JP2006267732A - Resin particulate dispersion and its manufacturing method, and toner for electrostatic image development and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particulate dispersion having polyester/vinyl compound resin particles which each have a polyester surface uniformly coated with vinyl-based resin, have a sharp particle size distribution, and are in a stable emulsion/dispersion state and its manufacturing method, and toner for electrostatic image development which uses the resin particulate dispersion and has sufficiently satisfactory toner characteristics and its manufacturing method. <P>SOLUTION: The resin particulate dispersion contains resin particulates obtained by coating polyester particles with vinyl resin by polymerizing a vinyl-based monomer in the presence of the polyester particles obtained by polycondensing a vinyl-based monomer in a water medium. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin fine particle dispersion in which resin fine particles are dispersed, which is used as a constituent material of an electrostatic charge image developing toner (hereinafter also referred to as electrophotographic toner), and a method for producing the same. The present invention also relates to an electrostatic charge image developing toner using the toner and a method for producing the same.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through transfer and fixing process steps. As the developer used here, a two-component developer comprising a toner and a carrier and a one-component developer using a magnetic toner or a non-magnetic toner alone are known, and the method for producing the toner is usually thermoplastic. A kneading and pulverizing method is used in which a resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and wax, and after cooling, is finely pulverized and classified. In these toners, if necessary, inorganic and organic fine particles for improving fluidity and cleaning properties may be added to the toner particle surface. Although these methods can produce very good toners, they have several problems as described below.

  In the ordinary kneading and pulverizing method, the toner shape and the surface structure of the toner are indeterminate, and although it varies slightly depending on the pulverization properties of the materials used and the conditions of the pulverization process, it is difficult to control the intentional toner shape and surface structure. . In the kneading and pulverizing method, the range of material selection is limited. Specifically, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized by an economically possible production apparatus. However, if the resin colorant dispersion is made brittle in order to satisfy these requirements, finer powder may be generated or the toner shape may be changed due to mechanical shearing force applied in the developing machine. Due to these effects, in the two-component developer, the charging deterioration of the developer due to adhesion of fine powder to the carrier surface is accelerated, and in the one-component developer, toner scattering occurs due to the expansion of the particle size distribution. Deterioration in developability due to changes in image quality tends to cause image quality degradation.

  In addition, when a toner is formed by adding a large amount of a release agent such as wax, exposure to the release agent on the surface is often affected by the combination with a thermoplastic resin. In particular, in a combination of a resin having increased elasticity due to a high molecular weight component and being slightly pulverized, and a brittle wax such as polyethylene, the toner surface is often exposed to polyethylene. This is advantageous for releasability at the time of fixing and cleaning of untransferred toner from the photoreceptor, but the polyethylene on the surface layer is easily transferred by mechanical force, resulting in contamination of the developing roll, photoreceptor and carrier. It becomes easy and leads to a decrease in reliability.

  Furthermore, due to the irregular shape of the toner, the fluidity may not be sufficient even with the addition of a fluidity aid, and over time due to the movement of fine particles on the toner surface to the toner recess due to mechanical shearing force during use. The developability, transferability, and cleaning properties deteriorate due to the decrease in fluidity and the embedding of the fluidity aid in the toner. Further, when the toner collected by cleaning is returned to the developing machine and used again, the image quality is likely to further deteriorate. In order to prevent these, if the flow aid is further increased, the generation of black spots on the photoreceptor and the scattering of the aid particles occur.

  As described above, in the electrophotographic process, in order to stably maintain the performance of the toner even under various mechanical stresses, the surface hardness can be maintained without suppressing the exposure of the release agent to the surface or the fixing property. In addition, it is necessary to improve the mechanical strength of the toner itself and to achieve both sufficient charging and fixing properties.

  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 for electrophotography having a wide fixing latitude, which is fixed at a low temperature and does not cause an offset to a higher temperature region.

  However, lowering the fixing temperature of the toner also lowers the glass transition point (Tg) of the toner at the same time, making it difficult to achieve both toner storage stability. In order to achieve both low-temperature fixability and toner storage stability, it is necessary to have a so-called sharp melt property that sharply lowers the viscosity of the toner in a high-temperature region while keeping the glass transition point of the toner higher.

  As a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of a toner resin (binder resin) is generally used. However, if the glass transition point is too low, toner powder aggregation (blocking) tends to occur, and the storage stability on a fixed image is deteriorated.

  For this reason, the lower limit of the glass transition point of the toner is practically about 60 ° C. Although this glass transition point is an important design point of many commercially available toner resins, at present, a toner that can be fixed at low temperature can be obtained by simply lowering the glass transition point of the resin. I could not.

  In addition, although the fixing temperature can be lowered by using a plasticizer, there is a problem that blocking easily occurs during storage or in the developing machine.

  Therefore, as means for achieving both low-temperature fixability, sharp melt properties, and blocking prevention, as a binder resin constituting the toner, a crystalline polyester is used as a polycondensation type polyester exhibiting sharp melting behavior with respect to temperature. A technique used for the above has been proposed.

  This crystalline resin is difficult to pulverize by the melt-kneading pulverization method and cannot be generally used, and a toner production method by an emulsion polymerization aggregation method has been proposed. In these methods, a resin fine particle dispersion is generally 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 size and heated. Is a method for producing a toner by fusing and uniting.

  In order to obtain such a polyester resin by polycondensation, it is usually carried out under a high heat of 200 ° C. or higher for a long time under stirring and under reduced pressure, which requires a large amount of energy consumption. Therefore, the reaction equipment is required to have high durability, and the capital investment is often excessive.

  Further, when emulsifying the obtained resin in water, non-emulsification such as emulsification at high shear at 150 ° C. or higher, or removing the solvent after dissolving the solution in a solvent to lower the viscosity. There is a problem that a process requiring high efficiency and energy consumption is required.

  However, reports have been taken that polycondensation of polyesters in water is possible (Saam JC, Chou YJ. US Patent, 4355154; 1982).

  If such polycondensation of polyester in water becomes possible, polycondensation at 100 ° C. or lower is achieved, so that the above-described polymerization under high heat and reduced pressure becomes unnecessary, and emulsification at high temperature / high shear. There is an advantage that energy consumption can be greatly reduced compared to the normal manufacturing method.

  As described above, although it is a crystalline polyester resin that is excellent in low-temperature fixability and sharp melt properties, a toner prepared using a crystalline resin has a drawback of causing a blocking phenomenon in a developing device or the like even at room temperature. Further, since the triboelectric chargeability and fluidity are poor, the developability is poor, and the resulting image has a blurry and unclear image quality. Further, since the toner is soft, a filming phenomenon that the toner particles adhere to the carrier particles and the surface of the photoconductor occurs due to a large number of copies, and further, the toner image is fused to a cleaning member such as a cleaning blade. There are many, and it becomes an unclear thing with a low density | concentration.

  As described above, it is difficult to apply the binder resin component to the toner as a single crystalline polyester because of the above-mentioned problems.

  For this reason, a method for producing a toner by using a crystalline polyester resin and an amorphous resin in combination or by combining a vinyl resin or the like without using a crystalline resin alone as a binder resin has been studied. ing.

  Under such circumstances, studies for obtaining a composite resin of polyester and vinyl have been conducted. However, in JP-A-7-207219, in this example, under the coexistence of a water-soluble polyester resin having a hydrophilic group in the molecule. An emulsion composite resin composition of polyester and vinyl is prepared by polymerizing a mixture of vinyl monomers. The polyester-vinyl composite resin is a resin containing both polyester and vinyl in one particle.

  According to this example, by using vinyl silanes, glycidyl group-containing vinyl monomers or the like as vinyl polymerizable monomers, polyester particles and vinyl resins are grafted or internally crosslinked to obtain composite particles. It states that it is possible.

  However, the structure of the composite particles is not controlled, and it is difficult to reproduce the toner performance with good reproducibility, and it cannot be put into practical use. Further, in this example, since the polyester is limited to water solubility, there is a problem that the toner performance cannot be expressed with good reproducibility from the viewpoint of chargeability and the like.

  In addition, as an example in which a polyester-vinyl composite resin is prepared and applied to a toner, for example, in Japanese Patent Application Laid-Open No. 2001-42564, a crystalline polyester and an amorphous vinyl copolymer are mixed and crystallized by an emulsion polymerization method. A toner composed of two types of resins, which is a polyester / amorphous vinyl, is produced.

  However, the polyester resin used in this example is only crystalline polyester and not amorphous polyester, which compensates for the weak mechanical strength and insufficient charge amount of crystalline resin. There is an unsolved problem.

  In addition, in the production method of this example, there is a possibility that the crystalline polyester may be exposed on the toner particle surface, and it is impossible to prevent the low charge amount of the crystalline resin and the weak mechanical strength of the resin. There is also a point.

Furthermore, the polyester resin is not produced in water, requires polycondensation and emulsification under high heat, and there is a problem of high energy consumption.
US Patent, 4355154 JP-A-7-207219 JP 2001-42564 A

  Another technique for producing polyester / vinyl composite particles is a mini-emulsion polymerization method. The mini-emulsion polymerization method mentioned here includes, for example, a method in which an oil phase in which polyester and vinyl monomers are dissolved is emulsified together with an activator and polymerized.

  However, composite particles produced by the mini-emulsion method are also difficult to achieve a complete two-layer structure, and there may be some variation in the thickness of the coating layer or the polyester may be exposed on the particle surface depending on the location. There are cases where structural control is difficult.

  When applying resin particles with exposed polyester particles to the toner, the polyester may also be exposed on the toner particle surfaces, reducing the charge amount of the crystalline resin and the mechanical strength of the resin. Sometimes it could not be prevented.

  The “two-layer structure” is a particle having a so-called core-shell structure in which the surface of a core particle made of resin is coated with a different kind of resin.

  Thus, in the past, polyester / vinyl bilayer structure that compensates for low charge amount or compensates for weak mechanical strength while taking advantage of low temperature fixability and sharp melt properties of polyester, particularly crystalline polyester. There is no example in which a resin having a toner is applied to a toner.

  Accordingly, it is an object of the present invention to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a resin fine particle dispersion having polyester / vinyl composite resin particles in which a vinyl resin is uniformly coated on a polyester surface, has a sharp particle size distribution, and has a stable emulsified and dispersed state. And a method of manufacturing the same. Another object of the present invention is to provide a toner for developing a toner electrostatic image sufficiently satisfying the toner characteristics by using this resin fine particle dispersion and a method for producing the same.

The above problem is solved by the following means. That is,
The resin fine particle dispersion of the present invention is a resin obtained by polymerizing a vinyl monomer in the presence of polyester particles prepared by polycondensation of a polyester monomer in an aqueous medium and coating the polyester particles with a vinyl resin. It is characterized by containing fine particles.

  In the resin fine particle dispersion of the present invention, the coverage of the vinyl resin on the polyester particles is preferably 92 mol% to 100 mol%. The median diameter of the polyester particles is preferably 0.05 μm or more and 2.0 μm or less. The median diameter of the resin fine particles is preferably 0.08 μm or more and 3.0 μm or less.

  In the resin fine particle dispersion of the present invention, the polyester particles are preferably crystalline polyester particles or amorphous polyester. The crystalline melting point of the crystalline polyester is preferably 50 ° C. or higher and lower than 140 ° C. The glass transition point of the amorphous polyester is preferably 50 ° C. or higher and lower than 80 ° C.

  In the resin fine particle dispersion of the present invention, it is preferable that the polyester monomer contains at least a diol and a polyvalent carboxylic acid. The weight ratio of the polyester monomer to the vinyl monomer (polyester monomer / vinyl monomer) is preferably 5/95 to 95/5.

The method for producing resin fine particles of the present invention is a method for producing a resin fine particle dispersion for obtaining the resin fine particle dispersion of the present invention,
Emulsifying or dispersing a polyester monomer in an aqueous medium, and polycondensation in the aqueous medium to form polyester particles;
Mixing the polyester particles and a vinyl monomer, polymerizing the vinyl monomer in the presence of the polyester particles, and forming resin particles in which the polyester particles are coated with a vinyl resin;
It is characterized by including.

  The electrostatic image developing toner of the present invention is characterized in that it is obtained by aggregating at least resin fine particles using the resin fine particle dispersion of the present invention, followed by heating and melting.

  In the toner for developing an electrostatic charge image of the present invention, the toner contains a crystalline polyester and an amorphous polyester, and an abundance ratio between the crystalline polyester and the amorphous polyester (crystalline polyester / amorphous polyester). ) Is preferably 30/70 to 70/30.

  In the toner for developing an electrostatic charge image of the present invention, the volume average particle size of the toner is preferably 3 μm or more and 10 μm or less.

  Further, the electrostatic image developing toner of the present invention uses the resin fine particle dispersion of the present invention, and agglomerates at least the resin fine particles using the resin fine particle dispersion of the present invention. And a step of melting by heating.

  According to the present invention, a resin fine particle dispersion having polyester / vinyl composite resin particles having a polyester resin surface uniformly coated with a vinyl resin, having a sharp particle size distribution, and having a stable emulsified / dispersed state, and its A manufacturing method can be provided. Further, by using this resin fine particle dispersion, it is possible to provide a toner for developing an electrostatic charge image sufficiently satisfying toner characteristics and a method for producing the same.

(Resin fine particle dispersion)
Hereafter, the manufacturing method of the resin fine particle dispersion of this invention is demonstrated with the resin fine particle of this invention.

  The resin fine particle dispersion of the present invention is a dispersion prepared as follows, in which polyester / vinyl composite resin fine particles are dispersed in an aqueous medium. First, a polyester monomer is emulsified or dispersed in an aqueous medium as a target resin fine particle raw material by, for example, mechanical shearing or ultrasonic waves. At this time, additives such as a catalyst and a surfactant are also added to the water-soluble medium as necessary. For example, by heating the solution, polycondensation is advanced to form polyester particles. Then, it is mixed with a vinyl monomer, and the vinyl monomer is polymerized in the presence of the polyester particles to obtain resin fine particles in which the polyester particles are coated with a vinyl resin.

  Usually, polycondensation resins typified by polyester do not proceed in water in principle because they are dehydrated during polymerization. However, when a polycondensable monomer is emulsified or dispersed in an aqueous medium together with a surfactant that forms micelles (oil phase) in the aqueous medium, the monomer is placed in a micro hydrophobic field in the micelle. As a result, a dehydration action occurs, and the produced water can be discharged into an aqueous medium outside the micelle and polymerization can proceed. In this way, a dispersion in which polycondensation resin fine particles are emulsified and dispersed in an aqueous medium is obtained with low energy.

  In order to obtain polyester / vinyl composite resin fine particles in such an aqueous medium, the polyester monomer and the vinyl monomer are simultaneously emulsified or dispersed in the aqueous medium, and then the polycondensation of the polyester monomer is performed. And the radical polymerization of the vinyl monomer simultaneously or separately. However, in this method, the vinyl resin is not uniformly coated on the surface of the polyester particles, and the polyester is exposed on the surface.

  Therefore, in the present invention, first, polyester particles are produced by polycondensation in water, then mixed with a vinyl monomer, and the vinyl monomer is polymerized in the presence of the polyester particles. Thereby, polyester / vinyl composite resin fine particles in which the vinyl particles are uniformly coated on the polyester particles are obtained.

  Further, in the present invention, by using a vinyl monomer, atomization of oil droplets (oil phase) containing polyester particles as a reaction field in an aqueous medium is promoted, and fine particles having a sharp particle size distribution and Become.

  Moreover, since the resin fine particles obtained are formed such that the surface thereof is coated with a relatively stable vinyl resin, for example, compared with polyester that is highly hydrophilic and chemically unstable to hydrolysis and the like, It is chemically stable, and as a result, it has excellent storage stability.

  When the obtained resin fine particle dispersion is applied to an electrostatic image developing toner, a toner having excellent toner characteristics can be obtained. Specifically, for example, the polyester monomer is uniformly coated with a vinyl monomer to suppress the exposure of the polyester, so that when the crystalline polyester is used as the polyester, the mechanical strength of the crystalline polyester The low-temperature fixing property and the sharp melt property of the crystalline polyester can be maintained while the weakness and the low charge amount are suppressed by the vinyl resin coating.

  In addition, since the production of polyester and the vinyl production process are independent, the particle size of the polyester and the thickness of the vinyl coating layer can be controlled independently. Therefore, the polyester particle diameter and the thickness of the vinyl coating layer can be freely combined. It is possible to provide a clear interface without causing the polyester and vinyl to be compatible with each other. Therefore, a toner can be obtained without impairing the low-temperature fixability and sharp melt property of polyester.

  In addition to this, polyester is chemically unstable as described above. However, as mentioned above, storage stability is improved by uniform coating of vinyl resin, so process conditions such as acidity and alkalinity are required. It is possible to maintain a stable state even during the production of the toner, and to impart a good particle size and particle size distribution.

  Thus, the resin fine particle dispersion of the present invention can obtain a toner having excellent toner characteristics, and can be suitably applied as a method for producing a resin fine particle dispersion for an electrostatic charge image developing toner.

  Here, as a technique for analyzing the core-shell structure (double-layer structure) in the polyester / vinyl composite resin fine particles, a cross-sectional TEM (transmission electron microscope) (JEOL) using an osmium oxide staining method or the like is basically used. 1010). In the TEM photograph obtained by observation, a difference occurs in contrast between the crystalline polyester phase, the amorphous polyester phase, and the vinyl resin phase, so that each phase can be identified.

  In the resin fine particle dispersion of the present invention, when the index that the vinyl-based resin is uniformly coated on the surface of the polyester is represented by the coverage, the coverage is preferably 92 mol% to 100 mol%, more preferably. Is 94 mol% to 100 mol%, more preferably 96 mol% to 100 mol%.

  Here, the coverage is measured as follows. In this method, the occupation ratio of the polyester / vinyl resin is calculated by measuring the occupation ratio of carbon atoms / oxygen elements on the outermost surface of the particle using XPS (X-ray photoelectron spectroscopy). Here, a specific example of a method for quantifying the outermost surface of the particle by XPS (X-ray photoelectron spectroscopy) is shown below. A small sample of the obtained resin dispersion is sampled and air-dried. The 1s spectrum of oxygen atoms and carbon atoms on the outermost surface of the obtained air-dried resin particles is measured, and the oxygen and carbon atoms obtained by the above method are measured. By comparing the area intensity of the spectrum, the occupation ratio of oxygen / carbon atoms on the surface was calculated, and further, the theoretical occupation ratio was calculated using the structural formula of polyester that can be polymerized from the composition. Similarly, the occupation ratio of theoretical oxygen / carbon was calculated from the structural formula of the vinyl multimer. The occupation ratio of polyester and vinyl on the resin surface can be calculated by solving the simultaneous oxygen and the theoretical oxygen atom / carbon atom content of the two types of multimers and the actual measurement value as the solution.

In addition, the measurement conditions of the occupation ratio of the particle | grain surface of the carbon atom and oxygen atom in XPS are as showing below.
XPS (X-ray photoelectron spectrometer): JPS-9000MX manufactured by JEOL Ltd.
Photoelectron excitation: MgKα ray (10 kv, 30 mA)
-Pass energy of photoelectron energy analyzer: 30kv

  Next, polyester and its polycondensation will be described. Polyester is a product of direct polycondensation in an aqueous medium, and it is desirable that the monomer contains a polyvalent carboxylic acid and a diol monomer. Specifically, for example, polyester is a direct esterification reaction or transesterification reaction using aliphatic, alicyclic or aromatic polyvalent carboxylic acids, alkyl esters thereof and polyhydric alcohols, ester compounds thereof or the like. It can be obtained by polycondensation, etc.

  The polyester preferably takes any form of amorphous polyester or crystalline polyester, but may take a mixed form thereof. In particular, it may be in the form of crystalline polyester.

  The crystalline melting point Tm of the crystalline polyester is preferably 50 ° C. or higher and lower than 140 ° C., particularly 55 or higher and lower than 110 ° C. When the melting point Tm is less than 50 ° C., the fluidity, developability, filming resistance, offset resistance, and durability of the obtained toner are impaired. When the melting point is 140 ° C. or more, sufficient melting is obtained. In some cases, the minimum fixing temperature rises and the fixability is impaired.

  The melting point can be measured by, for example, “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to differential scanning calorimetry (DSC). Specifically, about 10 mg of a sample is heated at a constant rate of temperature (10 ° C./min). The melting point is obtained from the intersection of the baseline and the endothermic peak slope.

  The glass transition point Tg of the amorphous polyester is preferably 50 ° C. or more and less than 80 ° C., particularly preferably 50 ° C. or more and less than 65 ° C. When the glass transition point Tg is less than 50 ° C., the cohesive force of the binder resin itself in a high temperature range is lowered, so that hot offset is likely to occur during fixing, and when it is 80 ° C. or more, sufficient melting occurs. This is because the minimum fixing temperature may rise without being obtained.

  The glass transition point refers to a value measured by a method (DSC method) defined in ASTM D3418-82.

  “Crystallinity” means that in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a step-like endothermic change. Specifically, it is measured at a heating rate of 10 ° C./min. It means that the half-value width of the endothermic peak is 6 ° C. or less. On the other hand, a resin having a half-value width of an endothermic peak exceeding 6 ° C. or a resin having no clear endothermic peak means amorphous.

  The polyvalent carboxylic acid as a polyester monomer is a compound containing two or more carboxyl groups in one molecule. Among these, a 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, hexahydroterephrine Tar acid, malonic acid, pimelic acid, tartaric acid, mucoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenedi Glycolic acid, p-phenylene diglycolic acid, o-phenylene jig Cholic 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, and pyrenetetracarboxylic acid.

  Among these polyvalent carboxylic acids, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, etc. should be used. Is preferred. Of polyvalent carboxylic acids, it is most preferable to use terephthalic acid, trimellitic acid, pyromellitic acid, adipic acid, or the like. Since these polyvalent carboxylic acids are hardly soluble or insoluble in water, the ester synthesis reaction proceeds in monomer droplets in which the polyvalent carboxylic acid is dispersed in water.

  A diol as a polyester monomer is a compound containing two or more hydroxyl groups in one molecule. Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4 butenediol, neopentyl glycol, 1,5-pentane. Glycol, 1,6-hexane glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, etc. Can be mentioned.

  A divalent polyol as a diol is a compound containing two hydroxyl groups in one molecule, for example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, etc. Can be mentioned. Examples of polyols other than divalent polyols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.

  Of these diols, divalent polyols such as 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferably used. Since these polyols are hardly soluble or insoluble in water, ester synthesis reaction proceeds in monomer droplets in which diol is dispersed in water.

  In addition, an amorphous polyester or a crystalline polyester can be easily obtained by a combination of these polyester monomers. In particular, by using crystalline polyester, low-temperature fixing of toner can be easily realized.

  For example, as a crystalline polyester, polyester obtained by reacting 1,9 nonanediol and 1,10 decamethylene carboxylic acid, or cyclohexanediol and adipic acid, and reacting 1,6 hexanediol and sebacic acid. Polyester obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, polyester obtained by reacting 1,4-butanediol and succinic acid Can be mentioned. Among these, polyesters obtained by reacting 1,9 nonanediol with 1,10 decamethylene carboxylic acid and 1,6 hexanediol with sebacic acid are more preferable.

  The polyester may have some branching or crosslinking depending on the selection of the carboxylic acid valence or alcohol valence as a monomer.

  A polyester monomer can be obtained by blending in an aqueous medium and performing polycondensation to obtain a polyester. In polycondensation of polyester using this polyester monomer in water, a known polycondensation catalyst is necessary. Can be blended in advance in the polyester monomer. In order to achieve polycondensation at a lower temperature, it is particularly effective to use a Bronsted polycondensation catalyst or an enzyme catalyst. For example, one or more of these catalysts are polycondensed at a temperature of 150 ° C. or less (preferably 100 ° C. or less) by adding them in advance to the aqueous medium together with the polyester raw material in a proportion of, for example, about 0.1 to 10000 ppm. can do.

  Examples of the Bronsted acid catalyst include inorganic acids, organic acids, and rare earth element catalysts. In particular, from the viewpoint of achieving polycondensation at a lower temperature, it is desirable to use a rare earth element catalyst containing a rare earth element selected from Y, Sc, Yb, and Sm as a Bronsted acid type catalyst.

  Examples of inorganic acids include sulfuric acid, hydrochloric acid, and odorous acid. Among these, inorganic acids having a sulfonic acid group are preferable.

  Examples of the organic acid include organic acids having a sulfonic acid group such as dodecylbenzene sulfonic acid, polystyrene sulfonic acid, and a styrene copolymer thereof.

  The rare earth element catalyst preferably contains at least one element selected from Y, Sc, Yb, and Sm as its constituent elements, and preferred catalyst forms include triflate forms and trisdodecyl sulfate type forms of these elements. Etc. can be illustrated. Specific examples include scandium trisdodecyl sulfate.

  On the other hand, examples of the enzyme catalyst include lipase, protease, cellulase, and lipase. Examples of these include those derived from Pseudomonas fluorescens, those derived from Pseudomonas cepasia, those derived from Porcine pancreas, Examples include those derived from Aspergillus niger, those derived from Rhizopus delemer, those derived from Rhizopus japonicus, and the like.

  These catalysts can be used alone, but a plurality of catalysts can be used as necessary. In addition, it is important to select the catalyst compound or surfactant-type catalyst having a higher hydrophobicity or molecular weight in consideration of the fact that the catalyst is distributed in the polyester emulsion or particles being polymerized and the aqueous medium. From the viewpoint, a surfactant type catalyst is particularly preferable. For example, preferred is scandium trisdodecyl sulfate.

  Here, the surface active catalyst, that is, the catalyst having surface active ability is a catalyst having a chemical structure composed of a hydrophobic group and a hydrophilic group. Usually, the catalyst is easy to migrate into water, but the surface active catalyst is adsorbed on the surface of the resin particles and easily participates in the polymerization reaction in the oil layer, so that the polymerization reaction can be promoted more effectively.

  These catalysts can be recovered and reused as necessary.

Next, the vinyl resin and radical polymerization thereof will be described.
The vinyl resin is obtained by radical polymerization of a vinyl monomer, and in the present invention, radical polymerization is performed in the presence of a polyester previously prepared by condensation in water.

  Examples of the vinyl monomer include α-substituted styrene such as styrene, α-methyl styrene, α-ethyl styrene, nucleus-substituted styrene such as m-methyl styrene, p-methyl styrene, 2,5-dimethyl styrene, and vinyl aromatics such as nucleus-substituted halogenated styrene such as p-chlorostyrene, p-bromostyrene, and dibromostyrene.

  As the radical polymerization method, a method using a radical polymerization initiator, a self-polymerization by heat, a method using ultraviolet irradiation, and a known polymerization method can be searched. 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-kumi Dialkyl peroxides such as peroxide and dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxide Peroxyesters such as oxylaurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2 , 5-dihydroperoxide, cumene hydroperoxide, hydroperoxide such as di-isopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, hydrogen peroxide, etc. Inorganic excess Products such as potassium persulfate, sodium persulfate, radical polymerization initiators such as persulfates such as ammonium persulfate. A redox polymerization initiator may be used in combination.

  Next, other characteristics of the resin fine particle dispersion of the present invention will be described. In the resin fine particle dispersion of the present invention, the resin fine particles have a weight average molecular weight of 1500 to 60000, preferably 3000 to 40000. When the weight average molecular weight is less than 1500, the cohesive force of the binder resin tends to decrease and the hot offset property may decrease. When the weight average molecular weight exceeds 60000, the hot fixing property is good but the minimum fixing temperature may increase. .

  Here, 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 some differences depending on the measurement methods, but in the present invention, the values are determined by the following measurement methods. is there. 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. .

The reliability of the measurement results is that the NBS706 polystyrene standard sample obtained under the above-described measurement conditions has a weight average molecular weight Mw = 28.8 × 10 ⁴ and a 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, for example, TSK-GEL, GMH (manufactured by Tosoh Corporation) or the like can be used. The solvent and measurement temperature are not limited to the described conditions, and may be changed to appropriate conditions.

  The resin fine particles are polyester / vinyl composite resin fine particles. The weight ratio of the polyester monomer to the vinyl monomer (polyester monomer / vinyl monomer) is 5/95 to 95/5. It is preferable that the ratio is 10/90 to 90/10. When the amount of the polyester-based resin is larger than this range, the characteristics of the crystalline polyester are dominant, and the mechanical strength is deteriorated and the charge amount is easily reduced. If the amount of the polyester resin is less than this range, the low-temperature fixing property and sharp melt property of the polyester are impaired.

  In the resin fine particle dispersion of the present invention, the center diameter (median diameter) of the polyester particles prepared in advance by polycondensation in water is preferably 0.05 μm or more and 2.0 μm or less, more preferably 0.08 μm or more and 1 0.0 μm or less, and more preferably 0.1 μm or more and 0.6 μm or less.

  On the other hand, the center diameter (median diameter) of the resin fine particles after the vinyl resin coating on the polyester particle surface is preferably 0.08 μm or more and 3.0 μm or less, more preferably 0.1 to 1.5 μm, still more preferably. It is 0.1 or more and 1.0 micrometer or less.

  If these median diameters are too small, the agglomeration property at the time of granulation is deteriorated, the generation of free resin particles is likely to occur, and the viscosity of the system is also likely to increase, making it difficult to control the particle size. On the other hand, if it is too large, the occurrence of coarse powder is likely to occur, the particle size distribution is deteriorated, and the release agent such as wax is likely to be liberated. There is.

  In addition, even if the center diameter (median diameter) of the polyester particles prepared in advance by underwater polycondensation is in the above range, the polyester particles can be uniformly coated with the polyester resin in the present invention.

  The resin fine particles are suitable not only for the median diameter but also for the generation of ultrafine powder or ultracoarse powder, and the ratio of the polycondensation resin fine particles having a median diameter of 0.03 μm or less or 5.0 μm or more is overall. 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 and obtaining from the frequency integration amount of 0.03 μm or less or 5.0 μm or more.

  Here, the median diameter can be measured, for example, with a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.).

  In order to obtain resin fine particles having a predetermined particle size in such an aqueous medium, as a polymerization method, suspension polymerization method, dissolution suspension method, miniemulsion method, microemulsion method, microemulsion method, multi-stage swelling method or seed It is preferable to use a heterogeneous polymerization form in a normal aqueous medium such as an emulsion polymerization method including polymerization. In this case, as shown above, the polycondensation reaction, and finally the final molecular weight and the polymerization rate depend on the final particle diameter of the particles, so that the most preferable particle diameter form of 1 μm is achieved, and the efficiency is high. As a production form capable of achieving the production, a polymerization method in which submicron particles of 1 μm or less, such as a miniemulsion method and a microemulsion method, are used as the final form is more preferable.

  Next, the method for producing resin fine particles of the present invention will be described in more detail. The method for producing water-dispersed resin fine particles of the present invention comprises a step of emulsifying or dispersing a polyester monomer in an aqueous medium as a resin fine particle raw material, and polycondensation in the aqueous medium to form polyester particles; And a vinyl monomer, and a step of polymerizing the vinyl monomer in the presence of polyester particles to form resin fine particles in which the polyester particles are coated with a vinyl resin. In this production method, a polyester monomer is first polycondensed to produce polyester particles, which are mixed with a vinyl monomer, and radical polymerization is performed in the presence of the polyester to coat the polyester resin with a vinyl resin. To give composite resin fine particles.

  Here, in the case of polycondensation of the polyester monomer in the aqueous medium, radical polymerization of the vinyl monomer, in addition to the monomer component before polycondensation or polymerization, a colorant, wax and the like are previously mixed. Is also possible. By doing so, it becomes possible to produce resin fine particles in a form incorporating a colorant and a release agent (wax).

  Further, in emulsification or dispersion, a co-surfactant can be used in combination in order to keep the average particle size of the oil phase containing the monomer within a specific range, and the co-surfactant is water-insoluble. Alternatively, those which are hardly soluble and monomer-soluble and which are used in the conventionally known “miniemulsion polymerization” described later in detail can be used. Examples of suitable co-surfactants 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 alkylthiols such as lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, and the like. In addition, resins such as polystyrene and polymethyl methacrylate, polyadducts, carboxylic acids, ketones, amines, and the like can be given.

  In emulsification and dispersion, a fine particle emulsion is formed. 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 combined with a piston homogenizer. The mixture is uniformly mixed and emulsified by a shearing mixing device such as a microfluidizer (eg, Microfluid, “Microfluidizer” manufactured by Dix) 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.

  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 critical micelle concentration (CMC) and the co-surfactant is, for example, P.I. L. Tang, E .; D. Sudol, C.I. A. Silebi, M.M. S. El-Asser; Appl. Polym. Sci. 43, page 1059 (1991), etc., known as so-called “miniemulsion polymerization”, in the presence of a surfactant amount exceeding the critical micelle concentration (CMC), about several μ The conventional emulsion polymerization, in which an aqueous emulsion of monomer particles having a particle size of 1 is polymerized using a water-soluble polymerization initiator, initiates polymerization in the surfactant micelles and diffuses the monomer from the monomer particles. On the other hand, the polymer particles grow and form upon receipt of the supply by the “mini-emulsion polymerization”, whereas the monomer is polymerized in the monomer fine particles, so that uniform polymer fine particles are formed. Furthermore, the “miniemulsion polymerization” of the polyester / vinyl composite polymer as in the present invention has an advantage that the polyester can exist in the polymer fine particles as it is because the monomer does not need to be diffused during the polymerization process. You .

  Also, for example, J.A. S. Guo, M.M. S. El-Asser, J.A. W. Vanderhoff; Polym. Sci. : Polym. Chem. Ed. 27, page 691 (1989), so-called “microemulsion polymerization” of fine particles having a particle diameter of 5 to 50 nm has the same dispersion structure and polymerization mechanism as “miniemulsion polymerization” in the present invention. In "microemulsion polymerization", a surfactant having a critical micelle concentration (CMC) or higher is used in a large amount, and a large amount of surfactant is mixed in the resulting polymer fine particles. Alternatively, there is a problem that a long time is required for the steps such as water washing, acid washing, or alkali washing for the removal.

  High shear mixing techniques such as homogenization or high pressure impingement mixing (impingement mixing) are useful to produce the required droplet size. A suitable high shear impingement mixer is a microfluidizer emulsifier available from Microfluidics Corporation (MICROFLUIDIZER® emulsifier). Such a mixing device is described in US Pat. No. 4,533,254. Ultrasonic mixing is also suitable. Electric dispersers and ultrasonic crushers that convert electrical energy into high frequency mechanical energy may also be used. In addition, mechanical dispersion devices such as IKA, OMNI type mixers can also be used to disperse the polyester monomer in the aqueous phase.

  On the other hand, in emulsification or dispersion, it is highly preferable that the aqueous phase contains a surfactant that stabilizes the particles. Oil droplet instability is generally caused by Brownian collisions and monomer diffusion from the droplets, where the monomer nucleates again to form new particles or replace existing particles. Swells. Instability due to Brownian collisions can be reduced by full coverage of the surfactant layer on the surface of the droplets. Monomer diffusion can be reduced by adequately stabilizing the droplets and producing smaller sized droplets. Surfactants are more soluble in the aqueous phase than droplets because they contain not only relatively hydrophobic groups but also relatively hydrophilic groups. The hydrophobic groups adsorb to the droplets, while the hydrophilic groups enter the aqueous phase and cause stabilization. The surfactant is preferably adsorbed on the dispersed droplets, reducing the interfacial tension between the droplets and the aqueous phase to 5 dynes / cm or less.

  Useful surfactants include a wide range of anionic, cationic and nonionic surfactants. Anionic and nonionic surfactants are generally preferred. Anionic and cationic surfactants are generally characterized by the fact that they contain one or more ionic (anionic or cationic) groups and hydrophobic groups. Suitable anionic groups include carboxylic acid groups and sulfonic acid groups. Suitable cationic groups include ammonium groups and phosphonium groups. The hydrophobic group is preferably an aromatic group having 6 or more carbon atoms, an aliphatic group having 6 or more, preferably 8 to 30 carbon atoms, or an aromatic group having a total of 6 to 30 carbon atoms and A combination of aliphatic groups. Preferred anionic and cationic surfactants contain at least one acyclic alkyl or alkenyl group having 6 or more carbon atoms. In addition, the anionic and cationic surfactants may contain other moieties such as oxyalkylene groups containing oxyethylene and / or oxypropylene groups. Examples of suitable anionic and cationic surfactants include sodium lauryl sulfate, linear dodecyl benzyl sulfonate, triethanolamine lauryl sulfate, sodium dodecyl diphenyl oxide disulfonate, sodium n -Decyl diphenyl oxide disulfonate, sodium hexyl diphenyl oxide disulfonate, dodecyl benzene sulfonate, sodium stearate, sodium stearate, sodium stearate, sodium stearate Examples of these types of commercially available surfactants include Polystep ™ A-15 and Bispot ™ S-100 from Stepan Chemical, Dessulf ™ TLS-40 from Defest, The Dow Chemical. Dowfax (TM) 2A1, 3B2 and C6L from Company, Emkapol (TM) PO-18 from Emkay, Dreinate (TM) TX from Hercules, and Triton (TM) X-100 from Union Carbide, X-405 and X-405 There is X-165.

(Electrostatic image developing toner)
The toner for developing an electrostatic charge image of the present invention (hereinafter referred to as the toner of the present invention) and the production method thereof will be described below. The electrostatic image developing toner of the present invention includes a step of aggregating the resin fine particles to obtain aggregated particles (aggregation step) at least in a dispersion liquid in which the resin fine particles are dispersed, and heating and aggregating the aggregated particles. And a process (fusion process). And in this manufacturing method called emulsion polymerization aggregation method, the resin fine particle dispersion of the present invention is applied as a dispersion in which resin fine particles are dispersed.

  In the aggregation step, the resin fine particles in the resin fine particle dispersion of the present invention are prepared in an aqueous medium, so that they can be used as they are as a resin dispersion, and this resin fine particle dispersion can be used as a colorant as necessary. Aggregated particles having a toner diameter can be formed by mixing with the particle dispersion and the release agent particle dispersion, adding an aggregating agent, and heteroaggregating these particles. Further, after forming the first aggregated particles by aggregating in this way, the resin fine particle dispersion of the present invention or another resin fine particle dispersion is further added to form the second shell layer on the surface of the first particles. Is also possible. In this illustration, the colorant dispersion is separately adjusted. However, when the colorant is mixed in advance with the polycondensation resin fine particles, the colorant dispersion is not necessary.

  Here, 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 cohesion control and toner chargeability. Further, for example, a surfactant can be used for resin emulsion polymerization, pigment dispersion, resin fine particle dispersion, release agent dispersion, aggregation, and aggregation particle stabilization. Specifically, sulfate surfactants, sulfonates, phosphates, soaps and other anionic surfactants, amine salts, quaternary ammonium salts and other cationic surfactants, polyethylene glycols, It is also effective to use a nonionic surfactant such as an alkylphenol ethylene oxide adduct system or a polyhydric alcohol system. Can be used

  Further, the toner of the present invention preferably contains crystalline polyester and amorphous polyester. This is because, since the softening point of the toner is mainly determined by the melting point of the crystalline polyester, the lowest fixing temperature is low by using a low melting point as the polyester, while the amorphous polyester resin is large when melted. This is because viscoelasticity is produced, and as a result, a toner having low-temperature fixability and excellent offset resistance can be obtained.

  In this case, two types of resin fine particle dispersions of the present invention containing crystalline polyester and amorphous polyester can be prepared and used. Moreover, the resin fine particle dispersion of the present invention containing a mixed form of crystalline polyester and amorphous polyester may be prepared and used.

  Here, the abundance ratio between the crystalline polyester and the amorphous polyester (crystalline polyester / amorphous polyester) is preferably 30/70 to 70/30, more preferably 40/60 to 60/40. is there. When the amount of the crystalline polyester is excessive, the characteristics of the crystalline polyester are dominant, and the mechanical strength is deteriorated and the charge amount is likely to be reduced. If the amount of amorphous polyester is too large, the low-temperature fixability and sharp melt properties of the polyester may be impaired.

  In addition to the resin fine particle dispersion of the present invention, addition polymerization resin fine particle dispersions prepared by using conventionally known emulsion polymerization can be used together.

  Examples of addition polymerization monomers for preparing these resin fine particle dispersions include styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, propion. Vinyl esters such as vinyl acrylate, vinyl benzoate, vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, Methylene aliphatic carboxylic acid esters such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide such as vinyl methyl ether, vinyl ethyl ether, Monomers having an N-containing polar group, such as N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, methacrylic acid, acrylic Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as acid, cinnamic acid and carboxyethyl acrylate, and various waxes can also be used.

  In the case of an addition polymerization monomer, emulsion polymerization can be performed using an ionic surfactant or the like to prepare a resin fine particle dispersion. In the case of other resins, the oil is water and the solubility in water is compared. If it is soluble in a low solvent, the resin is dissolved in those solvents and dispersed in an aqueous medium with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heated or decompressed. Then, the resin fine particle dispersion can be obtained by evaporating the solvent.

  Then, after the aggregation step, in the fusion step (fusion / unification step), the resin particles are heated to a temperature not lower than the glass transition point or the melting point or higher to fuse and coalesce the aggregated particles. The toner can be obtained by washing and drying.

  In addition, after completion of the fusion process, desired toner particles are obtained through an arbitrary washing process, solid-liquid separation process, and drying process. In consideration of charging properties, the washing process should be sufficiently washed with ion exchange water. Is desirable. 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.

Hereinafter, constituent components of the toner (raw materials used in the production method) will be described.
First, the following can be used as the colorant. Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, sren yellow, quinoline yellow, permanent yellow NCG and the like. be able to.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.
Red pigments include Bengala, Cadmium Red, Red Plum, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Risor Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C , Rose Bengal, Eoxin Red, Alizarin Lake and the like.
Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.
Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

  These colorants are used alone or in combination. As these colorants, for example, a dispersion of colorant particles can be prepared using a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high-pressure opposed collision type dispersing machine. Further, these colorants can be dispersed in an aqueous system by a homogenizer using a polar surfactant.

  The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.

  The colorant can be added in the range of 4 to 15% by weight with respect to the total weight of the toner constituting solids. When a magnetic material is used as the black colorant, 12 to 240% by weight can be added unlike other colorants.

  The blending amount of the colorant is a necessary amount for securing the color developability at the time of fixing. Moreover, OHP transparency and color developability can be ensured by setting the center diameter (median diameter) of the colorant particles in the toner to 100 to 330 nm.

  The center diameter (median diameter) of the colorant particles was measured, for example, with a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.).

  Further, when used as a magnetic toner, magnetic powder may be contained. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used. When obtaining toner in the aqueous phase, it is necessary to pay attention to the aqueous phase migration of the magnetic material, and it is preferable to modify the surface of the magnetic material in advance, for example, to perform a hydrophobic treatment or the like.

  In addition, magnetic materials such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese and other metals, alloys, and compounds containing these metals are used as internal additives, and quaternary ammonium salt compounds, nigrosine as charge control agents. Various charge control agents such as dyes consisting of complexes of aluminum compounds, aluminum, iron, chromium, etc. and triphenylmethane pigments can be used, but the ionic strength that affects the aggregation and temporary stability From the viewpoint of control of waste water and reduction of waste water contamination, materials that are difficult to dissolve in water are suitable.

  Specific examples of the release agent include, for example, various ester waxes, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that show a softening point by heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid Fatty acid amides such as amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin Examples thereof include mineral-based and petroleum-based waxes such as wax, microcrystalline wax, microcrystalline wax, Fischer-Tropsch wax, and modified products thereof.

  These waxes are hardly dissolved in a solvent such as toluene at room temperature or very little even if dissolved.

  These waxes are dispersed in an aqueous medium together with a polymer electrolyte such as an ionic surfactant, polymer acid or polymer base, heated above the melting point, and have a strong shearing ability and pressure discharge type. It can be dispersed in the form of particles with a disperser (Gorin homogenizer, manufactured by Gorin Co., Ltd.) to produce a dispersion of particles of 1 μm or less.

  It is desirable to add the release agent in the range of 5 to 25% by weight with respect to the total weight of the toner constituting solids, in order to ensure the peelability of the fixed image in the oilless fixing system.

  The particle size of the release agent particle dispersion was measured, for example, with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). In addition, when using a release agent, after the resin fine particles, colorant particles and release agent particles are aggregated, it is possible to add a resin fine particle dispersion to adhere the resin fine particles to the surface of the aggregated particles. From the viewpoint of securing the property

  Here, as examples of surfactants used for pigment dispersion, release agent dispersion, aggregation, or stabilization thereof, sulfate anionic surfactants such as sulfate, sulfonate, phosphate, and soap It is also effective to use a cationic surfactant such as an agent, an amine salt type, a quaternary ammonium salt type, or a nonionic surfactant such as a polyethylene glycol type, an alkylphenol ethylene oxide adduct type, or a polyhydric alcohol type. As a means for dispersion, general means such as a rotary shear type homogenizer, a ball mill having a media, a sand mill, a dyno mill, and the like can be used.

The cumulative volume average particle diameter D ₅₀ of the toner of the present invention is suitably in the range of 3.0 to 10.0 μm, preferably in the range of 3.0 to 5.0 μm. When D ₅₀ is _less than 3.0 μm, the adhesion is increased and the developability may be lowered. On the other hand, if it exceeds 10.0 μm, the resolution of the image may deteriorate.

  Further, the volume average particle size distribution index GSDv of the toner of the present invention is preferably 1.30 or less. When GSDv exceeds 1.30, the resolution is deteriorated, which may cause image defects such as toner scattering and fogging.

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 obtained toner is in the range of 100 to 140, preferably 110 to 135, from the viewpoint of image formability. The shape factor SF1 is obtained as follows. First, an optical microscope image of the toner dispersed on the slide glass is taken into a Luzex image analyzer through a video camera, and the peripheral length (ML) and the projection area (A) of 50 or more toners are measured. Multiplier / projection area = ML ² / A) was defined as the toner shape factor SF1.

  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 fine particles can be used by adding 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.

  The toner of the present invention described above is used as an electrostatic charge 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.

  The carrier is not particularly limited, and examples thereof include known carriers. For example, known carriers such as resin-coated carriers described in JP-A-62-39879, JP-A-56-11461, etc. Can be used.

  Specific examples of the carrier include the following resin-coated carriers. That is, examples of the core particle of the carrier include normal iron powder, ferrite, and magnetite molding, and the average particle diameter is about 30 to 200 μm. Examples of the coating resin for the core particles include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , Α-methylene fatty acid monocarboxylic acids such as methyl methacrylate, n-propyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl vinyls such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone Luketones, polyolefins such as ethylene and propylene, silicones such as methylsilicone and methylphenylsilicone, and vinylidene fluoride. Examples thereof include copolymers of vinyl-based fluorine-containing monomers such as tetrafluoroethylene hexafluoroethylene, polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and the like. These resins may be used alone or in combination of two or more. The amount of the coating resin is about 0.1 to 10 parts by weight, preferably 0.5 to 3.0 parts by weight with respect to the carrier. In the production of the carrier, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like can be used. it can.

  The mixing ratio of the toner and the carrier in the electrostatic image developer is not particularly limited and can be appropriately selected depending on the purpose.

  Further, the electrostatic image developer (electrostatic image developing toner) can be used in an ordinary electrostatic image developing system (electrophotographic system) image forming method. Specifically, the image forming method of the present invention includes, for example, an electrostatic latent image forming step, a toner image forming step, a transfer step, and a cleaning step. 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 electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming 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 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.

  The toner of this example was prepared by preparing the following resin fine 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 crystal melting point of the resin fine particles or the glass transition point 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.

(Preparation of monomer dispersion emulsion (1))
Dodecylbenzenesulfonic acid 12.1 parts by weight Ion exchange water 1000 parts by weight The above components are mixed and dissolved to prepare a dodecylbenzenesulfonic acid aqueous solution.

1,9 Nonanediol 26.7 parts by weight 1, 10 decamethylene dicarboxylic acid 38.4 parts by weight The above was mixed, heated to 120 ° C. and melted, and then poured into the above-mentioned dodecylbenzenesulfonic acid aqueous solution, and homogenizer (IKA) After being emulsified for 5 minutes with a product manufactured by Ultra Tarrax, Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was passed 5 times to obtain a monomer dispersed emulsion (1).

(Preparation of monomer dispersion emulsion (2))
Dodecylbenzenesulfonic acid 12.1 parts by weight Ion exchange water 1000 parts by weight The above components are mixed and dissolved to prepare a dodecylbenzenesulfonic acid aqueous solution.

Bisphenol A-EO 2 mol adduct 49.3 parts by weight 28.4 parts by weight of terephthalic acid The above components are mixed, heated to 120 ° C. and melted, and then added to the above aqueous solution of dodecylbenzenesulfonic acid, and homogenizer (manufactured by IKA). The emulsion was emulsified with Ultra Tarrax for 5 minutes, and then passed through Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) for 5 passes to obtain a monomer dispersed emulsion (2).

(Preparation of monomer dispersion emulsion (3))
Dodecylbenzenesulfonic acid 12.1 parts by weight Ion exchange water 1000 parts by weight The above components are mixed and dissolved to prepare a dodecylbenzenesulfonic acid aqueous solution.

1,6 Hexanediol 17.8 parts by weight Sebacic acid 30.7 parts by weight The above components were mixed, heated to 120 ° C. and melted, and then poured into the above-mentioned aqueous dodecylbenzenesulfonic acid solution, and homogenizer (manufactured by IKA, Ultra After emulsifying with Thalax) for 5 minutes, Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was passed 5 times to obtain a monomer-dispersed emulsion (3).

(Preparation of monomer dispersion emulsion (4))
Dodecylbenzenesulfonic acid 12.1 parts by weight Ion exchange water 1000 parts by weight The above components are mixed and dissolved to prepare a dodecylbenzenesulfonic acid aqueous solution.

Bisphenol A-EO 2 mol adduct / PO1 mol adduct 62.2 parts by weight Adipic acid 28.2 parts by weight The above components were mixed, heated to 120 ° C. and melted, and then charged into the above dodecylbenzenesulfonic acid aqueous solution. After being emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 5 minutes, Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was passed for 5 passes to obtain a monomer-dispersed emulsion (4).

(Preparation of monomer dispersion emulsion (5))
Dodecylbenzenesulfonic acid 12.1 parts by weight Ion exchange water 1000 parts by weight The above components are mixed and dissolved to prepare a dodecylbenzenesulfonic acid aqueous solution.

Ethylene glycol 10.6 parts by weight Glutaric acid 22.5 parts by weight Styrene 18.5 parts by weight n-Butyl acrylate 7.05 parts by weight Dodecanethiol 0.7 parts by weight After mixing the above components, heating to 120 ° C. and melting Then, the solution was put into the above dodecylbenzenesulfonic acid aqueous solution, emulsified with a homogenizer (IKA, Ultra Tarrax) for 5 minutes, then passed through a nanomizer (Yoshida Kikai Kogyo Co., Ltd.) for 5 passes, and a monomer dispersion emulsion (5) Obtained.

(Preparation of resin fine particle dispersion (1))
The emulsion obtained from the monomer-dispersed emulsion (1) was maintained at 70 ° C. in a flask while stirring with a stirrer, and held for 24 hours. As a result, a crystalline polyester resin fine particle dispersion (1) having a center diameter (median diameter) of fine particles of 300 nm, a melting point of 68 ° C., a weight average molecular weight of 5850, and a solid content of 16% was obtained.

Here, the solid content amount was determined by the following formula by collecting 5.0 g of the resin fine particle dispersion, measuring the weight of the dried solid after evaporation of water. The same applies hereinafter.
Formula: Solid content (%) = (weight of dried product after drying / 5.0) × 100

  The stability of the resulting resin fine particle dispersion was measured by weighing 100 g of the resin fine particle dispersion into a 300 ml stainless beaker, shear homogenizing with IKA Ultra Tarrax T50 for 1 minute in the beaker, and then resin fine particles with a 77 micron nylon mesh. When the dispersion was filtered and examined by the method of observing the presence or absence of aggregation (shear homogenization method), the occurrence of aggregation was not observed, and it was confirmed that the dispersion was sufficiently stable. Met. The evaluation method is the same below.

Further, the particle size distribution of the obtained resin fine particle dispersion was examined. As a result, the GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.29, which was a sharp particle size distribution. .

  Here, the particle size distribution was measured as follows. Using a laser diffraction / scattering particle size distribution measuring device (LA920, manufactured by Horiba, Ltd.), about 1 mL of a resin dispersion in which the solid content concentration of the obtained resin dispersion was adjusted to about 5% was dropped to observe the scattering. This was performed by automatically calculating the particle size distribution from the optical data using the Mie scattering theory. The same applies hereinafter.

(Preparation of resin fine particle dispersion (2))
The emulsion obtained in the monomer-dispersed emulsion (2) was maintained at 70 ° C. in a flask while stirring with a stirrer, and held for 24 hours. As a result, an amorphous polyester resin fine particle dispersion (2) having a center diameter of 300 nm, a glass transition point of 53.5 ° C., a weight average molecular weight of 5650, and a solid content of 16% was obtained.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.30, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (3))
The emulsion obtained in the monomer-dispersed emulsion (3) was maintained at 70 ° C. in a flask while stirring with a stirrer, and maintained for 24 hours. As a result, a crystalline polyester resin fine particle dispersion (3) having a fine particle central diameter of 360 nm, a melting point of 68 ° C., a weight average molecular weight of 5850, and a solid content of 16% was obtained.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.28, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (4))
The emulsion obtained in the monomer-dispersed emulsion (4) was maintained at 70 ° C. in a flask while stirring with a stirrer and maintained for 24 hours. As a result, an amorphous polyester resin fine particle dispersion (4) having a fine particle central diameter of 340 nm, a glass transition point of 54.5 ° C., a weight average molecular weight of 5550, and a solid content of 16% was obtained.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.30, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (5))
Resin fine particle dispersion (1) 250 parts by weight Styrene 20 parts by weight To a resin fine particle dispersion obtained by mixing the above-mentioned components, 0.8 g of ammonium persulfate dissolved in 10 g of ion-exchanged water was added, and a flask was added. The polymerization was carried out for 6 hours under a nitrogen atmosphere.

  As a result, a crystalline polyester-vinyl composite resin fine particle dispersion (5) having a fine particle central diameter of 770 nm and a styrene weight average molecular weight of 50,000 was obtained. In addition, evaluation of the structure of the obtained composite resin particle is performed with a cross-sectional TEM (transmission electron microscope) (1010 manufactured by JEOL) by osmium oxide staining, and a two-layer structure (core shell) covering the core and the core It was confirmed that the particles had a structure. Moreover, the coverage was 96.2 mol%. The confirmation method is the same below.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.29, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (6))
Resin fine particle dispersion (2) 250 parts by weight Styrene 20 parts by weight To a resin fine particle dispersion obtained by mixing the above components, 0.8 g of ammonium persulfate dissolved in 10 g of ion exchange water was added, and the flask was added. The polymerization was carried out for 6 hours under a nitrogen atmosphere.

  As a result, an amorphous polyester / vinyl composite resin fine particle dispersion (6) having a fine particle central diameter of 860 nm and a styrene weight average molecular weight of 62,000 was obtained. In addition, it confirmed that the structure of the obtained composite resin particle was a two-layer structure which coat | covers a nucleus and a nucleus. Moreover, the coverage was 95.8 mol%.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.27, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (7))
Resin fine particle dispersion (3) 250 parts by weight Styrene 20 parts by weight To a resin fine particle dispersion obtained by mixing the above components, a product obtained by dissolving 0.8 g of ammonium persulfate in 10 g of ion-exchanged water was added to a flask. The polymerization was carried out for 6 hours under a nitrogen atmosphere.

  As a result, a composite resin fine particle dispersion (7) of crystalline polyester and vinyl having a fine particle center diameter of 770 nm and a styrene weight average molecular weight of 50,000 was obtained. In addition, it confirmed that the structure of the obtained composite resin particle was a two-layer structure which coat | covers a nucleus and a nucleus. Moreover, the coverage was 96.3 mol%.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.27, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (8))
Resin fine particle dispersion (4) 250 parts by weight Styrene 20 parts by weight To a resin fine particle dispersion obtained by mixing the above components, a product obtained by dissolving 0.8 g of ammonium persulfate in 10 g of ion-exchanged water was added to a flask. The polymerization was carried out for 6 hours under a nitrogen atmosphere.

  As a result, an amorphous polyester / vinyl composite resin fine particle dispersion (8) having a fine particle central diameter of 860 nm and a styrene weight average molecular weight of 62,000 was obtained. In addition, it confirmed that the structure of the obtained composite resin particle was a two-layer structure which coat | covers a nucleus and a nucleus. Moreover, the coverage was 96.4 mol%.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that there was no occurrence of agglomeration and there was sufficient stability.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined, and GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.29, which was a sharp particle size distribution.

(Preparation of resin fine particle dispersion (9))
The emulsion obtained in the monomer-dispersed emulsion (5) was maintained at 70 ° C. in a flask while stirring with a stirrer, and held for 24 hours. As a result of sampling a small amount from this dispersion and measuring the particle and weight average molecular weight of the fine particles, resin fine particle dispersion containing polyester particles having a fine particle center diameter of 300 nm, a crystal melting point of 65 ° C., and a weight average molecular weight of 5650 A liquid (9) was obtained.

  A solution obtained by dissolving 0.8 g of ammonium persulfate in 10 g of ion exchange water is added to the polyester resin dispersion, and the temperature is maintained at 70 ° C. in a flask. Polymerization is performed for 6 hours in a nitrogen atmosphere. It was. As a result, polyester / vinyl composite particles having a vinyl weight average molecular weight of 54,000 were obtained.

  In addition, although the structure of the obtained composite resin particle was forming the two-layer structure which coat | covers a nucleus and a nucleus, it confirmed that the polyester was exposed to the surface about several places per particle | grain. Further, the vinyl coverage of the particles was 48.6 mol%, and it was confirmed that the particles were not completely covered.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that some aggregates remained on the 77 μm mesh, and the generation ratio of the aggregates was 3.3% by weight. It was confirmed that the stability was low.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined. As a result, the median diameter was 590 nm, GSDv (D84 / D50) measured on a volume basis was 1.71, and the particle size distribution was broad.

(Preparation of resin fine particle dispersion (10))
Propylene glycol 12.9 parts by weight Glutaric acid 22.46 parts by weight Dodecylbenzenesulfonic acid 12.1 parts by weight The above components were put into a separable flask equipped with a stirrer, and the temperature was raised to 120 ° C. while stirring was continued. After complete dissolution, the temperature of the oil phase was changed to 70 ° C. and polycondensation was performed over 8 hours. As a result, a polyester resin melt having a weight average molecular weight of 7600 was obtained.

  1000 parts by weight of an aqueous solution in which 12.1 parts by weight of dodecylbenzenesulfonic acid was dissolved in the polyester product was put into a separable flask equipped with a stirrer, and the mixture was kept at 70 ° C. for 5 minutes, By stirring for 5 minutes with a homogenizer (manufactured by IKA, Ultra Tarrax), a resin fine particle dispersion (10) was obtained.

The polyester resin particles obtained here had a median diameter of 920 nm, GSDv (D84 / D16) ^1/2 of 1.48 and a broad particle size distribution.

(Preparation of resin fine particle dispersion (11))
To the resin dispersion (10) obtained above, 0.8 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion exchange water was added, and the following components were further maintained while maintaining at 70 ° C. Was gradually added while stirring over a period of 1 hour.
-Styrene 18.5 parts by weight-n-butyl acrylate 7.05 parts by weight-Methacrylic acid 0.7 parts by weight-Dodecanethiol 0.7 parts by weight

  After completion of dropping, the mixture is further heated and stirred at 70 ° C. for 6 hours. A resin fine particle dispersion (11) containing a vinyl resin forming a shell layer was obtained, and the weight average molecular weight was 64800, and as a result, polyester / vinyl composite particles were obtained.

  Further, the structure of the obtained composite resin particles was a two-layer structure covering the core and the core, but it was confirmed that the polyester was exposed on the surface at several locations per particle. Moreover, the vinyl coverage of the said particle | grains is 85.8 mol%, and it was confirmed that it is not completely coat | covered.

Further, when the stability of the obtained resin fine particle dispersion was examined, it was confirmed that some aggregates remained on the 77 μm mesh, and the generation ratio of aggregates was 3.9% by weight. It was confirmed that the stability was low.
Further, the particle size distribution of the obtained resin fine particle dispersion was examined. The median diameter was 1020 nm, the GSDv (D84 / D16) ^1/2 measured on a volume basis was 1.43, and the particle size distribution was broad. Met.

(Preparation of colorant particle dispersion (1))
Yellow pigment (manufactured by Dainichi Seika Co., Ltd., Y74) 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight The above components are mixed and dissolved, and a homogenizer (manufactured by IKA) Ultra-Turrax) was dispersed for 5 minutes using an ultrasonic bath, and a yellow colorant particle dispersion (1) having a central diameter of 240 nm and a solid content of 21.5% was obtained.

(Preparation of colorant particle dispersion (2))
In the preparation of the colorant particle dispersion liquid (1), it was prepared in the same manner as the colorant particle dispersion liquid (1) except that a cyan pigment (manufactured by Dainichi Seika Co., Ltd., copper phthalocyanine B15: 3) was used instead of the yellow pigment. Thus, a Cyan coloring agent particle dispersion (2) having a center 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), except that a magenta pigment (manufactured by Dainichi Ink Chemical Co., PR122) was used instead of the yellow pigment, it was prepared in the same manner as the colorant particle dispersion (1). A colorant particle dispersion (3) having a center 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) was used instead of the yellow pigment, and the center diameter was 170 nm. A colorant particle dispersion (4) having a solid content of 21.5% was obtained.

(Preparation of release agent particle dispersion)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP9; melting point 70 ° C.) 50 parts by weight Anionic surfactant (Dow Chemical Dow Fax) 5 parts by weight Ion exchange water 200 parts by weight After sufficiently dispersing with IKA's Ultra Turrax T50), it is dispersed with a pressure discharge type homogenizer (Gorin homogenizer, Gorin) and dispersed with a release agent particle having a center diameter of 180 nm and a solid content of 21.5%. A liquid was obtained.

[Toner Example 1]
(Preparation of toner particles)
Resin fine particle dispersion (5) 150 parts by weight Resin fine particle dispersion (6) 150 parts by weight Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
40 parts by weight of release agent particle dispersion (8.6 parts by weight of release agent)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and maintained at 42 ° C. for 60 minutes, and then the pH in the system was adjusted to 6.0 with a 0.5 mol / liter sodium hydroxide aqueous solution. Heated to ° C.

  During the temperature increase up to 95 ° 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 4.28 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 131 potato shapes.

  1.4 parts by weight of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by weight of the toner particles, and mixed with 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 was weighed so that the toner concentration would be 8%. A developer was prepared by stirring and mixing for a minute.

(Evaluation of toner)
The obtained developer (toner) was evaluated as follows.
1) Evaluation of mechanical strength A device capable of driving a developing machine of a full color copying machine DocuCenterColor500 manufactured by Fuji Xerox Co., Ltd. alone was prepared, and the developer was put into the developing machine and driven under the same conditions as in the copying machine. Therefore, the developer in the developing machine was sampled at an arbitrary time, and the particle size distribution of the toner was measured with a Coulter Counter TAII (manufactured by Nikkaki Co., Ltd.). The driving time was plotted on the X axis, and the cumulative value of 3.0 μm or less in the number average distribution was plotted on the Y axis, the slope was defined as the mechanical strength index, and the mechanical strength was evaluated based on the numerical value. The larger this value, the easier the crushing occurs in the developing machine and the lower the mechanical strength.

  The developer was introduced into the developing machine and evaluated. As a result, the mechanical strength index was 0.16.

2) Fixation evaluation Using the developer described above, Fuji Xerox's DocuCenterColor500 modified machine uses Fuji Xerox's J-coated paper as the transfer paper, and the process speed is adjusted to 180 mm / sec to fix the toner. As a result, the oilless fixability by the PFA tube fixing roll is good, the minimum fixing temperature (the minimum fixing temperature is determined by image contamination by cloth rubbing of the image) is 120 ° C. or higher, and the image is It was confirmed that the transfer sheet showed sufficient fixing properties and was peeled without any resistance. The surface gloss of the image at a fixing temperature of 150 ° C. was as good as 65%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C.

  The surface gloss was evaluated by measuring an image formed on J-coated paper manufactured by Fuji Xerox Co., Ltd. with a gloss meter GMD manufactured by Murakami Color Research Laboratory, and measuring 75-degree gloss. The same applies hereinafter.

3) Evaluation of triboelectric charge amount (absolute value) 1.5 g of the obtained toner and 30 g of a carrier (a carrier for DocuCenterColor500 manufactured by Fuji Xerox) were left in a high temperature and high humidity (temperature 28 ° C., humidity 85%) environment for one day and night. . Then, both were mixed and stirred for 60 minutes, and the triboelectric charge amount was measured with a blow-off tribo measuring device.

  When the triboelectric charge amount of the developer was measured, the absolute value of the obtained charge amount was 24 μC / g.

[Toner Example 2]
In Example 1, the toner was changed in the same manner as in Example 1 except that the colorant particle dispersion (1) was changed to the colorant particle dispersion (2) and the pH during heating at 95 ° C. was maintained at 5.0. Particles were obtained. The cumulative volume average particle diameter D ₅₀ of the toner particles is 4.39 μm, and the volume average particle size distribution index GSDv is 1.19. The shape factor SF1 was slightly spherical with 122.

  Using this toner particle, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and was found to be 0.11. It was.

  Further, when the toner fixing property was examined, the oilless fixing property by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 115. It was confirmed that the image showed sufficient fixability at a temperature higher than 0 ° C. 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 65%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. Further, the absolute value of the obtained charge amount was 28 μC / g.

[Toner Example 3]
Toner particles in the same manner as in Example 1 except that the colorant particle dispersion (1) is changed to the colorant particle dispersion (3) and the amount of polyaluminum chloride is 0.12 parts by weight. Got. The cumulative volume average particle diameter D ₅₀ of the toner particles is 4.15 μm, the volume average particle size distribution index GSDv is 1.22, the shape factor SF1 is 117, and the toner particles are spherical.

  Using this toner particle, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and the result was 0.14. .

  Further, when the toner fixability was examined, the oilless fixability by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 110. It was confirmed that the image showed sufficient fixability at a temperature higher than 0 ° C. 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 64%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. The absolute value of the obtained charge amount was 29 μC / g.

[Toner Example 4]
Toner particles were obtained in the same manner as in Example 1, except that the colorant particle dispersion (1) was changed to the colorant particle dispersion (4). The toner particles had a cumulative volume average particle size D ₅₀ of 4.66 μm, a volume average particle size distribution index GSDv of 1.22, and a shape factor SF1 of 134.

  Further, using this toner particle, an externally added toner was obtained in the same manner as in Example 1, a developer was further prepared, and the mechanical strength index was measured in the same manner as in Example 1. The result was 0.15. It was.

  Further, when the toner fixing property was examined, the oilless fixing property by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 110. It was confirmed that the image showed sufficient fixability at a temperature higher than 0 ° C. 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 60%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. The absolute value of the obtained charge amount was 26 μC / g.

[Toner Example 5]
In Example 1, the toner particles were changed in the same manner as in Example 1 except that the resin fine particle dispersion (5) was changed to the resin fine particle dispersion (7) and the pH during heating at 95 ° C. was maintained at 5.0. Obtained.
The cumulative volume average particle diameter D ₅₀ of the toner particles is 4.06 μm, and the volume average particle size distribution index GSDv is 1.19. The shape factor SF1 was slightly spherical with 122.

  Using this toner particle, an external additive toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and the result was 0.17. It was.

  Further, when the toner fixing property was examined, the oilless fixing property by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 115. It was confirmed that the image showed sufficient fixability at a temperature higher than 0 ° C. 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 66%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. Further, the absolute value of the obtained charge amount was 28 μC / g.

[Toner Example 6]
In Example 1, the toner particles were changed in the same manner as in Example 1 except that the resin fine particle dispersion (6) was changed to the resin fine particle dispersion (8) and the pH during heating at 95 ° C. was maintained at 5.0. Obtained. The cumulative volume average particle diameter D ₅₀ of the toner particles is 4.12 μm, and the volume average particle size distribution index GSDv is 1.19. The shape factor SF1 was slightly spherical with 122.

  Using this toner particle, an external additive toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and the result was 0.17. It was.

  In addition, when the toner fixability was examined, the oilless fixability by the PFA tube fixing roll was good, and the image showed sufficient fixability at 115 ° C. or higher and the transfer paper was peeled off without any resistance. Was confirmed. The surface gloss of the image at a fixing temperature of 150 ° C. was as good as 65%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. The absolute value of the obtained charge amount was 32 μC / g.

[Toner Example 7]
Resin fine particle dispersion (5) 250 parts by weight Resin fine particle dispersion (6) 50 parts by weight Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
40 parts by weight of release agent particle dispersion (8.6 parts by weight of release agent)
Polyaluminum chloride 0.15 parts by weight Ion-exchanged water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and held at 42 ° C. for 60 minutes. Thereafter, 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 4.45 μm, and the volume average particle size distribution index GSDv is 1.19. The shape factor SF1 was 132 and became a potato shape.

  Using this toner particle, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and the result was 0.15.

  Further, when the toner fixing property was examined, the oilless fixing property by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 120. It was confirmed that the image showed sufficient fixability at a temperature higher than 0 ° C. 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 65%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. The absolute value of the obtained charge amount was 27 μC / g.

[Toner Example 8]
Resin fine particle dispersion (5) 50 parts by weight Resin fine particle dispersion (6) 250 parts by weight Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
40 parts by weight of release agent particle dispersion (8.6 parts by weight of release agent)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and held at 42 ° C. for 60 minutes. Thereafter, 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 4.13 μm, and the volume average particle size distribution index GSDv is 1.20. The shape factor SF1 was 135, which was a potato shape.

  Using this toner particle, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and the result was 0.15.

  In addition, when the toner fixability was examined, the oilless fixability by the PFA tube fixing roll was good, and the image showed sufficient fixability at 115 ° C. or higher and the transfer paper was peeled off without any resistance. Was confirmed. The surface gloss of the image at a fixing temperature of 150 ° C. was as good as 65%, both developability and transferability were good, and a high-quality image was displayed without image defects. Also, no hot offset was observed at a fixing temperature of 180 ° C. The absolute value of the obtained charge amount was 25 μC / g.

[Toner Comparative Example 1]
Resin dispersion (9) 300 parts by weight Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
40 parts by weight of release agent particle dispersion (8.6 parts by weight of release agent)
Polyaluminum chloride 0.15 parts by weight Ion-exchanged water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and held at 42 ° C. for 60 minutes. Thereafter, 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 4.63 μm, and the volume average particle size distribution index GSDv is 1.19. The shape factor SF1 was 135, which was a potato shape.

  Using this toner particle, an externally added toner was obtained in the same manner as in Example 1, and a developer was further prepared. The mechanical strength index was measured in the same manner as in Example 1, and the result was 0.86.

  Further, when the toner fixing property was examined, the oilless fixing property by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 120. Above the temperature, the image showed sufficient fixability, but the peeled-off state of the transfer paper was poor, and undulation and wrapping after fixing of the paper were confirmed. Further, occurrence of hot offset was observed from a fixing temperature of 160 ° C. Further, the absolute value of the charge amount of the obtained toner was 9 μC / g.

[Toner Comparative Example 2]
Resin fine particle dispersion (11) 300 parts by weight Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
40 parts by weight of release agent particle dispersion (8.6 parts by weight of release agent)
Polyaluminum chloride 0.15 parts by weight Ion-exchanged water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and held at 42 ° C. for 60 minutes. Thereafter, 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 4.43 μm, and the volume average particle size distribution index GSDv is 1.19. The shape factor SF1 was 131 and became a potato shape.

Using this toner particle, an externally added toner was obtained in the same manner as in Example 1, a developer was further prepared, and the mechanical strength index was measured in the same manner as in Example 1. The result was 0.84.
Further, when the toner fixing property was examined, the oilless fixing property by the PFA tube fixing roll was good, and the minimum fixing temperature (the minimum fixing temperature was determined by image contamination by cloth rubbing of the image) was 120. Above the temperature, the image showed sufficient fixability, but the peeled-off state of the transfer paper was poor, and undulation and wrapping after fixing of the paper were confirmed. Further, occurrence of hot offset was observed from a fixing temperature of 160 ° C. Further, the absolute value of the charge amount of the obtained toner was 19 μC / g.

  Table 1 shows the results of the toner examples and the toner comparative examples. In the table, the evaluation criteria for the hot offset temperature are “◯” for non-occurrence up to an offset generation temperature of 180 ° C. or higher, “Δ” for offset generation temperature or 170 ° C. to 180 ° C. It was set to below ℃.

  The offset generation temperature is measured by creating an unfixed image with the copying machine, transferring the toner image, performing the fixing process with the above-described fixing device, and then fixing the blank transfer paper under the same conditions. The operation of visually inspecting whether or not toner contamination occurs on the toner is repeated while the set temperature of the heat roller of the fixing device is sequentially increased, and the offset is performed with the lowest set temperature at which the toner contamination occurs. It was set as the generation temperature.

The evaluation criteria for mechanical strength are “◯” for mechanical strength index of 0.20 or less, “△” for mechanical strength index greater than 0.20 to 0.40 or less, and “×” for mechanical strength. The index was assumed to be larger than 0.40.

  In addition, the image quality is measured with a loupe for the fine line reproducibility of the image with the fine line fixed and the fog (visual) of the non-fixed part, and the evaluation standard of the image quality is “No” on the thin line and there is no fog at all “△” is a case where the image quality is slightly uneven, and “X” is a case where the image quality is uneven.

  In addition, the evaluation standard of the stability of the resin fine particle dispersion is “◯”. When the resin dispersion is filtered through a 77 μm mesh, no aggregate remains, and “△” indicates that the aggregate remaining on the mesh is solid. When the content was 0.1% or more and 3% or less by weight with respect to the amount, “x” was defined as the case where the aggregate remaining on the mesh was 3% by weight or more.

In addition, the evaluation standard of the particle size distribution of the resin fine particle dispersion is “◯” when the value of GSDv (D84 / D16) ^1/2 measured on the volume basis of the resin dispersion is ≦ 1.30, and “Δ” GSDv (D84 / D16) ^1/2 is 1.31 or more and 1.40 or less, and “X” is GSDv (D84 / D16) ^1/2 is 1.40 or more. did.

   From these examples and comparative examples, by adopting this example, the resin fine particle dispersion of this example is uniformly coated with a vinyl resin on the polyester surface, and has a sharp particle size distribution. It can be seen that polyester / vinyl composite resin particles having a stable emulsified and dispersed state are obtained.

  Further, in this embodiment, the mechanical strength by mechanical impact in the developing machine that could not be achieved with the toner of the conventional configuration is improved, the charge amount is also improved, and a stable image over a long period of time. It can be seen that a toner having high fixing performance including low temperature fixing performance can be obtained.

Claims (14)

  A resin comprising resin particles obtained by polymerizing a vinyl monomer in the presence of polyester particles prepared by polycondensation of a polyester monomer in an aqueous medium and coating the polyester particles with a vinyl resin. Fine particle dispersion.   The resin fine particle dispersion according to claim 1, wherein a coverage of the vinyl resin on the polyester particles is 92 mol% to 100 mol%.   2. The resin fine particle dispersion according to claim 1, wherein the median diameter of the polyester particles is 0.05 μm or more and 2.0 μm or less.   2. The resin fine particle dispersion according to claim 1, wherein a median diameter of the resin fine particles is 0.08 μm or more and 3.0 μm or less.   The resin fine particle dispersion according to claim 1, wherein the polyester particles are crystalline polyester particles or amorphous polyester particles.   6. The resin fine particle dispersion according to claim 5, wherein the crystalline polyester has a crystal melting point of 50 ° C. or higher and lower than 140 ° C.   6. The resin fine particle dispersion according to claim 5, wherein the glass transition point of the amorphous polyester is 50 ° C. or higher and lower than 80 ° C.   The resin fine particle dispersion according to claim 1, wherein the polyester monomer contains at least a diol and a polyvalent carboxylic acid.   2. The resin according to claim 1, wherein a weight ratio of the polyester monomer to the vinyl monomer (polyester monomer / vinyl monomer) is 5/95 to 95/5. Particle dispersion. A method for producing a resin fine particle dispersion for obtaining the resin fine particle dispersion according to any one of claims 1 to 9,
Emulsifying or dispersing a polyester monomer in an aqueous medium, and polycondensation in the aqueous medium to form polyester particles;
Mixing the polyester particles and a vinyl monomer, polymerizing the vinyl monomer in the presence of the polyester particles, and forming resin particles in which the polyester particles are coated with a vinyl resin;
The manufacturing method of the resin fine particle dispersion characterized by including.   An electrostatic charge image developing toner obtained by using the resin fine particle dispersion according to claim 1 and aggregating at least resin fine particles, followed by heating and melting.   The toner includes crystalline polyester and amorphous polyester, and the abundance ratio of the crystalline polyester to the amorphous polyester (crystalline polyester / amorphous polyester) is 30/70 to 70/30. The toner for developing an electrostatic charge image according to claim 11, wherein the toner is for developing an electrostatic image.   The toner for developing an electrostatic charge image according to claim 11, wherein the toner has a volume average particle diameter of 3 μm or more and 10 μm or less.   Using the resin fine particle dispersion according to any one of claims 1 to 9, comprising a step of aggregating at least the resin fine particles, and a step of heating and melting the obtained agglomerated particles, A method for producing a toner for developing an electrostatic image.