JP2007084603A - Resin particle dispersion, electrostatically charged image-developing toner, method for producing them, developer and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle dispersion having stably dispersed resin particles in an aqueous medium by a low energy, a method for producing the same, an electrostatically charged image-developing toner sufficiently satisfying toner characteristics by using the resin particle dispersion, a method for producing the same, an electrostatically charged image-developer and a method for forming the image. <P>SOLUTION: This resin particle dispersion obtained by dispersing resin particles containing at least a polycondensate resin obtained by performing the polycondensation of a polycondensable monomer in an organic solvent is characterized with that the polycondensate resin has ≥1 aromatic ring and/or alicyclic ring in its recurring unit, and the median diameter of the resin particles is ≥0.05 and ≤2.0 μm. The method for producing the same, the electrostatically charged image-developing toner by using the resin particle dispersion, the method for producing the same, the electrostatically charged image-developer and the method for forming the image are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used when developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, a manufacturing method thereof, and resin particles suitably used as a raw material thereof The present invention relates to a dispersion, a developer using the toner, and an image forming method.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In the electrophotographic method, an electrostatic image is formed on the photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process. The developer used here includes a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a non-magnetic toner alone. The toner is usually produced by using a thermoplastic resin as a pigment. In addition, a kneading and pulverizing method is used in which melt-kneading is performed together with a release agent such as a charge control agent and wax, and the mixture is cooled, finely pulverized, and further classified. In these toners, if necessary, inorganic and organic particles for improving fluidity and cleaning properties may be added to the toner particle surfaces.

  In recent years, color electrophotographic copying machines, printers, and multifunctional machines such as those and facsimiles have been widely used, but in order to achieve moderate gloss in color image reproduction and transparency to obtain excellent OHP images In general, it is difficult to use a release agent such as wax. For this reason, a large amount of oil is applied to the fixing roll to assist in peeling, so that it is difficult to add a copy image containing OHP, and it is difficult to add to the image with a pen or the like, and non-uniform glossiness is generated. There are also many. In normal black-and-white copying, commonly used waxes such as polyethylene, polypropylene, and paraffin are more difficult to use because they impair OHP transparency.

  For example, even if the transparency is sacrificed, it is difficult to suppress the toner exposure to the surface by the conventional toner production method by the kneading and pulverization method. Problems such as deterioration of the image quality and filming on the developing machine and the photoreceptor.

  As a fundamental improvement method for these problems, an oil phase composed of a monomer and a colorant as a resin raw material is dispersed in an aqueous phase and directly polymerized into a toner. There has been proposed a production method by a polymerization method in which the exposure to the surface is controlled by inclusion.

  In addition, as means for enabling intentional control of the toner shape and surface structure, Patent Documents 1 and 2 propose a toner manufacturing method using an emulsion polymerization aggregation method. In general, a resin particle dispersion is prepared by emulsion polymerization or the like, while a colorant dispersion in which a colorant is dispersed in a solvent is prepared and mixed to form an aggregate corresponding to the toner particle diameter and heated. Is a method for producing toner by fusing together.

  These manufacturing methods not only realize the inclusion of the wax, but also facilitate the reduction of the toner diameter, and enable higher resolution and clearer image reproduction.

  In order to provide high-quality images in the electrophotographic process as described above and maintain stable performance of the toner under various mechanical stresses, pigment, release agent selection, amount optimization, surface application In addition to suppressing the exposure of the mold release agent, it is extremely important to improve the mold release and suppress hot offset in the absence of gloss and fixing oil by optimizing the resin characteristics.

  On the other hand, in order to reduce energy consumption, a technology capable of fixing at a lower temperature is desired. Particularly in recent years, in order to save energy, it is desirable to stop energization of the fixing machine except during use. ing. Accordingly, the temperature of the fixing device needs to be energized and instantaneously raised to the operating temperature. For this purpose, it is desirable to make the heat capacity of the fixing machine as small as possible. In this case, however, the temperature fluctuation of the fixing machine tends to be larger than before. That is, the overshoot of the temperature after the start of energization increases, and on the other hand, the temperature drop due to paper passing also increases. In addition, when paper having a width smaller than the width of the fixing device is continuously passed, the temperature difference between the paper passing portion and the non-paper passing portion also increases. In particular, when used in high-speed copying machines and printers, the power supply capacity tends to be insufficient, and there is a strong tendency to cause the above phenomenon. Therefore, there is a strong demand for a toner having a wide so-called fixing latitude that can be fixed at a low temperature and does not cause an offset to a higher temperature region.

As a means for lowering the fixing temperature of the toner, it is known to use a polycondensation type crystalline resin showing a sharp melting behavior with respect to the temperature as a binder resin constituting the toner. The toner using a large amount of toner tends to cause yield deformation, and when actually used, troubles such as filming on the photosensitive member due to toner crushing and a decrease in transfer efficiency over time cannot be avoided.
In order to achieve both low-temperature fixability, photoconductor filming property, and transferability, it is inevitable to use a crystalline resin and an amorphous resin in combination, and there are particularly high performance requirements for an amorphous resin.

  In addition, when preparing the toner by the emulsion polymerization aggregation method as described above, after polymerizing the polycondensation type resin, it is emulsified in an aqueous medium and aggregated with a pigment or wax in a latex state, and then fused. Can unite.

  However, when the polycondensation resin is emulsified, it is emulsified by high shear under high heat exceeding 150 ° C., or the solvent is removed after the solution which has been dissolved in the solvent and reduced in viscosity is dispersed in an aqueous medium. It requires a very inefficient and energy consuming process.

  In addition, it is difficult to avoid problems such as hydrolysis during emulsification in an aqueous medium, and indeterminate factors are inevitable in material design.

Furthermore, the polycondensation of the polyester resin proceeds by a dehydration reaction, but the reached molecular weight may reach its peak as the polymerization proceeds. This is explained by the fact that dehydration hardly occurs from a certain value as the viscosity of the system increases. Compared to crystalline resins, which have a melting point and the resin viscosity decreases sharply at temperatures above the melting point, amorphous condensed resins are highly viscous even at temperatures above Tg, and severe conditions are required to promote polyester polymerization. Necessary, for example, a reaction over a period of 10 hours or more under high temperature exceeding 200 ° C., stirring with high power, and high pressure reduction is required, resulting in a large amount of energy consumption. For this reason, enormous capital investment is often required to obtain durability of the reaction equipment.
Furthermore, the monomer having an aromatic ring mainly used in amorphous polyester generally has low reactivity at low temperatures, and particularly exceeds 150 ° C. for producing a polyester resin in which a large number of rigid aromatic rings are introduced in a unit. Temperature conditions are indispensable, which often requires enormous capital investment in order to obtain durability of the reaction equipment.

For example, in Patent Document 3, a toner raw material containing at least a polyester resin is heated and melted to produce a melt of the toner raw material, and then the resin fine particles are obtained by emulsifying the melt in an aqueous medium. There has been proposed a method for producing a toner for developing an electrostatic charge image, characterized in that an aggregate of the resin fine particles is produced by aggregating and then fusing the resin fine particles.
In Patent Document 3, a conventional polycondensation catalyst such as tetrabutyl titanate is used as a catalyst, trimellitic anhydride (TMA) as a polyvalent carboxylic acid as a monomer, terephthalic acid (TPA) as a divalent carboxylic acid, Isophthalic acid (IPA), polyoxypropylene (2.4) -2,2-bis (4-hydroxyphenyl) propane (BPA-PO), polyoxyethylene (2.4) -2,2- as aromatic diol Using bis (4-hydroxyphenyl) propane (BPA-EO), ethylene glycol (EG) as an aliphatic diol, etc., reacting at 220 ° C. for 15 hours under a normal pressure nitrogen stream, then depressurizing sequentially and reacting at 10 mmHg To produce a polyester having a weight average molecular weight of about 5,000 to 90,000, and then with a colorant, wax, etc. After melt-kneading, melt-kneaded product MB1 is heated to 190 ° C. and charged into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) which is a dispersion emulsifier. A method is used in which the dispersion slurry is fed to the Cavitron at a rate of 1 L / min while being heated, and the dispersed dispersion slurry is cooled to 60 ° C. and taken out. In order to make a toner, this dispersion is further used for agglomeration, fusion, washing and drying. However, in such a method, energy during resin production and resin emulsification is enormous. It is clear that this is not practical.
In addition, such emulsification dispersion under high energy conditions tends to lead to decomposition of the resin, it is difficult to realize uneven distribution of the composition and uniformity in the particle size distribution of the resin particles in the dispersion, During storage of the dispersion, unintended particle aggregation occurred, which was a practical problem. In addition, toners using these materials are liable to cause problems in image quality stability during continuous printing as well as initial image quality.

There are also reports of synthesizing polycondensation resins in organic solvents. For example, Patent Document 4 discloses a method for producing an unsaturated polyester in which an aliphatic alcohol or an aliphatic polybasic acid is heated and dehydrated at 100 to 200 ° C. in an organic solvent. Patent Document 5 discloses an example of a method for producing an aliphatic polyester characterized by reacting at least two types of aliphatic polyester homopolymers with an organic solvent in the presence of a catalyst. Furthermore, Patent Document 6 discloses an example in which the hydroxycarboxylic acid is lactic acid and the polyhydroxycarboxylic acid is polylactic acid. Examples of the organic solvent include ether solvents, halogenated hydrocarbon solvents, hydrocarbons. System solvents are exemplified.
However, all of the above disclosed technologies relate to aliphatic polyesters, and when used in toner resins, resins using such aliphatic monomers have glass transition points below room temperature and are not suitable for toners. It turns out that it cannot be put into practical use at all. Furthermore, the provision of biodegradability, which is the main aim of the production method described in Patent Document 6, has nothing to do with the toner fixability, which is the technical problem of the present invention. There is no point of view suggested for solving the problem.

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP 2002-351140 A Japanese Patent Laid-Open No. 10-1536 JP-A-8-325362 JP-A-9-143253

  Accordingly, an object of the present invention is to solve the conventional problems and achieve the following object. That is, the present invention is to provide a resin particle dispersion in which resin particles are stably emulsified and dispersed in an aqueous medium with low energy, and a method for producing the same. Further, by using this, an electrostatic developing toner manufacturing method capable of manufacturing an electrostatic image developing toner sufficiently satisfying toner characteristics, an electrostatic image developing toner obtained by the manufacturing method, an electrostatic image developer, and It is to provide an image forming method.

The above-described problems of the present invention have been solved by the following means <1> to <6>.
<1> A resin particle dispersion in which resin particles containing at least a polycondensation resin obtained by polycondensation of a polycondensable monomer in an organic solvent are dispersed, wherein the polycondensation resin is in the repeating unit. 1 or more aromatic rings and / or alicyclic rings, and the resin particles have a median diameter of 0.05 μm or more and 2.0 μm or less,
<2> Resin particle dispersion in which resin particles containing at least a polycondensation resin having at least one aromatic ring and / or alicyclic ring in a repeating unit are dispersed in an aqueous medium with a median diameter of 0.05 μm to 2.0 μm. A polycondensation step in which a polycondensable monomer is polycondensed in an organic solvent using a polycondensation catalyst to obtain a polycondensation resin-containing product, and the polycondensation resin-containing product in an aqueous medium A method for producing a resin particle dispersion, comprising a dispersion step of dispersing resin to obtain a resin particle dispersion,
<3> A method for producing an electrostatic charge image developing toner comprising a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles, and a step of heating and aggregating the aggregated particles An electrostatic charge, wherein the resin particle dispersion is the resin particle dispersion described in <1> or the resin particle dispersion manufactured by the manufacturing method described in <2>. Image developing toner manufacturing method,
<4> An electrostatic image developing toner produced by the production method according to <3> above,
<5> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <4> and a carrier,
<6> A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a toner image is formed by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. An image development process, a transfer process for transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target, and a fixing process for thermally fixing the toner image transferred to the surface of the transfer target. A method for forming an image, wherein the electrostatic image developing toner according to <4> is used as the toner, or the electrostatic image developer according to <5> is used as the developer. .

According to the present invention, it is possible to provide a resin particle dispersion in which resin particles are stably emulsified and dispersed in an aqueous medium with low energy.
Further, by using this, a method for producing an electrostatic developing toner capable of producing an electrostatic image developing toner sufficiently satisfying toner characteristics, an electrostatic image developing toner obtained thereby, a developer using the toner, and An image forming method can be provided.

  Hereinafter, the present invention will be described in detail.

(Resin particle dispersion)
The resin particle dispersion of the present invention is a resin particle dispersion in which resin particles containing at least a polycondensation resin obtained by polycondensation of a polycondensable monomer in an organic solvent are dispersed, wherein the polycondensation resin However, the resin unit has one or more aromatic rings and / or alicyclic rings, and the median diameter of the resin particles is 0.05 μm or more and 2.0 μm or less.
The resin particle dispersion of the present invention is preferably produced by the method for producing a resin particle dispersion of the present invention described later, and is preferably used as a resin particle dispersion for an electrostatic charge image developing toner.

In such a resin particle dispersion of the present invention, by adopting the above configuration, the polycondensable monomer can be polycondensed in an organic solvent at a low temperature and dispersed at a low temperature. As a dispersion state of the polycondensation resin particles in the aqueous medium, for example, an isolated state in the aqueous medium can be realized even during storage, and agglomeration operation using a flocculant for toner formation Previously, it was stable for a long time, high controllability was possible only by the agglomeration operation, and formation of agglomerated particles was possible. Therefore, when this is used, the particle size distribution as a toner is improved, and polycondensation in the composition of each toner Since the glass transition point Tg of the resin is increased to a desired region, a toner sufficiently satisfying the toner characteristics can be obtained.
As a result, the initial image quality can be maintained as well as a stable image quality even during continuous printing. Moreover, it is satisfactory also about the storage property of a document.

Here, the median diameter (center diameter) of the resin particle dispersion of the present invention is from 0.05 μm to 2.0 μm, preferably from 0.1 μm to 1.5 μm, more preferably from 0.1 μm to 1. 0 μm or less. When the median diameter is in the above range, the dispersion state of the resin particles in the aqueous medium is stabilized as described above. Therefore, if the median diameter is too small at the time of toner preparation, the agglomeration property at the time of particle formation is deteriorated, free resin particles are easily generated, and the viscosity of the system is also easily increased. It becomes difficult to control the diameter. On the other hand, if the particle size is too large, coarse powder is likely to be generated, the particle size distribution is deteriorated, and a release agent such as wax is easily released.
The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

  The resin particle dispersion of the present invention is suitable not only for its median diameter but also for generation of ultrafine powder and ultracoarse powder, and a polycondensation resin having a particle diameter of 0.03 μm or less or 5.0 μm or more. The particle ratio is preferably 10% or less, more preferably 5% or less. This ratio can be obtained by plotting the relationship between the particle diameter and the frequency integration in the measurement result in LA-920 (manufactured by Horiba Ltd.) and obtaining from the frequency integration amount of 0.03 μm or less, or 5.0 μm or more. .

In order to obtain the resin particle dispersion of the present invention, for example, a polycondensable monomer is first dissolved or dispersed in an organic solvent as a target resin raw material, and then heated, stirred, and normal pressure with a catalyst at a low temperature. Or after holding under reduced pressure and, if necessary, to obtain a higher molecular weight polyester, the produced water or excess polycondensable monomer is distilled out together with an organic solvent to obtain a polymer. In a heated state, the mixture is dispersed by mixing, a homogenizer or the like, and further a radical polymerization initiator is added to form particles. Moreover, it is preferable to carry out emulsification dispersion using a surfactant, a co-surfactant, or the like during dispersion.
At this time, if necessary, other polycondensation catalysts can be used in combination.

When an organic solvent is used together with a polycondensable monomer, the viscosity of the resulting polycondensable resin can be effectively reduced during polymerization, allowing the polycondensation to proceed in a desired state, resulting in a higher molecular weight polyester. . That is, it is effective in proceeding with low-temperature polycondensation at 150 ° C. or lower. Furthermore, after polymerizing the polycondensable resin, the thickening of the polycondensation resin can be effectively suppressed even when dispersed in water, and dispersion of the resin particles at a low temperature of 150 ° C. or less can be realized. An object of the present invention is to provide a method for producing a resin particle dispersion containing a high-molecular-weight polycondensation resin suitable for toners by overcoming the above-mentioned problems as a resin particle dispersion, particularly a resin particle dispersion for toner.
Although the above is an outline, the polycondensation mechanism of the present invention will be further explained, and an effective polycondensation method of a polycondensable monomer will be exemplified.

As a method for synthesizing a polycondensation resin, for example, in the synthesis of polyester, polycondensation is generally carried out through esterification or transesterification, which is representative of direct polymerization. Since direct polymerization is a dehydration reaction, basically a reaction at a high temperature is advantageous for proceeding the polymerization. In order to proceed the reaction at a low temperature, it is necessary to create a hydrophobic environment as much as possible in the reaction field where the polycondensable monomer exists, and a mechanism for effectively removing water from the reaction field.
Furthermore, as the molecular weight of the polyester increases during polymerization, the end group concentration decreases significantly, and a decomposition reaction due to heating at the time of transesterification is also added, thereby limiting the increase in molecular weight. In order to suppress the thickening associated with the increase in molecular weight and allow the end groups to react effectively at low temperatures, it effectively increases when mixed with the polycondensable monomer and / or oligomer or polymer thereof. The presence of a medium that suppresses viscosity is inevitable.
Based on these technical ideas, it was found that when an organic solvent and a polycondensable monomer that can be used in the present invention are used, a resin particle dispersion suitable for toner can be produced. . The organic solvent can effectively reduce the viscosity of the produced polyester and produce an aqueous medium dispersion containing the polyester resin by a simple method. Furthermore, since the polycondensation resin that can be used in the present invention is subjected to polycondensation in an organic solvent, a low to high molecular weight region suitable for toner can be obtained, which is advantageous for fixability.

Furthermore, in order to produce a high molecular weight polycondensation resin in the present invention, polymerization may be carried out while distilling produced water or excess monomer out of the reaction system. In order to dehydrate water or distill excess polycondensable monomer out of the reaction system, azeotropy of the organic solvent used and water or the polycondensable monomer may be used. If the amount of water or polycondensable monomer contained in the organic solvent distilled by azeotropic distillation is greater than the saturated solubility of water or polycondensable monomer in the organic solvent, water or polycondensation is carried out by liquid separation. After removing the reactive monomer, it may be returned to the reaction system, and further treated with a dehydrating or de-monomer agent or distilled to remove water or polycondensable monomer dissolved in the organic solvent used. After reducing the content of water or the polycondensable monomer in the organic solvent by, for example, the organic solvent may be returned to the reaction system. Further, instead of the organic solvent distilled by azeotropic distillation, a new organic solvent having a low content of water or polycondensable monomer may be charged.
Also, water or excess polycondensable monomer is removed under reduced pressure at the beginning of the reaction, and then the organic solvent is added, and a part of the organic solvent is removed from the reaction mixture containing the organic solvent. The water or organic solvent of the reaction mixture can be set to a predetermined value. That is, the condensation reaction is advanced while removing water or the polycondensable monomer using an organic solvent at least at the stage of the reaction. In this embodiment, the organic solvent is azeotropic with water or the monomer. However, it may not be, and may or may not be separated from water or a polycondensable monomer. Other embodiments include a method in which an excess of an organic solvent is charged in advance and the organic solvent is dehydrated by simply extracting the organic solvent, and a method in which the organic solvent is dried using another solvent. As a further modification, the water may be removed while the organic solvent itself remains liquid.
Further, the organic solvent is more preferably recovered and reused from the viewpoint of reducing the environmental burden. As a specific example of solvent recovery, the solvent vapor generated in the solvent removal step can be cooled and condensed by a condenser and reused after recovery, or can be used by a conventionally used method such as recovery by a scrubber device.

The amount of the organic solvent remaining in the resin particles can be determined in consideration of the final toner characteristics and the remaining amount in the toner, but it is preferably as small as possible, more preferably 1% by weight or less, and further 0.5% by weight. Preferably, it is 0.1% by weight or less.
The volume average particle size of the resin particles dispersed in the resin particle dispersion of the present invention is preferably 0.05 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, and most preferably 0.15 μm to 1 μm. It is as follows. When the particle diameter is 2 μm or less, it is preferable because the production of the toner using the resin particle dispersion of the present invention is easy, the particle size distribution of the produced toner is good, and the image quality characteristics such as the resolution are excellent when using the toner. . The volume average particle diameter can be measured by a known method, and can be measured by, for example, a dynamic light scattering particle size distribution meter (LA920 manufactured by Horiba, Ltd.).

<Polycondensation resin>
The polycondensation resin that can be used in the present invention is a polycondensation having one or more aromatic rings and / or alicyclic rings in a repeating unit (hereinafter also referred to as “repeating unit”) in the chemical structure of the polycondensation resin. Resin, preferably 2 or more, more preferably 3 or more. The number of aromatic rings and / or alicyclic rings in the repeating unit is preferably 10 or less. When the polycondensation resin has no aromatic ring and / or no alicyclic ring in the repeating unit, it is difficult to raise the glass transition point Tg to a desired temperature range.
The “repeating unit” is preferably from an ester bond to an ester bond in the main chain of the polycondensation resin. Further, the main chain in the polycondensation resin may be branched or cross-linked.
The “aromatic ring” may be a monovalent or higher aromatic ring residue, and the “alicyclic ring” may be a monovalent or higher aliphatic ring residue. The aromatic ring or alicyclic ring is a divalent or higher aromatic ring. It is preferably a residue or a divalent or higher aliphatic ring residue. The alicyclic ring may have a double bond in the ring structure.
Further, the ring structure in the repeating unit in the polycondensation resin is more preferably an aromatic ring.
Further, the aromatic ring and / or alicyclic ring in the repeating unit in the polycondensed resin is preferably in the main chain of the polycondensed resin, that is, the aromatic ring and / or alicyclic ring forms part of the main chain. .
Examples of the polycondensation resin that can be used in the present invention include polyester and polyamide, and polyester is preferable. Further, the polycondensation resin may be a crystalline resin or an amorphous resin, but is preferably an amorphous resin, more preferably an amorphous polyester.
Further, the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the polycondensation resin is preferably 1 to 5, more preferably 1.5 to 4.5, and more preferably 2 to 3. Is more preferable.

The aromatic ring is preferably a hydrocarbon aromatic ring or heteroaromatic ring having 4 to 20 carbon atoms, more preferably a hydrocarbon aromatic ring or heteroaromatic ring having 4 to 10 carbon atoms, Ten hydrocarbon aromatic rings are more preferable, and a benzene ring is particularly preferable.
The aliphatic ring is preferably an alicyclic ring having 3 to 20 carbon atoms, more preferably an alicyclic ring having 5 to 10 carbon atoms, further preferably a cyclopentene ring or a cyclohexane ring, and a cyclohexane ring. It is particularly preferred that
In addition, the aromatic ring and the alicyclic ring are chemical structures in the repeating unit, and it goes without saying that any substituent or linking group may be present on the ring without departing from the scope of the present invention. Absent.
The aromatic ring and / or alicyclic ring in the polycondensed resin is preferably formed from a polycondensable monomer having an aromatic ring and / or alicyclic ring, which will be described later.

  Here, the glass transition point Tg in the case of non-crystallinity is preferably 45 to 75 ° C, more preferably 50 to 70 ° C, and further preferably 60 to 70 ° C. When the Tg is 45 ° C. or higher, the cohesive force of the binder resin itself in a high temperature range is good, and it is preferable that deterioration of peelability and hot offset do not occur during fixing. Further, it is preferable that the temperature is 75 ° C. or lower because sufficient melting can be obtained and the minimum fixing temperature does not increase.

Here, the glass transition point of an amorphous resin means the value measured by the method (DSC method) prescribed | regulated to ASTMD3418-82.
“Crystallinity” as shown in the above “crystalline polyester resin” means that, in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a stepwise endothermic change. Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 6 ° C.
On the other hand, a resin having an endothermic peak with a half-value width exceeding 6 ° C. or a resin having no clear endothermic peak means non-crystalline (amorphous).

  In addition, the polycondensation resin obtained by polycondensation of the polycondensable monomer preferably has a weight average molecular weight of 1,500 to 60,000, preferably 3,000 to 60,000. More preferably, it is 20,000-60,000, still more preferably 25,000-60,000. A weight average molecular weight of 1,500 or more is preferable because the cohesive strength of the binder resin is good and the hot offset property is excellent. Further, if it is 60,000 or less, it is preferable because the hot offset property is excellent and the minimum fixing temperature does not increase. Further, it may be partially branched or cross-linked by selecting the carboxylic acid valence and alcohol valence of the monomer, using a cross-linking agent, and the like.

<Polycondensable monomer>
In the present invention, examples of the polycondensable monomer that can be used for polycondensation include polyvalent carboxylic acids, polyols, and polyamines. In particular, as the polycondensable monomer, those that obtain a polyester through a direct ester reaction or a transesterification reaction containing a polycarboxylic acid, a polyol, and further an ester compound thereof are preferable. In this case, the polyester resin to be polymerized can take any form such as amorphous polyester (hereinafter also referred to as “amorphous (amorphous) polyester”), crystalline polyester, or a mixed form thereof. .
The polycondensable monomer polyvalent carboxylic acid and polyol preferably contain an aromatic ring and / or an alicyclic ring in a part thereof. This makes it possible to prepare the desired Tg.

The polyvalent carboxylic acid is a compound containing two or more carboxyl groups in one molecule. Among these, divalent carboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, Nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, malic acid, citric acid, hexahydroterephthalate Acid, malonic acid, pimelic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycol Acid, p-phenylene diglycolic acid, o-phenylene diglycol Examples include phosphoric acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, etc. Can do. Examples of the polyvalent carboxylic acid other than the divalent carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid and the like, and lower esters thereof. Etc. Furthermore, the acid chloride is not limited to this. The lower ester refers to an ester of an aliphatic alcohol having 1 to 8 carbon atoms.
These polyvalent carboxylic acids may be used alone or in combination of two or more. Further, a dicarboxylic acid component having a double bond can be contained in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above.

  A polyol is a compound containing two or more hydroxyl groups in one molecule. Among these, the diol is a compound containing two hydroxyl groups in one molecule, and examples thereof include ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, and dodecanediol. Can do. Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine, and these may be used alone. Two or more types may be used in combination.

  In the present invention, examples of the hydroxycarboxylic acid that can be used as the polycondensable monomer include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, and hydroxyundecanoic acid. These may be used alone or in combination of two or more.

  In the present invention, polyamines that can be used to obtain polyamide include ethylenediamine, diethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-butenediamine, Examples include 2,2-dimethyl-1,3-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), and the like. .

  Furthermore, for example, polyvalent carboxylic acids used to obtain crystalline polyesters and crystalline polyamides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, Sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutamic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid Examples thereof include acids, acid anhydrides thereof, and lower esters thereof. Furthermore, the acid chloride is not limited to this.

  Furthermore, for example, the polyol used to obtain the crystalline polyester includes ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, , 4-butenediol, neopentyl glycol, 1,5-pentane glycol, 1,6-hexane glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Mention may also be made of tetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A and the like.

The polycondensation resin contained in the resin particles dispersed in the resin particle dispersion of the present invention is a polycondensable monomer having one or more aromatic rings and / or alicyclic rings among the polycondensable monomers described above. It is preferable to synthesize using at least one body.
The polycondensation resin is a resin obtained by polycondensation of a polycarboxylic acid or a derivative thereof and a polyalcohol, and at least one of the polycarboxylic acid and / or the polyalcohol is an aromatic ring and / or an oil. A compound having a ring is preferable.
As the polycondensable monomer, a polycondensable monomer having an aromatic ring and / or an alicyclic ring and having a carboxyl group and / or a hydroxyl group directly bonded to the ring structure may be used. It is preferable to use a polycondensable monomer having an aromatic ring and having a carboxyl group and / or a hydroxyl group directly bonded to the ring structure, and among them, an aromatic polyvalent carboxylic acid is used. Is more preferable.

In addition, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers.
In the present invention, it is particularly desirable to use a non-crystalline resin that has a wide temperature range from the minimum fixing temperature to the offset and that can achieve a high level of toner powder fluidity.

  The non-crystalline resin is selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, fumaric acid, trimellitic acid, pyromellitic acid, fumaric acid, and acid anhydrides and lower esters thereof as polyvalent carboxylic acids. At least one polycarboxylic acid and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2 as polyalcohol At least one selected from the group consisting of -bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) ethane, cyclohexanedimethanol, bisphenol S A polyester obtained by reacting with a polyol is preferable.

  In addition, as crystalline resins, 1,9-nonanediol and 1,10-decanedicarboxylic acid, or polyester obtained by reacting cyclohexanediol and adipic acid, 1,6-hexanediol and sebacic acid are reacted. Polyester obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, obtained by reacting 1,4-butanediol and succinic acid Mention may be made of polyester. Among these, polyesters obtained by reacting 1,9 nonanediol with 1,10-decanedicarboxylic acid and 1,6-hexanediol with sebacic acid are more preferable, but not limited thereto.

<Organic solvent>
Specific examples of the organic solvent that can be used in the present invention include, for example, hydrocarbon solvents such as toluene, xylene, mesitylene, chlorobenzene, bromobenzene, iodobenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane. Halogen solvents such as p-chlorotoluene, ketone solvents such as 3-hexanone, acetophenone and benzophenone, dibutyl ether, anisole, phenetole, o-dimethoxybenzene, p-dimethoxybenzene, 3-methoxytoluene, dibenzyl ether, Ether solvents such as benzyl phenyl ether, methoxynaphthalene and tetrahydrofuran, thioether solvents such as phenyl sulfide and thioanisole, ethyl acetate, butyl acetate, pentyl acetate, methyl benzoate, methyl phthalate, phthalic acid Ester solvents such as chill and cellosolve acetate, diphenyl ether, or alkyl-substituted diphenyl ethers such as 4-methylphenyl ether, 3-methylphenyl ether, and 3-phenoxytoluene, or 4-bromophenyl ether, 4-chlorophenyl ether, 4 -Halogen-substituted diphenyl ethers such as bromodiphenyl ether and 4-methyl-4'-bromodiphenyl ether, or alkoxy such as 4-methoxydiphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether, 4-methyl-4'-methoxydiphenyl ether Examples thereof include diphenyl ether solvents such as substituted diphenyl ethers and cyclic diphenyl ethers such as dibenzofuran and xanthene, and these may be used in combination. A solvent that can be easily separated from water is preferable. In order to obtain a polyester having a high average molecular weight, an ester solvent, an ether solvent, and a diphenyl ether solvent are more preferable, and an alkyl-aryl ether solvent and an ester are preferable. System solvents are particularly preferred.

  Furthermore, in the present invention, in order to obtain a polyester having a high average molecular weight, a dehydration and demonomer may be added to the organic solvent. Specific examples of the dehydration and demonomer include, for example, molecular sieves such as molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X, alumina, silica gel, calcium chloride, calcium sulfate, diphosphorus pentoxide, concentrated Examples include sulfuric acid, magnesium perchlorate, barium oxide, calcium oxide, potassium hydroxide, sodium hydroxide, metal hydrides such as calcium hydride, sodium hydride, lithium aluminum hydride, or alkali metals such as sodium. It is done. Among these, molecular sieves are preferable because of easy handling and regeneration.

The amount of the organic solvent at the time of polycondensation is preferably 0.5 to 5 times, more preferably 0.7 to 3 times, and most preferably 0.8 to 2 times as a volume ratio with respect to the polycondensable resin. It is. A volume ratio of 0.5 or more is preferable because the resin viscosity can be effectively reduced and a high molecular weight polycondensable resin can be easily obtained. A volume ratio of 5 times or less is preferable because the resin concentration does not decrease and the production efficiency is excellent.
It is desirable that the amount of water contained in the organic solvent is as low as possible. This depends on the type of polycondensable monomer and the concentration of the organic solvent in the polycondensable monomer, but when the moisture content of the organic solvent is relatively high at 2 to 5% by weight, Since the molecular weight of the condensation resin is 40,000 or less, the water content in the organic solvent is preferably 2% by weight or less. In order to obtain a high molecular weight of 40,000 or more, the water content in the organic solvent is more preferably 1% by weight or less. The amount of moisture can be achieved by combining the types of organic solvents in a timely manner.
It is preferable that at least one of the polycondensable monomers is dissolved in the organic solvent. This relationship between the monomer and the organic solvent effectively promotes the polymerization, resulting in an increase in the molecular weight of the resin at low temperatures.

<Aqueous medium>
In the present invention, the dispersion medium of the resin particle dispersion is an aqueous medium.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used alone or in combination of two or more.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

Furthermore, the most preferable dispersion medium for the resin particle dispersion of the present invention is water, but the solid content in the resin particle dispersion of the present invention is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight. Parts, most preferably 15 to 25 parts by weight. It is preferable that the solid content of the resin particle dispersion of the present invention is 5 parts by weight or more because the viscosity of the polymer composition is appropriate, the particle stability is excellent, and the transportation cost is excellent. Moreover, it is preferable for it to be 40 parts by weight or less because the viscosity is appropriate, the uniformity of stirring can be maintained, and polycondensation proceeds sufficiently.
In the polymerization in the aqueous medium, it is possible to previously mix a colorant, a wax and the like in addition to the monomer components before polycondensation. By doing so, polycondensation resin composite particles can be obtained in a form incorporating a colorant and wax.
When dispersing in an aqueous medium, the polycondensed resin and organic solvent mixture is dispersed in the aqueous medium using, for example, mechanical shear or ultrasonic waves. An activator, a polymer dispersant, an inorganic dispersant, and the like can be added to the aqueous medium. Further, before dispersion, an organic solvent may be added to the polycondensation resin-containing material as necessary to adjust the solid content.

<Additives such as surfactants>
The resin particle dispersion of the present invention may contain additives such as a surfactant, a polymer dispersant, and an inorganic dispersant.
When dispersing the polycondensation resin in the aqueous medium, the above-mentioned materials are dispersed in the aqueous medium by using, for example, mechanical shear or ultrasonic waves. It is also possible to carry out emulsification and dispersion using a polymer, or to add a polymer dispersant, an inorganic dispersant or the like to an aqueous medium. In addition, a surfactant, a polymer dispersant, an inorganic dispersant and the like can be mixed and added to the polycondensable monomer.

  Examples of the surfactant that can be used in the present invention include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type. Agents: Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, and the like. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

Anionic surfactants include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3′-disulfonediphenylurea-4,4′-diazo-bis-amino-8-naphthol Sodium 6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2 ′, 5,5′-tetramethyl-triphenylmethane-4,4′-diazo-bis-β-naphthol-6-sulfone Sodium sulfate, sodium dialkylsulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, capron Examples thereof include sodium acid, potassium stearate, calcium oleate and the like.
Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters.

Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present invention.
Further, in order to prevent the Ostwald Ripping phenomenon of the monomer emulsion particles in an ordinary aqueous medium, a higher alcohol represented by heptanol or octanol or a higher aliphatic hydrocarbon represented by hexadecane is often added as a stabilizer. It is also possible.

If necessary, an addition polymerizable monomer, preferably a radical polymerizable monomer, may be added to the polycondensable monomer of the present invention or a polycondensation resin-containing product in which an organic solvent or the like is mixed with the polycondensation resin. In addition, polycondensation and addition polymerization may be performed simultaneously or separately to form a composite. Examples of the addition polymerizable monomer include a cationic polymerizable monomer and a radical polymerizable monomer, and a radical polymerizable monomer is preferable.
Specific examples of the radical polymerizable monomer used in this case include α-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, m-methylstyrene, p-methylstyrene, 2 , Vinyl aromatics such as nucleus-substituted styrene such as 5-dimethylstyrene, nucleus-substituted halogenated styrene such as p-chlorostyrene, p-bromostyrene and dibromostyrene, (meth) acrylic acid (in addition, “(meth) acrylic” "Means acrylic and methacrylic, and the same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate Unsaturated carboxylic acid esters such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide, etc. Unsaturated carboxylic acid derivatives, N-vinyl compounds such as N-vinyl pyridine and N-vinyl pyrrolidone, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, vinyl chloride, vinyl bromide, vinylidene chloride, etc. Halogenated vinyl compounds, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylo N-substituted unsaturated amides such as lumaleimide, conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythrito Tritrimethacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer. These can be used alone or in combination.

<Polymerization initiator>
The addition polymerizable monomer, particularly a radical polymerizable monomer, can be polymerized by a method using a radical polymerization initiator, a self-polymerization by heat, a method using ultraviolet irradiation, or a known polymerization method. In this case, the radical initiator may be oil-soluble or water-soluble as a method using a radical initiator, but either initiator may be used.
Specifically, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2 Azobisnitriles such as' -azobis (2-amidinopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxide such as oxide, di-t-butyl peroxide, t-butyl-α-cumyl peroxy And dialkyl peroxides such as dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxy Peroxyesters such as laurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2, Hydroperoxides such as 5-dihydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, inorganic such as hydrogen peroxide Peroxides, Examples include radical polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. A redox polymerization initiator may be used in combination.
Moreover, you may use a chain transfer agent at the time of addition polymerization. There is no restriction | limiting in particular as a chain transfer agent, Specifically, what has the covalent bond of a carbon atom and a sulfur atom is preferable, For example, thiols are mentioned preferably.

<Co-surfactant>
In the present invention, a co-surfactant can be used in combination in order to keep the average particle size of the polycondensation resin-containing product (oil phase) containing the addition polymerizable monomer within a specific range. As the surfactant, those that are water-insoluble or hardly soluble and monomer-soluble, and those used in the conventionally known “miniemulsion polymerization” described later in detail can be used.
Examples of suitable cosurfactants include alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane and octadecane, alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol, lauryl (meta ) C8-C30 alkyl (meth) acrylates such as acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, C8-C30 alkyl mercaptans such as lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, and the like. Other examples include polymers such as polystyrene and polymethyl methacrylate, polyadducts, carboxylic acids, ketones, and amines.

  Here, in order to form a fine particle emulsion, for example, a monomer solution to which a co-surfactant is added and an aqueous solution of a surfactant are mixed with a piston homogenizer, a microfluidizer (for example, “Microfluid” manufactured by Dix Corporation). The mixture is uniformly mixed and emulsified by a shear mixing device such as a microfluidizer ") or an ultrasonic disperser. At that time, the amount of monomer charged with respect to water is about 0.1 to 50% by weight with respect to the total amount with water, and the amount of surfactant used is the critical micelle concentration in the presence of the emulsion to be formed. The amount of cosurfactant used is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer. Part.

  In the present invention, the polymerization of the monomer in the presence of the polymerization initiator of the monomer emulsion by the combined use of the surfactant amount less than the aforementioned critical micelle concentration (CMC) and the co-surfactant is, for example, PL Tang, ED Sudol, CA Silebi, MS El-Aasser, J. Appl. Polym. Sci., 43, 1059 (1991), etc., known as “mini-emulsion polymerization”. Conventional emulsion polymerization in which an aqueous emulsion of monomer particles having a particle size of about several microns is polymerized using a water-soluble polymerization initiator in the presence of a surfactant amount equal to or higher than the critical micelle concentration (CMC). Polymerization starts in a surfactant micelle and is supplied by diffusion of monomer from monomer particles, and polymer particles grow and form. Uniform polymer particles are formed because the monomer is polymerized in the monomer particles. In addition, in the “miniemulsion polymerization” of the polycondensation resin / addition polymerization resin composite polymer, it is not necessary to diffuse the monomer in the polymerization process, so the polymerized addition polymerization resin is directly contained in the polymer particles. Has advantages that may exist.

  Further, for example, a particle size of 5 to 50 nm described in JS Guo, MS El-Aasser, JW Vanderhoff, J. Polym. Sci .: Polym. Chem. Ed., 27, 691 (1989), etc. The so-called “microemulsion polymerization” of the microparticles has a dispersion structure and a polymerization mechanism similar to those of “miniemulsion polymerization”. In “microemulsion polymerization”, a surfactant having a critical micelle concentration (CMC) or higher is used. It is used in a large amount, and a large amount of surfactant is mixed in the resulting polymer particles, or a lot of time is required for water washing, acid washing or alkali washing for the removal. There are problems such as.

(Method for producing resin particle dispersion)
In the method for producing a resin particle dispersion according to the present invention, a resin particle containing at least a polycondensation resin having at least one aromatic ring and / or alicyclic ring in a repeating unit has a median diameter of 0.05 μm or more and 2.0 μm or less. A method for producing a resin particle dispersion dispersed in a medium, comprising a polycondensation step of polycondensing a polycondensable monomer using a polycondensation catalyst in an organic solvent to obtain a polycondensation resin-containing material, and The method includes a dispersion step of dispersing the polycondensation resin-containing material in an aqueous medium to obtain a resin particle dispersion.
The resin particle dispersion produced by the method for producing a resin particle dispersion of the present invention is preferably used as a resin particle dispersion for an electrostatic charge image developing toner.

<Polycondensation process>
The method for producing a resin particle dispersion of the present invention includes a polycondensation step in which a polycondensable monomer is polycondensed in an organic solvent using a polycondensation catalyst to obtain a polycondensation resin-containing product.
During the production of the polycondensation resin in the polycondensation process, even if it is carried out in an inert gas (for example, dry nitrogen, argon, etc.) atmosphere so that moisture does not enter from the outside of the system, the inert gas is replaced or inert. You may carry out, bubbling with gas.
As a method for producing a polycondensation resin, for example, an organic solvent and a polycondensable monomer itself can be stirred together with a catalyst in a liquid state at an appropriate temperature to remove water and proceed with the reaction. Alternatively, the reaction can be carried out by distilling the polycondensable monomer together with the organic solvent while distilling out of the reaction system. Furthermore, the produced water or polycondensable monomer is distilled out of the reaction system together with the organic solvent, and the water or polycondensation monomer is the same as or lower than the water or polycondensable monomer dissolved in the distilled organic solvent. It is also possible to react while charging an organic solvent having a condensable monomer into the reaction system.
As a preferable example of the embodiment, an example using bisphenol A ethylene oxide adduct and dimethyl terephthalate as a polycondensable monomer and butyl acetate as an organic solvent will be described below.

  The reactor is charged with butyl acetate, a predetermined amount of bisphenol A ethylene oxide adduct, dimethyl terephthalate and a predetermined amount of catalyst, and the reactor is heated to proceed the reaction while distilling the produced water. The reactor is equipped with a water separator (for example, Dean Stark trap). Water having a solubility higher than that of butyl acetate is separated by the water separator and removed from the system. Return to reaction system. At this stage, the bisphenol A ethylene oxide adduct and dimethyl terephthalate are oligomerized. The weight average molecular weight at this stage is 500 to 1,000, and the weight average molecular weight may be up to about 5,000. The reaction time during this period is approximately 0.5 to several hours. This oligomerization reaction may be carried out in advance in a separate reactor without solvent, without catalyst, under reduced pressure, or without catalyst and at normal pressure. Moreover, it is not necessary to perform oligomerization. The water generated as the reaction proceeds may be removed at the butyl acetate distillation temperature, and the reaction may be continued while returning butyl acetate saturated with water to the reaction system. However, those having a weight average molecular weight of 15,000 to 50,000 are obtained. In order to obtain a higher molecular weight polymer, after the water in the raw material has almost distilled off, remove the water separator, attach a tube filled with a desiccant such as molecular sieve, and distillate butyl acetate passes through this tube. Or distilled butyl acetate is treated in a separate reactor containing a desiccant and returned to the reactor, or fresh low butyl acetate is added to the reactor. Insert. After completion of the reaction, a desired polymer composition is obtained.

The weight average molecular weight of the polycondensation resin obtained by the method of the present invention varies depending on the type of organic solvent, the type and amount of the catalyst, the reaction temperature, the reaction time, the treatment method distilled by azeotropic distillation, etc. Of 500 to 500,000. According to the method of the present invention, a polyester having a high molecular weight (weight average molecular weight (Mw): 4,000 to 500,000) can be easily produced by appropriately selecting reaction conditions.
The preferable polycondensation temperature in the method for producing the resin particle dispersion of the present invention is preferably low in consideration of energy saving, the production rate of the polymer and the thermal decomposition rate of the produced polymer, but preferably 60 to 150 ° C. Yes, more preferably 80 to 130 ° C. When the polycondensation temperature is 150 ° C. or lower, the required energy does not become excessive, and the resin does not decompose due to high heat, so that a peaking phenomenon in which the molecular weight does not increase any more does not occur. Moreover, since the reactivity is favorable and the polycondensation resin of desired molecular weight is obtained as it is 60 degreeC or more, it is preferable.
Furthermore, the polycondensation reaction may be carried out at the distillation temperature of the organic solvent used under normal pressure. When using a high-boiling polycondensable resin in order to bring the reaction temperature into a preferred range, it may be carried out under reduced pressure, and when using a low-boiling polycondensable resin, it may be carried out under pressure. Good.

<Polycondensation catalyst>
In the polycondensation step of the present invention, the reaction rate can be increased by using a polycondensation catalyst.
In the polycondensation of the polycondensable monomer in the present invention, a known polycondensation catalyst can be blended in the polycondensable monomer in advance if necessary. In addition, in order to polycondense the polycondensable monomer at a low temperature of 150 ° C. or lower or 100 ° C. or lower, a polycondensation catalyst is usually used. In addition, a rare earth-containing catalyst or a hydrolase can be used in combination.

As the acid catalyst, those showing acidity such as Bronsted acid are preferable. Specifically, sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, camphor sulfonic acid, and Na salts thereof are used. Can be mentioned.
Furthermore, an acid having a surface active effect may be used. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and has an acid structure in which at least a part of the hydrophilic group is composed of protons.
Examples of the acid having a surface active effect include alkylbenzene sulfonic acid such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, Higher fatty acid sulfates such as alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutylphenyl phenol sulfuric acid, dibutyl phenyl phenol sulfuric acid, dodecyl sulfuric acid , Higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alcohol Sulfated sulfate ester, naphthenyl alcohol sulfate, sulfated fat, sulfosuccinate ester, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate ester, resin acid, resin acid alcohol sulfate, naphthenic acid, p-toluenesulfonic acid and these Examples include all salt compounds, and a plurality of them may be combined as necessary.

As the rare earth-containing catalyst, scandium (Sc), yttrium (Y), as the lanthanoid element, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and the like are effective, especially alkylbenzenesulfone Acid salts, alkyl sulfate esters, or those having a triflate structure are effective.
As the rare earth-containing catalyst, those having a triflate structure such as scandium triflate, yttrium triflate, and lanthanoid triflate are preferable. The lanthanoid triflate is described in detail in Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54). An example of the triflate is X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is more preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.

  The hydrolase used in combination is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase include EC (enzyme number) 3.1 group (Maruo, Lipoprotein lipase, etc.) such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase and lipoprotein lipase. Hydrolase, epoxide hydrase, etc. classified into EC 3.2 group that acts on glycosyl compounds such as esterase, glucosidase, galactosidase, glucuronidase, xylosidase, etc. classified in “Enzyme Handbook” supervised by Tamiya (1982). It is classified into EC3.4 group that acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin etc. Hydrolase, mention may be made of hydrolytic enzymes such as classified into EC3.7 group such as furo retinoic hydrolase.

  Among these esterases, the enzyme that hydrolyzes glycerol esters and liberates fatty acids is called lipase, but lipase has high stability in organic solvents, catalyzes ester synthesis reaction in high yield, and can be obtained at a low price. There are advantages such as. Therefore, also in the manufacturing method of polyester of this invention, it is preferable to use a lipase from the surface of a yield or cost.

  Lipases of various origins can be used, but preferred are Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, steapsin and the like. Among these, it is preferable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

  These polycondensation catalysts may be used alone or in combination. Furthermore, these catalysts can be recovered and regenerated if necessary.

<Dispersing process>
The method for producing a resin particle dispersion of the present invention includes a dispersion step of dispersing the polycondensation resin-containing material in an aqueous medium to obtain a resin particle dispersion.
In the dispersion step, it is preferable to carry out emulsification dispersion by adding a surfactant or the like in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.
Polymerization of particles in these aqueous media obtained by dispersing and granulating the polycondensation resin polycondensed in an organic solvent solution includes suspension polymerization, dissolution suspension, and miniemulsion. It is possible to use a polymerization form in a normal aqueous medium such as a microemulsion method, a multistage swelling method, or an emulsion polymerization method including seed polymerization. In this case, as shown above, since the polycondensation reaction, particularly the final molecular weight and the polymerization rate depend on the final diameter of the particles, the median diameter of 1 μm or less as the most preferable particle form is achieved, and efficient production is achieved. As a method that can be achieved, it is most desirable to carry out the solvent removal after the particle tonality by the dissolution suspension method. Alternatively, the polycondensation resin-containing material may be introduced and dispersed in the aqueous medium, or the aqueous medium may be introduced into the polycondensation resin-containing material and dispersed while passing through the phase change.
Furthermore, the preferable emulsification temperature in the method for producing the resin particle dispersion of the present invention is preferably lower in consideration of energy saving, polymer production rate and thermal decomposition rate of the produced polymer, but preferably 40 to 150 ° C. More preferably, it is 80-130 degreeC. It is preferable that the emulsification temperature is 150 ° C. or lower because the required energy does not become excessive and the molecular weight is not lowered due to decomposition of the resin due to high heat. Moreover, it is preferable for the temperature to be 40 ° C. or higher because the resin viscosity is moderate and the formation of fine particles is easy.

The dispersing step preferably includes a step of removing at least part of the organic solvent and a step of forming resin particles.
For example, it is preferable to solidify as particles by removing part of the organic solvent after emulsifying the polycondensation resin-containing material. As a specific method of solidification, after the polycondensation resin-containing material is emulsified and dispersed in an aqueous medium, while stirring the solution, an inert gas such as air or nitrogen is fed into the organic solvent at the gas-liquid interface. A method of drying (waste wind drying method), a method of drying while holding under a reduced pressure and bubbling an inert gas as necessary (a reduced pressure topping method), and further a polycondensation resin-containing material in an aqueous medium There is a method in which an emulsified dispersion or emulsified dispersion of a polycondensation resin-containing material is discharged from the pores in a shower-like manner and dropped into a dish-shaped receiver (for example, a shower-type desolvent method). . It is preferable to remove the solvent by selecting or combining these methods as appropriate based on the evaporation rate of the organic solvent to be used, solubility in water, and the like.

(Electrostatic image developing toner and method for producing the same)
The method for producing an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”) of the present invention includes a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles (hereinafter referred to as “a toner”). A method for producing an electrostatic charge image developing toner comprising a step of heating and fusing the agglomerated particles (hereinafter also referred to as a “fusing step”), wherein the resin particle dispersion The liquid is the resin particle dispersion of the present invention.
In the method for producing an electrostatic image developing toner of the present invention, the dispersion containing at least the resin particle dispersion of the present invention, if necessary, particles containing colorant particles (the colorant is contained in the resin in the polycondensation step or the like). When added in advance, the particles themselves may be added), release agent particles, other resin particles, or dispersions thereof. The method for producing an electrostatic charge image developing toner according to the present invention comprises agglomerating (associating) toner particles by using a known aggregating method that agglomerates (associates) the resin particles and other added particles in the dispersion. It is possible to adjust the diameter and particle size distribution. Preferably, toner particle adjustment in an emulsion polymerization aggregation method is used. Specifically, the resin particle dispersion of the present invention is mixed with a colorant particle dispersion, a release agent particle dispersion, etc., and an aggregating agent is added to form heteroaggregation to form aggregated particles having a toner diameter. Then, it is obtained by heating to a temperature above the glass transition point of the resin particles or above the melting point to fuse and coalesce the aggregated particles, and wash and dry. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

In the agglomeration step of the present invention, the resin particle dispersion other than the resin particle dispersion of the present invention and the resin particle dispersion of the present invention can be mixed to carry out the steps after the aggregation. At that time, after the resin particle dispersion of the present invention is aggregated in advance and the first aggregated particles are formed, the resin particle dispersion of the present invention or another resin particle dispersion is further added to form a second shell on the surface of the first particles. It is also possible to make the particles multi-layered, such as forming a layer. Of course, it is also possible to produce multilayer particles in the reverse order of the above example.
Further, for example, in the aggregation step, the resin particle dispersion containing the polycondensation resin of the present invention and the colorant particle dispersion are aggregated in advance, and after forming the first aggregated particles, the resin particles further containing the polycondensation resin of the present invention It is also possible to add a dispersion or another resin particle dispersion to form a second shell layer on the surface of the first particles. In this illustration, the colorant dispersion is separately adjusted, but naturally, the colorant may be blended in advance with the polycondensation resin particles in the present invention.

  As a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as aggregation control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B, and those having a valence of 2 or more and soluble in the form of ions in the resin particle aggregation system. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, it is preferable that the valence of the inorganic metal salt is bivalent rather than monovalent, and trivalent or more valent than bivalent. A type of inorganic metal salt polymer is more suitable.

  In addition to the resin particle dispersion of the present invention, other polycondensation resin particle dispersions and addition polymerization resin particle dispersions prepared using conventionally known emulsion polymerization and the like can be used together. The median diameter of the resin particles in the addition polymerization resin particle dispersion that can be used in the present invention is preferably 0.02 μm or more and 2.0 μm or less. As addition polymerization resin, what superposed | polymerized the addition polymerizable monomer mentioned above is preferable.

In the present invention, the aggregating method of the colorant-containing polymer particles obtained by the above-described polymerization is not particularly limited, and the aggregating method conventionally used in the emulsion polymerization aggregating method of electrostatic image developing toner. For example, a method of reducing the stability of the emulsion by elevating temperature, changing pH, adding salt, etc., and stirring with a disperser or the like is used.
Further, after the agglomeration treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing colorant exudation from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

In addition, in the method for producing an electrostatic charge image developing toner of the present invention, a charge control agent used for this type of toner may be used, if necessary. It can be added as an aqueous dispersion or the like at the start of production of the fine particle emulsion, at the start of polymerization, or at the start of aggregation of the polymer particles. The amount of the charge control agent added is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.
As the charge control agent, for example, nigrosine dye, quaternary ammonium salt compound, triphenylmethane compound, imidazole compound, positive charge control agent such as polyamine resin, or chromium, cobalt, aluminum, Loads of metal-containing azo dyes such as iron, metal salts and metal complexes of hydroxycarboxylic acid such as salicylic acid or acrylsalicylic acid and benzylic acid, chromium, zinc and aluminum, amide compounds, phenolic compounds, naphtholic compounds and phenolamide compounds Known materials such as an electric charge control agent can be used.

Further, in the method for producing an electrostatic charge image developing toner of the present invention, if necessary, waxes as a release agent used for this kind of toner may be used. It can be added as an aqueous dispersion or the like at the start of production of the monomer fine particle emulsion, at the start of polymerization, or at the start of aggregation of the polymer fine particles. Further, the addition amount of the release agent is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.
As the release agent, for example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax such as ethylene-propylene copolymer, paraffin wax, hydrogenated castor oil, carnauba wax, rice wax and other plant wax, stearin Higher fatty acid ester waxes such as acid esters, behenic acid esters and montanic acid esters, higher fatty acids such as alkyl-modified silicone and stearic acid, higher alcohols such as stearyl alcohol, higher fatty acid amides such as oleic acid amide and stearic acid amide, di A well-known thing, such as a ketone which has long-chain alkyl groups, such as a stearyl ketone, can be used.
Furthermore, in the method for producing an electrostatic charge image developing toner of the present invention, various known internal additives such as antioxidants and ultraviolet absorbers used for this type of toner may be used as necessary.
The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention has an average particle diameter of about 1 to 10 μm, and is preferably contained in the particles with respect to 100 parts by weight of the binder polymer. Contains 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, particularly preferably 1 to 25 parts by weight of a colorant.

<Colorant>
Examples of the colorant that can be used in the present invention include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B. , Brilliantamine 6B, dapon oil red, pyrazolone red, risor red, rhodamine B rake, lake red C, rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare Various pigments such as rate, titanium black, acridine, xanthene, azo, benzoquinone, azine , Anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, xanthene, etc. Various dyes can be used alone or in combination of two or more.
Examples of the colorant include carbon black, nigrosine dye (CINo.50415B), aniline blue (CINo.50405), calco oil blue (CINo.azoic Blue3), chrome yellow (CINo.14090), ultramarine blue (CINo. .77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160), Malachite Green Oxalate (CINo.42000), Lamp Black ( CI No. 77266), Rose Bengal (CI No. 45435), a mixture thereof, and the like can be used.
The amount of the colorant used is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner.

  As these dispersion methods, any method such as a general dispersion method such as a rotary shear type homogenizer, a ball mill having media, a sand mill, or a dyno mill can be used, and is not limited at all. Further, these colorant particles may be added to the mixed solvent at the same time as other fine particle components, or may be divided and added in multiple stages.

The electrostatic charge image developing toner of the present invention may contain a magnetic material and a property improving agent as necessary.
As the magnetic material, ferrite, magnetite and other iron, cobalt, nickel and other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or containing no ferromagnetic elements, but by performing an appropriate heat treatment Mention may be made of alloys that exhibit ferromagnetism, such as alloys of the type called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide. For example, in the case of obtaining a black toner, it is particularly preferable to use magnetite which is black in itself and also functions as a colorant. In the case of obtaining a color toner, a toner having a small blackness such as metallic iron is preferable. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 to 70 parts by weight, more preferably 40 to 70 parts by weight per 100 parts by weight of the toner.

Examples of the property improver include a fixability improver and others.
Examples of fixability improvers include polyolefins, fatty acid metal salts, fatty acid esters and fatty acid ester waxes, partially saponified fatty acid esters, higher fatty acids, higher alcohols, fluid or solid paraffin waxes, polyamide waxes, polyhydric alcohol esters, Silicon varnish, aliphatic fluorocarbon, and the like can be used. In particular, a wax having a softening point (ring and ball method JIS K2531) of 60 to 150 ° C. is preferable.

Furthermore, the toner of the present invention is preferably used by mixing inorganic particles such as a fluidity improver.
The inorganic particles that can be used in the present invention are particles having a primary particle diameter of 5 nm to 2 μm, preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion mixed with the toner is 0.01 to 5% by weight, preferably 0.01 to 2.0% by weight. Examples of such inorganic powder include silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica 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, and silica powder is particularly preferable.
The silica powder here is a powder having a Si—O—Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable.
Specific examples of these silica powders include various commercially available silicas, but those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (manufactured by Aerosil Co., Ltd.) ), Thalax 500 (manufactured by Tarco) and the like. In addition, silica powder treated with a silane coupling agent, a titanium coupling agent, silicon oil, silicon oil having an amine in the side chain, or the like can be used.

  After the fusion process is completed, desired toner particles can be obtained through any washing process, solid-liquid separation process, and drying process. In consideration of the charging property, it is preferable that the washing step is sufficiently replaced with ion exchange water. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

The cumulative volume average particle diameter D ₅₀ of the toner obtained by the method for producing an electrostatic charge image developing toner of the present invention is preferably in the range of 3.0 to 9.0 μm, more preferably 3.0 to 5.0 μm. The range of is appropriate. It is preferable that D ₅₀ is 3.0 μm or more because the adhesive force is appropriate and the developability is good. Moreover, since it is excellent in the resolution of an image as it is 9.0 micrometers or less, it is preferable.

  Further, the volume average particle size distribution index GSDv of the obtained toner is preferably 1.30 or less. A GSDv of 1.30 or less is preferable because of excellent resolution and image defects such as toner scattering and fogging hardly occur.

Here, the cumulative volume average particle size D ₅₀ and the average particle size distribution index are, for example, the particle size distribution measured by a measuring instrument such as Coulter Counter TAII (manufactured by Nikka Kisha Co., Ltd.), Multisizer II (manufactured by Nikka Kisha Co., Ltd.), or the like. The particle size range (channel) divided based on the volume and number are cumulative distributions starting from the small diameter side, and the particle size that is 16% cumulative is the volume D _16v , the number D _16P , and the particle that is 50% cumulative The diameter is _defined as a volume D _50v and a number D _50P , and the particle diameter at a cumulative 84% is defined as a volume D _84v and a number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

  The shape factor SF1 of the toner of the present invention is preferably in the range of 100 to 140, more preferably in the range of 110 to 135, from the viewpoint of image formability. The shape factor SF1 of the present invention is obtained by the following method, for example. First, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and the absolute maximum length of toner particles and the projected area of toner particles are measured for 50 or more toners. It can obtain | require by the type | formula of.

式中、ＭＬ：トナー粒子の絶対最大長、Ａ：トナー粒子の投影面積と定義する。
これらは、主に顕微鏡画像または走査電子顕微鏡画像を画像解析装置によって解析することによって数値化される。

In the formula, ML is defined as an absolute maximum length of toner particles, and A is defined as a projected area of toner particles.
These are quantified mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer.

  The obtained toner is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, and resins such as vinyl resins, polyesters and silicones. The particles can be added to the surface of the toner particles while being sheared in a dry state.

  In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

(Electrostatic image developer)
The toner obtained by the method for producing an electrostatic image developing toner of the present invention can be used as an electrostatic image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development according to an electrostatic latent image can be applied.
The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
Further, the electrostatic image developer (electrostatic image developing toner) can be used in an ordinary electrostatic image developing system (electrophotographic system) image forming method.
The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing for thermally fixing the toner image transferred to the surface of the transfer target. An electrostatic charge image developing toner of the present invention as the toner, or an electrostatic charge image developer of the present invention as the developer.
Specifically, for example, a latent image forming process, a developing process, a transfer process, and a fixing process are included, and a cleaning process, a recycling process, and the like may be included as necessary.

Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.
The latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention.
The transfer step is a step of transferring the toner image onto a transfer body.
The fixing step is a step of thermally fixing the toner image transferred to the surface of the transfer target.
The cleaning step is a step of removing the electrostatic charge image developer remaining on the electrostatic latent image carrier.
In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

In the image forming method of the present invention, a developer is prepared using the specific toner as described above, and an electrostatic image is formed and developed with a conventional electrophotographic copying machine using the developer. The image is electrostatically transferred onto the transfer paper, and is fixed by a heating roller fixing machine in which the temperature of the upper heating roller is set to a constant temperature to form a copy image.
In the heat fixing by the fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.
The image forming method of the present invention is particularly preferably used for high-speed fixing in which the contact time between the toner on the transfer paper and the heating roller is within 1 second, particularly within 0.5 seconds.

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples. In the examples, “parts” means parts by weight unless otherwise specified.
The toner of this example was prepared by preparing the following resin particle dispersion, colorant particle dispersion, and release agent particle dispersion, respectively, and mixing and stirring them at a predetermined ratio, while polymerizing a metal salt. And are ionically neutralized to form agglomerated particles. Next, an inorganic hydroxide is added to adjust the pH in the system from weakly acidic to neutral, and then the mixture is heated to a temperature equal to or higher than the glass transition point of the resin particles to fuse and unite. After completion of the reaction, a desired toner is obtained through sufficient washing, solid-liquid separation, and drying processes. Hereinafter, each preparation method is demonstrated.

<Measurement of melting point>
According to the differential scanning calorimetry (DSC), it can be measured by, for example, “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.). The melting point was determined from the baseline and endothermic peak.

<Measurement of weight average molecular weight Mw and number average molecular weight Mn>
The values of the weight average molecular weight Mw and the number average molecular weight Mn can be determined by various methods, and there are slight differences depending on the measurement method, but in the present invention, the values are determined by the following measurement methods. That is, the weight average molecular weight Mw and the number average molecular weight Mn are measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml is injected as a sample weight for measurement. When measuring the molecular weight of a sample, select the measurement conditions that fall within the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are linear, using several monodisperse polystyrene standard samples. .
In addition, the reliability of the measurement results is that the NBS706 polystyrene standard sample performed under the above measurement conditions is
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
Can be confirmed.
As the GPC column to be used, any column may be adopted as long as it satisfies the above conditions. Specifically, TSK-GEL, GMH (made by Toyo Soda Co., Ltd.) etc. can be used, for example.
The solvent and the measurement temperature are not limited to the described conditions, and may be changed to appropriate conditions.
For example, when a resin particle dispersion using an aliphatic polyester as a polyester resin and an aromatic-containing monomer as a radical polymerizable resin is prepared, the molecular weight of the two is different from that of an ultraviolet (UV) detector as a GPC detector. An apparatus for separation using a refractive index (RI) detector can be retrofitted and the molecular weight of each can be analyzed.

<Stability of resin particle dispersion (latex)>
150 cc of the prepared resin particle dispersion was placed in a 300 cc glass bottle and left in a constant temperature bath at 70 ° C. for 1 week. The stability of the resin particle dispersion after one week was judged according to the following criteria.
◎ ... Sedimentation and separation are not observed and good dispersibility is exhibited. 〇 ... Sedimentation and separation are hardly exhibited. △ ・ ・ ・ Slight separation is observed. The above was regarded as passing.

Example 1
(Preparation of polycondensation resin 1)
Dodecylbenzenesulfonic acid (catalyst) 0.5 part by weight Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
346.7 parts by weight Terephthalic acid 99.63 parts by weight Fumaric acid (anhydride) 20.06 parts by weight Trimellitic acid 33.59 parts by weight Butyl acetate 500 parts by weight Mixing the above components, flowing nitrogen, 90 ° C./1 atm For 5 hours, and then at 105 ° C./1 atm for 2 hours, the mixture was heated and stirred while flowing water out of the system for oligomerization. To this was added 200 parts by weight of butyl acetate so that the distilled butyl acetate returned to the reactor. Thereafter, the reaction was carried out at 80 ° C./1 atm for 10 hours to obtain a viscous polymerization solution. The obtained polyester was air-dried and then dried with hot air at 60 ° C. to sufficiently remove butyl acetate and subjected to analysis. The weight average molecular weight was 41,000, and the value (molecular weight distribution) obtained by dividing the weight average molecular weight by the number average molecular weight was 2.3. Further, when the polyester was subjected to differential thermal analysis, Tg showed a value of 68.3 ° C.

(Preparation of resin particle dispersion (1))
<Preparation of oil phase 1>
Polycondensation resin 1 175 parts by weight Butyl acetate 250.4 parts by weight The above composition was weighed and heated to 75 ° C. to prepare a uniform oil phase 1. The amount of butyl acetate added was adjusted so that the weight ratio of the resin solids contained in the polycondensation resin 1 was 50% by weight.
<Preparation of aqueous phase 1>
Ion-exchanged water 1,500 parts by weight Dowfax 2A-1 (surfactant, manufactured by Dow Chemical) 9.5 parts by weight Dowfax 2A-1 was dissolved in ion-exchanged water heated to 80 ° C. to prepare an aqueous phase 1 Then, the mixture was emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 15 minutes, and then the oil phase 1 was charged and further emulsified at 8,000 rpm for 10 minutes. Furthermore, using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an emulsion was obtained by dispersing 5 passes at a discharge speed of 60 (discharge pressure of 504 kgf / cm ² ). The volume average diameter of the droplets was 0.25 μm. The above emulsion was put into a 1 liter reactor equipped with a stirrer, and the solvent was removed while stirring for 8 hours under a reduced pressure environment of 35 mmHg. As a result, a stable resin particle dispersion having a median diameter of 0.25 μm was obtained. .
Ion exchange water was added to the resin particle dispersion obtained as described above to adjust the solid content to 20%.
The particles of the resin particle dispersion (1) had an overall ratio of particles having a median diameter of 0.03 μm or less or 5.0 μm or more (hereinafter referred to as large / small particle overall ratio) of 3.5%.
Further, when the stability of the resin particle dispersion (1) was examined, no aggregates were observed and the dispersion was in a stable state (）).

(Example 2)
(Preparation of polycondensation resin 2)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
50 parts by weight of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
524 parts by weight fumaric acid 78 parts by weight terephthalic acid 289 parts by weight isophthalic acid 85 parts by weight dodecylbenzenesulfonic acid 0.5 parts by weight 2-methyltetrahydrofuran 854 parts by weight Then, the mixture was heated to 98 ° C./1 atm for 2 hours, and the mixture was heated and stirred while flowing out of the system to oligomerize. To this, 150 parts by weight of 2-methyltetrahydrofuran was added and a cooling tube was attached so that the distilled 2-methyltetrahydrofuran returned to the reactor. Then, reaction was performed at 120 ° C./600 mmHg for 10 hours to obtain a viscous liquid. For analysis of the obtained polyester, the polyester was air-dried and then subjected to an analysis in which styrene was sufficiently removed by drying at 60 ° C. with hot air. The weight average molecular weight was 28,000, and the molecular weight distribution was 2.8. As a result of differential thermal analysis of the polyester, Tg showed a value of 69.5 ° C.

(Preparation of resin particle dispersion (2))
<Preparation of oil phase 2>
Polycondensation resin 2 78 parts by weight 2-methyltetrahydrofuran 209.9 parts by weight The above composition was weighed and heated at 120 ° C. to prepare a uniform oil phase 2. The amount of styrene to be added was adjusted so that the weight ratio of polycondensation resin 2 to 2-methyltetrahydrofuran was 65% by weight.
<Preparation of aqueous phase 2>
Ion-exchanged water 200 parts by weight Sodium dodecylbenzenesulfonate 5.5 parts by weight Sodium dodecylbenzenesulfonate was dissolved in ion-exchanged water heated to 80 ° C. to prepare aqueous phase 2, and a homogenizer (manufactured by IKA, Ultra Turrax) After emulsifying for 15 minutes, oil phase 2 was added and further emulsified for 10 minutes at 8,000 rpm. Furthermore, using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an emulsion was obtained by dispersing 5 passes at a discharge speed of 60 (discharge pressure of 504 kgf / cm ² ). The volume average diameter of the droplets was 0.45 μm. The above emulsion was put into a 1 liter reactor equipped with a stirrer, and the solvent was removed for 6 hours while bubbling nitrogen from the bottom of the reactor under a reduced pressure of 35 mmHg. As a result, a stable resin with a median diameter of 0.45 μm was obtained. A particle dispersion was obtained. A small amount of the composite polymer was measured for physical properties. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 20%.
The particles of the resin particle dispersion (2) had a large / small particle ratio of 3.0%.
Further, when the stability of the resin particle dispersion (2) was examined, no agglomeration was observed and it was stable (◎).

(Example 3)
(Preparation of polycondensation resin 3)
Cyclohexanedimethanol 20 parts by weight Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
90 parts by weight Bisphenol S (manufactured by Meisei Chemical Co., Ltd.) 250 parts by weight phthalic acid 38 parts by weight dimethyl terephthalate 185 parts by weight pyromellitic acid 15 parts by weight sulfuric acid 2.5 parts by weight cellosolve acetate 450 parts by weight The mixture was oligomerized by heating and stirring with flowing nitrogen out at 89 ° C./1 atm for 5 hours and then at 95 ° C./1 atm for 2 hours with water flowing out of the system. To this, 200 parts by weight of cellosolve acetate was added and a cooling tube was attached so that the distilled cellosolve returned to the reactor. Then, reaction was performed at 130 ° C./590 mmHg for 10 hours to obtain a viscous liquid. In order to analyze the obtained polyester, it was air-dried and then subjected to an analysis in which the solvent was sufficiently removed by hot air drying at 60 ° C. The weight average molecular weight was 36,000, and the molecular weight distribution was 2.7. As a result of differential thermal analysis of the polyester, Tg showed a value of 67.9 ° C.

(Preparation of resin particle dispersion (3))
<Preparation of oil phase 3>
Polycondensation resin 3 90 parts by weight Cellosolve acetate 159 parts by weight The above composition was weighed and heated at 120 ° C. to prepare a uniform oil phase 3. The amount of cellosolve acetate added was adjusted so that the weight ratio of the polycondensation resin 3 to cellosolve acetate was 54% by weight.
<Preparation of aqueous phase 3>
Ion-exchanged water 200 parts by weight Dodecylbenzenesulfonic acid 1.6 parts by weight Dodecylbenzenesulfonic acid was dissolved in ion-exchanged water heated to 80 ° C. to prepare an aqueous phase 3 and a homogenizer (manufactured by IKA, Ultra Turrax) for 15 minutes. After emulsification, oil phase 3 was added and further emulsified at 8,000 rpm for 10 minutes. Furthermore, using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an emulsion was obtained by dispersing 5 passes at a discharge speed of 60 (discharge pressure of 504 kgf / cm ² ). The volume average diameter of the droplets was 0.10 μm. The emulsion was put into a 1 liter reactor equipped with a stirrer, and polymerization was carried out in a nitrogen atmosphere for 6 hours. As a result, a stable resin particle dispersion having a median diameter of 0.11 μm was obtained. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 20%.
The particles of the resin particle dispersion (3) had a large / small particle ratio of 0.8%.
Further, when the stability of the resin particle dispersion (3) was examined, almost no agglomeration was observed and it was stable (◯).

Example 4
(Preparation of polycondensation resin 4)
0.5 parts by weight of dodecylbenzenesulfonic acid polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) ethane
346.7 parts by weight Terephthalic acid 99.63 parts by weight Pyromellitic acid 15.06 parts by weight Trimellitic acid 33.59 parts by weight Butyl acetate 500 parts by weight The above ingredients were mixed and the above nitrogen was allowed to flow at 90 ° C / 1 atm. The mixture was heated and stirred for 2 hours at 105 ° C./1 atm for 2 hours, and the mixture was oligomerized by heating and stirring. To this was added 200 parts by weight of butyl acetate so that the distilled butyl acetate returned to the reactor. Thereafter, the reaction was carried out at 80 ° C./1 atm for 10 hours to obtain a viscous liquid. For analysis of the obtained polyester, it was air-dried and then dried with hot air at 60 ° C. to sufficiently remove butyl acetate and subjected to analysis. The weight average molecular weight was 39,000, and the value (molecular weight distribution) obtained by dividing the weight average molecular weight by the number average molecular weight was 3.0. Further, when the polyester was subjected to differential thermal analysis, Tg showed a value of 62.3 ° C.

(Preparation of resin particle dispersion (4))
<Preparation of oil phase 4>
250 parts by weight of the polycondensation resin 4 was weighed, stored in a desiccator at room temperature for 1 day, transferred to a vacuum dryer, and dried at 50 ° C. for 48 hours. The amount of butyl acetate contained in the polycondensation resin 4 after drying was 5.5% by weight. This was designated as polycondensation resin 4 ′.
Polycondensation resin 4 ′ 100 parts by weight Acrylic acid 1.5 parts by weight Butyl acrylate 10 parts by weight Dodecanethiol 1.5 parts by weight Styrene 69.7 parts by weight The above composition is weighed and heated at 120 ° C. to obtain a uniform oil phase 5. Prepared.
(Preparation of aqueous phase 4)
Ion-exchanged water 200 parts by weight Dodecylbenzenesulfonic acid 2.5 parts by weight Dissolved in ion-exchanged water heated to 80 ° C., adjusted the aqueous phase 4 and emulsified with a homogenizer (Ultra Turrax, manufactured by IKA) for 15 minutes. Phase 4 was charged and further emulsified at 8,000 rpm for 10 minutes. Furthermore, using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an emulsion was obtained by dispersing 5 passes at a discharge speed of 60 (discharge pressure of 504 kgf / cm ² ). The volume average diameter of the droplets was 0.50 μm. The emulsion was put into a 1 liter reactor equipped with a stirrer, and 1.6 g of ammonium persulfate dissolved in 10 g of ion-exchanged water was added, followed by polymerization in a nitrogen atmosphere for 6 hours. A stable resin particle dispersion of 0.51 μm was obtained. A small amount of the obtained resin particles were taken and the physical properties of the composite polymer were measured.
Weight average molecular weight of vinyl resin by GPC: 16,000
GPC polyester weight average molecular weight: 45,000
Tg of polyester: 65 ° C
It was confirmed that the polymer obtained as described above was a composite particle of polyester-vinyl resin. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 20%.
The particles of the resin particle dispersion (4) had a large / small particle ratio of 1.5%.
Further, when the stability of the resin particle dispersion (4) was examined, the occurrence of agglomeration was slightly observed, but the level was satisfactory (◯).

(Comparative Example 1)
(Preparation of polycondensation resin 5)
10-camphorsulfonic acid 0.5 part by weight polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
346.7 parts by weight Terephthalic acid 99.63 parts by weight Phthalic acid 15.06 parts by weight Trimellitic acid 33.59 parts by weight The above composition was weighed and the monomer was dissolved using a 120 ° C. mantle heater. This was transferred to a reactor, and polymerization was carried out by heating and stirring while flowing water out of the system at 90 ° C./1 atm for 5 hours and then at 105 ° C./1 atm for 2 hours while flowing nitrogen. The obtained polyester had a weight average molecular weight of 1,100, and a value (molecular weight distribution) obtained by dividing the weight average molecular weight by the number average molecular weight was 8.5. When the polyester was subjected to differential thermal analysis, Tg showed a value of 50.4 ° C.

(Preparation of resin particle dispersion (5))
<Preparation of oil phase 5>
Polycondensation resin 5 90 parts by weight Ethyl acetate 200 parts by weight The above composition was weighed and heated at 120 ° C. to prepare a uniform oil phase 5.
<Preparation of aqueous phase 5>
Ion-exchanged water 200 parts by weight Dowfax 2A-1 3.0 parts by weight Dowfax 2A-1 was dissolved in ion-exchanged water heated to 80 ° C. to prepare an aqueous phase 5 and a homogenizer (manufactured by IKA, Ultra Turrax). After emulsifying for 15 minutes, the oil phase 5 was added and further emulsified at 8,000 rpm for 10 minutes. The volume average diameter of the droplets was 7.8 μm. Further, the solvent was removed under a nitrogen atmosphere for 6 hours to obtain a resin particle dispersion having a median diameter of 6.5 μm.
The particles of the resin particle dispersion (5) had a large / small particle ratio of 25.9%.
Further, when the stability of the resin particle dispersion (5) was examined, a large amount of aggregation was observed (×).

(Comparative Example 2)
(Preparation of polycondensation resin 6)
1,9-nonanediol 140 parts by weight Cyclohexanedicarboxylic acid 190 parts by weight 1,6-hexanediol 110 parts by weight Dibutyltin oxide 0.5 parts by weight butyl acetate 550 parts by weight Heating reaction was performed at 1 atm for 5 hours and then at 110 ° C./150 mmHg for 12 hours. For analysis, it was air-dried and then hot-air dried at 60 ° C. and subjected to analysis. The weight average molecular weight was 1,200 and the molecular weight distribution was 6.7. As a result of differential thermal analysis of the polyester, Tg was 41.3 ° C.

(Preparation of resin particle dispersion (6))
<Preparation of oil phase 6>
Polycondensation resin 6 90 parts by weight Butyl acetate 151.8 parts by weight The above composition was weighed and heated at 120 ° C. to prepare a uniform oil phase 6. The amount of butyl acetate to be added was adjusted so that the weight ratio of the polycondensation resin 6 to butyl acetate was 55% by weight.
<Preparation of aqueous phase 6>
Ion-exchanged water 200 parts by weight Sodium dodecylbenzenesulfonate 3.0 parts by weight Sodium dodecylbenzenesulfonate was dissolved in ion-exchanged water heated to 80 ° C. to prepare aqueous phase 6, and an ultrasonic emulsifier (S8500, manufactured by Branson) ) For 15 minutes, the oil phase 6 was charged, and further emulsified at 8,000 rpm for 10 minutes. The volume average diameter of the droplets was 4.9 μm. The emulsion was charged into a 1 liter reactor equipped with a stirrer, and the solvent was removed under a nitrogen atmosphere for 6 hours. As a result, a resin particle dispersion having a median diameter of 5.6 μm was obtained.
The particles of the resin particle dispersion (6) had a large / small particle ratio of 25.7%.
Further, when the stability of the resin particle dispersion (6) was examined, the occurrence of aggregation was observed (×).

  Table 1 below shows the evaluation results of the resin particle dispersions (1) to (6) (Examples 1 to 4, Comparative Examples 1 and 2). In addition, the number of polyols, polyvalent carboxylic acids, and rings (aromatic rings and / or alicyclic rings) per repetition in Table 1 is described only for the main components.

Details of the abbreviations in Table 1 are as follows.
BisA-1EO: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (bisphenol A ethylene oxide 1 mol adduct)
BisS: Bisphenol S
BisE-1EO: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) ethane (bisphenol E ethylene oxide 1 mol adduct)
1,9-ND: 1,9-nonanediol 1,6-HD: 1,6-hexanediol TPA: terephthalic acid TPA-DM: dimethyl terephthalate CHDC: cyclohexanedicarboxylic acid Further, the pressure unit conversion in the present invention is: It is assumed that 1 atm = 760 mmHg = 1.03 × 10 ⁵ Pa.

(Preparation of colorant particle dispersion (1))
・ Yellow pigment (manufactured by Dainichi Seika Co., Ltd., CI Pigment Yellow 74)
50 parts by weight, anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R) 5 parts by weight, 200 parts by weight of ion-exchanged water According to the above composition, the components were mixed and dissolved, and a homogenizer (IKA, Ultra Turrax) 5 The mixture was dispersed for 10 minutes with an ultrasonic bath for 1 minute to obtain a yellow colorant particle dispersion (1) having a center diameter (median diameter) of 240 nm and a solid content of 21.5%.

(Preparation of colorant particle dispersion (2))
In the preparation of the colorant particle dispersion (1), a colorant particle dispersion (1) and a cyan pigment (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.) were used instead of the yellow pigment. In the same manner, a Cyan colorant particle dispersion (2) having a center diameter (median diameter) of 190 nm and a solid content of 21.5% was obtained.

(Preparation of colorant particle dispersion (3))
In the preparation of the colorant particle dispersion (1), a colorant particle dispersion (1) and a magenta pigment (Daiichi Ink Chemical Co., Ltd., CI Pigment Red 122) were used instead of the yellow pigment. In the same manner, a Magenta colorant particle dispersion (3) having a center diameter (median diameter) of 165 nm and a solid content of 21.5% was obtained.

(Preparation of colorant particle dispersion (4))
The colorant particle dispersion (1) was prepared in the same manner as the colorant particle dispersion (1) except that a black pigment (Cabot, carbon black BPL) was used instead of the yellow pigment. A Black colorant particle dispersion (4) having a median diameter of 170 nm and a solid content of 21.5% was obtained.

(Preparation of release agent particle dispersion)
Paraffin wax (Nippon Seiwa Co., Ltd., HNP9; melting point 70 ° C.) 50 parts by weight Anionic surfactant (Dowfax 2A-1) 5 parts by weight ion-exchanged water 200 parts by weight And then sufficiently dispersed with a homogenizer (IKA, Ultra Turrax T50), and then dispersed with a pressure discharge type homogenizer (Gorin homogenizer, Gorin), with a center diameter (median diameter) of 180 nm and a solid content. A 21.5% release agent particle dispersion was obtained.

[Toner Example 1]
(Preparation of toner particles)
-Resin particle dispersion (1) 210 parts by weight (42 parts by weight of resin)
Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
Release agent particle dispersion 40 parts by weight (release agent 8.6 parts by weight)
・ Polyaluminum chloride 0.15 parts by weight ・ Ion-exchanged water 300 parts by weight In accordance with the above composition, the components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50) and then heated. The flask was heated to 40 ° C. with stirring in an oil bath and held at 40 ° C. for 60 minutes, and then 105 parts by weight (21 parts by weight) of the resin particle dispersion (1) was added and gently stirred.

  Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 85 ° C. while stirring was continued. During the temperature rise to 85 ° C, the pH in the system usually drops to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 5.5 or less. did.

  After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. Then, it was redispersed in 3 liters of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then vacuum drying for 12 hours to obtain toner particles.

When the particle size of the toner particles was measured with a Coulter counter, the cumulative volume average particle size D ₅₀ was 4.5 μm, and the volume average particle size distribution index GSDv was 1.20. The shape factor SF1 of the toner particles obtained from the shape observation by Luzex was 132 potato shapes.

  To 50 parts by weight of the toner particles, 1.5 parts by weight of hydrophobic silica (manufactured by Cabot, TS720) was added and mixed by a sample mill to obtain an externally added toner.

  Then, using a ferrite carrier having an average particle diameter of 50 μm coated with 1% of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd.), the externally added toner is weighed so that the toner concentration becomes 5%. A developer was prepared by stirring and mixing for a minute.

(Evaluation of toner)
Using the developer described above, Fuji Xerox's DocuCenterColor500 modified machine uses Fuji Xerox J-coated paper as the transfer paper, and the process speed is adjusted to 180 mm / sec to examine the toner fixing property. The oil-less fixability by the PFA tube fixing roll is good, and the minimum fixing temperature (this temperature is determined by image rubbing by image cloth rubbing) is 110 ° C. or higher, and the image shows sufficient fixability. At the same time, it was confirmed that the transfer paper was peeled off without any resistance. The surface gloss of the image at a fixing temperature of 140 ° C. was as good as 65%, both developability and transferability were good, and there was no image defect and a high quality and good image (◯) was shown. The occurrence of hot offset was not observed even at a fixing temperature of 200 ° C.
In the modified machine, a continuous print test of 50,000 sheets was performed at 23 ° C. and 55% RH, and the initial good image quality was maintained until the end. (Continuous test maintenance: ○)

<Document offset evaluation>
A toner-fixed image of 5 cm × 5 cm was prepared with the above-described evaluation machine, and the image surfaces were laminated and left in a constant temperature chamber at 55 ° C. for 5 days with a 1.5 kg weight placed thereon.
The defect properties on both sides after the image was peeled were evaluated as follows.
There is almost no image loss.
Slightly chipped at the edge, but there is almost no center ....
Defects are conspicuous in both edge and center
In addition, ○ or more was regarded as passing.

<Non-visual offset (NVO) evaluation>
After running a 1,000-sheet running test using the evaluation machine, the NVO measuring jig was pressed against the fixing roll, and the soiling property of the jig was evaluated as follows.
There is almost no dirt.
There is a slight amount in the whole ...
Clean and noticeable dirt .... ×
In addition, ○ or more was regarded as passing.

[Toner Example 2]
In Example 1, the resin particle dispersion (1) is changed to the resin particle dispersion (2), the colorant particle dispersion (1) is changed to the colorant particle dispersion (2), and the mixture is heated at 95 ° C. Toner particles were obtained in the same manner as in Example 1 except that the pH was maintained at 5.0.

The cumulative volume average particle diameter D ₅₀ of the toner particles is 4.0 μm, and the volume average particle size distribution index GSDv is 1.21. The shape factor SF1 was slightly spherical with 124.

Using these toner particles, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The toner fixability was examined in the same manner as in Example 1. As a result, oil-less fixability with a PFA tube fixing roll was investigated. It was confirmed that the minimum fixing temperature was 110 ° C. or higher, the image showed sufficient fixability, and the transfer paper was peeled off without any resistance. The surface gloss of the image at a fixing temperature of 150 ° C. was as good as 70%, both developability and transferability were good, and there was no image defect and a high quality and good image (◯) was shown. Also, no hot offset was observed at a fixing temperature of 200 ° C.
In the modified machine, a continuous print test of 50,000 sheets was performed at 23 ° C. and 55% RH, and the initial good image quality was maintained until the end. (Continuous test maintenance: ○)

[Toner Example 3]
In Example 1, the resin particle dispersion (1) was changed to the resin particle dispersion (3), the colorant particle dispersion (1) was changed to the colorant particle dispersion (2), and the mixture was heated at 95 ° C. Toner particles were obtained in the same manner as in Example 1 except that the pH was maintained at 5.0.

The cumulative volume average particle diameter D ₅₀ of the toner particles is 4.50 μm, and the volume average particle size distribution index GSDv is 1.20. The shape factor SF1 was slightly spherical with 125.

Using these toner particles, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The toner fixability was examined in the same manner as in Example 1. As a result, oil-less fixability with a PFA tube fixing roll was investigated. It was confirmed that the minimum fixing temperature was 110 ° C. or higher, the image showed sufficient fixability, and the transfer paper was peeled off without any resistance. The surface gloss of the image at a fixing temperature of 150 ° C. was as good as 70%, both developability and transferability were good, and there was no image defect and a high quality and good image (◯) was shown. Also, no hot offset was observed at a fixing temperature of 200 ° C.
In the modified machine, a continuous print test of 50,000 sheets was performed at 23 ° C. and 55% RH, and the initial good image quality was maintained until the end. (Continuous test maintenance: ○)

[Toner Example 4]
In Example 1, the resin particle dispersion (1) is changed to the resin particle dispersion (4), the colorant particle dispersion (2) is changed to the colorant particle dispersion (4), and the amount of polyaluminum chloride is changed. Toner particles were obtained in the same manner as in Example 1 except that the amount of was 0.12 parts by weight.

The accumulated volume average particle diameter D ₅₀ of the toner particles 4.22Myuemu, volume average particle size distribution index GSDv of 1.24, a shape factor SF1 of a spherical 120.

Using these toner particles, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The toner fixability was examined in the same manner as in Example 1. As a result, oil-less fixability with a PFA tube fixing roll was investigated. It was confirmed that the minimum fixing temperature was 105 ° C. or higher, the image showed sufficient fixing properties, and the transfer paper was peeled off without any resistance. The surface gloss of the image at a fixing temperature of 150 ° C. was as good as 80%, both developability and transferability were good, and an extremely high quality image (◯) was obtained without image defects. No occurrence of hot offset was observed even at a fixing temperature of 200 ° C.
In the modified machine, a continuous print test of 50,000 sheets was performed at 23 ° C. and 55% RH, and the initial good image quality was maintained until the end. (Continuous test maintenance: ○)

[Toner Comparative Example 1]
In Example 1, toner particles were obtained in the same manner as in Example 1 except that the resin particle dispersion (1) was changed to the resin particle dispersion (5) and the colorant dispersion was changed to (2). .

The toner particles had a cumulative volume average particle diameter D ₅₀ of 7.80 μm, a volume average particle size distribution index GSDv of 1.45, a shape factor SF1 of 137 and a potato shape.

Using these toner particles, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The toner fixability was examined in the same manner as in Example 1. As a result, oil-less fixability with a PFA tube fixing roll was investigated. The image was satisfactory and the minimum fixing temperature was 130 ° C. or higher, and the image showed a sufficient fixing property, but the peeled state of the transfer paper was poor, and undulation and wrapping after fixing of the paper were confirmed. Hot offset was observed from a fixing temperature of 180 ° C. Coarse powder was generated in the toner, and defects such as white spots were observed in the image.
In the modified machine, a continuous print test was performed at 23 ° C. and 55% RH, but white spots in the image deteriorated further from the initial image quality, and the evaluation was terminated at 5,000 sheets. (Continuous test maintenance: x)

[Toner Comparative Example 2]
In Example 1, the resin particle dispersion (1) was changed to the resin particle dispersion (6), and toner particles were obtained in the same manner as in Example 1.

The cumulative volume average particle diameter D ₅₀ of the toner particles is 9.40 μm, the volume average particle size distribution index GSDv is 1.26, and the shape factor SF1 is 122.

  Using these toner particles, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The toner fixability was examined in the same manner as in Example 1. As a result, oil-less fixability with a PFA tube fixing roll was investigated. The image was not good, the minimum fixing temperature was 90 ° C. or more, and the image showed a sufficient fixing property, but the transfer paper was not peeled well, and undulation and winding after fixing of the paper were confirmed. In addition, significant hot offset was observed from the fixing temperature of 140 ° C., there were image defects (×), and sufficient image evaluation was not achieved, and the continuous print test could not be performed. (XX)

The results of toner examples 1 to 4 and comparative examples 1 and 2 are summarized in Table 2.
In Table 2, the image quality evaluation criteria are as follows:
“◎” is extremely good,
“○” is good,
“×” was defined as the occurrence of an image defect.

From these results, as in this example, the toner is polycondensed in an organic solvent at a low temperature and then converted into particles, and the median diameter of the resin particles is set within a predetermined range, thereby efficiently producing a toner using polycondensation resin as a raw material. It can be seen that the toner image quality and fixing performance can be dramatically improved.
In contrast, even in the case of the polycondensation resin particles in which the polycondensation resin is dispersed as in the comparative example, the median diameter deviates from the predetermined range, and the toner characteristics (image quality, fixability) are higher than those of the examples. It turns out that it is getting worse.

Claims (6)

A resin particle dispersion in which resin particles containing at least a polycondensation resin obtained by polycondensation of a polycondensable monomer in an organic solvent are dispersed,
The polycondensation resin has one or more aromatic rings and / or alicyclic rings in its repeating unit,
The resin particle dispersion liquid, wherein the median diameter of the resin particles is 0.05 μm or more and 2.0 μm or less. Method for producing a resin particle dispersion in which resin particles containing at least a polycondensation resin having at least one aromatic ring and / or alicyclic ring in a repeating unit are dispersed in an aqueous medium with a median diameter of 0.05 μm to 2.0 μm Because
A polycondensation step in which a polycondensable monomer is polycondensed in an organic solvent using a polycondensation catalyst to obtain a polycondensation resin-containing product; and
A method for producing a resin particle dispersion, comprising: a dispersion step of dispersing the polycondensation resin-containing material in an aqueous medium to obtain a resin particle dispersion. A step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles; and
A method for producing an electrostatic charge image developing toner comprising a step of heating and aggregating the aggregated particles,
The resin particle dispersion is a resin particle dispersion according to claim 1 or a resin particle dispersion produced by the production method according to claim 2. Method.   An electrostatic image developing toner produced by the production method according to claim 3.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 4 and a carrier. A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding body with a developer containing toner to form a toner image;
A transfer step of transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target;
A fixing step of thermally fixing the toner image transferred to the surface of the transfer material,
An image forming method using the electrostatic image developing toner according to claim 4 as the toner, or the electrostatic image developer according to claim 5 as the developer.