JP2008096788A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in developing property and transferability and having a wide fixing temperature range, and to provide a toner satisfying the above properties and excellent also in hot storage resistance. <P>SOLUTION: The toner has toner particles having a surface layer (B) including a polyurethane compound (b) on a surface of a toner base particle (A) including at least a binder resin (a), a colorant and a wax, wherein the binder resin (a) and the polyurethane compound (b) have a specific content of an ethyl acetate-insoluble component, the 1/2 melting temperature of all resin components of the toner measured with an elevated flow tester and the 1/2 melting temperature of an ethyl acetate-soluble component of the toner measured with the elevated flow tester satisfy specific relationships, and a total amount of the polyurethane compound (b) based on all toner base particles (A), a number average dispersion particle diameter of the wax present in the toner base particles (A) and an amount of wax particles having a dispersion particle diameter of ≥0.70 μm are a specific value each. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner that can be used in a wide range of output devices such as a copying machine, a printer, a facsimile, and a light printing system using an image forming method such as an electrophotographic method and an electrostatic recording method.

  Conventionally, many methods are known as electrophotographic methods. In general, a photoconductive material is used to form an electrical latent image on an image carrier (photoreceptor) by various means, and then the latent image is developed with toner to form a toner image (visualization) The toner image is transferred to a transfer material such as paper as necessary, and then the toner image is fixed on the transfer material by heat / pressure to obtain a copy.

  As a method for visualizing an electric latent image, a magnetic two-component developing method comprising a magnetic toner and a carrier, a non-magnetic two-component developing method comprising a non-magnetic toner and a carrier, and a non-magnetic toner using an external additive particle alone are not used. In general, a magnetic one-component development system and a magnetic one-component development system using a magnetic toner are widely used.

  In recent years, such copying apparatuses have been sought to be smaller, lighter, faster, and more reliable. In addition, it has begun to be used not only for office processing copying machines for copying original documents but also for copying high-definition images such as digital printers for computer output or graphic design.

  In addition to the viewpoint of miniaturization in this way, the user is required to stably output a large number of high-quality images with better color reproducibility and higher quality than ever before. At present, the desire is growing. Therefore, it is necessary to clear various technical problems, and various toner manufacturing methods have been proposed accordingly.

As a means of improving the image quality in electrophotography, it is generally considered to reduce the particle size of the toner. However, the pulverization method is limited to reducing the particle size due to problems with the equipment and energy efficiency. Currently, it is difficult to cope with further reduction in particle size.
In addition, in order to form a full-color image, a complicated process such as a transfer process from a plurality of color images to a final transfer medium such as an intermediate transfer medium or paper is required, or toner is formed in multiple layers. Due to the instability of charge control due to the toner, the influence of the toner shape, etc., the transfer characteristics are likely to deteriorate. Further, due to the poor transferability, there are problems such as missing transferred images and increased toner consumption to compensate for them.

In the manufacturing method by the pulverization method, since the particle shape is indefinite, the toner is further pulverized by stirring or contact stress in the developing device, and fine particles are generated or the fluidizing agent is embedded in the toner surface. The phenomenon that the image quality deteriorates occurs.
Further, due to its shape, the fluidity as powder is poor, a large amount of fluidizing agent is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing.

Under such circumstances, a toner shape closer to a spherical shape is being demanded, and in recent markets, many toners are obtained by a wet method represented by a suspension polymerization method, an emulsion aggregation method, and the like. Used.
In the suspension polymerization method, since droplets are formed in an aqueous system and toner particles are obtained by a polymerization reaction, it is possible to manufacture without requiring a great deal of energy for reducing the particle size. Compared to pulverized toner, it is easier to produce particles that are nearly spherical. In particular, a great effect can be obtained in creating a full-color image in that the toner can be made into a spherical shape.

It is already known that the toner shape particularly contributes greatly to the transfer characteristics, and when the toner becomes a true sphere, the surface contact changes from the surface contact to the point contact, the releasability increases, and high transfer efficiency is exhibited.
Further, by improving the transfer characteristics, it is possible to obtain a high-quality image with no image omission. Improved transfer characteristics eliminate the need for cleaning members to collect untransferred toner from the photoreceptor and transfer medium, reduce the size and cost of the equipment while maintaining high image quality, and eliminate waste toner The benefits are satisfied at the same time.
However, the true spherical toner has the following problems continuously. As one of them, since it is close to a true sphere, the packing property is high, the load on the member tends to be large at the developer regulating part and the cleaning part, the toner slips out, the developing member and the periphery of the photosensitive member There is a concern that the toner is easily fixed to the member. These are problems that are a concern regardless of manufacturing means such as a pulverization method and a polymerization method.

  On the other hand, energy saving is considered as a major technical problem in the electrophotographic apparatus, and the amount of heat applied to the fixing device is greatly reduced. Characteristics are being demanded.

  In general, for a toner obtained by the pulverization method described above, a polyester-based binder resin having high sharp melt properties is often used for general purposes, and the binder resin is heated and melted using a biaxial melt kneader or the like. A so-called thermoplastic resin can be used without any restriction so long as it performs the kneading step together with the material.

  On the other hand, when toner is obtained from a vinyl monomer by suspension polymerization or emulsion aggregation, it is possible to produce toner particles that are nearly spherical, but use a binder resin with high sharp melt properties such as polyester resin. Things are difficult. If a color toner is manufactured from a resin that does not have sharp melt properties, it is considered unsuitable for obtaining high color mixing properties and glossiness.

  When a resin having high sharp melt properties is used as a binder resin for toner, as described above, not only glossiness and color mixing properties, but also low-temperature fixability is advantageous, but on the contrary, high-temperature offset properties are not preferable and are on the market. In the toner, other components having a high molecular weight component are added, or some fixing auxiliary member is used. Further, since the sharp melt property is high, the heat-resistant storage property is weak, and the toner tends to clump in a block shape when left for a long time. Therefore, the use of a polyester-based binder resin having a high sharp melt property is often regarded as one of the causes for lowering the toner quality.

In order to achieve both of these heat-resistant storage stability and low-temperature fixability, a polyester partially crosslinked with a polyfunctional monomer is used as a toner binder resin, or a urethane-modified polyester is used as a toner binder resin. Things have been proposed.
However, these toners are insufficient in fluidity and transferability, and are difficult to achieve both heat-resistant storage stability and low-temperature fixability.
In order to improve powder flowability and transferability when the particle size is reduced, a vinyl monomer composition containing a colorant, a polar resin and a release agent is dispersed in water and then subjected to suspension polymerization. A toner obtained by spheroidizing a polymerized toner or a toner composed of a polyester resin with a solvent in water has been proposed, but both are not satisfactory in terms of low-temperature fixability and offset resistance.
Furthermore, a substantially spherical dry toner using a polyester resin modified with a urea bond has been developed. However, the toner is pulverized by agitation in the developing unit and a large amount of fine particles are generated, so that the image quality is easily deteriorated. .
Further, although a toner structure having a high polyester resin hardness on the toner surface and a low internal polyester resin hardness has been disclosed (Patent Document 1, etc.), since it is not a two-layer structure like a core / shell type, it is fixed at low temperature. It is difficult to say that it is a complete function separation type that satisfies both the heat resistance and heat storage stability.

As described above, the toners obtained by these various toner production methods have not yet achieved both low-temperature fixability and heat-resistant storage stability.
As a method for achieving both low-temperature fixability and heat-resistant storage stability, a production method called a dissolution suspension method has been studied. (Patent Document 2, Patent Document 3, etc.)
This method is a method of granulating a polymer dissolved in a low-boiling organic solvent or the like while the suspension polymerization method forms particles from monomers. Since this method does not have a polymerization step, it has advantages such as a wide selection of resin materials and easy polarity control. Therefore, it is possible to control the structure of the toner (preparation of the core / shell structure), and not only the monochrome toner but also the production of full-color toner that requires transparency and smoothness of the image area after fixing. It becomes.
Further, although the volumetric shrinkage of the droplets occurs during the manufacturing process, it is possible to obtain particles of various shapes by selecting a solid fine particle dispersant that does not dissolve in the aqueous medium as the dispersant.

By using the dissolution suspension method, a polyester resin having a low temperature fixability can be used. However, productivity problems such as polymer control for achieving oil-less fixing and widening the mold release range, and increase in liquid viscosity due to addition of high molecular weight components in the resin or colorant dissolution or dispersion process Is likely to occur. They have not been resolved yet.

Further, in Patent Document 2, the toner surface shape is improved by making the toner surface spherical and concavo-convex, but since it is an irregularly shaped toner with no regularity, charging stability is further improved. High durability design and high molecular weight design to ensure releasability have not been achieved, and satisfactory quality has not been obtained.
Further, when the amount of solid content in the solvent is increased in order to increase productivity, the viscosity of the dispersed phase increases, and the resulting particles have a large particle size and a large distribution. Conversely, when the viscosity of the dispersed phase is lowered by lowering the molecular weight of the resin used, there is a concern that the fixing property on the high temperature side deteriorates.

  As described in Non-Patent Document 1 (Takao Ishiyama, 2 others, “Characteristics and Future Prospects of New Processed Toner”, 4th Japan Imaging Society / Electrostatic Society Joint Symposium, July 29, 2000) In the suspension method, there is one aspect in which the core / shell structure can be easily controlled. However, with regard to the shell layer, in most cases, the purpose is to prevent the pigment and wax from being exposed on the surface, and the shell layer is formed only of a resin. For this reason, the thermal characteristics of the shell layer are not specified, and the toner aiming to improve the low-temperature fixability is not sufficient in terms of heat-resistant storage stability and charging stability.

  Further, Patent Document 4 attempts to obtain toner particles by reaction with amines in an aqueous medium in a toner obtained by subjecting an isocyanate group-containing prepolymer to an extension reaction and a crosslinking reaction. Although the particle size can be achieved, the manufacturing conditions for controlling the sphericity cannot be asked, and the desired shape control is difficult.

  When a solid fine particle dispersant that does not dissolve in an aqueous medium is selected as the dispersant, only amorphous particles can be obtained. When the solid content in the solvent was increased in order to increase productivity, the viscosity of the dispersed phase increased, and the resulting particles had a large particle size and a broad distribution. Conversely, when the molecular weight of the resin used is lowered and the viscosity of the dispersed phase is lowered, the fixability (particularly high temperature offset resistance) must be sacrificed.

On the other hand, the resin has a low molecular weight to lower the viscosity of the dispersed phase to facilitate emulsification and to improve the fixability by carrying out a polymerization reaction in the particles. (Patent Document 5 etc.)
However, the transferability and cleaning properties were not improved by adjusting the shape of the particles. However, a dry toner using a method of granulating in water such as these, specifically, a toner composition containing a binder resin, a colorant, and a wax is dissolved / dispersed in an organic solvent. The toner for electrophotography obtained by dispersing in an aqueous medium is obtained by dissolving or dispersing a pigment used as a colorant in an organic solvent and emulsifying it in an aqueous medium in the production process. There is a difference in dispersion stability at the oil / water interface due to the difference in hydrophobicity, and the dispersion state of the pigment changes. Since the dispersion state of the pigment affects the electrical characteristics of the toner, the actual situation is that trial and error of manufacturing stability and quality are repeated.
When a conductive pigment such as carbon black is used, non-uniform pigment dispersion adversely affects the electrical characteristics of the toner. For example, when the volume resistance is lowered, developability is deteriorated, and image worms and dust are generated.

In the conventional suspension polymerization method, the emulsion polymerization method, the dissolution suspension method, etc., styrene-acrylic acid ester copolymer is often used as a binder resin, and it is difficult to form particles. Polyester resins that are difficult to control the shape and the like but have excellent low-temperature fixability are not generally used.
Thus, from the viewpoint of improving heat-resistant storage stability and low-temperature fixability, it has been proposed to use a polyester resin modified with a urea bond (Patent Document 6, etc.). However, in this case, since the surface state of the toner particles has not been devised, there is a problem that the environmental charging stability under severe conditions such as low-temperature fixing conditions is not sufficient.

In this way, if a polyester resin that can be fixed at low temperature can be used, the advantage is great, but in the case of the dissolution suspension method, a high molecular weight component is added in the process of dissolving or dispersing the low temperature fixing resin and the colorant in a solvent. As a result, the viscosity of the liquid increases and productivity problems occur.
Further, in this dissolution suspension method, toner cleaning is improved by making the surface of the toner spherical and making the surface uneven (Patent Document 1, etc.). However, the toner produced by the dissolution suspension method has a uniform dispersibility and dispersion state (surface presence) of the wax and a uniform dispersibility of the pigment when the wax is added to the composition as a release agent. Compared to decrease. Furthermore, since the wax is particleized in the solvent, there are restrictions in terms of viscosity, so the degree of freedom in polymer design of the binder is reduced, and it is difficult to ensure releasability.

According to Patent Document 4, a practical sphericity composed of an elongation reaction product of a urethane-modified polyester as a toner binder for the purpose of improving toner fluidity, low-temperature fixability, and hot offset property is 0.90 to 1. 00 dry toner has been proposed.
In addition, a dry toner has been proposed that has excellent powder flowability and transferability when it is a small particle size toner, and also has excellent heat storage stability, low-temperature fixability, and hot offset resistance (Patent Document 4). And Patent Document 5). The toner production methods described in these publications include a high molecular weight process in which an isocyanate group-containing polyester prepolymer is subjected to a polyaddition reaction with an amine in an aqueous medium.
However, in the case of the toner obtained by this method, the dispersion of the pigment and wax is poor, and the pigment is unevenly dispersed in the toner. Therefore, the image obtained by this toner has low transparency and saturation. (Vividness) was inferior.
In particular, in oilless fixing, there is a problem that a sufficient release width cannot be obtained because there is no dispersion control of the release agent and the oilless fixing toner is not designed. In addition, when a color image is formed on an OHP sheet using the toner, the dispersion particle size of the release agent is large, so that there is a problem that the image becomes a dark image.

The particles produced by the dissolution suspension method as in the suspension polymerization method and the emulsion aggregation method are polar such as a suspension stabilizer, an emulsion stabilizer, and a surfactant in order to stably produce the particles in an aqueous medium. It is necessary to use the substance. Many of such polar substances cannot be removed by a simple cleaning method, and remain on the toner surface, which adversely affects charging characteristics particularly under high temperature and high humidity. In addition, the polar substance remaining on the toner surface adheres to the surface of the photoconductor during development, cleaning, etc., and the written latent image is blurred (a phenomenon in which the image flows and cannot be discriminated when it becomes intense). generate. In particular, when dot writing is performed with a digital machine, if the diffusion speed of the latent image is high, the phenomenon is remarkably deteriorated. Therefore, in order to obtain a consistent image that is not affected by the environment, it is necessary to keep the photoconductor warm in order to suppress the influence of humidity and the adsorption of polar substances, especially in machines that require high image quality. It was. As described above, a toner that is hardly affected by a high temperature and high humidity has been strongly desired among toners made in an aqueous medium.
JP 2004-4414 JP-A-9-15903 JP 7-152202 A JP-A-11-149180 JP-A-11-149179 JP-A-11-133667 Takao Ishiyama, two others "Characteristics and Future Prospects of Newly Toner", 4th Japan Imaging Society / Electrostatic Society Joint Symposium, July 29, 2002

An object of the present invention is to provide a toner having excellent developability and transferability and having a wide fixing temperature range.
Another object of the present invention is to provide a toner that satisfies the above characteristics and has excellent heat-resistant storage stability.

The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and are true spherical capsule type toners having a core / shell structure, in which the ethyl acetate insoluble component of the resin component of the shell portion and the resin of the core portion By specifying the content of the component insoluble in ethyl acetate, etc., the inventors have found that a toner having excellent developability, transferability and heat-resistant storage stability and a wide fixing temperature range can be obtained, and the present invention has been completed. That is, the gist of the present invention is as follows.
The toner of the present invention includes a toner particle having a surface layer (B) containing a polyurethane compound (b) on the surface of a toner base particle (A) containing at least a binder resin (a), a colorant and a wax. Because
(1) The binder resin (a) has an ethyl acetate insoluble component of 10.0% by mass or less, and the polyurethane compound (b) has an ethyl acetate insoluble component of 95.0% by mass or more,
(2) 1/2 melting temperature measured with an elevated flow tester of all resin components of the toner (Tm-T), 1/2 melting temperature measured with an elevated flow tester of ethyl acetate soluble components of the toner When (Tm-A) is satisfied, the following formulas (i) and (ii) are satisfied:
Formula (i) 5 ≦ (Tm−T) − (Tm−A) ≦ 15
Formula (ii) 80 ° C. ≦ Tm−A ≦ 100 ° C.
(3) The total amount of the polyurethane compound (b) with respect to the toner base particles (A) is 2.0 to 15.0% by mass,
(4) The number average dispersed particle diameter of the wax present in the toner base particles (A) is 0.10 to 0.60 μm, and the wax having a dispersed particle diameter of 0.70 μm or more is 10 number% or less. It is characterized by.

According to the present invention, it is possible to provide a color toner excellent in developability and transferability and having a wide fixing temperature range.
In addition, it is possible to provide a color toner that satisfies the above characteristics and has excellent heat-resistant storage stability.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
The toner of the present invention includes a toner particle having a surface layer (B) containing a polyurethane compound (b) on the surface of a toner base particle (A) containing at least a binder resin (a), a colorant and a wax. It is. The toner preferably has a true spherical capsule shape having a core / shell structure. In the core / shell structure, the core particles are toner base particles (A), and the shell is a surface layer (B).
The binder resin (a) forming the toner base particles (A) contains 10.0% by mass or less of an ethyl acetate insoluble component. Further, the binder resin (a) preferably has an ethyl acetate insoluble component of 3.0 to 10.0% by mass, particularly preferably 4.0 to 7.0% by mass. By making the ethyl acetate insoluble component of the binder resin (a) 10.0 mass% or less, the binder resin (a) can be easily melted at a low temperature. The fixing property on the side can be improved.

  On the other hand, the surface layer (B) containing the polyurethane compound (b) contains 95.0% by mass or more of ethyl acetate insoluble components. Moreover, 95.0-98.0 mass% of ethyl acetate insoluble components are preferable in the surface layer (B), and 96.0-98.0 mass% is especially preferable. By making the ethyl acetate insoluble component of the surface layer (B) 95.0% by mass or more, the surface layer (B) can be hardly melted at a low temperature, and heat resistant storage stability can be improved.

The content of the ethyl acetate insoluble component in the binder resin (a) forming the toner base particles (A) can be adjusted to the above range by using a linear polyester resin.
On the other hand, the ethyl acetate insoluble component content in the surface layer (B) containing the polyurethane compound (b) can be adjusted to the above range by using a hydrophilic urethane latex emulsion.
The toner of the present invention has a function-separated capsule toner structure in which the melting characteristics of the surface layer (B) of the toner particles and the melting characteristics of the binder resin (a) of the toner base particles (A) are different. Both low-temperature fixability and heat-resistant storage stability are achieved.

The toner of the present invention has a 1/2 melting temperature (Tm-T) measured with an elevated flow tester of all resin components of the toner, and a 1/2 measured with an elevated flow tester of ethyl acetate soluble components of the toner. When the melting temperature is (Tm-A), the following formulas (i) and (ii) are satisfied.
Formula (i) 5 ≦ (Tm−T) − (Tm−A) ≦ 15
Formula (ii) 80 ° C. ≦ Tm−A ≦ 100 ° C.

The 1/2 melting temperature indicates the temperature at the midpoint between the outflow start point and the outflow end point of the load stroke in the elevated flow tester. The 1/2 melting temperature is the elevated flow tester CFT500C. Measurement was performed using a mold (manufactured by Shimadzu Corporation). Details of the measurement will be described later.
The 1/2 melting temperature measured with an elevated flow tester for all the resin components of the toner (the 1/2 melting temperature measured with an elevated flow tester is also simply referred to as 1/2 melting temperature hereinafter) The fact that it is higher than the 1/2 melting temperature of the soluble component means that the 1/2 melting temperature of the ethyl acetate insoluble component contained in the toner is high. This means that the 1/2 melting temperature of the polyurethane compound present in the surface layer of the toner is high. Since a polyurethane compound having a high 1/2 melting temperature is present in the surface layer of the toner, problems such as coalescence are less likely to occur even when the toner is left at a high temperature.
On the other hand, the binder resin that forms the toner base particles contains many ethyl acetate-soluble components with a low 1/2 melting temperature, so in the fixing process, the melting inside the toner starts at a low temperature and the low-temperature fixability is improved. To do.

When the difference between (Tm-T) and (Tm-A) is lower than 5 ° C., it means that there is substantially no difference in the melting temperature characteristics of (Tm-A) and (Tm-T), In such a case, it is difficult to achieve both low temperature fixability and heat resistant storage stability.
On the other hand, if the difference between (Tm−T) and (Tm−A) is greater than 15 ° C., the melting characteristics of (Tm−A) and (Tm−T) are too far apart, and the fixing start point is higher. Although the heat-resistant storage stability can be achieved by shifting to the side, it is not satisfactory for improving the low-temperature fixability.

When (Tm-A) is lower than 80 ° C., it is difficult for the toner to hold the capsule structure, and the resin used in the toner may ooze out to the toner surface. As a result, the heat resistant storage stability is deteriorated and the toner is easily damaged. Therefore, when continuously used in the developing device, the toner may be fused to the developing sleeve or the toner may be cracked. There may be a problem that the amount of coarse powder increases and fog is likely to occur in the output image.
On the other hand, when (Tm-A) is higher than 100 ° C., the heat resistant storage stability is good, but the fixing start point shifts to the high temperature side, the fixing region becomes narrower, and a high gloss (glossiness) is obtained. When it is developed to color toner or the like, the color mixing property is inferior, and there is a concern that the color reproducibility of the resulting visible image is impaired.
Satisfying the above relational expression indicates that the toner particles have a capsule-type configuration including a core particle and a shell layer. In addition, as a feature of the present invention, the core particles are “soft” and the shell layer is “hard”, so that both heat storage stability and low-temperature fixability are achieved. In order to achieve these, raw materials having a difference in melting characteristics in the core / shell are indispensable. In the conventional toner manufacturing method using the “pulverization method”, the core / shell is made to melt and knead the raw materials all at once. Is difficult. In addition, the production method by the “polymerization method” has a problem that the material polarity and the like are greatly affected in the aqueous granulation step, and there are many restrictions on the materials that can be used. In the present invention, as a result of considering the restrictions in the production of these toners, it has become possible to derive capsule-type toner particles by satisfying the above relational expression by using the dissolution suspension method.

In the toner of the present invention, the total amount of the polyurethane compound (b) is 2.0 to 15.0% by mass with respect to the toner base particles (A). The total amount of the polyurethane compound (b) relative to the toner base particles (A) is preferably 3.0 to 15.0% by mass, particularly preferably 4.0 to 15.0% by mass.
The amount of the polyurethane compound can be confirmed by the following method.
A sample in which a metal salt compound such as a quaternary ammonium salt is previously contained in the polyurethane compound (b) at a certain ratio is prepared, and calibration curve data is prepared. In this case, calibration curve data is created using the same metal salt derived from the charge control agent or the like that may be contained in the polyurethane compound. The toner sample is measured by fluorescent X-rays, and the total amount is calculated from the output intensity and the calibration curve.
When the total amount of the polyurethane compound (b) with respect to the toner base particles (A) is less than 2.0% by mass, the toner has excellent properties with respect to low-temperature fixability, but heat-resistant storage stability when left at high temperatures. Gets worse. Further, when the toner particles of the present invention are produced in an aqueous medium, the amount of the polyurethane compound (b) that also acts as a dispersant is reduced, so that the granulation stability is lowered and the particle size distribution is broadened. It becomes easy to become.
On the other hand, when the total amount of the polyurethane compound (b) with respect to the toner base particles (A) is more than 15.0% by mass, the heat-resistant storage stability is improved, but the low-temperature fixability and the glossiness after fixing are lowered. In addition, the overall image quality is likely to deteriorate.
Further, when the toner particles of the present invention are prepared in an aqueous medium, the dispersibility of the polyurethane compound (b) particles in the aqueous system tends to be lowered, and many coalesced particles and irregular shaped particles are likely to be generated. .

The toner base particles (A) contain at least a binder resin, a colorant and a wax.
When polyester is used as the binder resin (a) constituting the toner base particles (A) and the toner particles are prepared in an aqueous medium, the polar group portion in the polyester exhibits affinity with water and the toner base Since the particles are selectively collected on the particle surface, the wax is hardly exposed on the surface. For this reason, in the toner of the present invention, the wax is likely to be contained in a finely dispersed state in the toner base particles. In addition, the average wax dispersion diameter becomes relatively uniform, and stable fixing performance can be derived.

In this case, the number average dispersed particle size of the wax present in the toner base particles (A) is 0.10 to 0.60 μm, preferably 0.20 to 0.50 μm.
It is difficult in production to make the number average dispersed particle size smaller than 0.10 μm. On the other hand, when the number average dispersed particle size is larger than 0.60 μm, the wax particle surface is likely to appear on the surface of the toner particle, so that the wax is easily oozed out. When wax exudes to the surface of the toner particles, the heat-resistant storage stability is deteriorated, and the possibility that the toner adheres to the internal member of the printer body is increased.
Further, in the dispersed particle size distribution of the wax dispersed in the toner base particles (A), the number of the wax having a dispersed particle size of 0.70 μm or more is 10% by number or less, preferably 3.0 to 8.0% by number. It is. When the number of the wax having a dispersed particle size of 0.70 μm or more is more than 10% by number, the heat-resistant storage stability is rapidly deteriorated due to the possibility that the waxes are easily united or exposed to the toner surface. there is a possibility.
By increasing the time for adjusting the wax dispersion, the wax having a number average dispersed particle size of the wax present in the toner base particles (A) of 0.10 to 0.60 μm and a dispersed particle size of 0.70 μm or more is obtained. Can be adjusted to 10% by number or less.

The content of the wax in the toner base particles (A) is preferably 2 to 20% by mass based on the solid content in the “oil phase” composed of the binder resin solution and the pigment dispersion. More preferably, it is 2-10 mass%.
When the wax content in the toner base particles (A) is less than 2% by mass, it becomes difficult to maintain the releasability of the toner. On the other hand, when the content of the wax in the toner base particles (A) is more than 20% by mass, the wax is likely to be exposed on the toner surface, which may lead to a decrease in heat resistant storage stability. Furthermore, when producing toner particles having a capsule structure in an aqueous system, the granulation stability of the toner particles decreases, and the resulting toner particles have a broad particle size distribution or a smaller particle size of the toner particles. May become difficult.

Known waxes can be used as the wax used in the present invention. Examples thereof include polyolefin waxes such as polyethylene wax and polypropylene wax; long-chain hydrocarbon waxes such as paraffin wax and sazol wax; carbonyl group-containing waxes and the like.
Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol-bis. A polyalkanoic acid ester such as stearate; a polyalkanol ester such as trimearyl trimelliate and distearyl maleate; a polyalkanoic acid amide such as ethylenediamine dibehenylamide; And dialkyl ketones such as distearyl ketone. Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

The melting point of the wax used in the present invention is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, still more preferably 60 to 90 ° C.
Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point.

In addition to increasing the dispersibility of the wax in the binder resin, a wax dispersant may be used as necessary.
The wax dispersant is obtained by dispersing wax in a wax dispersion medium and improving the dispersibility of the wax in the binder resin. The wax dispersion medium is preferably a reaction product of a polyolefin and a vinyl polymer, and more preferably a polyolefin polymer grafted with a vinyl polymer.

  Examples of vinyl monomers that can be used to obtain a vinyl polymer constituting the wax dispersion medium include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-phenylstyrene. P-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn -Styrene monomers such as octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene and derivatives thereof; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid -N-butyl, isobutyl methacrylate, methacrylic acid-n- Methacrylic acid monomers which are α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- Acrylic monomers that are acrylic esters such as chloroethyl and phenyl acrylate; nitrogen-containing acrylic acid such as acrylonitrile, methacrylonitrile, acrylamide or nitrogen-containing methacrylic acid derivative A nitrogen-containing vinyl monomer such as a body; these may be used alone or in combination.

  Examples of the vinyl monomer include unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, Unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester Unsaturated dibasic half-esters such as methyl itaconic acid half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated di-salt such as dimethyl fumaric acid Acid esters; α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, α, β- An anhydride of an unsaturated acid and a lower fatty acid; monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monoesters thereof can also be used.

  Furthermore, as the vinyl monomer, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- ( Monomers having a hydroxyl group such as 1-hydroxy-1-methylhexyl) styrene can also be used.

  Dispersion of the wax into the binder resin (wax dispersion) can be performed by a known method using a known mixing or stirring device. Specifically, the raw material solution in which wax and binder resin are dissolved is stirred in a dissolution tank and the like, and then wet pulverized by an apparatus equipped with granular media such as an attritor, a ball mill, a sand mill, and a vibration mill. . As the granular media, steels such as stainless steel and carbon steel, alumina, zirconia, silica and the like are preferably used.

In the toner base particles used in the present invention, a known resin can be used as the binder resin, but it is preferable to contain a polyester resin, and a non-condensation product composed of a polycondensate of an alcohol component and a carboxylic acid component. It is particularly preferable to contain a bisphenol-based polyester resin.
The non-bisphenol-based polyester resin refers to a polyester resin that does not use bisphenol A and its derivatives as a raw material for the polyester resin.
As a polyester monomer for producing the non-bisphenol-based polyester resin, a polyhydric alcohol and a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester can be used as a raw material monomer.

  The alcohol is preferably an aliphatic alcohol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Examples of the aliphatic alcohol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples thereof include diols such as neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, and 1,8-octanediol, and trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, and trimethylolpropane. Among these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable. Furthermore, from the viewpoint of durability, the content of the aliphatic alcohol is preferably 30 to 100 mol%, more preferably 50 to 100 mol% in the alcohol component.

  As said alcohol, alcohols other than C2-C8 aliphatic alcohol may contain, As this alcohol, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) Examples include propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane.

  On the other hand, bisphenol monomers such as bisphenol derivatives represented by the following formula (1) and diols represented by the formula (2) are poorly biodegradable in the alcohol component and are not decomposed for a long time when discarded. It may remain. Moreover, since it has an aromatic ring in a molecule | numerator, the bad effect that it is inferior in fading property is also considered.

  Examples of the carboxylic acid include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids and alkyls of these acids (1 to 8 carbon atoms) ) Esters and the like.

From the viewpoint of chargeability, the carboxylic acid preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol%, and 50 to 100 mol% in the carboxylic acid component. Is more preferable.
From the viewpoint of fixability, the raw material monomer preferably contains a trivalent or higher polyvalent monomer, that is, a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound. The content is preferably from 0.1 to 20 mol%, more preferably from 1 to 15 mol%, in the raw material monomer.

  The production of the polyester resin is not particularly limited, and a known method may be followed. For example, it can be produced by subjecting an alcohol component and a carboxylic acid component to condensation polymerization at a temperature of 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst as necessary.

  The binder resin preferably contains as a main component a polyester resin using the aliphatic alcohol as an alcohol component. On the other hand, even when the binder resin contains a polyester resin using a bisphenol monomer as an alcohol component, there is no significant difference in the melting characteristics of the binder resin. However, toner base particles using the binder resin have poor granulation properties, and it is difficult to obtain spherical toner base particles.

  The binder resin is a resin other than a polyester resin using a specific amount of an aliphatic alcohol as an alcohol component, for example, a polyester resin, a styrene-acrylic resin, a polyester and a styrene acrylic in which the amount of the aliphatic alcohol used is outside the above range. A mixed resin, an epoxy resin, or the like may be contained. In that case, the content of the polyester resin using a specific amount of aliphatic alcohol as an alcohol component is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and more preferably 50 to 100% with respect to the total amount of the binder resin. Mass% is particularly preferred.

  The colorant used for the toner base particles (A) is not particularly limited, and for example, the following are used.

As a colorant suitable for the yellow color, a pigment or a dye can be used.
Specifically, examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned. Examples of the dye include C.I. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 etc. are mentioned. These can be used alone or in combination of two or more.

As a colorant suitable for magenta, a pigment or a dye can be used.
Specifically, examples of the pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned. Examples of the dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. basic dyes etc. are mentioned. These can be used alone or in combination of two or more.

As a colorant suitable for cyan, a pigment or a dye can be used.
Specifically, examples of the pigment include C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 etc. are mentioned. Examples of the dye include C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 etc. are mentioned. These can be used alone or in combination of two or more.

  As the black pigment, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black can be used. Magnetic powders such as magnetite and ferrite can also be used.

  The content of the colorant in the toner base particles (A) is preferably 3.0 to 10.0% by mass, more preferably 5.0 to 8.0% with respect to the binder resin (a). % By mass.

  The toner base particles (A) can optionally contain components other than the binder resin, colorant, and wax as long as the effects of the present application are not impaired. Examples of such an optional component include a charge control agent for stabilizing charging characteristics, and a low molecular weight component having a molecular weight of 1000 to 3000 for improving fixability.

The surface layer (B) contains the polyurethane compound (b) as a main component.
Examples of the polyurethane compound (b) include a compound having an isocyanate group and a compound having an active hydrogen group (water, polyol [diol and trivalent or higher polyol], dicarboxylic acid, trivalent or higher polycarboxylic acid, polyamine, polythiol, etc. ) And the like.
The polyaddition product of the compound having an isocyanate group and the compound having an active hydrogen group is preferable because it has a feature that a fine spherical aqueous dispersion can be easily formed in an aqueous medium.

The polyurethane compound (b) preferably has a 1/2 melting temperature of 120 to 170 ° C. measured with an elevated flow tester.
When the ½ melting temperature is lower than 120 ° C., there is no significant difference from the melting temperature inside the toner (it may be lower than the melting temperature inside the toner depending on the configuration), the heat-resistant storage stability is deteriorated, and the long-term The toner lump is easily generated by leaving the toner.
On the other hand, if the ½ melting temperature is higher than 170 ° C., not only low-temperature offset is likely to occur, but also the glossiness is remarkably lowered, which becomes a factor of deteriorating image quality.
These are important for realizing the purpose of achieving both low-temperature fixability and heat-resistant storage stability. Although the toner is hard particles, the capsule structure is such that the inside of the toner is practically soft. It means that.
By adjusting the content of the isocyanate group (NCO group), it is possible to adjust the 1/2 melting temperature of the polyurethane compound (b) measured by an elevated flow tester within the above range.

  When the toner of the present invention is prepared using an aqueous medium, the polyurethane compound (b) preferably has a particle size distribution in the range of 10 to 150 nm and has a volume average particle size (Dv) of 10 to 150 nm. More preferably, it is 100 nm. Further, a volume average particle size of 20 to 60 nm is preferable for forming a capsule structure, and the same phenomenon as the relationship with the total amount of the polyurethane compound (b) with respect to the toner base particles (A) described above occurs. That is, when the volume average particle diameter (Dv) is smaller than 10 nm, as in the case where the total amount of the polyurethane compound (b) is small, when the toner of the present invention is prepared using an aqueous medium, Decreasing grain stability or the like makes it difficult to form a capsule structure and tends to deteriorate heat-resistant storage stability. On the other hand, when it is larger than 100 nm, as in the case where the total amount of the resin fine particles (b) is large, when the toner of the present invention is produced in an aqueous system, the dispersibility in the aqueous phase decreases, The coalescence of particles occurs, or irregularly shaped particles occur.

  As the compound having an isocyanate group constituting the polyurethane compound (b), an aromatic isocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), an aliphatic isocyanate having 2 to 18 carbon atoms, carbon C4-15 alicyclic isocyanate, C8-15 aromatic hydrocarbon) isocyanate and modified products of these isocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine) Groups, isocyanurate groups, oxazolidone group-containing modified products, etc.) and mixtures of two or more thereof.

  Specific examples of the aromatic isocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), crude tolylene diisocyanate, 2, 4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 5) 20% by weight of a mixture with a trifunctional or higher functional polyamine]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate DOO, m- isocyanatophenyl sulfonyl isocyanate and p- isocyanatophenyl sulfonyl isocyanate.

  Specific examples of the aliphatic isocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine. Diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. Is mentioned.

  Specific examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and the like.

Specific examples of the aromatic hydrocarbon isocyanate include m-xylylene diisocyanate, p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like. Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified products of isocyanate such as modified diphenylmethane diisocyanate modified with urethane, carbodiimide, trihydrocarbyl phosphate or the like, modified tolylene diisocyanate modified with urethane, and a mixture of two or more of these. Among these, preferred are 6 to 15 aromatic isocyanates, C4 to C12 aliphatic polyisocyanates, and C4 to C15 alicyclic isocyanates, and particularly preferred are tolylene diisocyanate and diphenylmethane diisocyanate. Hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate.

  Examples of the compound having an active hydrogen group constituting the polyurethane compound (b) include polyamines, polyols, and polymercaptans, and particularly preferable examples include blocked polyamines. Specifically, 4,4'-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof.

  The surface layer (B) can contain a charge control agent. In this case, not only the charging stability can be improved, but also the fluidity and fixability of the toner can be supplemented.

  A well-known thing can be used as said charge control agent. For example, nigrosine dye, triphenylmethane dye, metal-containing azo complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus Simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like.

Specifically, Nigrosine dye Bontron N-03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-4
15 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst), LRA-901, boron complex LR-147 (Nippon Carlit), copper phthalocyanine, perylene, quinacridone, azo pigment, other functional groups such as sulfonic acid group, carboxyl group and quaternary ammonium salt High molecular compounds having

  The content of the charge control agent in the surface layer (B) is preferably 0.2 to 1.2% by mass, more preferably 0.3 to 1.0% by mass with respect to the polyurethane compound (b). %.

  The charge control agent is preferably contained in at least the surface layer (B) in order to make the capsule structure exhibited by the toner of the present invention useful. However, it may be contained in both the toner base particles (A), the toner base particles (A) and the surface layer (B).

  In addition to the polyurethane compound (b) and the charge control agent, the surface layer (B) can optionally contain components usually used for toner particles as long as the effect of the present application is not impaired. Examples of such optional components include inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

The thickness of the surface layer (B) is preferably 0.03 to 0.20 μm in order to achieve both fixing properties and heat-resistant storage stability.
When the thickness of the surface layer (B) is smaller than 0.03 μm, it becomes difficult for the toner to take a capsule structure, and the heat resistant storage stability may be rapidly deteriorated. On the other hand, when the thickness of the surface layer (B) is larger than 0.20 μm, not only low-temperature offset is likely to occur, but also coalesced particles are likely to occur, which easily causes problems such as toner dropping off during development. Become.
It is possible to adjust the thickness of the surface layer (B) within the above range by changing the addition amount and particle diameter of the polyurethane compound (b).

Although the manufacturing method of the said polyurethane compound (b) is not specifically limited, It is preferable that the following process is included. In particular, in order to adjust the particle size distribution of the polyurethane compound (b) to 10 to 150 nm, the following steps may be used as an example. In the following description, “%” and “part” are “% by mass” and “part by mass”, respectively, unless otherwise specified.
(Process-1)
Dividing 600 parts by mass of a monomer mixture composed of 300 parts by mass of isophorone diisocyanate and 300 parts by mass of a polyester resin into 60 parts by mass of the initial addition monomer [I] and 540 parts by mass of the dropping monomer [II]. Then, each of the divided monomer mixture is replaced with nitrogen.
(Process-2)
In 1800 parts by mass of deionized water, 5.4 parts by mass of boric acid and 0.54 parts by mass of sodium carbonate are dissolved and placed in a 3 liter flask and purged with nitrogen.
(Process-3)
Next, deionized water in the flask was heated to 80 ° C., and stirred with nitrogen gas flowing in, as a persulfate initiator [III], 0.1 mass of potassium persulfate (hereinafter abbreviated as KPS). Part is dissolved in 50 parts by mass of deionized water purged with nitrogen and added. Immediately after that, 60 parts by mass of the monomer (I) for initial addition in the above (Step-1) is added and held for 20 minutes while stirring in a nitrogen atmosphere.
(Process-4)
Subsequently, as a persulfate initiator [IV], a solution obtained by dissolving 1.0 part by mass of KPS in 50 parts by mass of deionized water substituted with nitrogen is added to the flask. Immediately thereafter, the dropping of 540 parts by mass of the dropping monomer [II] in the above (Step-1) is started and dropped over 150 minutes. After stirring for 150 minutes under the nitrogen atmosphere from the end of dropping, a solution obtained by dissolving 0.4 parts by mass of KPS again in 50 parts by mass of deionized water substituted with nitrogen is added. Thereafter, the mixture is further stirred and held in a nitrogen atmosphere for 150 minutes and then cooled to complete the polymerization, thereby obtaining polyurethane compound (b) fine particles.

  In the present invention, a known external additive can be externally added to the toner particles to obtain a toner. Examples of the additive that can be used as the external additive for imparting various properties include a fluidizing agent and a cleaning property improving agent.

The fluidizing agent is used to assist the fluidity, developability, and chargeability of the toner. As the fluidizing agent, inorganic fine particles are preferable.
Specific examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, Examples include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. These inorganic fine particles may be used alone or in combination of a plurality of types.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.
The inorganic fine particles are preferably from 0.01 to 5% by mass, particularly preferably from 0.01 to 2.0% by mass, based on the toner particles.

  As the fluidizing agent, in addition to inorganic fine particles, polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization or dispersion polymerization; silicone, benzoguanamine, nylon, etc. And polycondensates thereof; polymer particles using a thermosetting resin, and the like. These fluidizing agents may be used alone or in combination.

The fluidizing agent can be further surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
Examples of the surface treatment agent for performing the surface treatment include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, and silicone. Examples thereof include oil and modified silicone oil.

The cleaning property improving agent is used for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium. Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. .
The cleaning property improver preferably has a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
The cleaning property improver is preferably 0.3 to 1.5% by mass, particularly preferably 0.5 to 1.0% by mass, based on the toner particles. The cleaning property improving agents may be used alone or in combination.

When the toner of the present invention is used as a two-component developer, it may be used by mixing it with a magnetic carrier. Part by mass is preferred.
As the magnetic carrier, known ones such as iron powder, ferrite powder, magnetite powder, and magnetic fine particle dispersed resin carrier having a particle diameter of about 20 to 200 μm can be used.

The toner particles of the present invention preferably have a weight average particle size (D4) of 3.0 to 8.0 μm.
Since the weight average particle diameter (D4) of the toner particles is 3.0 to 8.0 μm, when the toner is changed in the developing device, the fluctuation of the particle diameter of the toner particles is reduced and the development is performed. Stable developability and images can be obtained even in continuous use, without contamination of the member such as dropping off from the part.

In order to improve the image quality of electrophotography, it is generally said that the smaller the toner particle size, the higher the resolution and the higher quality the image can be obtained. Tend to be disadvantageous with respect to image quality such as roughness.
Further, in the toner particles having a capsule structure as in the present invention, when the weight average particle diameter of the toner particles is smaller than 3.0 μm, the toner filming on the developing sleeve or the toner on the peripheral member is performed. Not only does the fusion easily occur, but it also becomes difficult to form a capsule structure, and problems such as an increase in irregularly shaped toner particles and a rapid deterioration in heat-resistant storage stability are likely to occur.
On the other hand, when the weight average particle diameter of the toner particles is larger than 8.0 μm, the output of a line image or the like is likely to cause scattering and blurring, and the fine line reproducibility may be inferior.
By changing the particle diameter of the polyurethane compound (b), the amount ratio of the polyurethane compound (b) to the toner base particles (A), etc., the weight average particle diameter of the toner particles can be adjusted to the above range. .

The shape factor SF-1 value of the toner particles greatly contributes to the toner transfer characteristics. That is, the closer the toner particles are to a true sphere, the easier it is to improve transfer efficiency. The SF-1 value of the toner of the present invention is preferably 100 to 140, more preferably 100 to 130.
When the SF-1 value increases, the shape of the toner particles changes from a true sphere to an uneven shape, and the transfer characteristics tend to deteriorate.
The reason why the toner particle shape affects the transfer characteristics is that the toner particles and / or two-component developer, the contact point between the toner particles and the carrier is increased, and the releasability is impaired, thereby deteriorating the transferability. Conceivable.
By adjusting the manufacturing conditions, the shape factor SF-1 value of the toner particles can be adjusted within the above range.

Hereinafter, although the manufacturing method of the toner particle used for this invention is demonstrated in detail, it is not necessarily limited to this method. In the following description, “%” and “part” are “% by mass” and “part by mass”, respectively, unless otherwise specified.
The toner particles are preferably produced by a dissolution suspension method in order to take a true spherical capsule shape having a core / shell structure. Specifically, a binder obtained by dissolving or dispersing the binder resin (a), the colorant, and the wax (if necessary, the foam stabilizer) constituting the toner base particles in an organic medium or The dispersion (toner mother particle composition) is dispersed in an aqueous medium containing at least the fine particles of the polyurethane compound (b) and a dispersion stabilizer, and the organic medium is removed from the obtained dispersion, followed by heating and drying. A method for obtaining particles can be suitably exemplified.
When the toner base particle composition is dispersed in an aqueous medium, it is preferable to finely disperse and granulate and emulsify under high shear force to form emulsified resin particles. The formed emulsified resin particles are then preferably heated and dried at 100 ° C. or lower while reducing the pressure to atmospheric pressure or lower to form toner particles.

By heating, the fine particles of the polyurethane compound (b) covering the surface of the toner base particles can be integrated to form a surface layer, and the surface of the surface layer can be smoothed.
As conditions regarding the temperature and time of the said heating, 100 degrees C or less is preferable and 60-70 degreeC is especially preferable. In addition, it is preferable to raise the temperature from room temperature to the above temperature in about 5 minutes. The heating time is preferably about 30 minutes. These heating temperature and time vary depending on the material used for the surface layer, but can be appropriately adjusted by those skilled in the art.

  Solvents that can be used as the organic medium include hydrocarbon solvents such as toluene, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate. Examples include ester solvents, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, and methylcyclohexane.

As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols such as methanol, isopropanol, and ethylene glycol; dimethylformamide; tetrahydrofuran; cellsolves such as methyl cellsolve; and lower ketones such as acetone and methyl ethyl ketone.
The amount of the aqueous medium used relative to 100 parts by mass of the toner base particle composition is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner base particle composition is poor, and toner base particles having a predetermined particle diameter cannot be obtained. When it exceeds 2000 parts by mass, it is not economical.

The dispersion stabilizer has the effect of preventing the oil droplets from reaggregating by surrounding the oil droplets formed by finely dispersing the toner base particle composition with a high shear force.
Here, the fine particles of the above-mentioned polyurethane compound (b) also act as a dispersion stabilizer, but the above-mentioned dispersion stabilizer is fine particles of the polyurethane compound (b) in order to adjust the adsorptivity of the dispersion stabilizer to the droplets. It is preferable to use a dispersion stabilizer other than those in combination. The dispersion stabilizer other than the fine particles of the polyurethane compound (b) can be added before emulsification of the toner base particle composition or when the volatile component is removed after emulsification. The fine particles of the polyurethane compound (b) are preferably fine particles having a particle size distribution of 10 to 150 nm as described above.
As the dispersion stabilizer other than the fine particles of the polyurethane compound (b), known surfactants, inorganic dispersion stabilizers, organic dispersion stabilizers and the like can be used.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, and can be arbitrarily selected in accordance with the polarity at the time of toner particle formation. is there.
Specific examples of the surfactant include anionic ionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters; alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amines such as imidazoline Cationic surfactants of salt type, quaternary ammonium salt type such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride; fatty acid amide derivative , Nonionic surfactants such as polyhydric alcohol derivatives; amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Furthermore, the effect can be obtained in a small amount by using a surfactant having a fluoroalkyl group. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 to C11).
) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl Phosphate esters, and the like,

  On the other hand, as the cationic surfactant having a fluoroalkyl group that is preferably used, an aliphatic primary or secondary or secondary amine acid having a fluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, etc. Aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like can be mentioned.

  The inorganic dispersion stabilizer is preferably one that can be removed by an acid such as hydrochloric acid having no affinity with the solvent since the toner particles are granulated in a state of adhering to the particle surface after dispersion. For example, calcium carbonate, chloride Examples include calcium, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, and potassium hydroxide.

  Examples of the organic dispersion stabilizer include water-soluble polymers. Examples of the water-soluble polymer include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; or acrylic acid β- Hydroxyethyl, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide , Acrylic monomers or methacrylic monomers containing hydroxyl groups such as N-methylol methacrylamide; vinyl alcohol; or ethers with vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether; or Esters of compounds containing vinyl alcohol and carboxyl groups such as vinyl acetate, vinyl propionate and vinyl butyrate; acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride Homopolymers or copolymers having a nitrogen atom such as pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, or a heterocyclic ring thereof; polyoxyethylene, polyoxypropylene; Polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl Polyoxyethylenes such as phenyl esters; celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The amount of the dispersion stabilizer added is preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the aqueous medium. When the above dispersion stabilizer is used, the dispersion stabilizer can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner to be removed by dissolution washing or the like.

  In the production of the toner particles, the raw material for the toner base particles other than the binder resin such as the colorant and the wax is not necessarily mixed before the particles are formed in the aqueous medium. It may be added after forming. It is also possible to obtain composite particles by mixing different fine particles such as fine particles containing wax, fine particles containing a charge control agent, fine particles containing a fluidizing agent, fine particles containing a colorant, etc., together with the resin particles, prepared separately from the resin particles. it can. Further, it is possible to apply a mechanical impact force to the composite particles in order to prevent the detachment of the different types of particles.

The method for dispersing the toner base particle composition in the aqueous medium is not particularly limited, and general-purpose dispersion means such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic method can be used. In order to make the dispersed particle size about 2 to 20 μm, a high-speed shearing type dispersing means is preferable.
There is no restriction | limiting in particular as a high-speed shearing-type dispersion | distribution means, The emulsifier, disperser, etc. which are used widely can be used.
For example, Ultra Tarrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Machine Industries Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples include continuous type emulsifiers (made by Taiheiyo Kiko Co., Ltd.), batch types such as Claremix (made by M Technique Co., Ltd.), fill mix (made by Tokushu Kika Kogyo Co., Ltd.), and continuous two-way emulsifiers. .

When the high-speed shearing dispersion means is used, the number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.
In the case of a batch system, the dispersion time is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

The formed emulsified resin particles can be heated and dried at 100 ° C. or lower while reducing the pressure to atmospheric pressure or lower to form toner particles.
Before the heating and drying, in order to remove the organic solvent from the emulsified resin particles, it is possible to gradually raise the temperature of the entire system and completely evaporate and remove the organic solvent in the droplets.
Alternatively, the emulsified resin particles can be sprayed in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets, and the solution-form dispersion stabilizer can be removed by evaporation. In that case, the dry atmosphere in which the emulsified resin particles are sprayed is generally a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, etc., in particular, various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used. Used.

  The drying can be performed using a spray dryer, a belt dryer, a rotary kiln or the like. Moreover, it is possible to obtain the target quality sufficiently with a short processing time.

In the classification of the emulsified resin particles, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. It is preferable in terms of efficiency to carry out in a liquid.
On the other hand, when the emulsion resin particles have a wide particle size distribution and are washed, heated, and dried while maintaining the particle size distribution, the desired particle size distribution can be classified by a known method to adjust the particle size distribution.
The dispersion stabilizer used is preferably removed from the obtained emulsified resin particles as much as possible, but is preferably performed simultaneously with the classification operation.

Hereinafter, a method for measuring physical properties according to the present invention will be described.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
In the present invention, the weight average particle diameter (D4) of the toner particles is Coulter Counter Multisizer II (manufactured by Coulter Co.). As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. As the electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and a toner having a particle diameter of 2.00 to 40.30 μm using the 100 μm aperture as the aperture by the measurement device. The volume and number of particles are measured for each of the following channels to calculate the toner volume distribution and number distribution. From the calculation result, the weight average particle diameter (D4) of the toner particles is obtained.
As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00 to 40.30 μm are used (the median value of each channel is a representative value for each channel).

<Method for measuring molecular weight of binder resin>
In the present invention, the molecular weight and molecular weight distribution of the binder resin are measured by a chromatogram by GPC (gel permeation chromatography) using THF as a solvent for the tetrahydrofuran (THF) soluble content of the binder resin. The measurement conditions are as follows.
The measurement sample is prepared as follows.
The sample and THF are mixed at a concentration of about 0.5 to 5 mg / ml (for example, about 5 mg / ml) and allowed to stand at room temperature for several hours (for example, 5 to 6 hours). Shake and mix the sample with THF. Furthermore, it is allowed to stand at room temperature for 12 hours or longer (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing is set to 24 hours or longer.
Then, GPC was passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-2 manufactured by Tosoh Corporation, Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc. can be preferably used). This sample.
The column was stabilized in a 40 ° C. heat chamber, and THF was added to the column at this temperature as a solvent at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.5 to 5 mg / ml. Is measured by injecting 50 to 200 μl.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6.0 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8
. It is appropriate to use 6 × 10 ⁵ , 2.0 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As the column, in order to accurately measure the molecular weight region of 1 × 10 ³ to 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. In the present invention, the following conditions are satisfied. Measured in
[GPC measurement conditions]
Equipment LC-GPC 150C (Waters)
Column KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column temperature 40 ° C
Solvent THF (tetrahydrofuran)

In the measurement of the GPC chromatogram in the present invention, the high molecular weight side starts from the point where the chromatogram rises from the baseline, and the low molecular weight side measures up to a molecular weight of about 400.

<Measuring method of glass transition point (Tg)>
The measuring method of the glass transition point (Tg) in the present invention was performed according to ASTM (D3418-82) using DSC-7 (Perkin Elmer (manufactured by Perkin Elmer)) at a heating rate of 10 ° C./min. .
From the DSC curve at the second temperature increase, Tg was defined as Tg at the intersection of the base line (1) before the endothermic peak and the base line (2) after the endothermic peak and the rising curve as shown in FIG. .

<Method for extracting ethyl acetate soluble part of toner>
About 0.2 g of toner as a sample is weighed in a sample bottle, 5 ml of ethyl acetate is added as a solvent, shaken lightly by hand, and left at room temperature for 24 hours.
After standing, the remaining precipitate is filtered, dried, solidified, and crushed to calculate the amount of insoluble matter, and the ethyl acetate-soluble matter of the toner is obtained from the difference from the sample amount.

<Measuring method of 1/2 melting temperature with elevated flow tester>
The 1/2 melting temperature of the toner or the like is measured using a flow tester.
As a flow tester, an elevated flow tester CFT500C type manufactured by Shimadzu Corporation is used. Using this flow tester, the sample is measured under the following conditions. The flow curve based on the obtained data is in a state as shown in FIGS. 1A and 1B, from which each temperature can be read.
In FIG. 1, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method is the above-mentioned 1/2 melting temperature. The 1/2 melting temperature can be obtained as shown in FIG. In addition, the measurement was performed on the following measurement conditions using the above-mentioned apparatus.
"Measurement condition"
Melting temperature measurement method: 1/2 method
Load: 10 kg / cm ² ,
Temperature increase rate: 4.0 ° C./min,
Die diameter: 1.0 mm,
Die length: 1.0mm

<Method for measuring ethyl acetate insolubles>
A toner sample of 0.5 to 1.0 g is weighed (W1 g), put into a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), passed through a Soxhlet extractor, and extracted for 6 hours using 100 to 200 ml of ethyl acetate as a solvent. After evaporating the soluble component extracted with the ethyl acetate solvent, it is vacuum dried at 60 ° C. for several hours, and the amount of the ethyl acetate soluble resin component is weighed (W2 g). The mass of a component insoluble in ethyl acetate such as a pigment in the toner is defined as (W3 g). The ethyl acetate insoluble matter is obtained from the following formula.
Ethyl acetate insoluble matter (%) = W1- (W3 + W2) / (W1-W3) × 100

<Measurement Method of Toner Shape Factor SF-1)
In the present invention, the toner shape factor SF-1 is defined by the following equation and represents the degree of distortion from the sphere.
SF-1 = (L ² / S) × (π / 4) × 100
(Where L is the maximum length of the toner particle diameter, S is the projected area of the toner particle)
The above L and S are randomly sampled 100 particle images enlarged by a magnification of 500 times using FE-SEM (S-800) manufactured by Hitachi, Ltd., and the image information is analyzed by Nireco through the interface. It is obtained by introducing into an apparatus (Luzex III) and performing analysis. Let the average value of the shape factor SF-1 of 100 particle images be the shape factor SF-1 value.

<Measurement Method of Number Average Dispersion Particle Size of Wax>
In the present invention, the number average dispersion diameter and dispersion shape of the wax were performed as follows. An ultrathin section of the toner of the present invention was prepared, and ruthenium staining was applied to the cross section to dye the wax in the toner.
Subsequently, the transmission image of the dyed sample was observed at 14000 times with a transmission microscope (TEM) H-7500 manufactured by Hitachi, Ltd., and a digital observation image was obtained. Next, from the digital image, the shape of the wax portion in the toner was measured with image processing software Win-Roof as follows.
<Measurement of major axis / minor axis of wax>
Attention was paid to one wax particle dispersed in one toner on the image, and the longest part was defined as the long diameter. On the other hand, a line was drawn at right angles to the midpoint of the major axis of the wax, and the shortest diameter of the wax was defined between two points where the straight line contacted the outer shape of the wax grains.
When there are many wax particles in one toner, the same measurement is performed for all the wax particles in one toner, and the average value of the major axis and the minor axis in one toner is calculated. The dispersion diameter of the wax in one toner was used.
The major axis and minor axis were averaged over 50 toners, and the major axis and minor axis of the wax dispersed particles in the toner of the present invention were calculated.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following description, “%” and “part” are “% by mass” and “part by mass”, respectively, unless otherwise specified.

<Preparation of polyurethane compound constituting surface layer (B)>
(Preparation of polyurethane compound 1)
In a reaction vessel in which a stir bar, a thermometer and a nitrogen introduction tube are set, terephthalic acid 60 mol, isophthalic acid 40 mol, 1,2-propylene glycol 30 mol, diethylene glycol 100 mol, polyoxypropylene (2, 3) -2, 2-Bis (4-hydroxyphenyl) propane (5 mol) was added, reacted at 230 ° C. for 4 hours at normal pressure, and further reacted for 5 hours under reduced pressure of 10 mmHg to obtain [Intermediate Polyester 1].
Next, 400 parts by mass of the above [intermediate polyester 1], 90 parts by mass of isophorone diisocyanate, 5 parts by mass of triethylamine, a charge control agent (salicylic acid metal complex) in a reaction vessel equipped with a stirring bar, a cooling pipe, and a nitrogen introduction pipe. E-84: manufactured by Orient Chemical Co., Ltd.) 20 parts by mass and N-methyl-2-pyrrolidone 0.5 part by mass were reacted at 100 ° C. for 5 hours, and the weight average molecular weight (Mw) measured by GPC was 7500. A polyurethane compound 1 (resin fine particles 1: urethane latex particles) having a 1/2 melting temperature by a flow tester of 128 ° C. and an ethyl acetate insoluble content of 95.3% by mass was obtained.

(Preparation of polyurethane compound 2)
In the preparation of polyurethane compound 1, polyurethane compound 2 (resin fine particles 2) was prepared in the same manner except that the reaction was carried out at 230 ° C. for 6 hours at normal pressure and further reacted for 5 hours under reduced pressure of 10 mmHg to obtain an intermediate polyester. Obtained. The polyurethane compound 2 has a weight average molecular weight (Mw) measured by GPC of 7500 and a 1/2 melting temperature by a flow tester of 126 ° C.
The ethyl acetate insoluble content was 95.6% by mass.

(Preparation of polyurethane compound 3)
In the preparation of polyurethane compound 1, polyurethane compound 3 (resin fine particles 3) was prepared in the same manner except that the reaction was carried out at 230 ° C. for 6 hours at normal pressure and further reacted for 8 hours under reduced pressure of 10 mmHg to obtain an intermediate polyester. Obtained. The polyurethane compound 3 has a weight average molecular weight (Mw) measured by GPC of 15000, and a 1/2 melting temperature by a flow tester is 138.
C., ethyl acetate insoluble matter was 96.5% by mass.

(Preparation of polyurethane compound 4)
Polyurethane compound 4 (resin fine particles 4) was obtained in the same manner except that 100 parts by mass of isophorone diisocyanate and 6 parts by mass of triethylamine were used in the preparation of polyurethane compound 3. The polyurethane compound 4 had a weight average molecular weight (Mw) of 15000 measured by GPC, a 1/2 melting temperature by a flow tester of 141 ° C., and an ethyl acetate insoluble content of 97.1% by mass.

(Preparation of polyurethane compound 5)
Polyurethane compound 5 (resin fine particles 5) was prepared in the same manner except that the polyurethane compound 3 was reacted at 200 ° C. for 6 hours at normal pressure and further reacted for 8 hours under reduced pressure of 10 mmHg to obtain an intermediate polyester. Obtained. The polyurethane compound 5 has a weight average molecular weight (Mw) measured by GPC of 15000, and a 1/2 melting temperature by a flow tester is 133.
C., ethyl acetate insoluble matter was 95.4% by mass.

(Preparation of polyurethane compound 6)
In the preparation of polyurethane compound 1, polyurethane compound 6 (resin fine particles 6) was prepared in the same manner except that the reaction was carried out at 230 ° C. for 2 hours at normal pressure and further reacted for 4 hours under reduced pressure of 10 mmHg to obtain an intermediate polyester. Obtained. The polyurethane compound 6 has a weight average molecular weight (Mw) measured by GPC of 15000 and a 1/2 melting temperature of 115 by a flow tester.
C., ethyl acetate insoluble matter was 95.9% by mass.

(Preparation of polyurethane compound 7)
Polyurethane compound 7 (resin fine particles 7) was obtained in the same manner except that the intermediate polyester was changed to 350 parts by mass, isophorone diisocyanate 130 parts by mass, and triethylamine 10 parts by mass in the preparation of polyurethane compound 1. The polyurethane compound 7 has a weight average molecular weight (Mw) measured by GPC of 18000, and 1/2 by a flow tester.
The melting temperature was 176 ° C., and the ethyl acetate insoluble content was 95.1% by mass.

<Preparation of aqueous phase used for production of toner particles>
(Preparation of aqueous phase)
990 parts by mass of water, 99 parts by mass of polyurethane compound 1 (urethane latex particles), 35 parts by mass of a 50% aqueous solution of sodium dodecylbenzenesulfonate, 5 parts by mass of acetone, and 2 parts by mass of N-methyl-2-pyrrolidone were mixed and stirred. [Aqueous phase 1] containing a latex emulsion was obtained.

<Manufacture of toner particles>
(Preparation of polyester A)
60 parts by mass of terephthalic acid as a dicarboxylic acid component and 40 parts by mass of isophthalic acid, and 30 parts by mass of propylene glycol as a diol component, 100 parts by mass of ethylene glycol, and polyoxypropylene (2, 3) -2,2-bis ( 4 parts by mass of 4-hydroxyphenyl) propane and 2500 ppm of antimony trioxide as a catalyst were charged into a reaction vessel equipped with a distillation column and a stirring blade.
Next, the number of revolutions of the stirring blade in the reaction vessel is kept at 120 rpm, the temperature rise is started, the temperature in the reaction system is heated to 270 ° C. so as to become the esterification reaction temperature, and the pressure during the reaction is also increased. It was 450 kPa.
Water was distilled from the reaction system, and about 7 hours after the start of the esterification reaction, the reaction was terminated when the distillation of water ceased. Next, the temperature in the reaction system was raised and maintained at 290 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was 0.8 kPa, and a condensation reaction was performed while distilling the diol component from the reaction system. .
The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase of the viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. After completion of the reaction, the reaction system was returned to normal pressure, heating was stopped, and the reaction product was taken out over about 40 minutes by applying pressure with nitrogen to obtain polyester A.

(Preparation of polyester B)
In the production process of polyester A, polyester B was similarly prepared except that terephthalic acid was changed from 60 parts by weight to 40 parts by weight as a dicarboxylic acid component and 30 parts by weight of propylene glycol was changed to 40 parts by weight as a diol component. Obtained.

(Preparation of polyester C)
19 parts by mass of 1,4-butanediol, 1 part by mass of 1,6-hexanediol, 25 parts by mass of fumaric acid, 15 parts by mass of trimellitic anhydride and 5 parts by mass of hydroquinone were reacted at 160 ° C. for 5 hours in a nitrogen stream. Then, the temperature was raised to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain polyester C.

(Preparation of polyester D)
After reacting 20 parts by mass of 1,4-butanediol, 1 part by mass of 1,6-hexanediol, 25 parts by mass of fumaric acid and 5 parts by mass of hydroquinone at 160 ° C. for 5 hours in a nitrogen stream, the temperature is raised to 200 ° C. And reacted for 1 hour at 8.3 kPa to obtain polyester D.

(Preparation of polyester E)
30 parts by mass of ethylene glycol, 70 parts by mass of neopentyl glycol as alcohol components, 73 parts by mass of terephthalic acid, 8 parts by mass of trimellitic acid, and 2 parts by mass of dibutyltin oxide as carboxylic acid components at 220 ° C. for 5 hours. After making it react, it cooled to 160 degreeC, and after adding 25 mass parts of fumaric acids to this, it heated up to 200 degreeC and reacted for about 2 hours, and polyester E was obtained.

(Preparation of polyester F)
Ethylene glycol 30 parts by mass as an alcohol component, neopentyl glycol 70 parts by mass, terephthalic acid 70 parts by mass, trimellitic acid 10 parts by mass, bisphenol A propylene oxide 2 mol adduct 1 part by mass and dibutyltin oxide 2 parts by mass Part was reacted at 220 ° C. for 5 hours under a nitrogen atmosphere, then cooled to 160 ° C., 25 parts by weight of fumaric acid was added thereto, and then the temperature was raised to 200 ° C. and reacted for about 2 hours. Obtained.

(Preparation of polyester G)
Ethylene glycol 30 parts by mass as an alcohol component, neopentyl glycol 68 parts by mass, carboxylic acid component 70 parts by mass, trimellitic acid 12 parts by mass, bisphenol A propylene oxide 2 mol adduct 1 part by mass and dibutyltin oxide 2 parts by mass Part was reacted at 220 ° C. for 5 hours under a nitrogen atmosphere, then cooled to 160 ° C., 25 parts by weight of fumaric acid was added thereto, heated to 200 ° C. and reacted for about 2 hours. Obtained.

(Preparation of polyester H)
91 parts by mass of propylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol), 25 parts by mass of ethylene glycol, 43 parts by mass of terephthalic acid, 43 parts by mass of isophthalic acid, and 3 parts by mass of antimony trioxide in a reaction vessel The esterification reaction was carried out at 230 ° C. under normal pressure for 5 hours. Next, the pressure was gradually reduced over 40 minutes until the degree of vacuum became 1.0 mmHg at 240 ° C., and ethylene glycol was distilled off under this reduced pressure to obtain polyester H.

(Preparation of polyester I)
71 parts by mass of propylene oxide adduct of bisphenol A (average addition mole number: 2.2 mol), 66 parts by mass of ethylene oxide adduct of bisphenol A (average addition mol number: 2.2 mol), 52 parts by mass of isophthalic acid, Polyester I was obtained by reacting 7 parts by mass of isooctenyl succinic acid, 8 parts by mass of trimellitic acid and 2 parts by mass of dibutyltin oxide with stirring at 210 ° C. in a nitrogen stream.

(Preparation of polyester J)
Reaction of 72 parts by mass of an ethylene oxide adduct of bisphenol A (average addition mole number: 2.0 mol), 28 parts by mass of isophthalic acid, and 2 parts by mass of dibutyltin oxide at 230 ° C. under nitrogen flow for 8 hours. After further reacting under reduced pressure for 5 hours, the reaction mixture was cooled to 150 ° C., and 3 parts by mass of phthalic anhydride was added thereto and reacted for 2 hours.
Thereafter, the mixture was cooled to 80 ° C. and reacted with 18 parts by mass of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1).
Next, 26 parts by mass of prepolymer (1) and 1 part by mass of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester J having a weight average molecular weight of 64,000.

(Preparation of masterbatch)
[Masterbatch 1]
-Polyester resin (A) 60 mass parts-C.I. I. Paste pigment containing PB 15: 3 100 parts by mass * Paste pigment having a solid content of 40% by mass (remaining 60% by mass) obtained by removing water to some extent from the pigment slurry and without undergoing a drying process. Is water)
* The pigment / resin ratio in the solid content is 80% by mass.

First, the above raw materials are charged into a kneader-type mixer with the above formulation, and the temperature is raised under no pressure while mixing. Upon reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), it was confirmed that the pigment in the aqueous phase was distributed or transferred to the molten resin phase. Thereafter, the mixture is further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste. Thereafter, the mixer was once stopped, and hot water was discharged. Then, the temperature was further raised to 130 ° C., and the mixture was melted and kneaded for about 30 minutes to disperse the pigment and remove water. After the completion of the step, the mixture was cooled and the kneaded product was taken out to obtain a master batch 1.

(Preparation of pigment / wax dispersion 1)
378 parts by mass of polyester A, 50 parts by mass of ester wax (melting point: 82.9, acid value: 2.59) and 953 parts by mass of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, and stirred at 50 ° C. The temperature was raised to 3 hours and held there for 3 hours.
Then, it cooled to 30 degreeC in 1 hour, 100 mass parts of [masterbatch 1] and 500 mass parts of ethyl acetate were thrown into the container, and also after stirring for 1 hour, [raw material solution] was obtained.
1300 parts by mass of this [raw material solution] was transferred to another container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80. Cyan pigment and wax were dispersed under the condition of% volume filling and 3 passes to obtain [Pigment / Wax Dispersion 1].

(Preparation of pigment / wax dispersion 2)
In the preparation of the pigment / wax dispersion 1, a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.) was used. [Pigment / wax dispersion 2] was obtained in the same manner except that the conditions were 4 passes.

(Preparation of pigment / wax dispersion 3)
In preparation of the pigment / wax dispersion 2, a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.) was used. [Pigment / wax dispersion 3] was obtained in the same manner except that the conditions were 4 passes.

(Preparation of pigment / wax dispersion 4)
In preparing the pigment / wax dispersion 1, except that 378 parts by weight of polyester A, 60 parts by weight of ester wax and 976 parts by weight of ethyl acetate were charged, the temperature was raised to 50 ° C. with stirring, and maintained for 3 hours. Similarly, [Pigment / Wax Dispersion 4] was obtained.

(Preparation of pigment / wax dispersion 5)
In preparing the pigment / wax dispersion 2, 35 parts by weight of ester wax and a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.) were used. [Viscomil: manufactured by Imex Co., Ltd.], except that the liquid feed speed was 0.8 kg / hr, the disk peripheral speed was 10 m / sec, the 0.5 mm zirconia beads were filled in 80% volume, and the conditions of 4 passes were set in the same manner. Pigment / wax dispersion 5] was obtained.

(Preparation of pigment / wax dispersion 6)
In the preparation of the pigment / wax dispersion 4, the same procedure was followed except that the feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, the 0.8 mm zirconia beads were filled in 80% volume, and the conditions were two passes. [Pigment / wax dispersion 6] was obtained.

(Preparation of pigment / wax dispersion 7)
In the preparation of the pigment / wax dispersion 5, 400 parts by weight of polyester A, 10 parts by weight of ester wax, and a bead mill (Ultraviscomil: manufactured by IMEX) were used, and 800 parts by weight of [raw material solution] was added to another container. And using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), with a liquid feeding speed of 0.8 kg / hr, a disk peripheral speed of 10 m / sec, 80% volume filling of 0.5 mm zirconia beads, and 6 pass conditions. Obtained [Pigment / Wax Dispersion 7] in the same manner.

(Preparation of pigment / wax dispersion 8)
In the preparation of the pigment / wax dispersion 6, 110 parts by mass of ester wax, a feeding speed of 1 kg / hr, a disk peripheral speed of 4 m / sec, 80% volume filling of 0.8 mm zirconia beads are changed to two-pass conditions. Otherwise, [Pigment / Wax Dispersion 8] was obtained in the same manner.

(Emulsification and solvent removal process)
After putting 1100 parts by mass of [Aqueous Phase 1] in a container and stirring at 5000 rpm for 1 minute with Claremix (Mtechnic Co., Ltd.), 900 parts by mass of [Pigment / Wax Dispersion 1] and 5 parts by mass of triethylamine were added, The mixture was stirred for 5 minutes at 12000 rpm to obtain [Emulsion slurry 1].
Thereafter, a stirring blade was set in the container, and the temperature was raised to 40 ° C. while mixing at 600 rpm, and the solvent was removed over 4 hours to obtain [Dispersion Slurry 1]. Further, the surface of the particles was smoothed by raising the temperature to 65 ° C. and stirring and holding for 30 minutes.

(Washing and drying process)
After [Dispersion Slurry 1] was dried under reduced pressure,
1) 300 parts by mass of ion-exchanged water was added to the filter cake, mixed with a stirring blade at 600 rpm for 10 minutes, and then filtered.
2) 300 parts by mass of 10% by mass of sodium hydroxide was added to the filter cake of 1), mixed with a stirring blade at 600 rpm for 10 minutes, and then filtered under reduced pressure.
3) 300 parts by mass of 10% by mass hydrochloric acid was added to the filter cake of 2), mixed with a stirring blade at 600 rpm for 10 minutes, and then filtered.
4) 300 parts by mass of ion-exchanged water was added to the filter cake of 3), mixed with a stirring blade at 600 rpm for 10 minutes, and then filtered twice to obtain [filter cake 1].

[Filter cake 1] was dried with a dryer at 45 ° C. for 3 days, and sieved with a mesh opening of 75 μm to obtain [Toner Particles 1]. Table 2 shows the physical properties of [Toner Particles 1].

<Manufacture of toner>
(Manufacture of toner 1)
To 100 parts by mass of [Toner Particle 1], 1.0 part by mass of hydrophobic silica having an average particle diameter of 20 nm and 1.5 parts by mass of monodispersed silica having an average particle diameter of 120 nm are mixed with a Henschel mixer, and [Toner 1] was obtained. Table 2 shows the physical properties of [Toner 1].

(Manufacture of toner 2)
In the manufacturing process of [Toner 1], [Polyurethane compound 1] is changed to [Polyurethane compound 2], and polyester A used in [pigment / wax dispersion 1] is changed to polyester B. [Toner 2] was obtained. Table 2 shows the physical properties of [Toner 2].

(Manufacture of toner 3)
In the production process of [Toner 1], except that [Pigment / Wax Dispersion 1] was changed to [Pigment / Wax Dispersion 2] and [Polyurethane Compound 1] was changed to [Polyurethane Compound 3], the same procedure was followed. [Toner 3] was obtained. Table 2 shows the physical properties of [Toner 3].

(Manufacture of toner 4)
In the production process of [Toner 1], [Polyurethane Compound 1] is changed to [Polyurethane Compound 4], [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 3], and Polyester A [Toner 4] was obtained in the same manner except that was changed to Polyester B. Table 2 shows the physical properties of [Toner 4].

(Manufacture of toner 5)
[Toner 5] is similarly produced except that [Pigment / Wax Dispersion 2] is changed to [Pigment / Wax Dispersion 4] and Polyester A is changed to Polyester C in the production process of [Toner 3]. ] Was obtained. Table 2 shows the physical properties of [Toner 5].

(Manufacture of toner 6)
[Toner 6] was similarly manufactured except that [Pigment / Wax Dispersion 3] was changed to [Pigment / Wax Dispersion 4] and Polyester B was changed to Polyester F in the production process of [Toner 4]. ] Was obtained. Table 2 shows the physical properties of [Toner 6].

(Manufacture of toner 7)
[Toner 7] is the same as [Toner 7] except that [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 5] and Polyester A is changed to Polyester E in the production process of [Toner 1]. Got. Table 2 shows the physical properties of [Toner 7].

(Manufacture of toner 8)
[Toner 8] was similarly manufactured except that [Pigment / Wax Dispersion 1] was changed to [Pigment / Wax Dispersion 6] and Polyester B was changed to Polyester E in the production process of [Toner 2]. ] Was obtained. Table 2 shows the physical properties of [Toner 8].

(Manufacture of toner 9)
[Toner 9] was obtained in the same manner except that in the production process of [Toner 3], polyester A in [Pigment / Wax Dispersion 2] was changed to Polyester E. Table 2 shows the physical properties of [Toner 9].

(Manufacture of toner 10)
[Toner 10] was similarly produced except that [Pigment / Wax Dispersion 1] was changed to [Pigment / Wax Dispersion 2] and Polyester B was changed to Polyester C in the production process of [Toner 2]. ] Was obtained. Table 2 shows the physical properties of [Toner 10].

(Manufacture of toner 11)
In the production process of [Toner 1], except that [Polyurethane Compound 1] is changed to [Polyurethane Compound 6], and Polyester A of [Pigment / Wax Dispersion 1] is changed to Polyester E. [Toner 11] was obtained. Table 2 shows the physical properties of [Toner 11].

(Manufacture of toner 12)
In the production process of [Toner 2], except that [Polyurethane Compound 2] is changed to [Polyurethane Compound 7] and the polyester B of [Pigment / Wax Dispersion 1] is changed to Polyester C. [Toner 12] was obtained and a developer was prepared. Table 2 shows the physical properties of [Toner 12].

(Manufacture of toner 13)
In the manufacturing process of [Toner 3], [Polyurethane Compound 3] is changed to [Polyurethane Compound 5], [Pigment / Wax Dispersion 2] is changed to [Pigment / Wax Dispersion 3], and polyester is used. [Toner 13] was obtained in the same manner except that A was changed to polyester F. Table 2 shows the physical properties of [Toner 13].

(Manufacture of toner 14)
In [Preparation of aqueous phase] in the production process of [Toner 2], [Polyurethane compound 2] is contained in a proportion of 30 parts by mass, and [Pigment / wax dispersion 1] is replaced with [Pigment / wax dispersion 4]. [Toner 14] was obtained in the same manner except that polyester A was changed to polyester B. Table 2 shows the physical properties of [Toner 14].

(Manufacture of toner 15)
In [Preparation of aqueous phase] in the production process of [Toner 5], [Polyurethane compound 3] is contained at a ratio of 150 parts by mass, and [Pigment / wax dispersion 4] is replaced with [Pigment / wax dispersion 1]. [Toner 15] was obtained in the same manner except that polyester C was changed to polyester E. Table 2 shows the physical properties of [Toner 15].

(Manufacture of toner 16)
In the manufacturing process of [Toner 11], [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 3], and is prepared using Polyester E. While mixing, the temperature was raised to 40 ° C. and the reaction was carried out over 2 hours.
Toner 16] was obtained. Table 2 shows the physical properties of [Toner 16].

(Manufacture of toner 17)
[Toner 1] was similarly produced except that [Pigment / Wax Dispersion 1] was changed to [Pigment / Wax Dispersion 2] and Polyester A was changed to Polyester H in the production process of [Toner 1]. 17] was obtained. Table 2 shows the physical properties of [Toner 17].

(Manufacture of toner 18)
[Toner 18] was similarly produced except that [Pigment / Wax Dispersion 1] was changed to [Pigment / Wax Dispersion 4] and Polyester B was changed to Polyester I in the production process of [Toner 2]. Got. Table 2 shows the physical properties of [Toner 18].

(Manufacture of toner 19)
[Toner 19] is similarly produced except that [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 4] and Polyester A is changed to Polyester D in the production process of [Toner 1]. Got. Table 2 shows the physical properties of [Toner 19].

(Manufacture of toner 20)
[Toner 20] is similarly produced except that [Pigment / Wax Dispersion 2] is changed to [Pigment / Wax Dispersion 4] and Polyester A is changed to Polyester G in the production process of [Toner 3]. ] Was obtained. Table 2 shows the physical properties of [Toner 20].

(Manufacture of toner 21)
In the manufacturing process of [Toner 7], [Polyurethane Compound 1] is changed to [Polyurethane Compound 3], and [Pigment / Wax Dispersion 5] is changed to [Pigment / Wax Dispersion 2]. [Toner 21] was obtained in the same manner except that it was prepared. Table 2 shows the physical properties of [Toner 21].

(Manufacture of toner 22)
In the manufacturing process of [Toner 8], [Polyurethane Compound 2] is changed to [Polyurethane Compound 7], and [Pigment / Wax Dispersion 6] is changed to [Pigment / Wax Dispersion 4],
[Toner 22] was obtained in the same manner except that polyester E was changed to polyester C. Table 2 shows the physical properties of [Toner 22].

(Manufacture of toner 23)
In the manufacturing process of [Toner 9], [Pigment / Wax Dispersion 2] is changed to [Pigment / Wax Dispersion 1], and polyester B is used. [Toner 23] was obtained in the same manner except that 3] was contained in a proportion of 20 parts by mass. Table 2 shows the physical properties of [Toner 23].

(Manufacture of toner 24)
In the manufacturing process of [Toner 8], [Pigment / Wax Dispersion 6] is changed to [Pigment / Wax Dispersion 3], polyester E is used, and [Preparation of water phase] is [Polyurethane]. [Toner 24] was obtained in the same manner except that [Compound 2] was changed to [Polyurethane Compound 5] and contained in a proportion of 180 parts by mass. Table 2 shows the physical properties of [Toner 24].

(Manufacture of toner 25)
In the manufacturing process of [Toner 1], [Polyurethane Compound 1] is changed to [Polyurethane Compound 4], [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 7], and polyester is used. [Toner 25] was obtained in the same manner except that A was changed to polyester C. Table 2 shows the physical properties of [Toner 25].

(Manufacture of toner 26)
In the production process of [Toner 1], [Polyurethane Compound 1] is changed to [Polyurethane Compound 3], [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 8], and polyester is used. [Toner 26] was obtained in the same manner except that A was changed to polyester I. Table 2 shows the physical properties of [Toner 26].

(Manufacture of toner 27)
In the manufacturing process of [Toner 1], [Polyurethane Compound 1] is changed to [Polyurethane Compound 2], [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 2], and polyester is used. [Toner 27] was obtained in the same manner except that A was changed to polyester I. Table 2 shows the physical properties of [Toner 27].

(Manufacture of toner 28)
In the manufacturing process of [Toner 1], [Pigment / Wax Dispersion 1] is changed to [Pigment / Wax Dispersion 2], Polyester A is changed to Polyester I, and [Polyurethane Compound 1] is used instead. [Toner 28] was obtained in the same manner except that hydroxyapatite was used. Table 2 shows the physical properties of [Toner 28].

(Manufacture of toner 29)
[Toner 29] was similarly produced except that [Pigment / Wax Dispersion 1] was changed to [Pigment / Wax Dispersion 3] and Polyester A was changed to Polyester J in the production process of [Toner 1]. ] Was obtained. Table 2 shows the physical properties of [Toner 29].

<Example 1>
[Toner 1] A developer comprising 8 parts by mass and 92 parts by mass of a silicone-coated ferrite carrier having an average particle diameter of 35 μm was prepared, and the following image evaluation was performed using CLC5000 (manufactured by Canon Inc.). The results are shown in Table 3.

(1) Evaluation of image density fluctuation (initial and durability)
The above [Toner 1] was loaded into a CLC5000 (manufactured by Canon) shown in FIG. 2 and imaged in an environment of 23 ° C./60% RH in a single color mode. Image printing was performed on plain paper for copying machines (75 g / m ² ) in a monochrome mode so that the toner loading on the paper was 0.6 mg / cm ² . For the image density, the reflection density of the solid image at the initial stage (first sheet) and after 50,000 sheets is calculated as “X-Rite 500”.
"Series" (manufactured by X-Rite) was measured and evaluated.
The evaluation criteria are the initial (first image) image density value and the fluctuation range of the image density during the initial 50,000-image printing (image sampling and image density are measured every 1000 images, and 50,000 images are sent. The average fluctuation range up to the paper “difference from initial image density”) is indicated by “A to D” below. The fluctuation range is under the above environment.
A: Fluctuation range 0 to less than 0.1 B: Fluctuation range 0.1 to less than 0.2 C: Fluctuation range 0.2 to less than 0.3 D: Fluctuation range 0.3 or more

(2) Evaluation of transferability (transfer efficiency) Using CLC5000 (manufactured by Canon Inc.) shown in FIG. The potential contrast of the photoconductor is adjusted so that the density becomes 0.6 mg / cm ² , and the density of the image transferred onto the transfer paper and the residual image density on the photoconductor are measured by a densitometer (X-rite 500 Series, X-Rite). The measurement was performed using Regarding the image density of the transfer residue on the photoconductor, a mylar tape is attached to the transfer residual portion and pressed with a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) so that the photoconductor is not damaged. Collect the remaining toner. The toner collected and collected on the Mylar tape is directly attached to the non-image portion of the transfer paper where the visible image after transfer is present, and the density of the transfer afterimage is measured by the above-described X-rite 500 Series.
The transfer efficiency onto the transfer paper was determined from the ratio between the image transferred onto the transfer paper and the residual image density on the photoconductor. The transfer current was adjusted to maximize transfer efficiency.

(3) Evaluation of fixability (fixable area)
A fixing test was performed using an apparatus (see FIG. 2) in which a fixing device of CLC5000 (manufactured by Canon Inc.) was modified so that the fixing temperature could be manually set.
The development contrast was adjusted so that the amount of toner on the paper was 1.2 mg / cm ² in a single color mode under normal temperature and humidity (23 ° C / 60%), and A4 (TKCLA4, CLC recommended paper, manufactured by Canon Inc.) ) An unfixed image was created so that the image area ratio was 25%. In a room temperature and normal humidity environment (23 ° C./60%), the temperature of the fixing unit heater is increased by 10 ° C. in order from 120 ° C., and the fixing roller temperature range in which no offset or wrapping occurs is defined as a fixable region. . Fixability was evaluated in consideration of fixable area and glossiness.
The evaluation criteria are as follows.
A: High gloss without offset and wrapping.
B: No offset or wrapping but low gloss.
C: Minor offset occurs.
D: Offset or winding occurs.

(4) Evaluation of fixing start temperature (low temperature fixability)
(3) A device similar to that used in the evaluation of the fixing property was used. That is, the development contrast of CLC5000 (manufactured by Canon Inc.) shown in FIG. ² was adjusted so that the toner loading on the paper was 1.2 mg / cm ² , and a thick paper A4 paper (“Prober Bond Paper”: 105 g / m 2). ² (manufactured by Fox River) under a normal temperature and normal humidity environment (23 ° C./60%), a “solid” unfixed image having a front end margin of 5 mm, a width of 100 mm, and a length of 280 mm was created. The temperature of the heater of the fixing unit was controlled every 10 ° C. within a temperature range of 110 to 200 ° C., and the unfixed image was fixed at each temperature. A portion 5 cm from the rear end of the fixed image is rubbed 5 times with a soft thin paper (for example, trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 KPa, before rubbing (S1). Then, the image density after rubbing (S2) was measured, and the reduction rate ΔD (%) of the image density was calculated by the following formula. The image density was measured with X-Rite 500 Series (manufacturer X-Rite). The temperature at which ΔD (%) was less than 1% was determined as the fixing start temperature.
Formula: ΔD (%) = 100− (S2 / S1 × 100)

(5) Evaluation of high-temperature offset property (3) The high-temperature offset property was evaluated using the fixing device and the fixing unit used for the fixability evaluation. The image is CLC5000 (manufactured by Canon Inc.) shown in FIG. ^2, and the development contrast is adjusted so that the amount of applied toner on paper is 1.2 mg / cm ² in a single color mode under a normal temperature and humidity environment (23 ° C./60%). And an unfixed image was created on A4 (TKCLA4, CLC recommended paper, manufactured by Canon Inc.) so that the image area ratio was 25%. In a room temperature and normal humidity environment (23 ° C./60%), the temperature of the fixing unit heater is increased by 10 ° C. in order from 120 ° C., and the temperature at which offset (peeling) or winding occurs is visually confirmed. The temperature at which the offset phenomenon occurred was defined as the high temperature offset generation temperature.

(6) Evaluation of heat-resistant storage stability About 10 g of toner was put in a 100 ml polycup, left at 50 ° C. for 3 days, and then visually evaluated.
The evaluation criteria are as follows.
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Aggregates can be grasped and do not collapse easily.

<Examples 2 to 18>
A developer was prepared in the same manner as in Example 1 except that [Toner 1] was changed to [Toner 2] to [Toner 18], and image evaluation was performed in the same manner as in Example 1. Each result is shown in Table 3.

<Comparative Examples 2-11>
A developer was prepared in the same manner as in Example 1 except that [Toner 1] was changed to [Toner 19] to [Toner 29], and image evaluation was performed in the same manner as in Example 1. Each result is shown in Table 3.

The flow curve figure based on the data from a flow tester is shown. The cross-sectional schematic diagram of the image forming apparatus used for evaluation of this invention is shown. The calculation method of Tg by a DSC curve is shown.

Explanation of symbols

A Glass transition point (Tg)
B Softening temperature (Ts)
C Outflow start temperature (Tfb)
D 1/2 melting temperature (T1 / 2)
E Outflow end point 4 Photoconductor 9 Developing device 21 Exposure device 22 Laser unit 23 Transfer member 24 Transfer belt 25 Fixing roller 26 Cleaner 27 Transfer paper

Claims (8)

A toner having toner particles having a surface layer (B) containing a polyurethane compound (b) on the surface of toner base particles (A) containing at least a binder resin (a), a colorant and a wax,
(1) The binder resin (a) has an ethyl acetate insoluble component of 10.0% by mass or less, and the polyurethane compound (b) has an ethyl acetate insoluble component of 95.0% by mass or more,
(2) 1/2 melting temperature measured with an elevated flow tester of all resin components of the toner (Tm-T), 1/2 melting temperature measured with an elevated flow tester of ethyl acetate soluble components of the toner When (Tm-A) is satisfied, the following formulas (i) and (ii) are satisfied:
Formula (i) 5 ≦ (Tm−T) − (Tm−A) ≦ 15
Formula (ii) 80 ° C. ≦ Tm−A ≦ 100 ° C.
(3) The total amount of the polyurethane compound (b) with respect to the toner base particles (A) is 2.0 to 15.0% by mass,
(4) The number average dispersed particle diameter of the wax present in the toner base particles (A) is 0.10 to 0.60 μm, and the wax having a dispersed particle diameter of 0.70 μm or more is 10 number% or less.
Toner characterized by the above.   The toner according to claim 1, wherein the binder resin (a) contains a polyester resin.   The toner according to claim 2, wherein the polyester resin does not contain a polyester resin using a bisphenol monomer as an alcohol component.   The toner according to claim 1, wherein the polyurethane compound (b) has a 1/2 melting temperature measured by an elevated flow tester of 120 to 170 ° C. 5.   The toner according to claim 1, wherein a weight average particle diameter (D4) of the toner particles is 3.0 to 8.0 μm.   The toner according to claim 1, wherein the surface layer (B) has a thickness of 0.03 to 0.20 μm.   The toner according to claim 1, wherein the toner particle has a shape factor SF-1 value of 100 to 140. 8.   Disperse a dispersion or dispersion obtained by dissolving or dispersing the binder resin (a), colorant and wax in an organic medium in an aqueous medium containing at least the fine particles of the polyurethane compound (b) and a dispersion stabilizer. The toner according to claim 1, wherein the toner particles are obtained by removing an aqueous medium and an organic medium from the obtained dispersion and heating.

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