JP4858165B2 - Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  Many methods are known as electrophotographic methods. In general, a latent image is electrically formed on the surface of a photosensitive member (latent image holding member) using a photoconductive substance by various means, and the formed latent image is developed with toner to form a toner image. After the toner image is formed, the toner image is transferred to the surface of a transfer medium such as paper via an intermediate transfer body depending on the configuration, and is fixed by heating, pressurization, heat pressurization, solvent vapor, or the like. Through this, an image is formed. Further, the toner remaining on the surface of the photoreceptor is cleaned by various methods as necessary, and is used again for developing the toner image. In recent years, with the advancement of technology in the field of electrophotography, the electrophotographic process has been used not only for copying machines and printers but also for printing applications. There is an increasing demand for high image quality and hue.

  Conventionally, as a fixing technique for fixing the toner image transferred to the surface of the transfer target, a transfer target with the toner image transferred is inserted between a pair of rolls composed of a heating roll and a pressure roll, A heat roll fixing method for fixing is generally used. As a similar technique, a fixing method in which one or both of the rolls is replaced with a belt is also known. These techniques have a feature that heat efficiency is effective and fixing can be performed quickly as compared with other fixing methods, and are widely adopted.

  The toner image transferred to the surface of the transfer target through the transfer step is melted by being heated by the fixing member heated in the fixing step, and is fixed to the surface of the transfer target. In the fixing step, it is known that the toner image is not fixed unless the fixing member heats not only the toner image but also the transfer target. If the transfer medium is not sufficiently heated, only the toner is melted by the heating from the fixing member, and a so-called cold offset is generated in which the toner adheres to the fixing member.

  Further, when the transfer target or the toner image is excessively heated, the viscosity of the toner is reduced, and so-called hot offset occurs in which part or all of the toner image adheres to the fixing member side. Therefore, as the toner fixing characteristics, a toner having a low cold offset occurrence temperature, a high hot offset occurrence temperature, and a wide fixable region is desirable. In particular, this tendency is remarkable for recent miniaturization and high speed.

  Along with the increasing demand for power saving and print productivity in recent years, zero or almost no standby power is used in the fixing unit in the printer standby state to save power in the fixing process that occupies a large amount of power consumption. In order to reduce the warm-up time from the standby state, a small heat capacity fixing device is often introduced. When using a fuser with a small heat capacity, the temperature distribution of the fuser tends to increase, so the above fixable area is even more important, and the temperature of the fuser tends to drop due to continuous printing. Therefore, the low-temperature fixability of the toner is also an important characteristic from the viewpoint of print productivity.

  However, it lowers the toner fixing temperature and lowers the glass transition point of the toner particles, making it difficult to achieve compatibility with the storage stability of the toner. In order to achieve both low temperature fixing and toner storage stability, it is necessary to maintain the so-called sharp melt property that rapidly lowers the viscosity of the toner in a high temperature region while keeping the glass transition temperature of the toner higher. Although important, as described above, the surface temperature of the fixing member constantly changes due to fixing, so that the fixing performance varies depending on the setting of the temperature at which sharp melting occurs. In particular, when color toner is used, the gloss of the fixed image surface is required. The value is required to be higher than the image gloss required for black and white images.

  In order to increase the glossiness of the image, it is necessary to heat and melt the toner to the melted state at the time of fixing. However, fluctuations in the surface temperature of the fixing member affect the melted state of the toner and greatly affect the glossiness of the image. In addition, the image glossiness of the fixed image is remarkably changed between the initial stage and the later stage of continuous fixing, and the reliability of the image quality is significantly reduced. Furthermore, if the fixing substrate has irregularities, there will be a difference in the heat supply from the fixing member to the fixing substrate. Generally, the concave portion has a higher heat transfer than the convex portion. In comparison, it is fixed at a higher temperature. As a result, the glossiness due to the temperature difference changes, and the reliability of the image quality is lowered. In order to solve this problem, there is a method of controlling the molecular weight of the toner binder resin, and various reports have been made.

  In general, a low molecular weight resin has a low viscosity and sharp melt properties, which is advantageous for low-temperature fixing and flat fixed image formation, and can provide a high gloss image, but is inferior in offset resistance. High molecular weight resins have a high viscosity and are advantageous for offset resistance. However, since color developability and glossiness are lowered, they cannot cope with high image quality particularly required for color images. In addition, there is a method of reducing the difference in fixing temperature and decreasing the difference in glossiness by increasing the contact time between the fixing member and the fixing substrate. However, this method cannot cope with high speed copying machines. There is.

  Therefore, there are some attempts to satisfy both low temperature fixing property and offset resistance by combining a low molecular weight resin and a high molecular weight resin or defining a molecular weight distribution. For example, the molecular weight distribution is defined, the weight average molecular weight Mw / Mn is defined, the three maximum values, the ratio between the low molecular weight component and the high molecular weight component is finely defined, etc. (For example, see Patent Documents 1 to 4).

  Further, as a means for achieving both the low-temperature fixability and the prevention of blocking (solidification by heat), a method using a crystalline resin as a binder resin has been known for a long time (see, for example, Patent Documents 5 and 6). . Further, a technique has been proposed in which a crystalline resin is not used alone as a binder resin, but a crystalline resin and an amorphous resin are used in combination. Specifically, it is a method in which an amorphous polyester resin having a glass transition temperature of 40 ° C. or higher and a crystalline polyester resin having a melting temperature of 130 to 200 ° C. are mixed and used (see, for example, Patent Document 7).

On the other hand, a technique for obtaining low-temperature fixing by mixing a crystalline resin and an amorphous resin having a low melting temperature and controlling the degree of compatibilization has been proposed (see, for example, Patent Documents 8 and 9). Furthermore, a technology that uses a mixture of crystalline polyester and amorphous resin, and prevents blocking of paper during discharge without compromising transparency by compatibilizing the crystalline part due to the temperature history during fixing. Is introduced (for example, see Patent Document 10).
Japanese Patent Laid-Open No. 10-207126 JP-A-10-63035 Japanese Patent Laid-Open No. 10-228131 JP-A-3-278067 Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Publication No. 63-25335 JP 2004-206081 A Japanese Patent Laid-Open No. 2004-50478 Japanese Patent Laid-Open No. 2003-50478

  An object of the present invention is to provide an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, and a process capable of forming a fixed image with less surface roughness in the fixed image, a difference in glossiness depending on toner fixing conditions, and less uneven glossiness. To provide a cartridge and an image forming apparatus.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1 includes a binder resin including polyester resin A, polyester resin B, and polyester resin C, a colorant, and a release agent.
The polyester resin A is a branched amorphous polyester resin containing no tetrahydrofuran-insoluble matter, the polyester resin B is a linear amorphous polyester resin,
The polyester resin A and the polyester resin B are at least one selected from terephthalic acid, terephthalic anhydride, and alkyl esters of terephthalic acid, and at least one selected from alkyl succinic acid, alkenyl succinic acid, and anhydrides thereof. A resin component containing at least one species as an acid component, reacted with at least one selected from a bisphenol A ethylene oxide adduct and a bisphenol A propylene oxide adduct as an alcohol component,
The polyester resin C is a crystalline polyester resin,
Any of the carbon number of the alkyl succinic acid, alkenyl succinic acid and their acid anhydrides is greater than the carbon number of each of the monomer-derived components in the polyester resin C,
And an electrostatic charge image developing toner characterized by satisfying the following (1) to (3).
(1) The weight average molecular weight of the polyester resin A is from 25000 to 45000, the number average molecular weight of 4500 to 7000
(2) The weight average molecular weight of the polyester resin B is 14,000 to 18000, and the number average molecular weight is 5000 to 5500.
(3) Aliphatic crystalline polyester resin obtained by reacting polyester resin C with a dicarboxylic acid having 6 to 10 carbon atoms and a dialcohol having 6 to 10 carbon atoms

The invention according to claim 2 is an alkyl succinic acid, an alkenyl succinic acid, and acid anhydrides thereof among the constituent components derived from all monomers in the polyester resin A and the polyester resin B in the toner for developing an electrostatic charge image according to claim 1. Component amounts P and Q derived from at least one selected from are each in the range of 5 to 20 mol%,
The constituent component quantity P is not large toner for electrostatic image development than the constituent component quantity Q.

The invention according to claim 3 has a structure including a core particle and a shell layer covering the core particle,
The binder resin of the core particles includes the polyester resin A, the polyester resin B, and the polyester resin C,
2. The electrostatic charge image developing toner comprising the polyester resin A and the polyester resin B in the electrostatic charge image developing toner according to claim 1.

  The invention according to claim 4 is the toner for developing an electrostatic charge image in which the content of the polyester resin C is in the range of 1 to 20% by mass in the binder resin in the toner for electrostatic image development according to claim 1. is there.

  The invention according to claim 5 is the electrostatic charge image developer comprising the toner, wherein the toner is the electrostatic charge image developing toner according to claim 1.

  According to a sixth aspect of the present invention, there is provided a toner cartridge which contains at least toner, and the toner is the electrostatic charge image developing toner according to the first aspect.

  The invention according to claim 7 is a process cartridge including at least a developer holding member and containing the electrostatic charge image developer according to claim 5.

  According to an eighth aspect of the present invention, there is provided a latent image holding member, developing means for developing the electrostatic image formed on the latent image holding member as a toner image with a developer, and toner formed on the latent image holding member. The electrostatic charge image developer according to claim 5, further comprising: a transfer unit that transfers an image onto a transfer member; and a fixing unit that fixes a toner image transferred onto the transfer member. An image forming apparatus.

According to the first aspect of the present invention, the fixed image has less surface roughness in the fixed image, less difference in glossiness due to toner fixing conditions, and less gloss unevenness than in the case without the present configuration. Can be formed.
According to the second aspect of the present invention, an excellent full color image with less gloss unevenness and high glossiness can be secured even in the fixing temperature range from a low temperature to a high temperature range as compared with the case where the present configuration is not provided. .
According to the third aspect of the present invention, it is possible to perform image formation with a higher toner charge amount and without fog as compared with the case where the present configuration is not provided.
According to the fourth aspect of the present invention, it is possible to perform image formation in which the gloss level and the fog reduction are further balanced as compared with the case where the present configuration is not provided.
According to the fifth aspect of the present invention, compared to the case where the present configuration is not provided, a fixed image with less surface roughness on the fixed image and less gloss difference due to toner fixing conditions and less uneven gloss can be formed. .
According to the sixth aspect of the present invention, it is possible to facilitate the supply of toner for developing an electrostatic charge image capable of forming an image with little glossiness difference due to fixing conditions and without uneven glossiness, and to improve the maintainability of the above characteristics. .
According to the seventh aspect of the present invention, it is easy to handle an electrostatic charge image developer capable of forming an image with little glossiness difference due to fixing conditions and uniform glossiness, and adaptability to image forming apparatuses having various configurations. Can be increased.
According to the eighth aspect of the present invention, compared to the case where the present configuration is not provided, the surface roughness of the fixed image is small, the difference in glossiness due to the fixing conditions is small, and the image formation without uneven gloss is maintained. be able to.

Hereinafter, the present invention will be described in detail.
<Toner for electrostatic image development>
The electrostatic image developing toner of the present invention (hereinafter sometimes simply referred to as “toner”) includes a polyester resin A, a binder resin containing polyester resin B and polyester resin C, a colorant, and a release agent. The polyester resin A is a branched amorphous polyester resin containing no tetrahydrofuran-insoluble component, the polyester resin B is a linear amorphous polyester resin, and the polyester resin A and the polyester resin B Each contains a resin component obtained by reacting at least one selected from alkyl succinic acid, alkenyl succinic acid and their anhydrides as an acid component, and the polyester resin C is a crystalline polyester resin, and These satisfy the following (1) to (3).
(1) The polyester resin A has a weight average molecular weight of 25,000 to 60,000 and a number average molecular weight of 4,000 to 10,000.
(2) The polyester resin B has a weight average molecular weight of 10,000 to 25,000 and a number average molecular weight of 3000 to 8000.
(3) An aliphatic crystalline polyester resin obtained by reacting a polyester resin C with a dicarboxylic acid having 6 to 10 carbon atoms and a dialcohol having 6 to 10 carbon atoms. However, in the toner of the present invention, the polyester resin A and the polyester are used. As resin B, at least one selected from terephthalic acid, an anhydride of terephthalic acid, and an alkyl ester of terephthalic acid and at least one selected from alkyl succinic acid, alkenyl succinic acid and their anhydrides are at least an acid component A resin component obtained by reacting at least one selected from bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct as an alcohol component , and the alkyl succinic acid, alkenyl succinic acid, and Carbon number of acid anhydride In any case, the number of carbon atoms of the monomer-derived constituent component in the polyester resin C is larger .
Further, polyester resin A having a weight average molecular weight of 25,000 to 45000, a number average molecular weight of 4500 to 7000, a polyester resin B having a weight average molecular weight of 14,000 to 15000 and a number average molecular weight of 5000 to 5500 is employed.

  Generally, the glossiness of heat fixing toner is determined by the thermal characteristics of the resin. The toner transferred onto the transfer target is heated and fixed by the fixing member together with the transfer target in the fixing process. At this time, if the heating temperature is lower than the melting temperature of the resin, the toner is insufficiently melted. Then, it is fixed on the transfer material while maintaining the granularity of the powder. As a result, the image surface becomes rough, the glossiness is low, and the fixed image is brittle with respect to bending. For this reason, when the heating temperature is increased, the toner is melted and integration of the toner melt particles proceeds, so that the smoothness of the image surface is improved and the glossiness is increased.

On the other hand, in order to obtain a toner having a high glossiness in a lower temperature region, it is advantageous to use a resin having a low molecular weight that easily melts in a lower temperature region. However, since it melts too much in a higher temperature region, so-called hot offset occurs. If a resin having a large molecular weight is used to prevent the occurrence of hot offset, hot offset is prevented but cannot be fixed in a low temperature region.
Therefore, in general, by simply moving the molecular weight of the resin, the fixing temperature region (difference between the hot offset occurrence temperature and the cold offset disappearing temperature) can be increased or decreased depending on the fixing temperature, so that the fixing temperature region can be expanded. Not only is it impossible, but also gloss unevenness due to temperature changes on the surface of the fixing member cannot be solved.

  In order to expand the fixing temperature range, for example, as described above, there are methods such as combining a low molecular weight resin and a high molecular weight resin, or defining the molecular weight distribution. Since the glossiness is extremely low, it is not suitable for color toners. In contrast to the above, the present inventors have intensively studied a binder resin using a crystalline polyester resin for fixing in a low temperature region. As a result, an aliphatic crystalline polyester resin is used as the crystalline polyester resin, and a non-crystalline polyester resin having a long chain alkyl group or alkenyl group and having a different molecular weight is used together. It has been found that even when the amount of heat is changed during fixing, even if the amount of heat generation is suppressed, fixing defects such as offset and uneven image glossiness are not generated even in a high image density region, and a high-quality color image can be obtained.

  That is, a crystalline polyester resin (hereinafter sometimes simply referred to as “crystalline resin”) melts sharply in a temperature range above its melting point, and is therefore compatible with the crystalline resin as a binder resin for toner. When used in combination with amorphous polyester resins having different molecular weights (hereinafter sometimes referred to simply as “amorphous resins”), the binder resin does not melt sufficiently, ensuring a wide fixing temperature range, and the surface of the fixed image. Becomes smooth and a glossy image is obtained. However, in the case of a combination of resins that are excessively compatible, the storage property of the image is deteriorated by plasticizing the binder resin (decreasing the glass transition temperature). Also, when the compatibility is low, the crystalline resin and the amorphous resin cause phase separation, the crystalline resin domain is generated in the toner, the melt unevenness is generated even after fixing, and the minute image glossiness Unevenness occurs. Therefore, in order to make the above characteristics compatible, appropriate compatibility between the crystalline resin and the amorphous resin is required.

  Here, the present inventors examined the resin structure and compatibility between polyesters. As a factor related to compatibility, there is a conventionally known SP value (solubility parameter). Although the compatibility tends to be better as the SP value is actually closer, the above-mentioned appropriate compatibility was not obtained. . As a result of further detailed investigation, it was found that succinic acid having an alkyl group or alkenyl group having a longer chain length than the linear dicarboxylic acid and linear dialcohol, which are raw material components of the aliphatic crystalline resin to be used, and its anhydride. It has been found that the appropriate compatibility can be obtained in the fixing temperature region by using an amorphous polyester resin containing at least one of the constituents as a raw material component.

  When the amorphous resin has a long CC chain length in the side chain, the linearity of the molecule decreases, the intermolecular distance increases, and the long chain hydrophobic group and the CC chain of the aliphatic crystalline resin From this affinity, it is considered that the compatibility is improved. In addition, by using an amorphous polyester resin having a monomer component having an alkyl group or alkenyl group having a long chain length, compatibility with an internal additive such as a release agent is improved, and the dispersion state in the toner is improved. In addition, there is an effect of preventing the release agent from being exposed to the outside of the toner. The compatibility here means that the polyester resin and the release agent are not completely mixed, but basically incompatible, but at the molecular level at the interface between the materials. Points to the state.

Specifically, in the present invention, two amorphous polyester resins, polyester resin A and polyester resin B, are combined with aliphatic crystalline polyester resin (polyester resin C). (THF) is a branched amorphous polyester resin containing no insoluble matter, and polyester resin B is a linear amorphous polyester resin.
Here, the “branched” means that the molecule has a cross-linked structure due to a chemical bond, and the “linear” means that the molecule does not have the cross-linked structure. .

Polyester resin A is a branched amorphous resin obtained using an acid component containing a tri- or higher functional carboxylic acid component, but does not contain THF-insoluble matter. When the toner contains a THF-insoluble component, when a toner image on a transparent film is fixed, an unsharp blackish image tends to be formed in the low density portion and halftone portion of the image when the image is projected.
Note that the above-mentioned THF-insoluble content does not include that when the resin is heated and dissolved in THF at a concentration of about 10% by mass, the solution is transparent, and when filtered through a membrane filter, THF is added to the filter. This means that there is almost no residual content.

  Further, as the polyester resin A, those having a weight average molecular weight in the range of 25,000 to 60,000 and a number average molecular weight in the range of 4000 to 10,000 as measured by gel permeation chromatography described later are used. If at least one of the weight average molecular weight and the number average molecular weight is larger than the above range, the low-temperature fixability is poor and the fixing temperature rises and the power consumption increases. If at least one of the weight average molecular weight and the number average molecular weight is smaller than the above range, the releasability at the time of fixing the toner is reduced, and hot offset occurs when the toner is fixed in a high temperature range.

  The weight average molecular weight of the polyester resin A is preferably in the range of 35,000 to 55000, and more preferably in the range of 40000 to 50000. The number average molecular weight is preferably in the range of 5000 to 8000, and more preferably in the range of 6000 to 7000.

  Polyester resin B is a linear amorphous polyester resin that does not contain a chemical cross-linking moiety, and has a weight average molecular weight in the range of 10,000 to 25,000 and a number average molecular weight in the range of 3000 to 8,000. When at least one of the weight average molecular weight and the number average molecular weight is larger than the above range, the low temperature fixability and the image glossiness in the low temperature range are lowered, and an excellent full color image cannot be obtained. Further, when at least one of the weight average molecular weight and the number average molecular weight is smaller than the above range, the glass transition point of the resin component is lowered, so that the blocking property of the toner is deteriorated.

The weight average molecular weight of the polyester resin B is preferably in the range of 12000 to 20000, more preferably in the range of 14000 to 18000. The number average molecular weight is preferably in the range of 4000 to 7500, and more preferably in the range of 6000 to 7000.
Moreover, the range of 50-80 degreeC is suitable for the glass transition point by the differential thermal analysis (DSC) of the polyester resin B, and the range of 55-65 degreeC is especially suitable.

  When obtaining the molecular weight of each of the polyester resins for the binder resin contained in the toner, first, obtain the molecular weight of each resin separated by GPC (in this case, select the mobile phase solvent if necessary). The resin was identified for each corresponding molecular weight using GPC as will be described later, and each was analyzed.

  In order to obtain a high glossiness of color toner and a wide fixing temperature range in which no offset occurs, it is necessary to use a method in which the molecular weight distribution of the binder resin is expanded to some extent. First, the branched polyester resin A Can be used to synthesize a relatively high molecular weight, easily impart elasticity to the resin from its three-dimensional structure, and easily suppress the occurrence of offset in a high temperature range. On the other hand, the linear polyester resin B has a relatively low molecular weight and sharp melting characteristics as compared with the polyester resin A. Therefore, by using the polyester resin B in combination with the polyester resin A, the molecular weight distribution can be controlled relatively easily.

  The mixing ratio (A / B) between the polyester resin A and the polyester resin B is preferably in the range of 30/70 to 70/30 by mass ratio. If the ratio of the polyester resin A is lower than 30/70, it may be difficult to suppress the offset in the high temperature region, and if it exceeds 70/30, the low image fixing property and the high image gloss in the entire fixing temperature region. It may be difficult to obtain a degree.

  As the polyester resin C, an aliphatic crystalline polyester resin is used. Specifically, it is an aliphatic crystalline polyester resin obtained by reacting a dicarboxylic acid having 6 to 10 carbon atoms and a dialcohol having 6 to 10 carbon atoms. If the number of carbon atoms is less than 6, the melting point is low and the storage stability of the toner is deteriorated. When the number of carbon atoms exceeds 10, the melting point becomes too high and good low-temperature fixability cannot be obtained.

  The carbon number is preferably in the range of 8-10. In addition, about the said carbon number, in the case of dicarboxylic acid, it is a number which does not contain the carbon which comprises a carboxyl group.

  The polyester resin A and the polyester resin B each contain a resin component that is reacted with at least one selected from alkyl succinic acid, alkenyl succinic acid, and anhydrides as an acid component. Since the alkyl group and alkenyl group are lipophilic, they have good affinity with the aliphatic crystalline polyester resin, and the compatibility with the aliphatic crystalline polyester resin in the binder resin is improved. As a result, the aliphatic polyester resin in the toner is dispersed without variation, the melt viscosity unevenness of the toner binder resin is reduced, and the microscopic image gloss unevenness can be suppressed.

  In this case, among the constituent components derived from all monomers in the polyester resin A and the polyester resin B, the constituent amounts P and Q derived from at least one selected from alkyl succinic acid, alkenyl succinic acid and acid anhydrides thereof are respectively The range is preferably 5 to 20 mol%, and more preferably 10 to 20 mol%.

When the amount of the constituent component is less than 5 mol%, the micro compatibility between the amorphous polyester resin and the crystalline polyester resin is lowered, and micro melting unevenness occurs, resulting in uneven image glossiness. There is. If it exceeds 20 mol%, the glass transition temperature of the resin is lowered, which may cause a decrease in thermal storage properties such as toner blocking in a high temperature environment.
The “monomer-derived constituent component” means a constituent portion that was an acid component or an alcohol component before synthesis of the resin in the polyester resin.

  In addition, the inclusion of the branched polyester resin A having a relatively high molecular weight and a high melt viscosity in the binder resin makes it possible to suppress offset in the high-temperature fixing region, but is disadvantageous for low-temperature fixing. It is. Therefore, in the present invention, the amount P (mol%) of the constituent component derived from at least one selected from succinic acid having an alkyl group and an alkenyl group contained in the polyester resin A and anhydrides thereof is used in the polyester resin B. It is desirable to contain more than the said component amount Q (mol%).

Thereby, the polyester resin A which is a branched amorphous resin and the polyester resin C which is an aliphatic crystalline resin are more easily compatible with each other. As a result, it is possible to secure a sharp melted state even in the low temperature range while suppressing the occurrence of offset in the high temperature range, and there is little gloss unevenness and high glossiness even in the fixing temperature range from the low temperature to the high temperature range. An excellent full color image can be secured.
If the amount P of the constituent component is less than the amount Q of the constituent component, the compatibility between the polyester resin B and the polyester resin C, which are linear amorphous resins, is increased. It may be difficult to obtain glossiness.

Furthermore, in controlling the compatibility with the polyester resin C, which is an aliphatic crystalline polyester resin, the carbon number of the alkyl succinic acid, alkenyl succinic acid and acid anhydrides constituting the polyester resin A and the polyester resin B All of these are made into the structure which has more carbon numbers of each of the monomer-derived structural component in the polyester resin C.

When a long C—C chain is present in the side chain of the amorphous resin, the linearity of the molecule decreases, the intermolecular distance increases, and the alkyl and alkenyl groups are lipophilic. The affinity with the aliphatic crystalline resin is great, and the compatibility of the aliphatic crystalline polyester resin in the binder resin is improved. As a result, the crystalline polyester resin in the toner is dispersed without variation, the melt viscosity unevenness of the toner binder resin is reduced, and the microscopic image gloss unevenness can be suppressed.
The alkyl succinic acid, alkenyl succinic acid and acid anhydrides thereof preferably have 10 or more carbon atoms.

The structure and amount of the monomer-derived constituent component contained in each polyester resin contained in the toner can be analyzed, for example, by separating each resin using GPC.
That is, in GPC using THF or the like as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion equivalent to each polyester resin are collected. After concentrating and drying the collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, ¹ H-NMR measurement is performed, and the composition of each resin is determined from the integration ratio of each element. Monomer species and ratios can be calculated.

The structure of the electrostatic image developing toner of the present invention will be described in detail below.
The toner of the present invention needs to contain a binder resin including polyester resin A, polyester resin B, and polyester resin C, a colorant, and a release agent.

(Polyester resin A, polyester resin B)
Polyester resin A and polyester resin B used in the present invention are amorphous polyester resins. Here, the amorphous polyester resin means a polyester resin which does not show an endothermic peak corresponding to a crystalline melting point in addition to a stepwise endothermic point corresponding to a glass transition in differential scanning calorimetry (DSC).
A known polyester resin can be used as the amorphous polyester resin. The amorphous polyester resin is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In addition, as said amorphous polyester resin, a commercial item may be used and what was synthesize | combined may be used. The amorphous polyester resin may be one kind of amorphous polyester resin, but may be a mixture of two or more kinds of polyester resins.

  The polyvalent carboxylic acid and polyhydric alcohol used for the amorphous polyester resin are not particularly limited, and are, for example, monomer components described in “Polymer Data Handbook: Basic Edition” (Edition of Polymer Society, Baifukan) There are conventionally known divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols. In addition, since the polyester resin B in this invention is a linear amorphous polyester resin, the said trivalent or more carboxylic acid and alcohol are not used.

  Specific examples of these monomer components include divalent carboxylic acids such as succinic acid, alkyl succinic acid, alkenyl succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and phthalic acid. , Diphthalic acids such as isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, mesaconic acid, and their anhydrides and their lower alkyls Examples thereof include aliphatic unsaturated dicarboxylic acids such as esters, maleic acid, fumaric acid, itaconic acid and citraconic acid. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

Among these polyvalent carboxylic acids, especially when alkenyl succinic acid or its anhydride is used, it is more easily compatible with crystalline polyester resin due to the presence of alkenyl groups having higher hydrophobicity than other functional groups. Can do.
Examples of the alkyl succinic acid and alkenyl succinic acid and their anhydrides include n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, Examples thereof include n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, and anhydrides and lower alkyl esters thereof.

  The number of carbon atoms of the alkyl group and alkenyl group of the alkyl succinic acid, alkenyl succinic acid and their anhydrides satisfies the suitable characteristics as the above-mentioned resin, so that the constituent monomer used in the aliphatic crystalline polyester resin described later is used. It is desirable to have more carbon atoms. Among the above, n-dodecenyl succinic acid and its anhydride are most preferable because of compatibility with the aliphatic crystalline polyester resin and ease of adjusting the glass transition temperature of the amorphous polyester resin.

  Examples of the polyhydric alcohol include divalent alcohols such as hydrogenated bisphenol A, bisphenol derivatives such as ethylene oxide and propylene oxide adducts of bisphenol A; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like. Cyclic aliphatic alcohols; linear diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; 1,2-propanediol, Branched diols such as 1,3-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol; and the like, and from the viewpoint of chargeability and strength, ethylene oxide and pro Ren'okishido adduct is preferably used.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. From the viewpoint of low-temperature fixability and image gloss, a trivalent or higher crosslinkable monomer is used. The amount used is preferably 10 mol% or less of the total monomer amount. These may be used individually by 1 type and may use 2 or more types together.
If necessary, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can be used for the purpose of adjusting the acid value and the hydroxyl value.

Amorphous polyester resins can be used in any combination of the above monomer components, for example, polycondensation (chemical doujin), polymer experimental studies (polycondensation and polyaddition: Kyoritsu Publishing), and polyester resin handbook (Nikkan Kogyo Shimbun). Can be synthesized by using a conventionally known method described in the company edition, etc., and a transesterification method, a direct polycondensation method, or the like can be used alone or in combination.
Specifically, the polymerization can be carried out at a polymerization temperature of 140 to 270 ° C., and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during the condensation. When the monomer is not dissolved or compatible with the reaction temperature, a solvent having a high boiling point may be added as a solubilizing solvent and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. When a monomer having poor compatibility exists in the copolymerization reaction, the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component. The molar ratio (acid component / alcohol component) at the time of reacting the acid component and the alcohol component varies depending on the reaction conditions and the like, and thus cannot be generally stated. 1 to 1 / 0.9. In the case of transesterification, an excess of monomers that can be distilled off under vacuum such as ethylene glycol, propylene glycol, neopentyl glycol, and cyclohexanedimethanol is often used.

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium; Phosphorous acid compounds; phosphoric acid compounds; and; amine compounds and the like. Specific examples include sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate. , Zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributyl Ntimmon, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenylphos Examples thereof include compounds such as phyto, tris (2,4-di-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, and triphenylamine. In the present invention, two or more kinds can be used in combination, but among them, it is desirable to use a tin-based catalyst such as dibutyltin oxide from the viewpoint of chargeability.

The setting ranges of the weight average molecular weight and the number average molecular weight of the polyester resin A and the polyester resin B are as described above. The molecular weight and molecular weight distribution can be measured by a method known per se, but are generally measured by gel permeation chromatography (hereinafter abbreviated as “GPC”). In the present invention, the molecular weight distribution was measured under the following conditions.
As a GPC device, Tosoh Corporation HLC-8120GPC, SC-8020 device is used, TSK gei, SuperHM-H (6.0 mm ID × 15 cm × 2) is used as a column, and for chromatograph manufactured by Wako Pure Chemical Industries, Ltd. THF (tetrahydrofuran) was used. As experimental conditions, the sample concentration was 0.5%, and the flow rate was 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve is A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128, Made from 10 samples of F-700. The data collection interval in sample analysis was 300 ms.

The amorphous polyester resin preferably has an acid value in the range of 2 to 25 KOHmg / g and a hydroxyl value in the range of 5 to 40 KOHmg / g.
The glass transition temperature of the amorphous polyester resin is preferably in the range of 40 to 80 ° C., and more preferably in the range of 50 to 70 ° C. from the viewpoint of the balance between storage stability and toner fixability. desirable. When the glass transition temperature is less than 40 ° C., the toner may easily cause blocking (a phenomenon in which toner particles are aggregated into a lump) during storage or in a developing device. On the other hand, if the glass transition temperature exceeds 80 ° C., the toner fixing temperature may increase.

  The glass transition temperature of the amorphous polyester resin was measured using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001). Specifically, the temperature is raised from 0 to 150 ° C. at 10 ° C./min, held at 150 ° C. for 5 minutes, cooled from 150 ° C. to 0 ° C. at −10 ° C./min using liquid nitrogen, and at 0 ° C. It was set as the onset temperature analyzed from the endothermic curve at the time of the second temperature rise obtained by holding for 5 minutes and again raising the temperature from 0 ° C to 150 ° C at 10 ° C / min.

(Polyester resin C)
Polyester resin C, which is a crystalline resin, is used as a binder resin for toner to improve and stabilize image glossiness and to improve low-temperature fixability. As described above, the crystalline polyester resin in the present invention requires appropriate compatibility with the amorphous polyester resin. Among them, the aliphatic crystalline polyester resin has compatibility with the amorphous polyester resin. This is desirable because it has a high plasticizing effect and can provide low-temperature fixability and high image gloss.

  The crystalline polyester resin containing the polyester resin C used in the present invention is synthesized from a divalent acid (dicarboxylic acid) component and a divalent alcohol (diol) component. The “adhesive polyester resin” refers to a resin having a clear endothermic peak rather than a stepwise endothermic change in differential scanning calorimetry (DSC). In the case of a polymer obtained by copolymerizing other components with respect to the main chain of the crystalline polyester resin, when the other components are 50% by mass or less, this copolymer is also called a crystalline polyester resin.

In the crystalline polyester resin, examples of the acid to be an acid-derived constituent component include various aliphatic dicarboxylic acids, but the dicarboxylic acid as the acid-derived constituent component is not limited to one type, and two types You may include the above component derived from dicarboxylic acid. Further, the dicarboxylic acid may contain a sulfonic acid group in order to improve the emulsifiability in the emulsion aggregation method.
The “acid-derived constituent component” refers to a constituent portion that was an acid component before the synthesis of the polyester resin, and the “alcohol-derived constituent component” below is an alcohol component before the synthesis of the polyester resin. Refers to the constituent parts.

  As the aliphatic dicarboxylic acid, a linear carboxylic acid is particularly desirable. Examples of the linear carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10- Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, Or lower alkyl esters and acid anhydrides thereof.

Among these, a linear dicarboxylic acid having 6 to 10 carbon atoms is used for the synthesis of polyester resin C which is an aliphatic crystalline polyester resin. In addition, the said carbon number is a number which does not contain the carbon of the carboxyl group of both ends here.
When the number of carbon atoms is 11 or more, the problem of cost and the melting point become too high, and it is difficult to obtain low-temperature fixability or image gloss. When the number of carbon atoms is 5 or less, the ester group concentration of the resin becomes high, so that the volume resistance is reduced, and when the crystalline resin is exposed on the surface, the charge amount is reduced due to charge leakage or toner development. At this time, the charge of the photosensitive member is injected, and toner contamination (fogging) or the like occurs in the non-image area, which is not desirable. In order to improve crystallinity, these linear dicarboxylic acids are preferably used in an amount of 95 mol% or more, more preferably 98 mol% or more of the acid constituent.

  In the crystalline polyester resin, examples of the alcohol to be an alcohol-derived constituent component include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like.

Among these, a linear dialcohol having 6 to 10 carbon atoms is used for the synthesis of polyester resin C which is an aliphatic crystalline polyester resin.
When the number of carbon atoms is 11 or more, the melting point becomes too high, and it is difficult to obtain low-temperature fixability or image gloss. When the number of carbon atoms is 5 or less, the ester group concentration of the resin is increased, so that the volume resistance of the resin is decreased. When the crystalline resin is exposed on the surface, the charge amount is decreased due to charge leakage or the toner. When developing, the charge of the photoreceptor is injected, and toner contamination (fogging) or the like occurs in the non-image area. In order to improve crystallinity, it is desirable to use these linear dialcohols in an amount of 95 mol% or more, more preferably 98 mol% or more of the alcohol constituents.

If necessary, monovalent acids such as acetic acid and benzoic acid, monovalent alcohols such as cyclohexanol and benzyl alcohol, benzenetricarboxylic acid, and naphthalenetricarboxylic acid for the purpose of adjusting the acid value and hydroxyl value. Trivalent alcohols such as acids and the like, anhydrides thereof, lower alkyl esters thereof, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol can also be used.

  The crystalline polyester resin can be synthesized according to the amorphous polyester resin. Moreover, as the catalyst that can be used in the production, those according to the amorphous polyester resin can be used.

The melting point of the polyester resin C, which is a crystalline polyester resin, is preferably in the range of 50 to 120 ° C, and more preferably in the range of 50 to 80 ° C. If the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, if the temperature is higher than 120 ° C., sufficient low-temperature fixing may not be obtained as compared with conventional toners.
The melting point of the crystalline polyester resin is measured as the melting peak temperature of the input compensated differential scanning calorimetry shown in JIS K-7121 by a method according to the glass transition temperature measurement of the amorphous polyester resin. it can. A crystalline resin may show a plurality of melting peaks, but the maximum peak is regarded as the melting point.

  The molecular weight of the polyester resin C is preferably in the range of 5,000 to 100,000, more preferably 10,000 to 50,000, as measured by the GPC method for the content of the tetrahydrofuran (THF) soluble component. The number average molecular weight (Mn) is preferably in the range of 2000 to 10,000, the molecular weight distribution Mw / Mn is preferably in the range of 1.5 to 100, and more preferably in the range of 2 to 20. It is a range. When the weight average molecular weight and number average molecular weight are smaller than the above ranges, it is effective for low-temperature fixability, but it is low and soft as a resin and may adversely affect storage stability such as toner blocking. On the other hand, if the molecular weight is larger than the above range, the oozing out from the toner becomes insufficient, which may adversely affect the document storage stability.

  The content of the polyester resin C in the binder resin is desirably in the range of 1 to 20% by mass, and more desirably in the range of 2 to 14% by mass. When the addition amount of the crystalline polyester resin is more than 20% by mass, the domain size of the crystalline polyester resin becomes large and is easily exposed on the toner surface, which may cause a decrease in toner powder fluidity and a deterioration in chargeability. . If it is less than 1% by mass, good low-temperature fixability may not be obtained.

The binder resin in the toner is configured to include the polyester resin A, the polyester resin B, and the polyester resin C. The loss elastic modulus G ″ of the binder resin (measurement frequency: 1 rAd / s, strain amount: 20% or less) When the temperature at which (measurement) is 10,000 PA is defined as Tm, Tm is preferably in the range of 80 to 150 ° C.
Here, the loss elastic modulus is measured as follows. The measuring device is a rheometer manufactured by Rheometrics, trade name “RDA II” (RHIOS system ver. 4.3), the measuring plate is a parallel plate with a diameter of 8 mm, the zero point adjustment temperature is 90 ° C., the plate At a gap of 3.5 mm, a heating rate of 1 ° C. per minute, an initial measurement strain of 0.01, and a measurement start temperature of 30 ° C., the strain is adjusted so that the detected torque becomes about 10 gcm as the temperature rises, and the maximum strain is 20% The measurement was terminated when the detected torque fell below the lower limit of the guaranteed measurement value.

The binder resin preferably has a softening point in the range of 80 to 140 ° C, and more preferably in the range of 95 to 135 ° C. When the softening point of the binder resin is less than 80 ° C., the toner and the image stability of the toner after fixing and storage may be deteriorated. On the other hand, when the softening point exceeds 140 ° C., the low-temperature fixability may be deteriorated.
In addition, the softening point of the binder resin is as follows. Using a flow tester (manufactured by Shimadzu Corporation: CFT-500C), sample amount: 1.05 g, preheating: 300 ° C. at 65 ° C., plunger pressure: 0.980665 MPA, die size : Diameter 1 mm, temperature increase rate: An intermediate temperature between the melting start temperature and the melting end temperature measured under the conditions of 1.0 ° C./min.

(Coloring agent)
Examples of the colorant used in the toner of the present invention include yellow pigments such as yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa Yellow, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Slen Yellow, Quinoline yellow, permanent yellow NCG and the like. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 185 or the like is preferably used.

Magenta 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, eoxine red, alizarin lake, as the naphthol-based pigments, pigment Red 31, the 146, 147, 150, the 176, the 238, such as the 269 and the like, as the quinacridone pigments, pigment Examples thereof include Red 122, 202, and 209. Among these, Pigment Red 185, 238, 269, and 122 are particularly preferable from the viewpoints of manufacturability and chargeability.

  As cyan pigments, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare Rate, and the like. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 or the like is preferably used.

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. 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 the black pigment used for the black toner include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like, and carbon black is particularly preferably used. Since carbon black has relatively good dispersibility, it does not require any special dispersion, but it is desirable that it be produced by a production method according to the colorant.

  The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The colorant is preferably added in the range of 4 to 15% by mass with respect to the total toner mass. Moreover, when using a magnetic body etc. as a black coloring agent, unlike other coloring agents, it can add at 12-240 mass%. 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 desirable to modify the surface of the magnetic material in advance, for example, to perform a hydrophobic treatment or the like.

(Release agent)
The toner of the present invention contains a release agent for the purpose of improving fixability and image storage stability. The release agent used is preferably a substance having a main maximum endothermic peak in DSC measured in accordance with ASTM D3418-8 at 50 to 140 ° C. and a melt viscosity of 1 to 50 mPAs at 140 ° C. . If the melting point is less than 50 ° C., offset may easily occur during fixing. When the temperature exceeds 140 ° C., the fixing temperature increases, the surface roughness of the fixed image increases, and the glossiness may be impaired.

  The release agent preferably has an endothermic start temperature of 40 ° C. or higher in the DSC curve, and more preferably 50 ° C. or higher. When the temperature is lower than 40 ° C., toner aggregation may occur in the copying machine or the toner bottle. The endothermic start temperature depends on the molecular weight distribution of the wax, which has a low molecular weight, and the type and amount of polar groups of the structure. In general, the higher the molecular weight, the higher the endothermic start temperature as well as the melting point. However, in this method, the inherent low melting temperature and low viscosity of the wax are lost. Accordingly, it is effective to select and remove only those having a low molecular weight from the molecular weight distribution of the wax. Examples of this method include molecular distillation, solvent fractionation, and gas chromatography fractionation.

On the other hand, if the melt viscosity is higher than 50 mPAs, elution from the toner is weak at the melt viscosity, and fixing releasability may be insufficient.
The melt viscosity of the release agent is measured with an E-type viscometer. For the measurement, an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with an oil circulation type thermostat is used. For the measurement, a cone plate / cup combination plate having a cone angle of 1.34 degrees is used. A sample is put into the cup, the temperature of the circulation device is set to 140 ° C., an empty measurement cup and cone are set to the measurement device, and the temperature is kept constant while circulating the oil. When the temperature is stabilized, 1 g of the sample is put in the measuring cup, and the cone is left still for 10 minutes. After stabilization, rotate the cone and measure. The rotational speed of the cone is 60 rpm. The measurement is performed three times, and the average value is taken as the melt viscosity η.

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

(Other additives)
If necessary, inorganic or organic particles can be added to the toner of the present invention. Due to the reinforcing effect of the particles, the storage elastic modulus of the toner may be increased, and the offset resistance and the peelability from the fixing device may be improved. The particles may improve the dispersibility of internal additives such as a colorant and a release agent.

  Examples of the inorganic particles include silica, hydrophobized silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, alumina-treated colloidal silica, cationic surface-treated colloidal silica, anion surface-treated colloidal silica, and the like. It can be used alone or in combination, and among them, it is desirable to use colloidal silica from the viewpoint of OHP transparency and dispersibility in the toner. The particle size is preferably 5 to 50 nm. It is also possible to use particles having different particle sizes in combination. The particles can be added directly at the time of toner production, but it is preferable to use particles dispersed in a water-soluble medium such as water in advance using an ultrasonic disperser in order to improve dispersibility. In the dispersion, the dispersibility can be improved by using an ionic surfactant, a polymer acid, a polymer base, or the like.

  In addition, a known material such as a charge control agent may be added to the toner. The average particle size of the material added at that time is desirably 1 μm or less, and more preferably 0.01 to 1 μm. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained electrophotographic toner may be broadened, or free particles may be generated, which may lead to a decrease in performance and reliability. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous. The average particle diameter can be measured using, for example, a microtrack.

Further, the toner for developing an electrostatic charge image of the present invention will be described in more detail together with its production method.
The method for producing the toner of the present invention is not particularly limited, but is preferably a wet granulation method. Suitable examples of the wet granulation method include known melt suspension methods, emulsion aggregation methods, and dissolution suspension methods. Hereinafter, the emulsion aggregation method will be described as an example.

The emulsion aggregation method includes a step (aggregation step) of forming an aggregated particle dispersion in a dispersion liquid (hereinafter sometimes referred to as “emulsion liquid”) in which at least resin particles are dispersed, and the aggregation This is a production method including a step of fusing the aggregated particles by heating the particle dispersion (fusion step).
When the emulsion aggregation method is used, for example, a resin particle dispersion in which particles composed of an aliphatic crystalline polyester resin (polyester resin C) having a particle size of 1 μm or less are dispersed, Mixing resin particle dispersion in which particles composed of crystalline polyester resin (polyester resin A and polyester resin B) are dispersed, colorant particle dispersion in which colorant particles are dispersed, and release agent particle dispersion And a first aggregating step for forming an agglomerated particle (core particle) including the crystalline resin particle, the amorphous resin particle, the colorant particle, and the release agent particle, and a core on the surface of the core agglomerated particle. A second agglomeration step of forming a shell layer containing two types of amorphous polyester resins used for agglomeration to obtain core / shell agglomerated particles; and the core / shell agglomerated particles as amorphous resin particles. It is produced through the fusion heating to coalescence than the melting point of the glass transition point or the crystalline resin particles, the desirable.

  By producing the toner using the above production method, generation of fine particles can be suppressed, the particle size distribution of the obtained toner can be sharpened, and the image quality can be improved. Further, by providing the second aggregation step, a pseudo shell structure can be formed, and the toner surface exposure of an internal additive such as an aliphatic crystalline polyester resin, a colorant or a release agent can be reduced, As a result, it is possible to improve the chargeability and life, and maintain the particle size distribution at the time of fusion in the fusion process, suppress the fluctuation, and improve the stability at the time of fusion. And the addition of a stabilizer such as a base or an acid is unnecessary, or the amount thereof can be suppressed to the minimum. In the method, a core-shell structure is formed by an operation of adding additional particles, but the polyester resin A and the polyester resin B, which are the main components of the core particles, are the resin for the shell layer. It is suitable. If this method is used, toner shape control can be easily performed by adjusting temperature, number of stirring, pH, and the like in the fusing step.

When an amorphous polyester resin or a crystalline polyester resin is used in the emulsion aggregation method, for example, an emulsification step of emulsifying the amorphous polyester resin to form emulsified particles (droplets) is preferably used.
In the emulsification step, for example, the emulsion particles (droplets) of the amorphous polyester resin are mixed with an aqueous medium and a mixed liquid (polymer liquid) containing a polyester resin and, if necessary, a colorant. It is formed by applying a shearing force. At that time, the viscosity of the polymer liquid can be lowered to form emulsified particles by heating to a temperature equal to or higher than the glass transition temperature of the amorphous polyester resin. Moreover, a dispersing agent can also be used for stabilization of emulsified particles and thickening of an aqueous medium. Hereinafter, such a dispersion of emulsified particles may be referred to as a “resin particle dispersion”.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. The size of the emulsified particles (droplets) of the polyester resin is preferably 0.005 to 0.5 μm, and more preferably 0.01 to 0.3 μm, in terms of the average particle size (volume average particle size). When it is 0.005 μm or less, it is almost dissolved in water, making it difficult to produce particles, and when it is 0.5 μm or more, it is difficult to obtain particles having a desired particle size of 3.0 to 7.5 μm. There is. In addition, the volume average particle diameter of the resin particles was measured with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).

Moreover, since the melt viscosity of the resin at the time of emulsification is not reduced to the desired particle size, by raising the temperature using an emulsifier that can pressurize above atmospheric pressure, emulsifying in a state where the resin viscosity is lowered, A resin particle dispersion having a desired particle size can be obtained.
In the emulsification step, a method of previously adding a solvent to the resin may be used for the purpose of improving the emulsifiability by lowering the viscosity of the resin. The solvent used is not particularly limited as long as it dissolves the polyester resin, but is not limited to ketone solvents such as tetrahydrofuran (THF), methyl acetate, ethyl acetate, and methyl ethyl ketone, and benzene solvents such as benzene, toluene, and xylene. However, from the viewpoints of solubility and solvent removal, it is preferable to use ester solvents and ketone solvents such as ethyl acetate and methyl ethyl ketone.

In addition, for the purpose of improving the affinity with water as a medium and controlling the particle size distribution, an alcohol solvent such as ethanol or isopropyl alcohol may be directly added to water or a resin.
For the purpose of controlling the particle size distribution, a salt such as sodium chloride or potassium chloride, ammonia or the like may be added. Of these, ammonia is preferably used.

  Further, a dispersant may be added for the purpose of controlling the particle size distribution. Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate. Anionic surfactants such as; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, Surfactants such as nonionic surfactants such as polyoxyethylene alkylamine; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate Um, and inorganic compounds such as barium carbonate. Among these, anionic surfactants are preferably used. As the usage-amount of the said dispersing agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of said polyester resins (binder resin).

  In the emulsification step, the polyester resin is copolymerized with a dicarboxylic acid having a sulfonic acid group (that is, a suitable amount of a dicarboxylic acid-derived component having a sulfonic acid group is included in the acid-derived component. ) And a dispersion stabilizer such as a surfactant can be reduced, or emulsified particles can be formed without using it, but the hygroscopicity of the resin is increased and the chargeability may be deteriorated. The addition amount is preferably 10 mol% or less in the acid component, but it is better not to add as much as possible when emulsifiability can be secured by the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of hydroxyl value, etc. .

  Further, a phase inversion emulsification method may be used. In the phase inversion emulsification method, at least a polyester resin is dissolved in an organic solvent, a neutralizing agent and a dispersion stabilizer are added as necessary, and an aqueous solvent is dropped under stirring to obtain emulsified particles. In this method, the solvent in the resin dispersion is removed to obtain an emulsion. At this time, the order of adding the neutralizing agent and the dispersion stabilizer may be changed.

  Examples of the organic solvent (resin dissolving solvent) for dissolving the resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, etc.) esters such as formic acid, acetic acid, butyric acid, acetone, MEK, MPK, MIPK, Methyl ketones such as MBK and MIBK, ethers such as diethyl ether and diisopropyl ether, heterocyclic substituents such as toluene, xylene and benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2- Halogenated carbons such as trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, etc. can be used singly or in combination of two or more, but they are easily available, easy to recover during solvent removal, From the point of consideration, acetates, methyl ketones, Le acids is usually preferably used, in particular, acetone, methyl ethyl ketone, acetic acid, ethyl acetate, butyl acetate is preferred. If the organic solvent remains in the resin particles, it may become a VOC causative substance, and therefore, it is preferable to use a solvent having a relatively high volatility.

  As the aqueous solvent, ion-exchanged water is basically used, but a water-soluble organic solvent may be included so as not to destroy the oil droplets. Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol and other short carbon chain alcohols; ethylene glycol monomethyl ether, ethylene glycol Examples include ethylene glycol monoalkyl ethers such as monoethyl ether and ethylene glycol monobutyl ether; ethers, diols, THF, acetone and the like. The mixing ratio of these water-soluble organic solvents to ion-exchanged water is selected in the range of 1% to 50%, more preferably 1% to 30%, and used as an aqueous component. In addition, the water-soluble organic solvent may be added to the resin solution and used in addition to the ion-exchanged water to be added. In the case of adding a water-soluble organic solvent, the wettability between the resin and the resin dissolving solvent can be adjusted, and a function of reducing the liquid viscosity after the resin is dissolved can be expected.

Moreover, you may add a dispersing agent to a resin solution and an aqueous component as needed so that the said emulsion may maintain a dispersed state stably. As the dispersant, a hydrophilic colloid is formed in an aqueous component, and in particular, cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylate, Examples thereof include synthetic polymers such as polymethacrylate, and dispersion stabilizers such as gelatin, gum arabic, and agar. Solid fine powders such as silica, titanium oxide, alumina, tricalcium phosphate, calcium carbonate, calcium sulfate, and barium carbonate can also be used. These dispersion stabilizers are usually added so that the concentration in the aqueous component is 0 to 20% by mass, preferably 0 to 10% by mass. A surfactant is also used as the dispersant. As examples of the surfactant, those according to those used in the colorant dispersion described later can be used. For example, in addition to natural surfactant components such as saponins, cationic surfactants such as alkylamine hydrochlorides / acetates, quaternary ammonium salts, glycerols, fatty acid soaps, sulfates, alkylnaphthalene sulfonates, sulfones Anionic surfactants such as acid salts, phosphoric acid, phosphate esters, sulfosuccinates and the like can be mentioned, and anionic surfactants and nonionic surfactants are preferably used. In order to adjust the pH of the emulsion, a neutralizing agent may be added. As the neutralizing agent, general acids such as nitric acid, hydrochloric acid, sodium hydroxide and ammonia, and alkalis can be used.
As a method for removing the organic solvent from the emulsion, a method in which the organic solvent is volatilized at room temperature (15 to 35 ° C.) or under heating, and a method in which reduced pressure is combined with this are preferably used.

  As a dispersion method of the colorant and the release agent, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having media, a sand mill, or a dyno mill can be used, and is not limited at all. .

  If necessary, an aqueous dispersion of these colorants can be prepared using a surfactant, or an organic solvent dispersion of these colorants can be prepared using a dispersant. Hereinafter, the dispersion of the colorant and the release agent may be referred to as “colorant dispersion” or “release agent dispersion”. As the surfactant and dispersant used for dispersion, those according to the dispersant that can be used when dispersing the polyester resin or the like can be used.

  In the aggregation step, it is preferable to use an aggregating agent in order to form aggregated particles. Examples of the flocculant used include a surfactant having a polarity opposite to that of the surfactant used in the dispersant, a general inorganic metal compound (inorganic metal salt), or a polymer thereof. The metal element constituting the inorganic metal salt has a divalent or higher charge belonging to the 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, 3B group in the periodic table (long periodic table). There is no limitation as long as it dissolves in the form of ions in the aggregation system of resin particles.

  Specific examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

  The amount of the flocculant added varies depending on the type and valence of the flocculant, but is generally in the range of 0.05 to 0.1% by mass. The aggregating agent does not always remain in the toner due to outflow into the aqueous medium or formation of coarse powder during the toner forming process. In particular, when the amount of the solvent in the resin is large in the toner forming step, the solvent and the flocculant interact and easily flow out into the aqueous medium, so it is necessary to adjust the amount according to the amount of the remaining solvent.

  The toner of the present invention contains at least one metal element selected from aluminum, zinc, and calcium in an amount of 0.05 to 0.30% in terms of elemental composition ratio, due to the addition of the flocculant. Preferably it is. When these metal atoms are contained in the above range, a polar component of the polyester resin is formed with ionic crosslinks, the strength of the fixed image is improved, and hot offset is improved. On the other hand, if the content is too large, the melt viscosity also increases, and the fixed image gloss may be lowered and the low-temperature fixability may be impaired. Here, the content of the metal element is determined from the total elemental analysis using a fluorescent X-ray apparatus. The sample was 6 g of toner, pressure-molded with a pressure molder with a load of 10 t and a pressurization time of 1 minute. Using a fluorescent X-ray (XRF-1500) manufactured by Shimadzu Corporation, the measurement conditions were a tube voltage of 40 kV, It is obtained from the elemental composition ratio measured at a tube current of 90 mA and a measurement time of 30 minutes.

  In the fusion step, the agglomeration suspension is brought to a pH of 5 to 10 under stirring according to the agglomeration step to stop the agglomeration, and the resin has a glass transition temperature (Tg) or higher. The aggregated particles are fused and united by heating at a temperature (or a temperature equal to or higher than the melting point of the crystalline resin). The heating time may be as long as desired coalescence is achieved, and may be performed for about 0.2 to 10 hours. Thereafter, when the temperature is lowered to Tg or less of the resin to solidify the particles, the particle shape and surface properties change depending on the temperature lowering rate. For example, when the temperature is lowered at a high speed, the spheroidization and the surface are likely to be smooth, and conversely, when the temperature is slowly lowered, the particle shape becomes indefinite and irregularities are likely to occur on the particle surface. Therefore, it is preferable to lower the temperature to at most Tg of the resin at a rate of at least 0.5 ° C./min, more preferably at a rate of 1.0 ° C./min or more.

  Further, while heating at a temperature equal to or higher than the Tg of the resin, particles are grown by adding a pH or a flocculant according to the aggregation step, and when the desired particle size is reached, at least 0.5 ° C. according to the case of the fusion step. It is preferable in terms of simplification of the process because the aggregation process and the fusion process can be performed at the same time if the particle growth is stopped simultaneously with the solidification by lowering the temperature to the Tg of the resin at a rate of / min. It may be difficult to make a core-shell structure.

  After completing the fusing step, the particles are washed and dried to obtain toner particles. Considering the chargeability of the toner, it is preferable to perform substitution cleaning with ion-exchanged water, and the degree of cleaning is generally monitored by the conductivity of the filtrate, so that the conductivity finally becomes 25 μS / cm or less. It is preferable to make it. A step of neutralizing ions with an acid or alkali at the time of washing may be included, and it is preferable that the treatment with an acid has a pH of 4.0 or less, and the treatment with an alkali has a pH of 8.0 or more. The solid-liquid separation after washing is not particularly limited, but from the viewpoint of productivity, suction filtration, pressure filtration such as a filter press, and the like are preferably used. Further, the drying method is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used, and the final toner moisture content is 1% by mass or less. More preferably, drying is performed so that the content is 0.7% by mass or less.

  The toner particles obtained as described above can be externally mixed with inorganic particles and organic particles as fluidity aids, cleaning aids, abrasives, and the like. Examples of the inorganic particles include all particles usually used as external additives on the toner surface, such as silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. These inorganic particles preferably have a hydrophobic surface, and are used to control various toner characteristics such as chargeability, powder characteristics, and storage stability, and system suitability such as developability and transferability. It is done. As organic particles, for example, they are usually used as external additives on the surface of toner such as vinyl resins such as styrene polymers, (meth) acrylic polymers, and ethylene polymers, polyester resins, silicone resins, and fluorine resins. All particles.

  These particles are added for the purpose of improving transferability, and the primary particle size is preferably 0.05 to 1.0 μm. Further, a lubricant can be added. Examples of the lubricant include fatty acid amides such as ethylene bisstearyl amide and oleic acid amide, and higher alcohols such as fatty acid metal salt unilin such as zinc stearate and calcium stearate. These are generally added for the purpose of improving the cleaning property, and those having a primary particle size of 0.150 μm are used.

  Further, at least two kinds of the inorganic particles are used, and at least one kind of the inorganic particles preferably has an average primary particle diameter of 30 nm to 200 nm, more preferably 30 nm to 180 nm. As the toner particle size is reduced, non-electrostatic adhesion to the photoconductor increases, which causes transfer defects and image loss called hollow characters, and causes uneven transfer such as superimposed images. Therefore, it is preferable to add a large external additive having an average primary particle diameter of 30 nm to 200 nm to improve transferability. If the average primary particle size is smaller than 30 nm, the initial toner fluidity is good, but the non-electrostatic adhesion between the toner and the photoreceptor cannot be reduced, the transfer efficiency is lowered, The uniformity of the image is deteriorated, and the stress in the developing machine over time causes the particles to be embedded in the toner surface, resulting in a change in chargeability, which may cause problems such as a decrease in density and fogging on the background. . On the other hand, if the average primary particle size is larger than 200 nm, the particles may be easily detached from the toner surface, and the fluidity may be deteriorated.

Specifically, silica, alumina, and titanium oxide are preferable, and it is particularly preferable to add hydrophobized silica as an essential component. It is particularly preferable to use silica and titanium oxide in combination. It is also preferable to improve the transferability by using organic particles having a particle size of 80 to 500 nm in combination. Examples of the hydrophobizing agent for hydrophobizing the external additive include known materials, such as silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents. Examples include silicone oil and polymer coating treatment.
The external additive is adhered or fixed to the toner surface by applying a mechanical impact force with a sample mill or a Henschel mixer.

(Toner characteristics)
The volume average particle size of the toner in the present invention is preferably in the range of 4 to 9 μm, more preferably in the range of 4.5 to 8.5 μm, and still more preferably in the range of 5 to 8 μm. When the volume average particle size is smaller than 4 μm, the toner fluidity is lowered, the chargeability of each particle is likely to be lowered, and the charge distribution is widened, so that fogging on the background and toner spillage from the developing device are likely to occur. . On the other hand, if it is smaller than 4 μm, the cleaning property may be extremely difficult. If the volume average particle size is larger than 9 μm, the resolution decreases, so that sufficient image quality cannot be obtained, and it may be difficult to satisfy recent high image quality requirements.

In addition, the toner of the present invention draws a cumulative distribution from the small diameter side for each of the volume and number, and the particle size range (channel) obtained by dividing the particle size distribution measured by the following method. Is the volume average particle size calculated from (D84% / D16%) ^{1/2, where the} particle size at which volume D16% is defined and the particle size at which volume D50% is accumulated 84% is defined as volume D84%. The distribution index (GSDv) is preferably 1.15 to 1.30, and more preferably 1.15 to 1.25.

  The volume average particle diameter and the like can be measured using Multisizer II (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 50 μm. At this time, the measurement was performed after the toner was dispersed in an electrolyte aqueous solution (Isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more.

Further, the toner of the present invention preferably has a spherical shape with a shape factor SF1 in the range of 110 to 140. When the shape is spherical in this range, transfer efficiency and image density are improved, and high-quality image formation can be performed.
The shape factor SF1 is more preferably in the range of 110 to 130.

Here, the shape factor SF1 is obtained by the following equation (1).
SF1 = (ML ² / A) × (π / 4) × 100 (1)
In the above formula (1), ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and can be calculated as follows, for example. That is, an optical microscope image of toner particles dispersed on the surface of a slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and the average value thereof Is obtained.

  The toner of the present invention preferably has an absolute charge in the range of 10 to 70 μC / g, and more preferably in the range of 15 to 50 μC / g. If the charge amount is less than 10 μC / g, background stains are likely to occur, and if it exceeds 70 μC / g, the image density may be easily decreased. In addition, the ratio of charge amount (HH / LL) in the range of 0.5 to 1.5 under high temperature and high humidity (HH) of 30 ° C and 80RH% and low temperature and low humidity (LL) of 10 ° C and 20RH% Is preferable, and the range of 0.7 to 1.2 is more preferable. When the ratio is within the range, a clear image can be obtained without being affected by the environment.

<Electrostatic image developer>
The electrostatic image developing toner of the present invention is used as it is as a one-component developer or as a two-component developer composed of a carrier, but a two-component developer excellent in charge maintenance and stability is desirable.

  The carrier is preferably a carrier coated with a resin, and more preferably a carrier coated with a nitrogen-containing resin. Examples of the nitrogen-containing resin include acrylic resins containing dimethylaminoethyl methacrylate, dimethylacrylamide, acrylonitrile and the like, amino resins containing urea, urethane, melamine, guanamine, aniline, amide resins, and urethane resins. These copolymer resins may also be used. As the carrier coating resin, two or more of the nitrogen-containing resins may be used in combination. Moreover, you may use combining the said nitrogen containing resin and resin which does not contain nitrogen. The nitrogen-containing resin may be used in the form of particles and dispersed in a resin not containing nitrogen. In particular, urea resins, urethane resins, melamine resins, and amide resins have high negative chargeability and high resin hardness, so that a decrease in charge amount due to peeling of the coating resin can be effectively suppressed.

In general, the carrier needs to have an appropriate electric resistance value, and specifically, an electric resistance value of about 10 ⁹ to 10 ¹⁴ Ωcm is required. For example, when the electrical resistance value is as low as 10 ⁶ Ωcm as in the case of an iron powder carrier, the carrier adheres to the image portion of the photoreceptor due to charge injection from the sleeve, or the latent image charge escapes through the carrier, and the latent image In some cases, problems such as disturbance of the image or loss of images may occur. On the other hand, if an insulating resin (volume resistivity of 10 ¹⁴ Ωcm or more) is thickly coated, the electric resistance value becomes too high and carrier charges are less likely to leak, resulting in an edged image. On the other hand, there may be a problem of an edge effect that the image density in the central portion becomes very thin on a large image area. Therefore, it is desirable to disperse the conductive powder in the resin coating layer in order to adjust the resistance of the carrier.

  Specific examples of the conductive powder include metals such as gold, silver and copper; carbon black; semiconductive oxides such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate, aluminum borate and potassium titanate. And the like, such as powder coated with tin oxide, carbon black, or metal. Among these, carbon black is preferable from the viewpoint of production stability, cost, and conductivity.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spraying method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution in a kneader coater to remove the solvent. Examples of the coater method include a powder coating method in which a coating resin is formed into particles and mixed at a temperature equal to or higher than the melting point of the coating resin in a carrier core material and a kneader coater and then cooled to form a coating. The kneader coating method and the powder coating method are particularly preferably used. The average film thickness of the resin coating layer formed by the above method is usually in the range of 0.1 to 10 μm, more preferably 0.2 to 5 μm.

The core material (carrier core material) used for the carrier is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel, and cobalt, or magnetic oxides such as ferrite and magnetite, glass beads, and the like. From the viewpoint of using the magnetic brush method, a magnetic carrier is desirable. As an average particle diameter of a carrier core material, generally 10-100 micrometers is preferable and 20-80 micrometers is more preferable.
The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is in the range of toner: carrier = 1: 100 to 30: 100, more preferably in the range of 3: 100 to 20: 100. desirable.

<Image forming apparatus>
Next, the image forming apparatus of the present invention using the electrostatic image developing toner of the present invention will be described.
The image forming apparatus of the present invention includes an image carrier, a developing unit that develops an electrostatic image formed on the image carrier as a toner image with a developer, and a toner image formed on the image carrier. The image forming apparatus includes a transfer unit that transfers onto a transfer body and a fixing unit that fixes a toner image transferred onto the transfer body, and uses the electrostatic image developer of the present invention as the developer.

In this image forming apparatus, for example, the part including the developing unit may have a cartridge structure (process cartridge) that can be attached to and detached from the image forming apparatus main body. As the process cartridge, a developer holding body is used. The process cartridge of the present invention that contains at least the electrostatic image developer of the present invention is preferably used.
Hereinafter, an example of the image forming apparatus of the present invention will be shown, but the present invention is not limited to this. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  FIG. 1 is a schematic diagram showing a quadruple tandem full-color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter simply referred to as “units”) 10Y, 10M, 10C, and 10K are juxtaposed at a predetermined distance in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. It is designed to travel in the direction toward 10K. The support roller 24 is biased in a direction away from the drive roller 22 by a spring or the like (not shown), and a predetermined tension is applied to the intermediate transfer belt 20 wound around both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K includes yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The four color toners can be supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. Note that the second to fourth units are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of 10M, 10C, 10K is omitted.

The first unit 10Y has a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, an electrostatic charge image is formed by exposing the surface of the photoreceptor 1Y to a predetermined potential with a charging roller 2Y and the charged surface with a laser beam 3Y based on the color-separated image signal. An exposure device 3; a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image; a primary transfer roller 5Y (primary) for transferring the developed toner image onto the intermediate transfer belt 20; A transfer unit), and a photoconductor cleaning device (cleaning unit) 6Y for removing toner remaining on the surface of the photoconductor 1Y after the primary transfer.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) by the developing device 4Y.

  In the developing device 4Y, for example, yellow toner having a volume average particle diameter of 7 μm including at least a yellow colorant, a crystalline resin, and an amorphous resin is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a predetermined primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y generates a toner image. The toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner.

  The intermediate transfer belt 20 onto which the four color toner images have been transferred in multiple layers through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20 and the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording paper (transfer object) P is fed at a predetermined timing into a gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via a supply mechanism, and a predetermined secondary transfer bias is supported. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, and the transfer bias is applied to the intermediate transfer belt 20. The toner image is transferred onto the recording paper P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

Thereafter, the recording paper P is sent to a fixing device (fixing means) 28, where the toner image is heated, and the color-superposed toner image is melted and fixed on the recording paper P. The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but the present invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing a preferred example of a process cartridge containing the electrostatic charge image developer of the present invention. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are attached to a rail 116 together with the photoconductor 107. Are combined and integrated with each other.
The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components (not shown). It forms a forming apparatus. Reference numeral 300 denotes a recording sheet.

  The process cartridge shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Can be selectively combined. In the process cartridge of the present invention, in addition to the photosensitive member 107, from the charging device 108, the developing device 111, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. It comprises at least one selected from the group consisting of.

  Next, the toner cartridge of the present invention will be described. The toner cartridge of the present invention is detachably attached to the image forming apparatus, and at least the toner cartridge for storing toner to be supplied to the developing means provided in the image forming apparatus, the toner described above. Toner. The toner cartridge of the present invention only needs to contain at least toner, and may contain developer, for example, depending on the mechanism of the image forming apparatus.

  Therefore, in an image forming apparatus having a configuration in which a toner cartridge can be attached and detached, the storage stability can be maintained even in a toner cartridge whose container is miniaturized by using the toner cartridge containing the toner of the present invention. This makes it possible to achieve low-temperature fixing while maintaining high image quality.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K can be attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are respectively the developing devices ( And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, the toner cartridge can be replaced.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to them.
In this embodiment, the toner is obtained by the following method. That is, first, the following resin dispersion, colorant dispersion, and release agent dispersion are prepared. Next, while mixing and stirring a predetermined amount of these, a metal salt flocculant is added thereto and ionically neutralized to form agglomerated particles of the respective particles. Resin particles are additionally added before reaching the desired toner particle diameter to obtain the toner particle diameter. Thereafter, the pH of the system is adjusted from a weakly acidic to a neutral range with an inorganic hydroxide, and then heated to the glass transition temperature or higher (or the melting point or higher) of the resin particles to unite them. After completion of the reaction, desired toner particles are obtained through sufficient washing, solid-liquid separation, and drying processes. Hereinafter, it demonstrates along the above.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.
(Measurement method of molecular weight and molecular weight distribution of resin)
In the present invention, the molecular weight and molecular weight distribution of the crystalline polyester resin and the like were measured by GPC using the “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation) apparatus” under the above-mentioned conditions.

(Volume average particle diameter of resin particles, colorant particles, etc.)
Volume average particle diameters of resin particles, colorant particles, and the like were measured with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).

(Measuring method of melting point and glass transition temperature of resin)
The melting point of the crystalline resin and the glass transition point (Tg) of the amorphous resin were determined according to ASTM D3418-8, using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001) under the conditions described above. It was measured by. In addition, melting | fusing point was made into the peak temperature of an endothermic peak, and the glass transition point was made into the temperature of the intermediate point in the step-like endothermic change.

(Resin acid value)
2 g of the resin was weighed and dissolved in 160 ml of acetone-toluene, or those having insufficient solubility were heated and dissolved, and then the acid value was measured by the potentiometric titration method of JIS K0070-1992 using this sample.

<Preparation of each dispersion>
(Amorphous polyester resin dispersion (1))
-Bisphenol A ethylene oxide 2 mol adduct: 60 mol%
-Bisphenol A propylene oxide 2 mol adduct: 40 mol%
・ Dimethyl terephthalate: 65 mol%
-Dodecenyl succinic acid: 30 mol%
-Trimellitic acid: 5 mol%
(In the above, the alcohol component and the acid component were each 100 mol%. The same applies to the following.)
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours, with a glass transition point of 58 ° C. and an acid value of 15. A branched amorphous polyester resin (1) having 0 mKOH / g, a weight average molecular weight of 40000, and a number average molecular weight of 6500 was obtained.

  A 5 L separable flask is charged with a considerable amount of a mixed solvent of ethyl acetate and isopropyl alcohol capable of dissolving the resin, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and oil dissolved. Got the phase. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added dropwise to ion-exchanged water for phase inversion emulsification, and the solvent is removed while the pressure is reduced with an evaporator. An amorphous polyester resin dispersion (1 ) The volume average particle diameter of the resin particles in this dispersion was 0.15 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (2))
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 2 mol adduct: 50 mol%
・ Terephthalic acid: 75 mol%
-Dodecenyl succinic acid: 20 mol%
-Trimellitic acid: 5 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours, with a glass transition point of 54 ° C. and an acid value of 14. A branched amorphous polyester resin (2) having 5 mg KOH / g, a weight average molecular weight of 28000, and a number average molecular weight of 6000 was obtained.

  A 5 L separable flask is charged with a considerable amount of a mixed solvent of ethyl acetate and isopropyl alcohol capable of dissolving the resin, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and oil dissolved. Got the phase. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added dropwise to ion-exchanged water for phase inversion emulsification, and the solvent is removed while the pressure is reduced with an evaporator. An amorphous polyester resin dispersion (2 ) The volume average particle size of the resin particles in this dispersion was 0.16 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (3))
-Bisphenol A ethylene oxide 2 mol adduct: 70 mol%
-Bisphenol A propylene oxide 2 mol adduct: 30 mol%
・ Terephthalic acid: 95 mol%
-Trimellitic acid: 5 mol%
The above monomer was charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature was raised to 190 ° C. over 1 hour, and the reaction system was stirred uniformly. Then, 1.0% by mass of dibutyltin oxide was added. Further, 6 hours from the same temperature was required while distilling off the generated water, the temperature was raised to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours. g. A branched amorphous polyester resin (3) having a weight average molecular weight of 30,000 and a number average molecular weight of 5,500 was obtained.

  A 5 L separable flask is charged with a considerable amount of a mixed solvent of ethyl acetate and isopropyl alcohol capable of dissolving the resin, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and oil dissolved. Got the phase. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added to ion-exchanged water for phase inversion emulsification, and the solvent is removed while depressurizing with an evaporator to obtain an amorphous polyester resin dispersion (3 ) The volume average particle size of the resin particles in this dispersion was 0.14 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (4))
-Bisphenol A ethylene oxide 2 mol adduct: 30 mol%
-Bisphenol A propylene oxide 2 mol adduct: 70 mol%
・ Terephthalic acid: 55 mol%
Dodecenyl succinic acid: 40 mol%
・ Trimellitic acid: 5 mol A monomer having the above composition ratio was charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature was raised to 190 ° C. in 1 hour. After confirming that the reaction system was stirred uniformly, 1.0% by mass of dibutyltin oxide was added. Further, 6 hours from the same temperature was required while distilling off the generated water, the temperature was raised to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours, with a glass transition point of 48 ° C. and an acid value of 12. A branched amorphous polyester resin (4) having 0 mg KOH / g, a weight average molecular weight of 35000, and a number average molecular weight of 6200 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is dropped into this stirred oil phase, and further dropped into ion-exchanged water to effect phase inversion emulsification, and the solvent is removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (4 ) The volume average particle diameter of the resin particles in this dispersion was 0.17 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (5))
-Bisphenol A ethylene oxide 2 mol adduct: 70 mol%
-Bisphenol A propylene oxide 2 mol adduct: 30 mol%
・ Terephthalic acid: 75 mol%
N-butyl succinic acid: 20 mol%
・ Trimellitic acid: 5 mol%
The above monomer was charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature was raised to 190 ° C. over 1 hour, and the reaction system was stirred uniformly. Then, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, it took 6 hours from the same temperature to raise the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 2 hours. The glass transition point was 63 ° C., the acid value was 16 mgKOH / g. A branched amorphous polyester resin (5) having a weight average molecular weight of 25000 and a number average molecular weight of 4500 was obtained.

  A 5 L separable flask was charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent capable of dissolving the resin, and the resin was gradually added thereto, stirred with a three-one motor, and dissolved to obtain an oil phase. . An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added dropwise to ion-exchanged water, phase-inverted and emulsified, and the solvent is removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (5 ) The volume average particle diameter of the resin particles in this dispersion was 0.15 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (6))
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 2 mol adduct: 50 mol%
・ Terephthalic acid: 65 mol%
N-octenyl succinic acid: 20 mol%
・ Fumaric acid: 10 mol%
-Trimellitic acid: 5 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours. The glass transition point was 62 ° C., the acid value was 15 mgKOH / g. A branched amorphous polyester resin (6) having a weight average molecular weight of 45,000 and a number average molecular weight of 7,000 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added to ion-exchanged water for phase inversion emulsification, and the solvent is removed while depressurizing with an evaporator to obtain an amorphous polyester resin dispersion (6 ) The volume average particle diameter of the resin particles in this dispersion was 0.18 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (7))
-Bisphenol A ethylene oxide 2 mol adduct: 60 mol%
-Bisphenol A propylene oxide 2 mol adduct: 40 mol%
・ Terephthalic acid: 65 mol%
-Dodecenyl succinic acid: 30 mol%
-Trimellitic acid: 5 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. The glass transition point was 64 ° C., the acid value was 11 mgKOH / g. A branched amorphous polyester resin (7) having a weight average molecular weight of 80000 and a number average molecular weight of 10500 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added to ion-exchanged water for phase inversion emulsification, and the solvent is removed while reducing the pressure with an evaporator. ) The volume average particle diameter of the resin particles in this dispersion was 0.20 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (8))
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 2 mol adduct: 50 mol%
・ Terephthalic acid: 70 mol%
-Dodecenyl succinic acid: 25 mol%
-Trimellitic acid: 5 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, 6 hours from the same temperature was required while distilling off the generated water, the temperature was increased to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours. g. A branched amorphous polyester resin (8) having a weight average molecular weight of 20000 and a number average molecular weight of 5800 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added to ion-exchanged water for phase inversion emulsification, and the solvent is removed while the pressure is reduced by an evaporator, and an amorphous polyester resin dispersion (8 ) The volume average particle size of the resin particles in this dispersion was 0.12 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (9))
-Bisphenol A ethylene oxide 2 mol adduct: 15 mol%
-Bisphenol A propylene oxide 2 mol adduct: 85 mol%
・ Terephthalic acid: 50 mol%
・ Fumaric acid: 30 mol%
-Dodecenyl succinic acid: 20 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours. The glass transition point was 58 ° C., the acid value was 16 mgKOH / g, a linear amorphous polyester resin (9) having a weight average molecular weight of 15000 and a number average molecular weight of 5500 was obtained.

  A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent capable of dissolving the resin, and the resin is gradually added thereto, stirred with a three-one motor, and dissolved to obtain an oil phase. It was. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, and further added to ion-exchanged water to effect phase inversion emulsification. Further, the solvent is removed while reducing the pressure with an evaporator, and an amorphous polyester resin dispersion (9 ) The volume average particle size of the resin particles in this dispersion was 0.16 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (10))
-Bisphenol A ethylene oxide 2 mol adduct: 15 mol%
-Bisphenol A propylene oxide 2 mol adduct: 85 mol%
・ Terephthalic acid: 60 mol%
・ Fumaric acid: 30 mol%
Dodecenyl succinic acid: 10 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, it took 6 hours from the same temperature to raise the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 2 hours. The glass transition point was 60 ° C., the acid value was 10 mgKOH / g, a linear amorphous polyester resin (10) having a weight average molecular weight of 14,000 and a number average molecular weight of 5,000 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added to ion-exchanged water for phase inversion emulsification, and the solvent is removed while reducing the pressure with an evaporator. ) The volume average particle diameter of the resin particles in this dispersion was 0.15 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (11))
-Bisphenol A ethylene oxide 2 mol adduct: 15 mol%
-Bisphenol A propylene oxide 2 mol adduct: 85 mol%
・ Terephthalic acid: 30 mol%
・ Fumaric acid: 70 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours. The glass transition point was 61 ° C., the acid value was 12 mgKOH / g, a linear amorphous polyester resin (11) having a weight average molecular weight of 12,000 and a number average molecular weight of 4500 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, the solvent is removed while reducing the pressure with an evaporator, and an amorphous polyester resin dispersion (11 ) The volume average particle size of the resin particles in this dispersion was 0.12 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (12))
-Bisphenol A ethylene oxide 2 mol adduct: 15 mol%
-Bisphenol A propylene oxide 2 mol adduct: 85 mol%
・ Terephthalic acid: 50 mol%
・ Fumaric acid: 30 mol%
・ Dodecenyl succinic acid: 20 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was raised from the same temperature to 240 ° C. to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for a further 1.5 hours, with a glass transition point of 54 ° C. and an acid value of 18. A linear amorphous polyester resin (12) having 5 mg KOH / g, a weight average molecular weight of 8000, and a number average molecular weight of 3000 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added dropwise to ion-exchanged water for phase inversion emulsification, and the solvent is removed while reducing the pressure with an evaporator. ) The volume average particle size of the resin particles in this dispersion was 0.14 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Amorphous polyester resin dispersion (13))
-Bisphenol A ethylene oxide 2 mol adduct: 15 mol%
-Bisphenol A propylene oxide 2 mol adduct: 85 mol%
・ Terephthalic acid: 50 mol%
・ Fumaric acid: 30 mol%
・ Dodecenyl succinic acid: 20 mol%
A monomer with the above composition ratio is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, so that the reaction system does not vary. After confirming that the mixture was stirred, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, it took 6 hours from the same temperature to increase the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 3 hours. The glass transition point was 64 ° C., the acid value was 15 mgKOH / g, a linear amorphous polyester resin (13) having a weight average molecular weight of 22,000 and a number average molecular weight of 7,000 was obtained.

  Into a 5 L separable flask, a mixed solvent of a considerable amount of ethyl acetate and isopropyl alcohol capable of dissolving the resin is added, and the resin is gradually added thereto, stirred by a three-one motor, dissolved, and dissolved in an oil phase. Got. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water to effect phase inversion emulsification. Further, the solvent is removed while reducing the pressure with an evaporator, and an amorphous polyester resin dispersion (13 ) The volume average particle diameter of the resin particles in this dispersion was 0.15 μm (the resin particle concentration was adjusted to 30% by mass with ion-exchanged water).

(Crystalline polyester resin dispersion (I))
Into a heat-dried three-necked flask, 100 mol% of 1,10-decanedicarboxylic acid and 100 mol% of 1,9-nonanediol are added in a monomer composition ratio, and dibutyltin oxide becomes 0.3 mass% as a catalyst. Then, the air in the container was brought into an inert atmosphere with nitrogen gas by a depressurization operation, and stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (I) was synthesized.
The obtained crystalline polyester resin (I) had a weight average molecular weight of 25,000 and a number average molecular weight of 5,800. Further, when the melting point (Tm) of the crystalline polyester resin (A) was measured by the above-described measurement method using a differential scanning calorimeter (DSC), it showed a clear endothermic peak, and the endothermic peak temperature was 75 ° C. there were.

-Crystalline polyester resin (I): 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 2.0 parts by mass-Ion exchange water: 210 parts by mass The above is mixed and heated to 100 ° C Then, after dispersion with IKA Ultra Turrax T50, the dispersion was heated to 110 ° C. with a pressure discharge type gorin homogenizer for 1 hour, the volume average particle size was 0.15 μm, and the solid content was 30% by mass. A crystalline polyester resin dispersion (I) was obtained.

(Crystalline polyester resin dispersion (II))
Into a heat-dried three-necked flask, 100 mol% of dimethyl 1,8-sebacate and 100 mol% of 1,6-hexanediol are added in a monomer composition ratio, so that dibutyltin oxide becomes 0.3 mass% as a catalyst. Then, the air in the container was brought into an inert atmosphere with nitrogen gas by a depressurization operation, and stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (II) was synthesized.
The obtained crystalline polyester resin (II) had a weight average molecular weight of 22,000 and a number average molecular weight of 4400. Further, when the melting point (Tm) of the crystalline polyester resin (II) was measured using a differential scanning calorimeter (DSC) by the above-described measurement method, it showed a clear endothermic peak, and the endothermic peak temperature was 72 ° C. there were.

-Crystalline polyester resin (II): 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 1.8 parts by mass-Ion exchange water: 210 parts by mass The above is mixed and heated to 100 ° C Then, after dispersion with IKA Ultra Turrax T50, the dispersion is heated to 110 ° C. with a pressure discharge type gorin homogenizer for 1 hour, the volume average particle size is 0.14 μm, and the solid content is 30% by mass. A crystalline polyester resin dispersion (II) was obtained.

(Crystalline polyester resin dispersion (III))
To a heat-dried three-necked flask, 100 mol% of dimethyl 1,8-sebacate and 100 mol% of ethylene glycol were added in a monomer composition ratio, and dibutyltin oxide as a catalyst was added to 0.2 mass%. After that, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and stirred and refluxed at 180 ° C. for 5 hours by mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (III) was synthesized.
The obtained crystalline polyester resin (III) had a weight average molecular weight of 18,000 and a number average molecular weight of 4,000. Further, when the melting point (Tm) of the crystalline polyester resin (III) was measured by a differential scanning calorimeter (DSC) by the above-described measuring method, it showed a clear endothermic peak, and the endothermic peak temperature was 70 ° C. there were.

-Crystalline polyester resin (III): 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 2.0 parts by mass-Ion exchange water: 210 parts by mass After dispersion with IKA Ultra Turrax T50, heat treatment is performed at 110 ° C. with a pressure discharge type gorin homogenizer and dispersion treatment is carried out for 1 hour. Crystalline polyester having a volume average particle size of 0.15 μm and a solid content of 30% by mass Resin dispersion (III) was obtained.

(Crystalline polyester resin dispersion (IV))
Into a heat-dried three-necked flask, 100 mol% of dimethyl terephthalate and 100 mol% of 1,6-hexanediol are added in a monomer composition ratio, and dibutyltin oxide is added to a mass of 0.2% by mass as a catalyst. After that, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (IV) was synthesized.
The obtained crystalline polyester resin (IV) had a weight average molecular weight of 20,000 and a number average molecular weight of 8,000. Further, when the melting point (Tm) of the crystalline polyester resin (IV) was measured by the above-described measurement method using a differential scanning calorimeter (DSC), it showed a clear endothermic peak, and the endothermic peak temperature was 135 ° C. there were.

-Crystalline polyester resin (IV): 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 2.0 parts by mass-Ion exchange water: 210 parts by mass The above is mixed and heated to 100 ° C Then, after dispersion with IKA Ultra Turrax T50, the dispersion was heated to 110 ° C. with a pressure discharge type gorin homogenizer for 1 hour, the volume average particle size was 0.23 μm, and the solid content was 30% by mass. A crystalline polyester resin dispersion (IV) was obtained.
The summary of the above amorphous polyester resin dispersion and crystalline polyester resin dispersion is shown in Tables 1 to 3 collectively.

(Colorant dispersion)
20 parts by mass of a cyan pigment (manufactured by Dainichi Seika Co., Ltd .: ECB-301), 2 parts by mass of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC (10% by mass relative to the colorant as an active ingredient)), and After mixing 78 parts by mass of ion-exchanged water, using a homogenizer (IKA, Ultra Tarrax T50), the mixture was dispersed at 6000 rpm for 5 minutes, and then stirred for one day with a stirrer to defoam, and then the dispersion was added. Dispersion was performed at a pressure of 240 MPa using a high-pressure impact disperser ultimateizer (manufactured by Sugino Machine, HJP30006). Dispersion was performed for 25 passes. Thereafter, ion exchange water was added to adjust the solid content concentration to 25% by mass. The volume average particle size of the obtained colorant dispersion was measured and found to be 0.12 μm.

(Release agent dispersion)
Carnauba wax (melting point: 81 ° C.) 40 parts by mass, anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 2 parts by mass, and ion-exchanged water 58 parts by mass are mixed, and a homogenizer (manufactured by IKA, Ultra Turrax). Using T50), the mixture is dispersed for 5 minutes at 6000 rpm, stirred for one day with a stirrer to defoam, and then dispersed with a pressure discharge type gorin homogenizer, and then ion-exchanged water is added to adjust the solid content concentration. It adjusted to 25 mass%. When the particle size distribution of the obtained release agent dispersion was measured, the volume average particle size was 0.23 μm.

<Example 1>
(Manufacture of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin (1) dispersion: 150 parts by mass-Amorphous polyester resin (9) dispersion: 150 parts by mass-Crystalline polyester resin (I) dispersion: 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

  To 100 parts by mass of the toner particles obtained, 1.5 parts by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) are added, Using a sample mill, mixing blending was performed at 10,000 rpm for 30 seconds. Thereafter, the toner was obtained by sieving with a vibrating sieve having an opening of 45 μm.

(Preparation of electrostatic charge image developer)
Mixing and stirring 2 parts by mass of a styrene / methyl methacrylate copolymer (copolymerization ratio: 15/85) in a carbon dispersion obtained by mixing 14 parts by mass of toluene with 0.2 parts by mass of carbon black and stirring and dispersing with a sand mill for 20 minutes. The prepared coating agent resin solution and ferrite particles (volume average particle size: 50 μm) were put into a kneader, and the pressure was reduced while stirring, followed by drying to prepare a carrier.
100 parts by mass of this carrier and 8 parts of the toner were mixed with a V blender to obtain a developer.

(Evaluation)
-Dispersibility of crystalline polyester resin in toner particles-
The cross section of the toner particles was observed with a transmission electron microscope and evaluated. The evaluation criteria are as follows.
○: A state in which the domains of the crystalline polyester resin whose major axis is ½ or less of the toner particle diameter are uniformly dispersed in the toner particles.
X: A state in which a crystalline resin domain having a major axis of ½ or more of the toner particle diameter is present, or a state in which a crystalline polyester resin component is observed in the toner surface.

-Actual machine characteristics-
・ Image Glossiness Using a Docu Center Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd., an unfixed image including a solid part is formed on Fuji Xerox J paper, and the surface temperature of the fixing member using an offline fixing bench The surface temperature of the fixing roll was adjusted at intervals of 20 ° C. from 140 ° C. to 180 ° C. to fix the aforementioned unfixed image. About the obtained image, the glossiness of the solid part was measured using the gloss meter by Murakami Color Materials. In the measurement, the incident light density incident at an angle of 45 degrees with respect to the image surface and the reflected light density at 135 degrees were measured for each temperature, and the ratio of the reflected light density to the incident light density was defined as the glossiness. A glossiness of 50% or more is preferable because it has appropriate color high-quality images.
Further, regarding the uneven glossiness of the fixed image, the uneven glossiness of the solid image portion was visually evaluated.

-Image density The image density was obtained by measuring the density of the solid portion with an X-rite 404 density measuring device. If the image density is 1.20 or more, there is no problem in practical use.

・ Image quality, fog 32 ° C, relative humidity 75% In the environmental room, set the developer to the developer of Fuji Xerox Co., Ltd. Docu Center Color 400 remodeling machine, and print out 50000 sheets continuously. The fog of the background portion of the obtained image and the sharpness of the character image were evaluated. The fog was evaluated by visually observing the non-image area and graded from G1 (without fog) to G5 (with fog). Usually, if it is G2 or more, it can be determined that there is no problem in image quality. The sharpness of character images is evaluated from the visual readability of Japanese characters with different sizes. The evaluation criteria are as follows.
○: 4-point Japanese characters can be read, fog is G2 or higher
Δ: 6-point Japanese characters can be read, fog is G2 or higher ×: 6-point Japanese characters are difficult to read or can be read, or fog is G3 or lower Evaluation results are summarized in Table 4

<Example 2>
(Manufacture of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (II): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 4.

<Example 3>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 167 parts by mass-Amorphous polyester resin dispersion (9): 167 parts by mass-Crystalline polyester resin dispersion (I): 33 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 4.

<Example 4>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 150 parts by mass-Amorphous polyester resin dispersion (10): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co.) When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (10) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 4.

<Example 5>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (2): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (2) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 4.

<Example 6>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 230 parts by mass-Amorphous polyester resin dispersion (9): 100 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co.) When the volume average particle size became 5.5 μm, 135 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 55 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 4.

<Example 7>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (6): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co.) When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (6) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 4.

<Example 8>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 50 parts by mass-Amorphous polyester resin dispersion (9): 50 parts by mass-Crystalline polyester resin dispersion (I): 267 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 5.

< Reference Example 9>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (5): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (5) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 5.

<Example 10>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (4): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -The particle diameter was measured by Coulter Co., Ltd., and when the volume average particle diameter became 5.5 μm, 90 parts by mass of the amorphous polyester resin dispersion (4) and the amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 5.

<Comparative Example 1>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (3): 150 parts by mass-Amorphous polyester resin dispersion (11): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter, Inc.) When the volume average particle size became 5.5 μm, 90 parts by mass of the amorphous polyester resin dispersion (3) and the amorphous polyester resin dispersion (11) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 6.

<Comparative example 2>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (9): 333 parts by mass-Crystalline polyester resin dispersion (I): 67 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. ), Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature was controlled at 30 ° C. while controlling the temperature with a mantle heater from the outside. The mixture was held at a stirring speed of 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -The particle diameter was measured by Coulter Co., Ltd., and when the volume average particle diameter became 5.5 μm, 187 parts by mass of the amorphous polyester resin dispersion (9) was added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 6.

<Comparative Example 3>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (3): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co.) When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (3) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 6.

<Comparative example 4>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (III): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 6.

<Comparative Example 5>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 280 parts by mass-Crystalline polyester resin dispersion (I): 67 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. ), Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature was controlled at 30 ° C. while controlling the temperature with a mantle heater from the outside. The mixture was held at a stirring speed of 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -The particle diameter was measured by Coulter Co., Ltd., and when the volume average particle diameter became 5.5 μm, 187 parts by mass of the amorphous polyester resin dispersion (1) was added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 6.

<Comparative Example 6>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 183 parts by mass-Amorphous polyester resin dispersion (9): 183 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku ( Co., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature was controlled with a mantle heater from the outside. The temperature was kept at 30 ° C. for 30 minutes at 150 ° C.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 7.

<Comparative Example 7>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (1): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (IV): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (1) and amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 7.

<Comparative Example 8>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (8): 150 parts by mass-Amorphous polyester resin dispersion (12): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -Particle size measured by Coulter Co., Ltd. When the volume average particle size became 5.5 μm, 90 parts by mass of amorphous polyester resin dispersion (8) and amorphous polyester resin dispersion (12) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 7.

<Comparative Example 9>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (7): 150 parts by mass-Amorphous polyester resin dispersion (13): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -The particle diameter was measured by Coulter Co., Ltd., and when the volume average particle diameter became 5.5 μm, 90 parts by mass of the amorphous polyester resin dispersion (7) and the amorphous polyester resin dispersion (13) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 7.

<Comparative Example 10>
(Production of toner)
-Ion exchange water: 280 parts by mass-Amorphous polyester resin dispersion (8): 150 parts by mass-Amorphous polyester resin dispersion (9): 150 parts by mass-Crystalline polyester resin dispersion (I): 67 Part by mass / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, 20% by mass): 2.8 parts by mass The above was placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer. Then, the temperature was controlled from the outside with a mantle heater, and the temperature was kept at 30 ° C. and the stirring rotation speed was 150 rpm for 30 minutes.

  Thereafter, 60 parts by mass of the colorant dispersion and 80 parts by mass of the release agent dispersion were added and held for 5 minutes. The 1.0 mass% nitric acid aqueous solution was added as it was, and pH was adjusted to 3.0. While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and Multisizer II (aperture diameter: 50 μm, Beckman). -The particle diameter was measured by Coulter Co., Ltd., and when the volume average particle diameter became 5.5 μm, 90 parts by mass of the amorphous polyester resin dispersion (9) and the amorphous polyester resin dispersion (9) 90 parts by mass were added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner particles were obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

The toner particles were subjected to external additive treatment and developer preparation according to Example 1, and evaluated according to Example 1.
The results are summarized in Table 7.

As shown in the examples of Tables 4 and 5, by using the specific polyester resin A, polyester resin B and polyester resin C as a binder resin, there are no image quality defects such as offset, image density and fog, and fixing. Even if the temperature fluctuates, it is possible to obtain a high-quality full-color image with high image glossiness and no glossiness unevenness.
On the other hand, as shown in Comparative Examples in Tables 6 and 7, for example, in Comparative Example 1, the constituent component in the amorphous resin does not have alkyl succinic acid or alkenyl succinic acid, or an acid anhydride thereof. The dispersion state of the crystalline resin was poor, the image glossiness was uneven, and the image had a low image glossiness. Since all of the amorphous resins of Comparative Example 2 are linear polyester resins having a low molecular weight, high image glossiness can be obtained, but offset occurs at high temperature fixing. Further, in Comparative Example 4, since ethylene glycol having a small number of carbon atoms is used in the crystalline resin, the resin volume resistance becomes low and fogging occurs. Also in Comparative Example 7, since the aromatic crystalline resin is used as the crystalline resin, the melting point of the crystalline resin is high, the compatibility with the amorphous polyester resin is low, and the image gloss unevenness is poor. High image gloss cannot be obtained. Furthermore, in Comparative Examples 8 to 10 where the amorphous resin does not satisfy the required molecular weight condition, some problem occurred in fogging, glossiness, and offset.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic block diagram which shows an example of the process cartridge of this invention.

Explanation of symbols

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3 Exposure device 4Y, 4M, 4C, 4K, 111 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller (transfer means)
28, 115 Fixing device (fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 Recording paper (transfer object)

Claims (8)

A binder resin including a polyester resin A, a polyester resin B, and a polyester resin C, a colorant, and a release agent;
The polyester resin A is a branched amorphous polyester resin containing no tetrahydrofuran-insoluble matter, the polyester resin B is a linear amorphous polyester resin,
The polyester resin A and the polyester resin B are at least one selected from terephthalic acid, terephthalic anhydride, and alkyl esters of terephthalic acid, and at least one selected from alkyl succinic acid, alkenyl succinic acid, and anhydrides thereof. A resin component containing at least one species as an acid component, reacted with at least one selected from a bisphenol A ethylene oxide adduct and a bisphenol A propylene oxide adduct as an alcohol component,
The polyester resin C is a crystalline polyester resin,
Any of the carbon number of the alkyl succinic acid, alkenyl succinic acid and their acid anhydrides is greater than the carbon number of each of the monomer-derived components in the polyester resin C,
And an electrostatic charge image developing toner characterized by satisfying the following (1) to (3).
(1) The weight average molecular weight of the polyester resin A is from 25000 to 45000, the number average molecular weight of 4500 to 7000
(2) The polyester resin B has a weight average molecular weight of 14,000 to 15000 and a number average molecular weight of 5000 to 5500.
(3) Aliphatic crystalline polyester resin obtained by reacting polyester resin C with a dicarboxylic acid having 6 to 10 carbon atoms and a dialcohol having 6 to 10 carbon atoms Among the constituent components derived from all monomers in the polyester resin A and the polyester resin B, the constituent amounts P and Q derived from at least one selected from alkyl succinic acid, alkenyl succinic acid and acid anhydrides thereof are 5 to 5 respectively. In the range of 20 mol%,
The toner according to claim 1, wherein the constituent component quantity P is equal to or not larger than the constituent component quantity Q. Having a structure including core particles and a shell layer covering the core particles;
The binder resin of the core particles includes the polyester resin A, the polyester resin B, and the polyester resin C,
The electrostatic image developing toner according to claim 1, wherein the shell layer contains the polyester resin A and the polyester resin B.   2. The electrostatic image developing toner according to claim 1, wherein the content of the polyester resin C in the binder resin is in the range of 1 to 20% by mass.   An electrostatic image developer comprising: a toner, wherein the toner is the electrostatic image developing toner according to claim 1.   A toner cartridge comprising at least toner, wherein the toner is the electrostatic image developing toner according to claim 1.   A process cartridge comprising at least a developer holder and containing the electrostatic charge image developer according to claim 5.   A latent image holding member, developing means for developing the electrostatic image formed on the latent image holding member as a toner image with a developer, and transferring the toner image formed on the latent image holding member onto the transfer target An image forming apparatus comprising: a transfer unit configured to transfer a toner image transferred onto a transfer target; and a developer configured to fix the toner image transferred onto the transfer target, wherein the developer is the electrostatic charge image developer according to claim 5. apparatus.