JP2007171927A - Method for manufacturing electrostatic charge image developing toner, and electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a toner which exhibits stable fixing characteristics and has a stable volume average grain size and sharp grain size distribution by suppressing the adhesion of an emulsified dispersion liquid within a storage tank and simultaneously having thermal characteristics maintained. <P>SOLUTION: In the method for manufacturing the toner having a step of emulsifying and dispersing an organic solvent composition containing at least a binder resin and a colorant in an organic solvent in an aqueous medium to obtain the emulsified dispersion liquid and storing the same into the storage tank, a step of adding deionized water to the liquid at need, and a step of removing the organic solvent, the electrostatic charge image developing toner is so manufactured that the weight Wa of the emulsified dispersion liquid and the weight Wb of the deionized water to be added before the removal of the organic solvent have a relation: formula (1): 0≤Wb/(Wa+Wb)≤0.4. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner and an electrostatic charge image developing toner.

In recent years, the market demanded smaller particle size for higher image quality and low-temperature fixing for energy saving. In particular, image formation is possible after the image forming apparatus is ready for energy saving. In order to reduce as much as possible the amount of power required for the waiting time (warm-up time of the apparatus) until the time is reached, there is a strong demand for shortening the waiting time.
However, the toner obtained by the ordinary kneading and pulverization method is approaching the limit of reducing the particle size technically, its shape is irregular, the particle size distribution is broad, and the fixing energy is high. was there.
In particular, in the case of fixing, a kneading and pulverizing type toner prepared by a pulverization method has a large amount on the surface because pulverization is broken at the interface of the release agent (wax). Adhesion was likely to occur, and the performance was unsatisfactory.

On the other hand, in order to overcome the problems associated with the kneading and pulverizing method described above, a toner manufacturing method using a polymerization method has been proposed.
This method makes it easy to reduce the particle size of the toner, and the particle size distribution is sharper than the particle size distribution of the toner obtained by the pulverization method. In addition, wax can be included.
For example, an emulsion polymerization aggregation method has been proposed (see, for example, Patent Documents 1 and 2), and further, a technique for improving the problems associated with the use of surfactants in the emulsion aggregation method has also been proposed. (For example, refer to Patent Documents 3 and 4).

In addition, a dry toner having a practical sphericity of 0.90 to 1.00 comprising a urethane-modified polyester extension reaction product as a toner binder for the purpose of improving toner fluidity, low-temperature fixability, and hot offset property. It has been proposed (see, for example, Patent Document 5).
Also, proposals have been made for dry toners that are excellent in powder flowability and transferability in the case of a toner having a small particle diameter, and also excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance (for example, And Patent Documents 6 and 7).
The toner production methods described in these publications include a step of polymerizing an isocyanate group-containing polyester prepolymer with an amine in an organic solvent and an aqueous medium, a step of removing the organic solvent by heating, and the like. Is included. In particular, the following Patent Document 8 describes in detail a method for removing an organic solvent.

  In addition, techniques for obtaining a sharp particle size distribution and efficiently removing residual polymerizable monomers by controlling the liquid level during the production of polymerized toner have been introduced (see, for example, Patent Documents 9 and 10). .)

However, in the production method of the polymerized toner, it is also important to achieve efficient productivity as well as quality.
In particular, in a method for producing a polymerized toner having a step of removing an organic solvent from an emulsified / dispersed liquid stored in a storage tank under heating, skinning / adhesion in the tank can be a serious problem.
In general, this problem has been dealt with by using high-pressure water or a solvent to clean the inside of the tank, but the skinning / adherent matter generated at the top of the liquid surface is solidified and removed. It has become difficult.
In particular, in the method of obtaining an emulsified dispersion in a continuous mode, unlike the batch method, the resulting emulsified dispersion often varies, so efficiency is maintained while maintaining stable quality, which is representative of thermal characteristics. Good continuous production is very difficult. In addition, by heating the emulsification / dispersion liquid, the stability of the emulsification / dispersion liquid is reduced, and the occurrence of coarse powder due to aggregation is also confirmed, which is a major obstacle to achieving efficient productivity. It has become.

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP 2000-275907 A JP 2001-305797 A Japanese Patent Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Japanese Patent Laying-Open No. 2005-77776 JP 2001-242663 A JP 2005-156586 A

  Therefore, in the present invention, in view of the above-mentioned conventional problems, the thermal characteristics are simultaneously suppressed while suppressing the adhesion of organic solvents and the occurrence of coarse powder during the reaction / ripening due to heating. It was decided to produce a toner that maintained a stable fixing characteristic and had a stable volume average particle diameter and a sharp particle size distribution.

In the present invention, at least an organic solvent composition containing a binder resin and a colorant in an organic solvent is emulsified and dispersed in an aqueous medium, and the resulting emulsion dispersion is stored in a storage tank; A toner manufacturing method comprising a step of adding water as necessary and a step of removing the organic solvent, wherein the weight Wa of the emulsified dispersion stored in the storage tank and the organic solvent are removed. Provided is a method for producing a toner for developing an electrostatic charge image, wherein the weight Wb of deionized water to be added has a relationship represented by the following formula (1).
0 ≦ Wb / (Wa + Wb) ≦ 0.4 (1)

  In the invention of claim 2, the storage tank for performing the step of removing the organic solvent is provided with a jacket or a heater, and the organic solvent is removed by heating with warm water, steam, or a heater. The emulsion / dispersion liquid is diluted with the deionized water within a range that satisfies the relationship of the above formula (1) so that the boundary is equal to or greater than the boundary of the jacket or heater. A method for producing a toner for developing an electrostatic image is provided.

  Further, in the invention of claim 3, for electrostatic image development according to claim 1 or 2, heating with warm water, steam, or a heater is performed during or after the step of removing the organic solvent. A method for producing a toner is provided.

  In the invention of claim 4, the weight ratio of the organic solvent composition to the aqueous dispersion medium is 60:40 to 20:80. A method for producing a toner for developing an electrostatic image is provided.

  Further, in the invention of claim 5, at least the binder resin in the organic solvent composition contains a polyester resin, and the electrostatic charge image according to any one of claims 1 to 4. A method for producing a developing toner is provided.

  Moreover, in invention of Claim 6, the said organic solvent composition and the said aqueous medium are given the shear force, supplying a disperser or an emulsifier continuously. A method for producing a toner for developing an electrostatic charge image according to claim 1 is provided.

  Further, in the invention of claim 7, the organic solvent composition is obtained by dissolving or dispersing at least a polymer having a site capable of reacting with a compound having an active hydrogen group and a colorant in the organic solvent. And having the step of reacting the polymer having a site capable of reacting with the compound having an active hydrogen group after or while dispersing the organic solvent composition in an aqueous medium by mechanical shearing force. A method for producing a toner for developing an electrostatic image according to any one of claims 1 to 6 is provided.

  In the invention of claim 8, the electrostatic charge image according to any one of claims 1 to 7, wherein the volume average particle diameter of the toner particles present in the emulsified dispersion is 3 to 8 μm. A method for producing a developing toner is provided.

  In the invention of claim 9, the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner particles present in the emulsion dispersion is 1.20 or less. A method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 8 is provided.

  In the invention of claim 10, the average circularity of the toner particles present in the emulsified dispersion is 0.92 to 1.00. A method for producing a toner for developing an electrostatic image is provided.

Further, in the invention of claim 11, when the toner base softening point produced without dilution with deionized water is Ta, the toner base softening produced through the step of diluting with deionized water is used. The toner for developing an electrostatic image obtained by the production method according to claim 1, wherein the relationship represented by the following formula (2) is satisfied between the point Tb and the point Tb: I will provide a.
Ta-Tb ≦ 5 (° C.) (2)
Here, the toner base means a state in which various additives, inorganic particles, and the like are added after a predetermined organic solvent removing step, a washing step, and a drying step.

  According to the method of the present invention, it is possible to maintain the thermal characteristics while suppressing the adhesion in the storage tank and the generation of coarse powder that occur during the reaction / ripening due to the removal of the organic solvent and the heating, and the stable fixing characteristics. A toner having a stable volume average particle diameter and a sharp particle size distribution was obtained.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following examples.

In the present invention, at least an organic solvent composition containing a binder resin and a colorant in an organic solvent is emulsified and dispersed in an aqueous medium, and the resulting emulsion dispersion is stored in a storage tank; A toner manufacturing method comprising a step of adding deionized water as required and a step of removing the organic solvent, wherein the weight Wa of the emulsified dispersion stored in the storage tank and the organic solvent are removed. The toner for developing an electrostatic charge image is produced so that the weight Wb of deionized water added before has the relationship of the following formula (1).
0 ≦ Wb / (Wa + Wb) ≦ 0.4 (1)

In the above formula (1), Wb / (Wa + Wb) represents the degree of dilution of the emulsified dispersion stored in the storage tank with deionized water.
By diluting this, the organic solvent in the emulsified dispersion droplets moves to water diluted by the solubility. At that time, non-uniformity due to uneven distribution of the organic solvent composition present in the droplets is promoted, but maintaining Wb / (Wa + Wb) at 0.4 or less can maintain the thermal characteristics. This makes it possible to obtain a toner having stable fixing characteristics and finally having a stable volume average particle size and a sharp particle size distribution. Moreover, in order to suppress generation | occurrence | production of coarse powder, the range of Wb / (Wa + Wb) is preferable in the range of 0.1-0.4 from the meaning which reduces a particle density, More preferably, it is 0.2-0.4. Range.

In the step of removing the organic solvent, when using a storage tank equipped with a jacket or a heater and warming with warm water, steam or a heater, and removing the organic solvent, the position of the jacket or heater functioning for heating By diluting the emulsified / dispersed liquid so as to be above the boundary, it is possible to suppress the occurrence of ring-like skinning and deposits on the upper part of the liquid surface.
As a result, cleaning of the storage tank can be simplified, or continuous use without cleaning becomes possible.
In addition, by performing dilution so as to satisfy the above formula (1), it is possible to maintain thermal characteristics, exhibit stable fixing characteristics, and always have a toner having a stable volume average particle diameter and a sharp particle size distribution. It was confirmed that it could be produced.

  In the method of the present invention, during or after the step of removing the organic solvent, warming with warm water, steam, or a heater is performed so that ring-like skinning or deposits on the liquid surface are generated. It can be effectively suppressed. As a result, the cleaning of the storage tank can be surely simplified or can be continuously used without cleaning.

The weight ratio of the organic solvent composition or polymerizable monomer composition to the aqueous dispersion medium in the mixed solution is preferably in the range of 60:40 to 20:80, and more preferably 50:50 to 30 : 70 is preferable.
When the weight ratio of the organic solvent composition or the polymerizable monomer composition is large, the emulsified state becomes unstable, the coarsening of the emulsion becomes remarkable, and a continuously stable particle diameter cannot be obtained. In addition, when the weight ratio of the aqueous dispersion medium is large, the oil droplet particles are not sufficiently cut by the shearing force, and it is difficult to reduce the particle size of the target toner.

The binder resin in the organic solvent composition preferably contains a polyester resin, and the acid value of the organic solvent composition is preferably in the range of 2 to 30 KOHmg / g.
The polyester resin is easy to reduce the molecular weight and excellent in low-temperature fixability as compared with the styrene acrylic resin, and is a preferable material for energy saving.
The provision of an acid value is advantageous for improving the adhesion of toner to paper, and an acid value of 2 KOHmg / g or more is required. However, if it is 30 KOHmg / g or more, the stability in the system during emulsification increases, and the coalescence of fine particles does not proceed, so that it becomes difficult to obtain a toner having a sharp particle size distribution.

As a method for measuring the acid value, a method based on JIS K0070 can be applied.
However, if the sample does not dissolve, a solvent such as dioxane or THF may be used as the solvent.

In the method of the present invention, for example, by using a disperser such as a pipeline homomixer, or an emulsifier, an organic solvent composition and an aqueous medium are continuously supplied and mixed to obtain an emulsion. It is suitable from an industrial viewpoint.
When mass production is performed in batch mode, the capacity of the tank for emulsification increases, and the size of the dispersing machine or emulsification machine that conforms to it increases, which requires a very large energy load. Can be mass-produced with a small running cost by using a small disperser or an emulsifier.

  In addition, considering that it is difficult to dissolve or disperse the polymer component in which the reaction has been completed in an organic solvent, the polymer component necessary for developing offset resistance is uniformly introduced into the particles. Therefore, the organic solvent composition is obtained by dissolving or dispersing at least a polymer having a site capable of reacting with a compound having an active hydrogen group and a colorant in an organic solvent, and the organic solvent composition is dissolved in an aqueous medium. It is preferable to provide a step of reacting a compound having an active hydrogen group with a polymer having a site capable of reacting after being dispersed by a shearing force or while being dispersed.

The volume average particle size of the toner particles present in the emulsified dispersion obtained by the method of the present invention is preferably 3 to 8 μm, and the volume average particle size (Dv) and the number average particle size (Dn). The ratio (Dv / Dn) is preferably 1.20 or less. By defining Dv / Dn in this way, it is possible to obtain a toner with high resolution and high image quality.
In order to obtain a higher quality image, the toner has a volume average particle diameter of 3 to 7 μm, a ratio (Dv / Dn) to the number average particle diameter of Dv / Dn of 1.17 or less, and 4 μm or less. It is preferable that the number of particles is 1 to 10% by number, and the particle size of 12.7 μm or more is preferably 3% or less by volume. Further, the volume average particle size is 4 to 7 μm, and Dv / Dn is 1. It is desirable to make it 15 or less.
Such a toner is free from scattering and fog, especially when a full-color copying machine or the like is used, and can form a high-quality image with good developability over the long term.

In the present invention, the average particle size and particle size distribution of the toner particles present in the emulsified dispersion can be measured by, for example, Coulter Counter TA-II or Coulter Multisizer II (both manufactured by Coulter). The measuring method is as follows.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used.
Next, 2 to 20 mg of a measurement sample is added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated.
From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained.

The toner particles present in the emulsified dispersion produced by the method of the present invention preferably have a specific shape and shape distribution.
If the average circularity is less than 0.92, the fine particles are not sufficiently coalesced, and it is difficult to obtain satisfactory transferability and high-quality images free from dust.
As a method for measuring such a shape, for example, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. It is mentioned as a thing. A toner having an average circularity of 0.92 to 1.00, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has a high reproducibility with an appropriate density. It was confirmed as preferable for forming a fine image.

The average circularity of the toner particles present in the emulsified dispersion can be measured by, for example, a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.).
A specific measurement method is shown below.
100-150 ml of water from which impure solids have been removed is placed in a container, a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, 0.1-0.5 ml, and a measurement sample is added at 0.1-0. About 5 g is added, and the suspension in which the sample is dispersed is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser so that the concentration of the dispersion is 3000 to 10,000 / μl. Measure the shape and distribution of the toner.

According to the method of the present invention, regarding the toner base, nonuniformity due to uneven distribution of the organic solvent composition present in the droplets that may occur due to dilution is effectively suppressed, and maintenance of thermal characteristics is achieved. This can be confirmed by the toner base softening point.
That is, it is confirmed that the relationship between the toner base softening point Ta obtained without dilution and the toner base softening point Tb obtained through the dilution step satisfies the following formula (2).
Ta-Tb ≦ 5 (° C.) (2)
The softening point here is the melting temperature in the 1/2 method, and if a decrease of 5 ° C. or more is observed, the influence on the fixing characteristics becomes large.
The method for measuring the softening point is shown below.
An example of a flow tester for measuring the thermal characteristics of the toner is an elevated flow tester CFT500 manufactured by Shimadzu Corporation.
(Measurement condition)
Load: 30 kg / cm ² , heating rate: 3.0 ° C./min, die diameter: 0.50 mm, die length: 1.0 mm
The flow curve of the flow tester thus obtained is data as shown in FIGS. 1 and 2, and a predetermined temperature can be read from this data.
In FIG. 1, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method in FIG. 2 corresponds to the softening point shown in the above formula (2).

  Furthermore, in the method of the present invention, a high molecular weight process is performed in which an isocyanate group-containing polyester prepolymer A dispersed in an aqueous medium containing inorganic fine particles and / or polymer fine particles is reacted with amine B. Is preferred.

Next, the material applied to the toner production of the method of the present invention will be described.
As the binder resin, in addition to the polyester resin, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and the like, a polymer of its substitution, a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, styrene -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Methyl ketone copolymer, styrene-buta Styrene copolymers such as ene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, polymethyl methacrylate, poly Butyl 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 Aromatic 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 polyester resin is usually obtained by condensation polymerization of alcohol and carboxylic acid.
Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane and bisphenol A, and other dihydric alcohols. Body, a trihydric or higher polyhydric alcohol monomer, and the like.
Examples of carboxylic acids include divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, 1,2,4-benzenetricarboxylic acid, 1 , 2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxy Examples thereof include trivalent or higher polyvalent carboxylic acid monomers such as propane and 1,2,7,8-octanetetracarboxylic acid.

In the method of the present invention, a prepolymer can be applied. As the prepolymer, a polyester-based prepolymer A containing an isocyanate group is preferable, which is a polycondensation of a polyol (PO) and a polycarboxylic acid (PC). And a polyester having an active hydrogen group can be obtained by further reacting with a polyisocyanate (PIC).
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, and alcoholic hydroxyl groups are particularly preferable.

Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable.
Diols (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol, triethylene glycol, etc.). Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, Bisphenol S, etc.), alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols, the above bisphenols Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts.
Preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and combinations thereof with alkylene glycols having 2 to 12 carbon atoms. .
The trivalent or higher polyol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.), and alkylene oxide adducts of the above trivalent polyphenols.

Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC). (DIC) may be used alone, but is more preferably used as a mixture of (DIC) and a small amount of (TC).
Examples of the dicarboxylic acid (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.), alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.), and aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid). , Naphthalenedicarboxylic acid, etc.). Of these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as polycarboxylic acid (PC), what reacted with polyol (PO) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the material mentioned above may be applied. Good.

  The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1.5 / as the equivalent ratio OH / COOH of the hydroxyl group (OH) to the carboxyl group (COOH). 1-1 / 1, and more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (PIC) include aliphatic polyisocyanates (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, the above polyisocyanates as phenol derivatives, oximes And those blocked with caprolactam or the like. Two or more of these may be used in combination.

When obtaining a polyester-based prepolymer having an isocyanate group, the ratio of the polyisocyanate (PIC) and the polyester-based resin (PE) having active hydrogen is such that the isocyanate group (NCO) and the hydroxyl group (OH) of the polyester having a hydroxyl group are The equivalent ratio NCO / OH is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1.
The content of the polyisocyanate (PIC) component in the prepolymer A having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. It is preferable.

As the amine B, polyamines and / or amines having an active hydrogen-containing group can be applied. In this case, the active hydrogen-containing group includes a hydroxyl group and a mercapto group.
Examples of such amines include diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and B1-B5 amino groups blocked ( B6) and the like.
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.), alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diamine). Cyclohexane, isophorone diamine, etc.) and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
Among these amines B, (B1) and a mixture of (B1) and a small amount of (B2) are preferable.

Furthermore, when the prepolymer A and the amine B are reacted, the molecular weight of the polyester may be adjusted by using an elongation terminator if necessary.
As the elongation terminator, monoamines having no active hydrogen-containing groups (diethylamine, dibutylamine, butylamine, laurylamine, etc.) and those blocked (ketimine compounds) can be applied.
The amount added is appropriately selected in relation to the molecular weight desired for the urea-modified polyester to be produced.

  The ratio of the amine B and the prepolymer A having an isocyanate group is an isocyanate group (NCO) in the prepolymer A having an isocyanate group and an amino group (NHx) in the amine B (x represents a number of 1 to 2). ) Equivalent ratio (NCO / NHx) is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. Is preferred.

As the colorant applied in the method of the present invention, all known dyes and pigments can be used.
Specifically, 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, Anthra Zan Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast scarlet , Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzy Orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), Indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Acid Titanium fluoride, zinc white, lithobon, and mixtures thereof.
The content of the colorant is usually from 1 to 15% by weight, more preferably from 3 to 12% by weight, based on the toner.

The colorant described above can also be used as a master batch combined with a resin.
As the binder resin used in the production of the masterbatch or kneaded together with the masterbatch, the above-described polyester resin can be applied, and in addition, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the substitution products thereof. Polymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-Chloromethyl methacrylate copolymer Styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymer such as acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Examples thereof include acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used alone or in combination of two or more.

The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear.
At this time, an organic solvent may be used in order to enhance the interaction between the colorant and the resin.
In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Can be used as it is, and therefore, a drying step is not necessary and is preferably used.
In the mixing and kneading step, a high shear dispersion device such as a three roll mill is suitable.

Moreover, you may contain a wax with binder resin and a coloring agent.
A known wax can be used. For example, polyolefin wax (polyethylene wax, polypropylene wax, etc.), long chain hydrocarbon (paraffin wax, sasol wax, etc.), carbonyl group-containing wax, and the like can be mentioned.
Of these, carbonyl group-containing waxes are particularly preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate), polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.), polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.), polyalkylamides (trimellitic acid tristearyl amide, etc.) , And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
The melting point of the wax to be applied is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset during fixing at a low temperature.
Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.
The content of the wax in the toner is usually 0 to 40% by weight, and preferably 3 to 30% by weight.

The toner produced by the method of the present invention may contain a charge control agent as necessary.
A known material can be used as the charge control agent. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Or a simple substance of tungsten, a simple substance or compound of tungsten, a fluorine-based activator, a salicylic acid metal salt, a metal salt of a salicylic acid derivative, and the like. Specific materials include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, and 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.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene, Nakuridon, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

A charge control agent may be added to the toner produced by the method of the present invention. The amount of the charge control agent used is determined by the conditions including the type of the binder resin, the additive used as necessary, and the dispersion method. For example, it can be used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin, and particularly preferably in the range of 0.2 to 5 parts by weight.
If the addition amount of the charge control agent exceeds 10 parts by weight, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, and the fluidity of the developer is lowered. In addition, the image density is reduced. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent. May be.

As an external additive for assisting fluidity, developability and chargeability, inorganic fine particles are suitable.
The primary particle diameter of the inorganic fine particles is preferably 5 μm to 2 μm, particularly preferably 5 μm to 500 μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.
The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.
Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, oxidation Examples thereof include chromium, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles, such as soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polystyrene, methacrylate ester, acrylate copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Resin polymer particles can also be applied.

The fluidization aid as described above can prevent the deterioration of flow characteristics and charging characteristics even under high humidity by performing surface treatment to increase hydrophobicity.
For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferred surface treatment agents. It is done.

Examples of the cleaning performance improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles. And polymer fine particles produced by soap-free emulsion polymerization and the like.
The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  Hereinafter, although the specific example of the manufacturing method of the toner for electrostatic image development of this invention is shown, this invention is not limited to the example shown below.

(Production of polyester resin)
Polyhydric alcohol (PO) and polyhydric carboxylic acid (PC) are produced at 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate, dibutyltin oxide, etc., and reduced pressure if necessary. Water is distilled off to obtain a polyester resin.

(Prepolymer production)
Polyester having a hydroxyl group obtained by the same method as the above polyester resin is reacted with polyvalent isocyanate (PIC) at 40 to 140 ° C. to obtain a polyester prepolymer (A) having an isocyanate group.
When reacting polyvalent isocyanate (PIC), a solvent can be used as necessary.
Usable solvents include aromatic solvents (toluene, xylene, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, etc.), amides, which are inert to isocyanate compounds. (Dimethylformamide, dimethylacetamide, etc.) and ethers (tetrahydrofuran, etc.).

(Production of modified polyester resin)
The reaction between the polyester prepolymer (A) and the amines (B) may be carried out by mixing with other toner constituent materials, or may be prepared in advance.
In the case of producing in advance, the polyester prepolymer (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester resin.
Also in the case of reacting the polyester prepolymer (A) and the amines (B), a solvent can be used as necessary, as in the case of the prepolymer (A).
Any of the solvents described above can be applied.

(Toner production method in aqueous medium)
As an aqueous medium to be applied, water alone may be used, or a solvent miscible with water may be used in combination.
Examples of the miscible solvent include alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The toner particles may be formed by reacting a dispersion composed of a polyester prepolymer (A) having an isocyanate group in an aqueous medium with amines (B), or using a modified polyester resin prepared in advance. good.
As a method for stably forming a dispersion composed of a polyester resin or a polyester prepolymer (A) in an aqueous medium, a toner constituent material composed of a polyester resin or a polyester prepolymer (A) is added to the aqueous medium. The other toner constituent materials such as wax and charge control agent may be mixed when forming the dispersion in the aqueous medium, but after mixing these toner constituent materials in advance, More preferably, the mixture is added and dispersed in an aqueous medium.
In the present invention, toner constituent materials such as wax and charge control agent do not necessarily have to be mixed when particles are formed in an aqueous medium, and may be added after particles are formed. .

(Solid fine particle dispersant)
Further, by adding a solid fine particle dispersant in advance to the aqueous medium, the dispersion of oil droplets in the aqueous phase can be made uniform.
This is because the solid fine particle dispersant is arranged on the surface of the oil droplets at the time of dispersion, and the dispersion of the oil droplets is made uniform, and at the same time, coalescence of the oil droplets is prevented and the particle size distribution is sharp. Toner can be obtained.
The solid fine particle dispersant is present in a solid state hardly soluble in water in an aqueous medium, and is preferably inorganic fine particles having an average particle diameter of 0.01 to 1 μm.
Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite and the like can also be applied.
In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under basic conditions is preferable.

  Dispersants for emulsifying and dispersing the oil phase in which the toner composition is dispersed in an aqueous medium include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and alkylamines. Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl- N, N-di Amphoteric surfactants such as chill ammonium betaine.

Further, the effect of the surfactant having a fluoroalkyl group is exhibited in a very small amount.
Suitable anionic surfactants having a fluoroalkyl group include, for example, fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C6- C11) sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and its metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N- Propyl-N- (2-hydroxy Til) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphoric acid Examples include esters.

  Specific product names include Surflon S-111, S-112, S-113 (Asahi Glass), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M), Unidyne. DS-101, DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-l10, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xt Top EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

Examples of the cationic surfactant include aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts.
Specific product names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries Co., Ltd.), Megafuck F-150, F-824 ( Dainippon Ink Co., Ltd.), Xtop EF-132 (manufactured by Tochem Products), Footgent F-300 (manufactured by Neos), and the like.

Further, the dispersed droplets may be stabilized by a polymer protective colloid.
For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and other acids or hydroxyl groups containing (meth) acrylic Monomers such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3 -Chloro 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like, vinyl alcohol, for example, ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group, such as vinyl acetate, Vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide, or these methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, nitrogen such as vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine Homopolymers or copolymers such as those having an atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine Polyoxy such as polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Celluloses such as ethylene, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like can be applied.

In addition, as the dispersion stabilizer, a substance that can be dissolved in acid or alkali, such as calcium phosphate salt, can be applied.In this case, by dissolving the calcium phosphate salt with an acid such as hydrochloric acid, washing with water, etc., Remove calcium phosphate and the like from the fine particles.
It can also be removed by an operation such as degradation with an enzyme.

  When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. It is.
The reaction temperature is usually 0 to 150 ° C., preferably 40 to 98 ° C.
Moreover, you may use a well-known catalyst as needed.
Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a storage tank to be applied to remove the organic solvent from the emulsified dispersion, any known one can be applied as long as it has a stirrer and a jacket or heater for heating, In view of efficiently removing the organic solvent, those with a decompression facility or those with a specification of blowing compressed air, nitrogen, or the like are preferable.
In addition, it is particularly preferable that the jacket or the heater is divided into multiple stages so that the dilution ratio satisfying the relationship of the above formula (1) can be easily achieved regardless of the yield of the emulsified dispersion.

The toner powder obtained after the drying treatment is mixed with different kinds of particles such as a charge control agent, a fluidizing agent, and a colorant, or given impact on the toner surface by applying a mechanical impact force to the mixed powder. Can be prevented from being detached from the surface of the finally obtained composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. Is mentioned.
As an apparatus used in this process, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, a hybridization system (Nara Machinery Co., Ltd. Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

Furthermore, the toner obtained by the method of the present invention can be used as a magnetic toner containing a magnetic substance. In this case, the magnetic material contained in the toner includes iron oxides such as magnetite, hematite and ferrite, metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium, tin and zinc of these metals. Metal alloys such as antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. Magnetite is particularly preferable from the viewpoint of magnetic properties.
These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm. The amount of the ferromagnetic material to be contained in the toner is about 15 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component, with respect to 100 parts by weight of the resin component. 20 to 100 parts by weight per part.

〔Example〕
Hereinafter, although the specific Example of this invention is given and demonstrated, this invention is not limited to the example shown below.
In the following description, parts represent parts by weight.

[Example 1]
(Manufacture of polyester)
690 parts of bisphenol A ethylene oxide 2-mol adduct and 335 parts of terephthalic acid were charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, respectively, and 210 ° C. under a normal pressure nitrogen stream. For 10 hours.
Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain polyester (1).
The obtained polyester (1) resin had a weight average molecular weight of 6000, an acid value of 10 KOH mg / g, and a glass transition point of 48 ° C.

(Prepolymer production)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mol adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide, respectively The mixture was charged and subjected to a condensation reaction at 210 ° C. for 8 hours under a normal pressure nitrogen stream.
Next, the reaction is continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 170 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and prepolymer (1) Obtained.
The weight average molecular weight of the obtained prepolymer (1) was 5000.

(Production of organic solvent composition)
In a tank, 170 parts of 35% carnauba wax ethyl acetate dispersion, 120 parts of the above polyester (1), 20 parts of PY155 (manufactured by Clariant), 70 parts of ethyl acetate, and 2 parts of isophorone diamine were respectively added. The mixture was stirred and dissolved for 2 hours.
Next, the mixture was circulated and mixed for 1 hour using a high-efficiency disperser Ebara Milder (manufactured by Ebara Seisakusho) to obtain an organic solvent composition (1).
The acid value of the obtained organic solvent composition (1) was 4.5 KOH mg / g.
In another tank, 25 parts of the prepolymer (1) and 25 parts of ethyl acetate were added and dissolved and mixed for 4 hours with stirring to obtain an organic solvent composition (2).

(Manufacture of aqueous dispersion media)
In the tank, 945 parts of water, 40 parts of a 20% aqueous dispersion of styrene-methacrylic acid-butyl acrylate copolymer, and 160% of a 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) And 90 parts of ethyl acetate were added and mixed and stirred to obtain an aqueous dispersion medium (1).

(Manufacture of toner)
The above-mentioned organic solvent composition (1) is 3560 g / min, the organic solvent composition (2) is 440 g / min, and the aqueous dispersion medium (1) is 6000 g / min. 850 kg of an emulsified dispersion was obtained by continuous operation for 85 minutes at a rotation speed of 2960 rpm.
The emulsified dispersion was stored in a tank made of SUS having a configuration capable of storing 1000 kg, having a decompression line, and having a warm water jacket divided into two stages of a 400 kg portion and an 800 kg portion.
The volume average particle diameter Dv of the toner particles in the obtained emulsified dispersion is 5.9 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1. The average circularity was 0.96.
Since the obtained emulsified dispersion was not less than the boundary of the position of the second-stage tank jacket, no dilution was performed, that is, the weight Wa of the emulsified dispersion and the weight Wb of deionized water were Wb / In the state where (Wa + Wb) = 0, the solvent was removed as follows.
The temperature was raised to 45 ° C., and the pressure was gradually reduced while avoiding bumping while stirring at the outer peripheral edge peripheral speed of 10.5 m / sec. Finally, the solvent was removed under the condition of −90 kPa. This solvent removal time required 5 hours.
Thereafter, the temperature was raised to 60 ° C. and an additional reaction was performed for 5 hours, followed by filtration, washing, and drying to obtain a toner base.
The resulting toner base had a softening point of 138 ° C.
Moreover, when the inside of the storage tank emptied by the above operation was visually confirmed, it was confirmed that the SUS surface of the tank wall was in a clean state that can be used continuously.
Next, 100 parts of the obtained toner base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were mixed using a Q-type mixer (manufactured by Mitsui Mining Co., Ltd.).
Next, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed.
Further, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with a Henschel mixer, and coarse particles were removed with a screen having an opening of 37 μm to obtain yellow toner (1).

[Example 2]
(Manufacture of toner)
The continuous operation time in the toner production process was 70 minutes, and other conditions were the same as in Example 1 to obtain 700 kg of an emulsified dispersion.
Further, the volume average particle diameter Dv of the toner particles in the emulsified dispersion obtained by passing through the same conditions as in Example 1 is 5.9 μm, and the volume average particle diameter (Dv) and the number average particle diameter (Dn). ) (Dv / Dn) was 1.13, and the average circularity was 0.96.
The emulsified dispersion was stored in the same tank as in Example 1. However, since the emulsified dispersion did not reach the boundary of the position of the second tank jacket, it was diluted with 150 kg of deionized water.
By dilution, the weight Wa of the emulsified dispersion and the weight Wb of deionized water satisfied the relationship of Wb / (Wa + Wb) = 0.18.
Subsequently, the steps after solvent removal were carried out in the same manner as in Example 1 to obtain a toner base.
The resulting toner base had a softening point of 137 ° C.
The toner base softening point (Ta) obtained without dilution in Example 1 is 138 ° C., whereas the toner base softening point (Tb) of Example 2 obtained by dilution is 137 ° C. there were. That is, Ta—Tb was 1 ° C.
Moreover, when the inside of the emptied storage tank was visually confirmed, it was confirmed that the SUS surface of the tank wall was in a clean state that can be continuously used.
The toner base was treated in the same manner as in Example 1 to obtain yellow toner (2).

Example 3
(Manufacture of toner)
The continuous operation time in the toner production process was 30 minutes, and other conditions were the same as in Example 1 to obtain 300 kg of an emulsified dispersion.
Further, the volume average particle diameter Dv of the toner particles in the emulsified dispersion obtained by passing through the same conditions as in Example 1 is 5.9 μm, and the volume average particle diameter (Dv) and the number average particle diameter (Dn). ) (Dv / Dn) was 1.13, and the average circularity was 0.96.
The emulsified dispersion was stored in the same tank as in Example 1. However, since the emulsified dispersion did not reach the boundary of the position of the first stage tank jacket, it was diluted with 150 kg of deionized water.
By dilution, the weight Wa of the emulsified dispersion and the weight Wb of deionized water satisfy the relationship of Wb / (Wa + Wb) = 0.33.
Subsequently, using only the first-stage jacket, the steps after the solvent removal step were performed in the same manner as in Example 1 to obtain a toner base. The resulting toner base had a softening point of 134 ° C.
The toner base softening point (Ta) obtained without dilution in Example 1 was 138 ° C., whereas the toner base softening point (Tb) obtained by dilution was 134 ° C., and Ta-Tb Was 4 ° C.
Moreover, when the inside of the empty storage tank was visually confirmed, it was confirmed that the SUS surface of the tank wall was in a clean state to the extent that it can be used continuously.
The obtained toner base was treated in the same manner as in Example 1 to obtain a yellow toner (3).

Example 4
(Manufacture of toner)
Under the same conditions as in Example 2 above, 700 kg of an emulsified dispersion was obtained.
Further, the volume average particle diameter Dv of the toner particles in the emulsified dispersion obtained through the same conditions as in Example 2 is 5.9 μm, and the volume average particle diameter (Dv) and the number average particle diameter ( The ratio (Dv / Dn) to Dn) was 1.13, and the average circularity was 0.96.
When the emulsified dispersion was stored in the same tank as in Example 2, it did not reach the boundary of the second tank jacket, but was not diluted. That is, the weight Wa of the emulsified dispersion and the weight Wb of deionized water were set to Wb / (Wa + Wb) = 0, and then the steps after the solvent removal step were performed in the same manner as in Example 2 to obtain a toner base. . The resulting toner base had a softening point of 136 ° C.
Further, when the inside of the emptied storage tank was visually confirmed, skinning occurred in a state where the SUS surface could not be confirmed in the 700 kg to 800 kg portion corresponding to the portion where the emulsified dispersion was not immersed.
The obtained toner base was treated in the same manner as in Example 1 to obtain yellow toner (4).

[Comparative Example 1]
(Manufacture of toner)
Under the same conditions as in Example 3 above, 300 kg of an emulsified dispersion was obtained.
The volume average particle diameter Dv of the toner particles in the emulsion dispersion obtained through the same conditions as in Example 3 is 5.9 μm, and the volume average particle diameter (Dv) and the number average particle diameter (Dn). (Dv / Dn) was 1.13, and the average circularity was 0.96.
The emulsified dispersion was stored in the same tank as in Example 3, and diluted with 550 kg of deionized water in order to make it equal to or higher than the boundary of the second tank jacket.
By dilution, the weight Wa of the emulsified dispersion and the weight Wb of deionized water satisfied the relationship of Wb / (Wa + Wb) = 0.65.
Subsequently, the steps after solvent removal were carried out in the same manner as in Example 1 to obtain a toner base.
The resulting toner base had a softening point of 125 ° C.
The toner base softening point (Ta) obtained without dilution in Example 1 is 138 ° C., whereas the toner base softening point (Tb) obtained by dilution is 125 ° C., and Ta-Tb Was 13 ° C.
Moreover, when the inside of the emptied storage tank was visually confirmed, it was confirmed that the SUS surface of the tank wall was in a clean state that can be used continuously.
The obtained toner base was treated in the same manner as in Example 1 to obtain a yellow toner (5).

[Comparative Example 2]
(Manufacture of toner)
Under the same conditions as in Example 3 above, 300 kg of an emulsified dispersion was obtained.
The volume average particle diameter Dv of the toner particles in the emulsion dispersion obtained through the same conditions as in Example 3 is 5.9 μm, and the volume average particle diameter (Dv) and the number average particle diameter (Dn). (Dv / Dn) was 1.13, and the average circularity was 0.96.
The emulsified dispersion was stored in the same tank as in Example 3 and exceeded the boundary of the first stage tank jacket, but 250 kg of deionized water was used so as not to reach the boundary of the second stage tank jacket. Diluted.
By dilution, the weight Wa of the emulsified dispersion and the weight Wb of deionized water were set to Wb / (Wa + Wb) = 0.45.
Subsequently, using up to the second-stage jacket, the steps after solvent removal were performed in the same manner as in Example 1 to obtain a toner base.
The resulting toner base had a softening point of 130 ° C.
In contrast to 138 ° C. of the toner base softening point (Ta) obtained without dilution in Example 1, the toner base softening point (Tb) obtained by dilution is 130 ° C., and Ta-Tb is 8 ° C. there were.
Further, when the inside of the evacuated storage tank was visually confirmed, skinning occurred in a state where the SUS surface could not be confirmed in the second-stage jacket portion where the emulsified dispersion was not immersed.
The obtained toner base was treated in the same manner as in Example 1 to obtain a yellow toner (6).

The fixing characteristics were evaluated using the yellow toners (1) to (4) prepared in Examples 1 to 4 above.
For comparison, the same fixing characteristics were evaluated using the yellow toners (5) and (6) prepared in Comparative Examples 1 and 2.
Toner evaluation items and evaluation methods are shown below.
Using a device obtained by remodeling the fixing unit of RICOH Co., Ltd. MF2200 using a Teflon (registered trademark) roller as a fixing roller, type 6200 paper manufactured by RICOH was set in this, and a copying test was performed.
The hot offset temperature (anti-hot offset temperature) was determined by changing the fixing temperature.
The evaluation conditions of the high temperature offset were set such that the paper feed linear velocity was 50 mm / sec, the surface pressure was 2.0 kgf / cm ² , and the nip width was 4.5 mm.
The criteria for characteristic evaluation are shown below.
Hot offset property (three-step evaluation)
201 ° C or higher: ○
200-181: △
180 ° C or lower: ×

  Table 1 below shows the weight Wa of the emulsion dispersion, the weight Wb of deionized water, the values of Wb / (Wa + Wb), and the toner base softening obtained without dilution in Examples 1 to 4 and Comparative Examples 1 and 2. The values of the point Ta and the toner base softening points Tb and Ta-Tb obtained by dilution are shown, and the evaluation of the tank wall state and the fixing characteristics at high temperature offset are shown.

As is clear from the evaluation results in Table 1 above, when the yellow toners (1) to (4) of Examples 1 to 4 prepared by the method of the present invention were used, Ta-Tb was within 5 ° C. In the high temperature offset evaluation, a result of 200 ° C. or higher is obtained.
Therefore, by setting the value of Wb / (Wa + Wb) to 0.4 or less in the weight Wa of the emulsified dispersion and the weight Wb of deionized water, the uneven distribution of the organic solvent composition is suppressed and stable heat is generated. It was confirmed that the characteristics were obtained.
On the other hand, when the yellow toners (5) and (6) of Comparative Examples 1 and 2 were used, Ta-Tb exceeded 5 ° C., and remarkable deterioration was observed in the high temperature offset evaluation.
Further, in Example 4 and the yellow toners (4) and (6) of Comparative Example 2 prepared in a state where the liquid level after dilution was less than the functioning jacket height, Skinning was observed and the device could not be used continuously. However, the yellow toner of Example 4 has good offset evaluation as described above.

The flow curve of the thermal characteristic of a toner is shown. The figure which measured the melting temperature in the 1/2 method especially among the flow curves of the thermal characteristic of a toner is shown.

Claims (11)

At least a step of emulsifying and dispersing an organic solvent composition containing a binder resin and a colorant in an organic solvent in an aqueous medium, and storing the obtained emulsified dispersion in a storage tank;
Adding deionized water as needed;
A method for producing a toner comprising a step of removing the organic solvent,
The electrostatic charge image, wherein the weight Wa of the emulsified dispersion stored in the storage tank and the weight Wb of deionized water added before removing the organic solvent have the relationship of the following formula (1): A method for producing a developing toner.
0 ≦ Wb / (Wa + Wb) ≦ 0.4 (1) The storage tank for performing the step of removing the organic solvent is equipped with a jacket or a heater, and the organic solvent is removed by warming with warm water, steam, or a heater,
The said emulsification / dispersion liquid is diluted in the range with which the relationship of said Formula (1) is satisfy | filled with the said deionized water so that it may become more than the boundary of the position of the said jacket or a heater. A method for producing a toner for developing an electrostatic image.   3. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein heating with warm water, steam, or a heater is performed during or after the step of removing the organic solvent.   4. The electrostatic charge image developing toner according to claim 1, wherein a weight ratio of the organic solvent composition to the aqueous dispersion medium is 60:40 to 20:80. 5. Production method.   5. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein at least the binder resin in the organic solvent composition contains a polyester resin. 6.   The electrostatic charge image according to any one of claims 1 to 5, wherein a shearing force is applied while the organic solvent composition and the aqueous medium are continuously supplied to a disperser or an emulsifier. A method for producing a developing toner. The organic solvent composition is obtained by dissolving or dispersing at least a polymer having a site capable of reacting with a compound having an active hydrogen group in an organic solvent, and a colorant,
After the organic solvent composition is dispersed in an aqueous medium by mechanical shearing force or while being dispersed,
The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6, further comprising a step of reacting a polymer having a site capable of reacting with the compound having an active hydrogen group.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 7, wherein the toner particles present in the emulsified dispersion have a volume average particle diameter of 3 to 8 µm.   The ratio (Dv / Dn) of the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles present in the emulsified dispersion is 1.20 or less. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 8.   10. The toner for developing an electrostatic charge image according to claim 1, wherein the toner particles present in the emulsified dispersion have an average circularity of 0.92 to 1.00. 11. Production method. When the toner base softening point prepared without dilution with deionized water is Ta, the following formula (to the toner base softening point Tb prepared through the step of dilution with deionized water: 11. The electrostatic image developing toner obtained by the production method according to claim 1, wherein the relationship shown in 2) is satisfied.
Ta-Tb ≦ 5 (° C.) (2)

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