have.
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 collection container 35 containing an aqueous solution of a compound containing an active hydrogen group, which collects dried and solidified toner particles that have passed through a toner collecting tube 34 communicating with the chamber 31. ing.

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 is passed through the liquid supply pipe 16 by a liquid circulation pump 15 for circulating the toner composition liquid 14, and then 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.
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 apply 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, a piezoelectric body that excites bimorph-type flexural vibration in the thin film is preferable.
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, a piezoelectric body that excites bimorph-type flexural vibration in the thin film is preferable. 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 propagate the vibration generated by the vibration means to the thin film 310 having a plurality of discharge holes 314 facing the liquid flow path 311 in the droplet discharge head 312. Then, the thin film 310 is periodically vibrated, a plurality of discharge holes 314 are arranged in a relatively large area, and droplets are periodically and stably formed and discharged from the plurality of discharge holes 314. Will be able to.

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). 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. As shown in FIGS. 8B and 9B, the ejection hole 314 is disposed at the center of the thin film 310 of the droplet ejection head 312.
8B and 9B, the plurality of discharge holes are arranged in a concentric regular hexagonal shape, but this arrangement is not particularly limited and can be appropriately selected according to 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 cycle is 20 kHz or more, the dispersion of the fine particles such as the colorant and the 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. In the liquid droplet forming unit 104 shown on the left side, the right side The liquid supply path is exactly the same as that of the droplet forming unit 104 shown in FIG.

  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 ejection hole, and if P1 <P2, gas may enter the ejection means and the ejection may stop. ≈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.

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 to the piezoelectric body 301 between the electrodes 302 of the vibration generating means 303 to excite vibrations in the vibration generating means 303, and this vibration is amplified by the vibration amplifying means 304 and arranged in parallel with the thin film 310. The vibration surface 313 vibrates periodically, and the thin film 310 vibrates at a required frequency by the periodic pressure due to 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.

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 drying the organic solvent in the toner composition liquid formed into droplets in the droplet forming step to form particles.
The method for drying the droplets is not particularly limited as long as the droplets can be made into particles, and a known method can be appropriately selected according to the purpose. For example, the organic solvent contained in the droplets is evaporated into a dry gas. And a method of shrinking and solidifying by drying.

As the content of the organic solvent in the particles obtained in the drying step, liquid droplets are formed into particles, and in the next collecting step, crosslinking is performed between the prepolymer in the particles and the active hydrogen group-containing compound. There is no particular limitation as long as the extension reaction proceeds, and it can be appropriately selected according to the purpose, but 5% by mass to 15% by mass is preferable. When the content is less than 5% by mass, the crosslinking or elongation reaction may not proceed in the next collection step, and when it exceeds 15% by mass, the droplets may not be sufficiently formed into particles.
Here, the content of the organic solvent is, for example, the difference between the mass of the particles obtained in the drying step and the mass when the particles are heated at a temperature equal to or higher than the boiling point of the organic solvent using an oven. It can be obtained by measuring the amount of.

The content of the organic solvent in the particles can be set to the preferred range by appropriately adjusting conditions such as the size of the droplets, the air velocity, the transport distance, the drying temperature, and the drying time.
The conditions cannot be uniquely determined depending on the composition of the toner composition liquid, but the droplet size is preferably 3 μm to 10 μm, the air velocity is preferably 1 m / s to 5 m / s, and the transport distance is 1 m to 5 m is preferable, the drying temperature is preferably 20 ° C. to 50 ° C., and the drying time is preferably 0.5 seconds to 2.5 seconds.

  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.

  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 in a laminar state on the spiral airflow. In the present invention, the dried and formed toner particles are collected in an aqueous medium containing a compound containing an active hydrogen group even when the toner particles are collected at a predetermined place by the toner collecting means. During this period, it is included in the drying process.

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 by the droplet forming process is conveyed from the raw material container 201 to the droplet forming unit 104 by 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 of a primary conveyance airflow, Although it can select suitably according to the objective, Although it is preferable that it is the same as that of a droplet discharge speed or it is faster than it, it does not need to be significantly quick. . 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.

  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 °. The angle of the next transport airflow 208 is preferably less than 120 ° with respect to the primary transport airflow 207, more preferably 45 ° or more and less than 100 °, and particularly preferably 60 ° or more and 90 ° or less. If the angle is 120 ° or more, the discharged toner droplets 21 return to the discharge unit side by the secondary transport airflow 208, so that the toner droplets 21 are likely to adhere to the droplet discharge head 312. The adhering liquid droplets block the discharge hole 314, so that the discharge may stop. Further, if the angle is less than 45 °, the effect of reducing the coalescence probability generated when the ejection direction of the toner droplet 21 is forcibly bent is small.

  There is no restriction | limiting in particular as the airflow speed V of the secondary conveyance airflow 208, Although it can select suitably according to the objective, Ratio of the airflow speed V of the secondary conveyance airflow 208 with respect to the airflow speed H of the primary conveyance airflow 207 (V / H) is preferably 0.5 to 3.0, more preferably 0.75 to 2.0, and even more preferably 1.0 to 1.5 in terms of preventing adhesion of the toner droplets 21. preferable. When the ratio V / H is less than 0.5, the effect of forcibly bending the discharge direction by the secondary transport airflow inlet 209 may be weak and the effect of preventing coalescence may be small, and if it exceeds 3.0 In addition, since the ejection trajectory of the toner droplets 21 ejected in the horizontal direction 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 due to drying of the toner 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 with the probability of coalescence kept low, and become dry particles 23 that are not coalesced. The dry particles 23 are collected in an aqueous medium containing a compound having an active hydrogen group in the subsequent collection step.

  The particle size distribution of the toner thus obtained is, for example, as shown in FIG. This is an example of 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. As a result, dry particle 24 is 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 toner particles 21 that did not coalesce with the dry particles that form the peak indicated by the basic particle diameter in the figure are dried and solidified as they are. The dry particles forming the peak described as two are obtained by drying and solidifying after two toner droplets 21 are joined after ejection. Similarly, it can be inferred from the particle size distribution measurement results that three, four, or more coalescences have progressed.

  A toner manufacturing apparatus 210 shown in FIG. 10A has a dry collection unit 220 and a chamber 206 that is a space for discharging toner droplets. The droplet forming unit 104 shown in FIG. It is. 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 are no particular restrictions on the flow direction of the liquid, and it can be set as appropriate. However, dry particles formed by drying the droplets in the chamber 206 are less likely to adhere to the walls of the chamber 206, and may flow downward from above. preferable.

A droplet (not shown) ejected from the droplet forming unit 104 is ejected in the direction of the primary transport airflow 207, and then the direction is forcibly bent by the secondary transport airflow 208. Draw a locus as shown, can prevent the adhesion of the droplets, from the volatilization of the organic solvent contained in the droplets during the transport in the primary transport airflow 207, secondary transport airflow 208, Particle coalescence can be prevented and dry particles with a narrow particle size distribution are generated 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 means 213, and are collected in a recovery container 214 containing an aqueous solution of a compound containing active hydrogen groups. As the toner collecting means 213, a general apparatus can be used, and a cyclone collecting machine is preferably used.

10B and 10C are schematic views 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 in FIG. 10B, four droplet forming units 104 are arranged in the chamber 206, all of which discharge droplets toward the center of the chamber 206, and are discharged by a primary conveying airflow 207 that conveys the droplets. It is shown that all of the toner droplet trajectories 500 are directed toward the center of the chamber 206, and while moving toward the center, the droplets are conveyed downward by a secondary conveyance air flow (not shown).
In the chamber 206 in FIG. 10C, four droplet forming units 104 are disposed in the chamber 206, but are disposed at an angle with respect to the center. The droplets are ejected in a direction deviating from the center of the chamber 206, and the trajectory 500 of the discharged toner droplets is all deviated from the center of the chamber 206 by the primary conveying airflow 207 that conveys the droplets. It is shown that you are heading. By providing an angle to the droplet forming unit 104, it is not necessary to consider the coalescence with droplets discharged from the opposing discharge unit, and the volume of the chamber 206 can be used efficiently. It is suitable for the arrangement. The angle with respect to the center of the droplet forming unit 104 can be arbitrarily adjusted.

<Collection process>
The collection step is a step of collecting the particles obtained in the drying step in an aqueous medium containing a compound having an active hydrogen group.
In the collecting step, the prepolymer contained in the toner composition and the compound having an active hydrogen group undergo a crosslinking or elongation reaction to form a crosslinked or elongated polymer. For this reason, the said collection process can be paraphrased as a bridge | crosslinking thru | or extension reaction process.
The toner base particles obtained in the collecting step have the active hydrogen group in a site that can react with the compound having the active hydrogen group derived from the prepolymer present in the outer shell of the particle obtained in the drying step. It has a structure covered with a layer with improved strength by crosslinking or elongation reaction with the compound. A toner having such a structure can achieve both low-temperature fixability and heat-resistant storage stability.

  A method for collecting the particles obtained in the drying step is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a compound having an active hydrogen group at the most downstream of the toner collecting means. And a method of attaching the collection container containing the aqueous medium containing, and collecting the particles obtained in the drying step.

  The compound having an active hydrogen group is as described above.

  The aqueous medium is not particularly limited as long as it can dissolve the compound having an active hydrogen group and does not dissolve dry particles, and can be appropriately selected from known ones according to the purpose. Alcohol miscible with water, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and the like, and mixtures thereof. Among these, water is particularly preferable.

The aqueous medium containing the compound having an active hydrogen group can be prepared, for example, by adding the compound having an active hydrogen group to the aqueous medium and stirring and mixing.
The content of the compound having an active hydrogen group in the aqueous medium varies depending on the type of the compound having an active hydrogen group and cannot be uniquely determined, but is preferably 1% by mass to 20% by mass, and preferably 5% by mass. % To 10% by mass is more preferable. If the content is less than 1% by mass, crosslinking or elongation reaction may not be sufficient, and if it exceeds 20% by mass, adsorption to the surface of the particles often occurs, which may adversely affect the charging performance. .

  The reaction time for the crosslinking or elongation reaction is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of achieving both reactivity and productivity, 1 to 72 hours are preferable, and 12 to 36 hours. Time is more preferred. When the reaction time is less than 1 hour, the crosslinking or extension reaction may not be sufficient. When it exceeds 72 hours, it takes too much time to produce the toner, and the productivity is lowered.

  The reaction temperature of the crosslinking or elongation reaction is not particularly limited and can be appropriately selected according to the purpose, but is preferably 25 ° C. to 50 ° C. from the viewpoint of securing the amount of energy used and the reactivity during production, 30 to 40 degreeC is more preferable. When the temperature is less than 25 ° C., the reaction may not proceed satisfactorily, and when it exceeds 50 ° C., the toner base particles may be dissolved.

<< Other processes >>
The other step is not particularly limited and may be appropriately selected depending on the purpose. If necessary, the particles collected in the collecting step may be further subjected to a secondary step such as fluidized bed drying or vacuum drying. It is preferable to have a secondary drying step of drying.
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 a binder resin and a release agent, and further contains other components as necessary.
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.

<< Flowability 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 silica such as silica and dry process silica; fine powder unoxidized titanium; fine powder unalumina; treated silica, treated titanium oxide, treated alumina with surface treatment with silane coupling agent, titanium coupling agent or silicone oil Etc. These may be used alone or in combination of two or more.
Among these, fine powder silica, fine powder unoxidized titanium oxide, and fine powder unalumina are preferable, and treated silica obtained by surface-treating the fine powder silica with a silane coupling agent or silicone oil is more preferable.

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

  The silica fine powder produced by vapor phase oxidation of a silicon halogen compound may be appropriately prepared, or a commercially available product may be used. Examples of the commercially available product include AEROSIL-130 and AEROSIL- 300, AEROSIL-380, AEROSIL-TT600, AEROSIL-MOX170, AEROSIL-MOX80, AEROSIL-COK84 (above, manufactured by 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 (WACK ER-CHEMIE); D-CFineSi1ica (Dow Corning); Franco1 (Fransi1).

  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, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, having 2 to 12 siloxane units per molecule Silicone such as dimethylpolysiloxane and dimethylsilicone oil containing 0 to 1 hydroxyl groups bonded to Si in units located at the end Yl, and the like. 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 and particle size distribution of the said polymer fine particle, Although it can select suitably according to the objective, As a weight average particle diameter, 0.01 micrometer-1 micrometer are preferable, and a particle size distribution is narrow Is preferred.

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 toner of this invention, Although it can select suitably according to the objective, 1 micrometer-10 micrometers are preferable, and 3 micrometers-6 micrometers are more preferable. If the weight average particle diameter of the toner is less than 1 μm, the cohesive force and power of the toner will be too high, it will be difficult to transfer 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 weight average particle size (Dw) and the number average particle size (Dn), and can be expressed as Dw / Dn.
A general pulverized toner has a Dw / Dn of about 1.15 to 1.25. Further, a general polymerization toner has Dw / Dn = 1.10 to 1.15. However, in an electrophotographic system, a narrow particle size distribution is required for a development process, a transfer process, and a fixing process. Such a broadening of the particle size distribution is undesirable.
On the other hand, the Dw / Dn of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. To 1.15 is preferable, 1.00 to 1.12 is more preferable, and 1.00 to 1.09 is particularly preferable.
In addition, when Dw / Dn is 1.00, it shows that all the particle sizes are the same, and it shows that a particle size distribution is so wide that Dw / 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 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%-5 mass% with respect to 100 mass parts of resin coat carriers Is preferable, and 0.1% by mass to 1% by mass is more preferable.

  There is no restriction | limiting in particular as a usage example which coat | covers a carrier core particle (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 of amorphous resin>
<< Synthesis Example 1: Synthesis of Prepolymer A1 >>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, bisphenol A ethylene oxide 2-mole adduct, isophthalic acid, adipic acid, and trimellitic anhydride are mixed in a molar ratio of hydroxyl group to carboxyl group, OH / COOH. 1.3, the component ratio of the diol component is 100 mol% of bisphenol A ethylene oxide 2-mol adduct, the component ratio of the dicarboxylic acid component is 80 mol% of isophthalic acid and 20 mol% of adipic acid, and trimellitic anhydride content in all monomers Titanium tetraisopropoxide (1,000 ppm by mass with respect to the resin component) was added so that the amount was 1 mol%. The condensation reaction was carried out at 210 ° C. for 8 hours under normal pressure and nitrogen stream.
Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 mmHg to 15 mmHg, then cooled to 80 ° C., and reacted with isophorone diisocyanate in ethyl acetate for 5 hours to obtain [Prepolymer A]. At this time, OH / NCO was set to 2.2.
The obtained prepolymer had a weight average molecular weight (Mw) of 25,000 and a solid content of 50% by mass. The weight average molecular weight was measured by gel permeation chromatography (GPC; solid content concentration 2 mass%) using THF as a solvent.

<< Synthesis Example 2: Synthesis of Prepolymer A2 >>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, bisphenol A ethylene oxide 2-mole adduct, isophthalic acid, adipic acid, and trimellitic anhydride are mixed in a molar ratio of hydroxyl group to carboxyl group, OH / COOH. 1.3, the component ratio of the diol component is 100 mol% of bisphenol A ethylene oxide 2-mol adduct, the component ratio of the dicarboxylic acid component is 80 mol% of isophthalic acid and 20 mol% of adipic acid, and trimellitic anhydride content in all monomers Titanium tetraisopropoxide (1,000 ppm by mass with respect to the resin component) was added so that the amount was 1 mol%. The condensation reaction was carried out at 210 ° C. for 8 hours under normal pressure and nitrogen stream.
Subsequently, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 mmHg to 15 mmHg, then cooled to 80 ° C., and reacted with isophorone diisocyanate in ethyl acetate for 5 hours to obtain [Prepolymer B]. At this time, OH / NCO was set to 3.0.
The obtained prepolymer had a weight average molecular weight (Mw) of 13,000 and a solid content of 49.5% by mass.

<< Synthesis Example 3: Prepolymer A3 >>
As a styrene-butadiene copolymer (SBR) prepolymer, a prepolymer (TP-2001, solid content 50.0% by mass) manufactured by Nippon Soda Co., Ltd. was used.

<< Synthesis Example 4: Synthesis of Polyester Resin B >>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 66.0 parts by mass of an ethylene oxide 2-mole adduct of bisphenol A, 2.3 parts by mass of propylene glycol, 2.4 parts by mass of trimellitic anhydride, and dibutyltin 0.2 parts by mass of oxide was added and reacted at 170 ° C. for 1 hour under normal pressure. Next, 31.5 parts by mass of adipic acid was added, reacted at 230 ° C. under normal pressure for 4 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain polyester resin B. The obtained polyester resin B had a glass transition temperature (Tg) of 28.9 ° C. The Tg was measured using a differential scanning calorimeter (DSC 6220 ASD-2, manufactured by SII).

<Synthesis of crystalline polyester resin>
<< Synthesis Example 5: Synthesis of crystalline polyester resin C1 >>
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, and then raised the temperature to 200 ° C. for 1 hour, Furthermore, the crystalline polyester resin C was synthesize | combined by making it react at 8 kPa for 1 hour. The obtained crystalline polyester resin C1 had a weight average molecular weight (Mw) of 17,000 and a Tg of 52.6 ° C.

<< Synthesis Example 6: Synthesis of Crystalline Polyester Resin C2 >>
In Synthesis Example 5, the alcohol component was changed from 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol to 0.7 mol of bisphenol A propylene oxide adduct (BPA-PO) and bisphenol A ethylene. Synthesis Example 5 except that the oxide adduct (BPA-EO) was changed to 0.3 mol and the carboxylic acid component was changed from 1 mol of fumaric acid to 0.9 mol of terephthalic acid and 0.07 mol of trimetic anhydride. Similarly, a crystalline polyester resin C2 was synthesized. The obtained crystalline polyester resin C2 had a weight average molecular weight (Mw) of 95,000 and a Tg of 60.3 ° C.

<Preparation Example 1: Preparation of colorant dispersion>
First, 20 parts by mass of carbon black (Regal 400, manufactured by Cabot) and 2 parts by mass of a dispersant (Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd.) are dispersed in 78 parts by mass of ethyl acetate using a mixer having stirring blades. It was. 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 colorant dispersion was prepared by passing through a filter (made of PTFE) having pores of 0.45 μm and dispersing to a submicron region.

<Preparation Example 2: Preparation of mold release agent (wax) dispersion>
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: Dissolution of polyester resin B>
9 parts by mass of ethyl acetate was mixed with 1 part by mass of the polyester resin B, and the resin was completely dissolved to prepare a solution of the polyester resin B.

<Preparation Example 4: Preparation of solution of crystalline polyester resin C1>
10 parts by mass of the crystalline polyester resin C1 synthesized in Synthesis Example 5 and 90 parts by mass of ethyl acetate were charged, and the crystalline polyester resin C1 was completely dissolved at 30 ° C. This solution was kept at 30 ° C.

<Preparation Example 5: Preparation of solution of crystalline polyester resin C2>
10 parts by mass of the crystalline polyester resin C2 synthesized in Synthesis Example 6 and 90 parts by mass of ethyl acetate were charged, and the crystalline polyester resin C2 was completely dissolved at 30 ° C. This solution was kept at 30 ° C.

<Preparation Example 6: Preparation of toner composition liquid>
The prepolymers A1 to A3, the polyester resin B solution, the crystalline polyester resin C1 solution, the crystalline polyester resin C2 solution, the colorant dispersion, and the wax dispersion so as to have the composition and blending amount shown in Table 1 below. , And ethyl acetate were mixed to obtain a toner composition liquid having a solid content of 10% by mass. 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. In addition, the unit of the numerical value of Table 1 is a mass part.

<Preparation of aqueous solution of compound having active hydrogen group and preparation of collection container>
<< Isophoronediamine aqueous solution >>
By adding 90 parts by mass of ion-exchanged water to 10 parts by mass of isophorone diamine, a 10% by mass isophorone diamine aqueous solution was prepared. 100 g of the aqueous solution was put into a 200 mL ointment bottle to make a recovery container.

<< Ammonia aqueous solution >>
A commercially available 10% (mass / volume) ammonia aqueous solution (manufactured by Kishida Chemical Co., Ltd.) was diluted with 50 parts by mass of ion-exchanged water to prepare a 5% (mass / volume) aqueous ammonia solution. 100 g of the aqueous solution was put into a 200 mL ointment bottle to make a recovery container.

Example 1
<Preparation of toner base particles 1-1>
Using the toner manufacturing apparatus shown in FIG. 3, the toner composition liquid 1 was ejected by the liquid droplet ejection head using the liquid column resonance principle shown in FIGS. 4A and 4B under the following conditions (droplet formation process) ). Thereafter, the droplets were dried (drying step), and the obtained particles were collected with a cyclone in a recovery container containing an aqueous solution of a compound having an active hydrogen group attached to a toner collection tube. In the collection container, the particles and the compound having an active hydrogen group are reacted at 40 ° C. for 24 hours (collecting step), and then the obtained particles are dried at 35 ° C. for 48 hours (secondary drying step). Thus, toner base particles 1-1 were produced. Here, the compound having an active hydrogen group contained in the recovery container was isophoronediamine.
Moreover, content of the organic solvent in the particle | grains obtained at the said drying process was 11.2 mass%. The content of the organic solvent was determined by weighing 1 g of the particles in an aluminum cup, weighing the residue after heating at 150 ° C. for 1 hour using an oven, and determining the weight loss as the amount of organic solvent.
[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 gas temperature: 40 ° C
Gas type: Nitrogen Airflow velocity: 2m / s
Transport distance: 2m
Drying time: 1 second
Applied voltage: 10.0V
Drive frequency: 395 kHz

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

(Example 2)
<Preparation of toner base particles 1-2>
Toner base particles 1-2 were produced from the toner composition liquid 1 using the toner production apparatus shown in FIGS. 9A, 9B and 10A. That is, droplets were ejected by vibrating a thin film having ejection holes under the toner base particle production conditions shown below (droplet formation step). Thereafter, the droplets were dried (drying step), and the obtained particles were collected with a cyclone in a recovery container containing an aqueous solution of a compound having an active hydrogen group attached to a toner collection tube. In the collection container, the particles and the compound having an active hydrogen group are reacted at 40 ° C. for 24 hours (collecting step), and then the obtained particles are dried at 35 ° C. for 48 hours (secondary drying step). Thus, toner base particles 1-2 were produced. Here, the compound having an active hydrogen group contained in the recovery container was isophoronediamine.
Moreover, it was 9.5 mass% when content of the organic solvent in the particle | grains obtained at the said drying process was measured like the said Example 1. FIG.
[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 gas temperature: 40 ° C
Gas type: Nitrogen Airflow velocity: 2m / s
Transport distance: 1.5m
Drying time: 0.75 seconds Applied voltage: 45.0V
Drive frequency: 80 kHz

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

(Example 3)
A toner 2-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 2 in Example 1.

Example 4
In Example 2, a toner 2-2 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 2 and the compound having an active hydrogen group was changed from isophoronediamine to ammonia. .

(Example 5)
A toner 3-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 3 and the compound having an active hydrogen group was changed from isophoronediamine to ammonia in Example 1. .

(Example 6)
A toner 3-2 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 3 in Example 2.

(Example 7)
A toner 4-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 4 in Example 1.

(Example 8)
In Example 2, a toner 4-2 was obtained in the same manner as in Example 2, except that the toner composition liquid 1 was changed to the toner composition liquid 4.

Example 9
A toner 5-1 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 5 in Example 1.

(Example 10)
A toner 5-2 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 5 in Example 2.

(Example 11)
A toner 6-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 6 in Example 1.

(Example 12)
In Example 2, Toner 6-2 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 6 and the compound having an active hydrogen group was changed from isophoronediamine to ammonia. .

(Example 13)
A toner 7-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 7 and the compound having an active hydrogen group was changed from isophoronediamine to ammonia in Example 1. .

(Example 14)
In Example 2, a toner 7-2 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 7.

(Example 15)
A toner 9-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 9 in Example 1.

(Comparative Example 1)
A toner 8-1 was obtained in the same manner as in Example 1 except that the toner composition liquid 1 was changed to the toner composition liquid 8 in Example 1.

(Comparative Example 2)
In Example 2, a toner 8-2 was obtained in the same manner as in Example 2 except that the toner composition liquid 1 was changed to the toner composition liquid 8.

(Comparative Example 3)
Toner 1-3 was obtained in the same manner as in Example 1, except that the aqueous solution of the compound having an active hydrogen group in the recovery container in Example 1 was changed to ion-exchanged water.

(Comparative Example 4)
In Example 2, a toner 2-3 was obtained in the same manner as in Example 2 except that the aqueous solution of the compound having an active hydrogen group in the recovery container was changed to ion-exchanged water.

(Comparative Example 5)
Toner in the same manner as in Example 1 except that the toner composition liquid 1 is changed to the toner composition liquid 7 and the aqueous solution of the compound having an active hydrogen group is changed to ion-exchanged water. 7-3 was obtained.

(Comparative Example 6)
In Example 1, the toner composition liquid 1 is changed to a toner composition liquid 10 in which 0.6 parts by mass of isophorone diamine, which is a compound having an active hydrogen group, is further added to the components of the toner composition liquid 1 and put into a collection container. A toner 10-1 was obtained in the same manner as in Example 1 except that the aqueous solution of the compound having an active hydrogen group was changed to ion-exchanged water.

(Comparative Example 7)
In Example 2, the toner composition liquid 1 is changed to a toner composition liquid 10 in which 0.6 parts by mass of isophoronediamine, which is a compound having an active hydrogen group, is further added to the components of the toner composition liquid 1 and put into a collection container. A toner 10-2 was obtained in the same manner as in Example 1 except that the aqueous solution of the compound having an active hydrogen group was changed to ion-exchanged water.

<Evaluation of particle size distribution>
Using the particle size measuring device (Multisizer III, manufactured by Beckman Coulter, Inc.), the weight average particle size (Dw) and the number average particle size (Dn) of each toner obtained in Examples 1 to 15 and Comparative Examples 1 to 7 were used. Then, measurement was performed with an aperture diameter of 100 μm, and 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 stirred with a micropartel, and then 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 weight and number of toners using Multisizer III, the weight 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 3.
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.

<Evaluation of clogged discharge holes>
In Examples 1 to 15 and Comparative Examples 1 to 7, when each toner base particle was produced, the droplet discharge head was observed with a CCD camera, and it was confirmed over time whether discharge droplets had come out from the discharge port. According to the evaluation criteria, the clogging of the discharge port was evaluated. The results are shown in Table 3 below.
[Evaluation criteria]
○: Continuously formed droplets without clogging the discharge holes for 3 hours. Δ: Clogging occurred in less than 50% of the discharge holes in 1 hour. ×: Clogged in 50% or more of the discharge holes in 1 hour. Occurred

<Evaluation of heat-resistant storage stability>
Each toner obtained in Examples 1 to 15 and Comparative Examples 1 to 7 was filled in a 50 mL glass container and left in a thermostatic bath at 50 ° C. for 24 hours. Then, it cooled to 24 degreeC, the penetration was measured by the penetration test (JIS K2235-1991), and the heat-resistant storage stability was evaluated by the following reference | standard. The results are shown in Table 3.
In addition, the greater the penetration, the better the heat-resistant storage stability. If the penetration is less than 5 mm (“×” in the following evaluation criteria), there is a possibility that problems will occur in use. Is expensive.
〔Evaluation criteria〕
○: Needle penetration is 10 mm or more △: Needle penetration is 5 mm or more and less than 10 mm ×: Needle penetration is less than 5 mm

<Evaluation of low-temperature fixability>
In order to evaluate the low-temperature fixability of each toner obtained in Examples 1 to 15 and Comparative Examples 1 to 7, a developer containing each of the toners and the carrier was prepared using the following carrier, and this developer was used. Produced.

<< Career preparation >>
Ingredients having the following composition were 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

<< Development of Developer >>
For each toner obtained in Examples 1-15 and Comparative Examples 1-7, 4 parts by mass of 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 low-temperature fixability by the following method.

<< Evaluation Method for Low Temperature Fixability >>
A copying test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus in which a fixing unit of a copying machine MF2200 (manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) was determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm. The evaluation criteria for low-temperature fixability were as follows. The results are shown in Table 3.
〔Evaluation criteria〕
○: Lower limit fixing temperature is less than 110 ° C. Δ: Lower limit fixing temperature is 110 or more and less than 120 ×: Lower limit fixing temperature is 120 ° C. or more

From the results of Table 3, the toners of Examples 1 to 15 have good manufacturability, a small particle size toner having a narrow particle size distribution with Dw / Dn of 1.10 or less, and can be fixed at low temperature. The toner had good heat storage stability.
On the other hand, the toners of Comparative Examples 1 and 2 were inferior in heat-resistant storage stability although they had good low-temperature fixability. Regarding the cause of the deterioration in heat-resistant storage stability, in Comparative Examples 1 and 2, no prepolymer was present in the binder resin, and a reaction between the prepolymer in the toner and the active hydrogen group-containing compound in the collecting portion occurred. The cause is not.
Further, the toners of Comparative Examples 3, 4 and 5 had good low-temperature fixability but were inferior in heat resistant storage stability and particle size distribution. The reason for the deterioration of heat-resistant storage stability is that there is no active hydrogen group capable of reacting with the prepolymer in the collecting part, so that no prepolymer elongation reaction occurs, and no prepolymer extension exists in the outer shell of the toner. This is because the shell structure due to the prepolymer stretch was not formed. The reason why the particle size distribution is deteriorated is that the toner base is easily deformed by an external force and an aggregate is easily formed because there is no shell structure of the prepolymer.
Further, in the toners of Comparative Examples 6 and 7, the viscosity of the toner composition liquid increased due to the crosslinking or elongation reaction between isophoronediamine and the prepolymer, and the ejection stability deteriorated. In addition, the cross-linking or elongation reaction proceeded in a region other than the vicinity of the toner surface, resulting in poor low-temperature fixability.

The aspect of the present invention is as follows.
<1> A toner composition liquid preparation step of preparing a toner composition liquid in which a toner composition containing a binder resin and a release agent is dissolved or dispersed in an organic solvent, and discharging the toner composition liquid from at least one discharge hole A droplet forming step for forming droplets, a drying step for drying the organic solvent in the toner composition liquid that has formed the droplets, and a compound having an active hydrogen group formed by the particles obtained in the drying step. A collecting step of collecting in an aqueous medium containing, wherein the binder resin contains two or more amorphous resins, and at least one of the amorphous resins contains the active hydrogen group. A method for producing a toner, comprising: an amorphous resin having a site capable of reacting with a compound having at least one amorphous resin.
<2> In the droplet forming step, vibration is applied 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 standing The method for producing a toner according to <1>, wherein the toner composition liquid is ejected from the ejection holes formed in an area where the wave becomes an antinode 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 toner production method according to <1>.
<4> A polyester resin in which the amorphous resin having a site capable of reacting with a compound having an active hydrogen group is a polyester resin having a functional group capable of being bonded with urethane or urea, and having a functional group capable of being bonded with urethane or urea The toner production method according to any one of <1> to <3>, wherein the content in the binder resin is 5% by mass to 20% by mass.
<5> The binder resin according to any one of <1> to <4>, wherein the binder resin includes a crystalline polyester resin, and the crystalline polyester resin is dissolved in the toner composition liquid in the toner composition liquid preparation step. This is a toner production method.
<6> The method for producing a toner according to <5>, wherein the crystalline polyester resin has a weight average molecular weight of 1,000 to 100,000.
<7> Obtained by the toner production method according to any one of <1> to <6>, wherein the weight average particle size is 1 μm to 10 μm, and the particle size distribution (weight average particle size / number average particle size) Is a toner of 1.00 to 1.15.
<8> A developer comprising the toner according to <7> and a carrier.

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 fixing property and heat-resistant storage stability, 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 pipe 23 Dry particles not coalesced 24 Dry particles coalesced 30 Dry collection unit (particle formation means)
31, 206 Chamber 32, 213 Toner collecting means 33 Downstream air 34 Toner collecting tube 35, 214 Recovery container 41 Wall of liquid column resonance liquid chamber 103 Shroud airflow outlet 104 Droplet forming unit 105 Shroud airflow 108 Shroud cover 203 Liquid feeding Means 204 Valve 207 Primary transport airflow 208 Secondary transport airflow 209 Secondary transport airflow inlet 212 Guide tube 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 column resonance liquid chamber 18 smell The length from the end of the frame on the fixed end side to the end on the liquid common supply path 17 side 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 h2 The liquid common Height of communication port on supply path 17 PG1, PG2, P1, P2 Pressure gauge

JP 07-152202 A 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 JP 2007-003780 A JP 2008-065005 A JP 2008-0665220 A

Claims (8)

A toner composition liquid preparation step of preparing a toner composition liquid in which a toner composition containing a binder resin and a release agent is dissolved or dispersed in an organic solvent;
A droplet forming step of forming droplets by discharging the toner composition liquid from at least one discharge hole;
A drying step of drying the organic solvent in the toner composition liquid that has formed the droplets;
Collecting the particles obtained in the drying step in an aqueous medium containing a compound having an active hydrogen group,
The binder resin includes two or more amorphous resins;
At least one of the amorphous resins is an amorphous resin having a site capable of reacting with the compound having an active hydrogen group,
A method for producing a toner, wherein at least one of the amorphous resins is an amorphous polyester resin.   In the droplet forming step, vibration is applied 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 is formed. The toner manufacturing method according to claim 1, wherein the toner composition liquid is ejected from the ejection holes formed in a region 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 amorphous resin having a site capable of reacting with a compound having an active hydrogen group is a polyester resin having a functional group capable of being bonded with urethane or urea,
4. The method for producing a toner according to claim 1, wherein a content of the polyester resin having a functional group capable of being bonded with urethane or urea in the binder resin is 5% by mass to 20% by mass. 5. The binder resin includes a crystalline polyester resin;
The method for producing a toner according to claim 1, wherein the crystalline polyester resin is dissolved in the toner composition liquid in the toner composition liquid preparation step.   The toner production method according to claim 5, wherein the crystalline polyester resin has a weight average molecular weight of 1,000 to 100,000. It is obtained by the method for producing a toner according to any one of claims 1 to 6,
The weight average particle size is 1 μm to 10 μm,
A toner having a particle size distribution (weight average particle diameter / number average particle diameter) of 1.00 to 1.15. A developer comprising the toner according to claim 7 and a carrier.