WO2017221997A1

WO2017221997A1 - Toner set for developing electrostatic images, black toner and magenta toner

Info

Publication number: WO2017221997A1
Application number: PCT/JP2017/022933
Authority: WO
Inventors: 太田　匡哉; 智子中川; 勇樹生川; 岡本　真明
Original assignee: 三菱ケミカル株式会社
Priority date: 2016-06-22
Filing date: 2017-06-21
Publication date: 2017-12-28
Also published as: JP2018018060A

Abstract

This toner set comprises at least a black toner for developing electrostatic images and a magenta toner for developing electrostatic images; and if TP1 is the first measurement value of the maximum tan δ observed from 40°C to 80°C (inclusive) by means of a rheometer and TP2 is the second measurement value of the maximum tan δ observed from 40°C to 80°C (inclusive) by means of a rheometer, the value of TP2/TP1 of the black toner for developing electrostatic images is from 1.03 times to 1.32 times (inclusive) the value of TP2/TP1 of the magenta toner for developing electrostatic images.

Description

Toner set for developing electrostatic image, black toner and magenta toner

The present invention relates to an electrostatic image developing toner set, a black toner, and a magenta toner that realize low-temperature fixability while maintaining blocking resistance and obtain a high-quality image even at low-temperature fixing.

The black toner or magenta toner for developing an electrostatic image is used for image formation for visualizing an electrostatic image in a printer, a copying machine, a facsimile machine, or the like. For example, when an image is formed by electrophotography, an electrostatic latent image is first formed on a photosensitive drum, then developed with toner, transferred to transfer paper, and fixed by heat or the like. Image formation is performed.
As a black toner or a magenta toner for developing an electrostatic image, usually a binder resin and a colorant are dry-mixed with a charge control agent, a release agent, a magnetic material, etc. as necessary, and then melt-kneaded with an extruder or the like. Then, for the purpose of imparting various properties such as fluidity to the toner particles obtained by the so-called melt-kneading pulverization method, which are pulverized and classified, for example, solid fine particles such as silica are adhered to the surface as an external additive. The thing of the form made to use is used. Furthermore, due to the recent demand for higher definition, production methods such as a suspension polymerization method, an emulsion aggregation method, and a dissolution suspension method that can easily control the particle size and particle size distribution of the toner have been proposed.

In recent years, there have been many efforts to apply images obtained by electrophotographic methods such as copiers and color printers to the professional field, and images such as photographs and graphics can be output beautifully from the purpose of printing characters so far. It has become necessary to do. Therefore, it has been strongly desired that the output image has higher gloss (high gloss) than ever before. As a toner set used for the same model in such a color printer, the composition other than the pigment is usually used without changing for each color from the viewpoint of cost and performance (see Patent Document 1).

On the other hand, low energy and high speed printing of electrophotographic apparatus are also desired at the same time, so the toner melts with low thermal energy (time x temperature), is fixed on the medium, and the image quality has high glossiness. However, low-temperature fixability and high gloss have a trade-off relationship with blocking resistance, and it is desired to achieve both of these three points.
Various studies have been made on the problem of achieving both low-temperature fixability and blocking resistance. For example, there is a toner containing a crystalline polyester resin and a release agent, and there is a structure in which the crystalline polyester resin is in contact with the release agent on the cross section of the ruthenium-dyed toner. A, where B is the sectional area of the release agent alone and C is the sectional area of the crystalline polyester resin alone, 40 ≦ 100 × A / (A + B + C) ≦ 70, 10 ≦ 100 × B / (A + B + C) ≦ An electrostatic charge image developing toner satisfying 30, 20 ≦ 100 × C / (A + B + C) ≦ 30 is disclosed (see Patent Document 2).

In addition, for the purpose of heat-resistant storage and low-temperature fixing, a crystalline organic compound having a melting point of 50 to 150 ° C. is contained as a fixing aid, and the resin and the fixing aid are compatibilized during heating. The endothermic amount of the melting maximum derived from the fixing assistant at the second temperature increase is smaller than that at the first temperature increase, the glass transition temperature of the toner is lower than the glass transition temperature of the resin, and the glass transition temperature at the second temperature increase. There has been proposed a black toner for developing an electrostatic charge image in which the temperature becomes smaller than that at the first temperature increase (see Patent Document 3).

Toner set includes yellow toner, magenta toner, cyan toner and black toner to maintain excellent releasability and good glossiness in oilless fixing, and improve fixing characteristics such as fixed image surface glossiness and OHP transparency Among the color toners having a frequency of 6.28 rad / s for each color toner and a storage elastic modulus G1 ′ determined by dynamic viscoelasticity measurement at a temperature of 160 ° C. within a specific range, and the frequency of each color toner is 6.28 rad / s. s, a technology is disclosed in which a storage elastic modulus G2 ′ obtained from dynamic viscoelasticity measurement at a temperature of 180 ° C. has a specific relationship (see Patent Document 4).

Japanese Unexamined Patent Publication No. 2014-11949 Japanese Unexamined Patent Publication No. 2008-033057 Japanese Unexamined Patent Publication No. 2012-022331 Japanese Unexamined Patent Publication No. 2005-274963

However, in any patent document, the blocking resistance and the low-temperature fixability have been studied, but the focus is not on the fixing temperature or the transport temperature. When evaluated as a toner used in a toner set, a difference between colors occurs, and there is a problem that the full color image quality is not satisfactory. This problem was particularly noticeable during low-temperature fixing or high-speed printing where little heat energy is applied to the toner.
The problem to be solved by the present invention is that, while maintaining blocking resistance, good fixability can be realized even during low-temperature fixing or high-speed printing, and the color and density of magenta and black as output pictures Another object of the present invention is to provide a toner set capable of expressing an original beautiful color gamut without difference in glossiness and the like and providing an excellent output image.

The present inventors have measured the first measured value of the tan δ maximum value (measured with a rheometer) as a form that can achieve both fixability and high gloss even at low temperature fixing or high speed printing while maintaining blocking resistance ( The ratio of TP1) to the second measured value (TP2) is important, and it is also effective to adjust the ratio of TP2 / TP1 of black toner and TP2 / TP1 of magenta toner to be within a specific range. And found out that the present invention.

The present invention is based on the above-described findings, and aspects of the present invention are as follows.
<1>
A toner set including at least an electrostatic charge image developing black toner and an electrostatic charge image developing magenta toner, wherein a first measured value of a tan δ maximum value observed at 40 ° C. or more and 80 ° C. or less by a rheometer is TP1, When the second measured value of the tan δ maximum value observed between 40 ° C. and 80 ° C. is TP2, TP2 / TP1 of the electrostatic charge image developing black toner is TP2 / TP1 of the electrostatic charge image developing magenta toner. 1.03 times or more and 1.32 times or less of the toner set.

<2>
The toner set according to <1>, wherein the electrostatic charge image developing black toner and the electrostatic charge image developing magenta toner include at least a binder resin, a colorant, a release agent, and an external additive.
<3>
The toner set according to <1> or <2>, wherein TP2 / TP1 of the electrostatic image developing magenta toner and the electrostatic image developing black toner is 1.20 or more and 2.50 or less.
<4>
The toner set according to any one of <1> to <3>, wherein TP2 / TP1 of the magenta toner for developing an electrostatic charge image is 1.28 or more and 1.49 or less.
<5>
The toner set according to any one of <1> to <4>, wherein TP2 / TP1 of the black toner for developing an electrostatic charge image is 1.45 or more and 1.77 or less.
<6>
The black toner for developing an electrostatic charge image contains carbon black, and the magenta toner for developing an electrostatic charge image contains at least one of a quinacridone dye / pigment and a monoazo dye / pigment, <1> to < The toner set according to any one of 5>.

<7>
A toner cartridge containing the toner set according to any one of <1> to <6>.
<8>
An image forming apparatus comprising the toner set according to any one of <1> to <6>.
<9>
An image forming method for forming an image using the toner set according to any one of <1> to <6>.

<10>
A toner set including at least a magenta toner for developing an electrostatic image, a cyan toner for developing an electrostatic image, a yellow toner for developing an electrostatic image, and a black toner for developing an electrostatic image. When the first measured value of the tan δ maximum value observed below is TP1, and the second measured value of the tan δ maximum value observed at 40 ° C. or more and 80 ° C. or less is TP2, the magenta toner for developing the electrostatic charge image is used. TP2 / TP1 is 0.817 times or more and 0.951 times or less of the average value of TP2 / TP1 of the cyan toner for developing electrostatic images, the yellow toner for developing electrostatic images, and the black toner for developing electrostatic images. A toner set characterized by

<11>
A tan δ maximum value observed in a rheometer at 40 ° C. or higher and 80 ° C. or lower, wherein the electrostatic image developing black toner is used in a toner set including at least an electrostatic image developing black toner and an electrostatic image developing magenta toner. The first measured value of TP1 is TP1, and the second measured value of the tan δ maximum value observed between 40 ° C. and 80 ° C. is TP2, and TP2 / TP1 of the black toner for developing electrostatic images is the electrostatic charge. A black toner for developing an electrostatic charge image, which is 1.03 times or more and 1.32 times or less of TP2 / TP1 of magenta toner for image development.
<12>
The electrostatic charge image development according to <11>, wherein TP2 / TP1 of the electrostatic charge image developing black toner is 1.13 times or more and 1.20 times or less of TP2 / TP1 of the electrostatic charge image developing magenta toner. For black toner.
<13>
The toner comprises toner base particles containing at least a core component containing a binder resin and a colorant and a high heat-resistant resin fine particle component present around the core component, and the core component and the high component when measured with a transmission electron microscope. The black toner for developing electrostatic images according to <11> or <12>, wherein the heat-resistant resin fine particle component has no shadow difference.

<14>
An electrostatic image developing magenta toner used in a toner set including at least an electrostatic image developing magenta toner, an electrostatic image developing cyan toner, an electrostatic image developing yellow toner, and an electrostatic image developing black toner, When the first measured value of the tan δ maximum value observed at 40 ° C. or higher and 80 ° C. or lower with a rheometer is TP1, and the second measured value of the tan δ maximum value observed at 40 ° C. or higher and 80 ° C. or lower is TP2, TP2 / TP1 of the electrostatic image developing magenta toner is 0.817 times the average value of TP2 / TP1 of the electrostatic image developing cyan toner, electrostatic charge image developing yellow toner, and electrostatic charge image developing black toner. A magenta toner for developing an electrostatic charge image, wherein the magenta toner is 0.951 times or more.
<15>
TP2 / TP1 of the electrostatic image developing magenta toner is 0.849 of an average value of TP2 / TP1 of the electrostatic image developing cyan toner, electrostatic image developing yellow toner, and electrostatic image developing black toner. The magenta toner for developing an electrostatic charge image according to <14>, which is not less than 2 times and not more than 0.900 times.
<16>
The toner comprises toner base particles containing at least a core component containing a binder resin and a colorant and a high heat-resistant resin fine particle component present around the core component, and the core component and the high component when measured with a transmission electron microscope. The magenta toner for developing an electrostatic charge image according to <14> or <15>, wherein the heat-resistant resin fine particle component has no shadow difference.

According to the present invention, it is possible to realize a fixing property and a high gloss property as a toner set even at low temperature fixing or high speed printing while maintaining blocking resistance, and further, magenta and black colors and It is possible to provide an electrostatic image developing black toner and an electrostatic image developing magenta toner that can express an original beautiful color gamut without differences in color density, glossiness, etc., and that can output an excellent output image. A toner set, a toner cartridge, and an image forming apparatus can be provided.
In addition, when performing high-adhesion-amount printing that prints three or more colors, it is possible to achieve good low-temperature fixability, and to express the original beautiful color gamut without any color difference as an output picture. Output image can be provided.

FIG. 1 is a conceptual view of a cross-section of a molded product when the electrostatic charge image developing black toner of the present invention is measured for the first time with a rheometer. FIG. 2 is a conceptual diagram when TP1 and TP2 are measured. FIG. 3 is a graph showing the relationship between blocking resistance (collapse load) and TP2 / TP1 of the black toner and the magenta toner used in Examples 1 to 4 and Comparative Examples 1 and 2. FIG. 4 is a graph showing the relationship between fixability (residual ratio) of the black toner and magenta toner used in Examples 1 to 4 and Comparative Examples 1 and 2, and TP2 / TP1. FIG. 5 is a diagram illustrating the relationship between the blocking resistance (collapse load) of each color toner used in Example 11 and Comparative Example 11 and TP2 / TP1. FIG. 6 is a graph showing the relationship between the fixability (remaining rate) of each color toner used in Example 11 and Comparative Example 11 and TP2 / TP1. FIG. 7 is an SEM image in which a portion of one toner of the representative toner of the present invention is enlarged. There are few thin heat-resistant resin fine particle components in the concave portions of the toner surface, and there are many such components in the convex portions. It is a figure (photograph) which shows the mode to do.

1. Measurement Method and Definition In the present invention, the one before having the external additive is referred to as “toner mother particle”. Giving an external additive to the surface of the toner base particles may be simply referred to as “external addition” or “external addition”. Those having an external additive on the surface of the toner base particles may be referred to as “electrostatic image developing toner” or simply “toner”. In addition, leaving only the color portions of “black toner for developing electrostatic image”, “magenta toner for developing electrostatic image”, “cyan toner for developing electrostatic image”, and “yellow toner for developing electrostatic image”, respectively. These may be simply referred to as “black toner” or “Bk toner”, “magenta toner” or “Ma toner”, “cyan toner” or “Cy toner”, “yellow toner” or “Ye toner”.

The rheometer measurement of the toner is carried out by the method described in the examples, and the temperature, storage elastic modulus (G ′), loss elastic modulus (G ″), tan δ (= G ″ / G ′), tan δ maximum value, “40”. TP1 which is the first measured value of the tan δ maximum value observed at -80 ° C. or higher and “TP2 which is the second measured value of the tan δ maximum value observed at 40 ° C. or higher and 80 ° C. or lower”, etc. Defined by the measurement method described in the above.
In addition, “first temperature increase” (and “second temperature increase”) in the present invention is also defined as a temperature increase during the measurement in the measurement method described in Examples and the like.
The measurement method and definition of BETN, BETF, and “BETN-BETF” are also defined as those measured by the method described in Examples and the like and measured by the measurement methods described in Examples.
The “volume average particle diameter” in the present invention means “volume median diameter (Dv ₅₀ )” measured by the method described in Examples unless otherwise specified.

The electrostatic image developing toner of the present invention is a toner having (showing) the numerical values (parameters) defined in the claims of the present application when measured by the measuring method (apparatus, setting, etc.) described in the examples and the like. It is.
That is, even when the numerical value (parameter) is measured with another device or other setting, the numerical value (parameter) is not measured when the toner itself is measured by the measuring method described in the examples and the like of the present specification. Anything that has (as shown) is included in the present invention.

Although details will be described later, the electrostatic charge image developing black toner and the electrostatic charge image developing magenta toner preferably contain at least a binder resin, a colorant, a release agent, and an external additive. In particular, the toner preferably contains toner base particles containing at least a binder resin and a colorant, and an external additive.
In addition, the toner of the present invention may include “a central portion (core) containing at least a binder resin and a colorant”, “a high heat-resistant resin fine particle component existing around the core”, and an external additive. Particularly preferred.

In any method for preparing toner base particles as described below, the high heat-resistant resin fine particle component is unevenly distributed on the surface of the toner base particles. The shape of the high heat-resistant fine particle component when it becomes a toner may be a fine particle or a thin film, and further, it may cover the core component continuously or discontinuously. However, it is preferable that the high heat-resistant resin fine particles are thinned into a flat shape and have a high coverage with respect to the amount of the high heat-resistant resin particles added. At the boundary between the thin film of the high heat-resistant resin fine particles and the surface of the core component A state having no step is more preferable, and the thin film is selectively attached to the convex portion A compared to the concave portion B on the toner surface (that is, the portion where the background of the core component is visible is a convex portion compared to the concave portion). Is less preferred).

For example, FIG. 7 is an enlarged photograph of a part of one toner of the representative toner of the present invention, and many skins appearing black (core component background) are observed in the concave portions B of the toner surface, and the convexity of the toner surface is observed. In part A, a thinned skin (high heat-resistant resin fine particle component) having no wrinkles is observed.
The conventional core-shell structure of the toner base particles of the toner is a structure in which the core is entirely covered by the shell or the core is partially covered by the shell regardless of the irregularities on the surface of the toner base particles. It was a structure that covered the surface of the core as an independent skin (in which case the shell may look like a “scab”).

When preparing toner base particles in a wet medium (aqueous and / or organic solvent as a continuous phase), high heat-resistant fine particles are added simultaneously with the core component, and the interface between the core component and the wet medium is thermodynamically added. There is a method of arranging high heat-resistant fine particles on the surface (controlling the polarity) and a method of adding high heat-resistant fine particles after the core component and physically arranging them on the surface of the core component. It is also possible to use a combination of a method of arranging in a controlled manner and a method of arranging physically (in the order of addition).

In addition, when the high heat-resistant fine particles are added after the core component, after the composition and / or shape of the core (core) component is determined (by subsequent heating, aging, stirring, etc., the core (core) The shape, physical properties, compatibility, and the like may change.
Hereinafter, the high heat-resistant resin fine particle component surrounding the core may be abbreviated as “shell”.
In a toner in which an external additive is externally added to a toner base particle, the “structure consisting of a high heat-resistant resin fine particle component and an external additive” is an object with respect to the “core” in the rheometer measurement. Conceptually important in the present invention. Hereinafter, the “structure comprising a high heat-resistant resin fine particle component and an external additive” may be simply abbreviated as “structure”.

In the present specification, all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.

2. Specification of toner for developing electrostatic image 2.1. TP2, TP1, TP2 / TP1
The black toner for developing an electrostatic image of the present invention is used in a toner set including a black toner for developing an electrostatic image and a magenta toner for developing an electrostatic image, and has a tan δ maximum observed at 40 ° C. or more and 80 ° C. or less with a rheometer. When the first measured value is TP1, and the second measured value of the tan δ maximum value observed between 40 ° C. and 80 ° C. is TP2, TP2 / TP1 of the electrostatic charge image developing black toner is It is 1.03 times or more of TP2 / TP1 of the magenta toner for developing a charge image, and preferably 1.13 times or more from the viewpoint of blocking resistance. The upper limit is 1.32 times or less, and from the viewpoint of fixability, it is preferably 1.20 times or less. Specifically, TP2 / TP1 of the black toner is 1.03 to 1.32 times, more preferably 1.13 to 1.20 times that of the magenta toner TP2 / TP1.

The magenta toner for developing an electrostatic image of the present invention is used in a toner set including at least a magenta toner for developing an electrostatic image, a cyan toner for developing an electrostatic image, a yellow toner for developing an electrostatic image, and a black toner for developing an electrostatic image. When the first measured value of the tan δ maximum value observed at 40 ° C. to 80 ° C. with the rheometer is TP1, and the second measured value of the tan δ maximum value observed at 40 ° C. to 80 ° C. is TP2. TP2 / TP1 of the electrostatic image developing magenta toner is 0.817 of an average value of TP2 / TP1 of the electrostatic charge image developing cyan toner, electrostatic charge image developing yellow toner and electrostatic charge image developing black toner. From the viewpoint of blocking resistance, it is preferably 0.849 times or more. The upper limit is 0.951 times or less, and from the viewpoint of low temperature fixability when performing high adhesion amount printing in which three or more colors are overlaid, it is preferably 0.900 times or less. Specifically, TP2 / TP1 of magenta toner is 0.817 to 0.951 times the average value of TP2 / TP1 of cyan toner, yellow toner and black toner, and is 0.849 to 0.900 times. The following is more preferable.

In magenta toner, TP2 / TP1 that can have preferable fixing property and anti-blocking property is a smaller value than other colors. Therefore, TP2 / TP1 of magenta toner is a constant ratio from the average value of TP2 / TP1 of other color toners. It is necessary to make it smaller.
In particular, when three or more colors are superimposed, setting the TP2 / TP1 of the magenta toner to a specific range provides the same fixability as the other color toners, and the difference in the glossiness of all colors including the overlaid colors. As a result, high glossiness is realized as a whole toner set, and as a result, a good image can be obtained.

TP2 / TP1 represents a change in the surface state of the toner due to heating and shearing. When TP2 / TP1 is large, the ratio of the high heat-resistant resin fine particles (components) and the external additive to form a continuous phase at the first measurement is relatively high, and the rheological behavior of the structure appears. It is estimated that G ′ is relatively large compared to G ″ (TP1 is relatively small).
On the other hand, when TP2 / TP1 is small, the ratio of the high heat-resistant resin fine particles and the external additive forming a continuous phase in the first measurement is relatively small, and the rheological behavior of the structure is difficult to appear. It is estimated that G ″ is relatively large compared to (TP1 is relatively large).

In the black toner for developing an electrostatic charge image of the present invention, it is preferable that TP2 and TP1 measured with a rheometer do not have the same value. The same applies to the magenta toner for developing an electrostatic image used in the toner set. This is considered to indicate that the structure of the toner has changed due to the heating during the first measurement, and the reason is estimated as follows.
In the first measurement, as described in the examples, the toner is not heated as much as possible and is molded into pellets having no voids between the toners as much as possible. It is presumed that a sample having a “structure comprising a heat-resistant resin fine particle component and an external additive” is measured.

Since the high heat-resistant resin fine particle component, which is a shell component having a lower molecular entanglement density than the central component (core) component of the toner base particle, forms a structure, the toner is more elastic in the first measurement. It is estimated that tan δ (TP1) is in a direction of decreasing because G ′ increases in comparison with G ″.
On the other hand, in the second measurement, the core component, the high heat-resistant resin fine particle component, and the external additive are melted and mixed as compared with the first measurement by heating and shearing during the first measurement, and a composition is formed. Is considered to be measured in an averaged state compared to the first measurement.

Therefore, the property of the core component having a higher molecular entanglement density than the high heat-resistant resin fine particles (component) is emphasized and behaves more plastically, so that G ″ is larger than G ′. TP2) is presumed to take a larger value than the value of the first measurement, that is, the rheological behavior is relatively measured the rheology of the structure at the first time and 1 at the second time. Rheology closer to the mixture is measured compared to the second measurement.

The “heating and shearing” at the first measurement with the rheometer is performed under static conditions, and the “heating and shearing” causes a small portion of toner particles (see, for example, FIG. 1). ) Is happening.

In the toner set of the present invention, the TP2 / TP1 of the magenta toner and the black toner is 1.20 or more and 2 in order to realize excellent fixability at low temperature fixing or high speed printing while maintaining blocking resistance. .50 or less is preferable.

In order to achieve excellent fixability in a high adhesion amount printing in which three or more colors are developed while maintaining low blocking resistance or at high speed printing, the black toner TP2 / TP1 of the present invention is From the viewpoint of easily ensuring blocking resistance, it is preferably 1.45 or more, more preferably 1.50 or more, further preferably 1.52 or more, and 1.53 or more. Is particularly preferred.
Further, from the viewpoint of easily ensuring low-temperature fixability (tape peeling residual rate), TP2 / TP1 of the black toner of the present invention is preferably 1.77 or less, and more preferably 1.69 or less. 1.64 or less, more preferably 1.60 or less, and most preferably 1.55 or less. Specifically, the TP2 / TP1 of the black toner is preferably 1.45 or more and 1.77 or less.

On the other hand, TP2 / TP1 of the magenta toner is preferably 1.21 or more, more preferably 1.28 or more, and more preferably 1.32 or more from the viewpoint of easily ensuring blocking resistance. More preferably, it is particularly preferably 1.33 or more.
Further, from the viewpoint of easily ensuring low temperature fixability, it is preferably 1.54 or less, more preferably 1.49 or less, further preferably 1.46 or less, and 1.41 or less. It is particularly preferred. Specifically, TP2 / TP1 of magenta toner is more preferably 1.28 or more and 1.49 or less. The low temperature fixability can be evaluated by the tape peeling residual rate.

TP2 / TP1 of the cyan toner is preferably 1.42 or more and more preferably 1.47 or more from the viewpoint of easily ensuring blocking resistance.
Further, from the viewpoint of easily ensuring low-temperature fixability, it is preferably 1.86 or less, and more preferably 1.76 or less.

The TP2 / TP1 of the yellow toner is preferably 1.35 or more and more preferably 1.41 or more from the viewpoint of easily ensuring blocking resistance.
Further, from the viewpoint of easily ensuring low temperature fixability, it is preferably 1.74 or less, and more preferably 1.68 or less.

It is important to eliminate the difference in blocking resistance and fixing property for each color as a toner set. Even if it is outside the preferable range of TP2 / TP1, blocking resistance can be achieved by devising a packaging method for transportation. It can be implemented in use, and the low-temperature fixability can be temporarily improved by increasing the pressure of the fixing device and extending the nip time.
However, by adjusting TP2 / TP1 to the above-described preferable value, it is possible to eliminate excessive packaging, or to reduce the load on the fixing device and suppress deterioration of the fixing device.

The black toner and magenta toner in which TP2 / TP1 is in this range are in a state where the high heat-resistant resin fine particle component is thinly present in a state of covering the surface of the toner base particles, and an external additive is added to the outside thereof. Furthermore, the fine heat-resistant resin fine particle component and the core component are constituted with an exquisite polarity balance in which the second measurement is more compatible with the second measurement than the first measurement.
For example, if the core component and the high heat-resistant resin fine particle component are completely different chemical components, or the high heat-resistant resin fine particle component is an extremely high Tg component such as a salt, before and after the first measurement with a rheometer, TP2 / TP1 approaches 1 because no structural change occurs (for example, incompatible).

Since the above structure is formed of the high heat-resistant resin fine particle component and the external additive, it is important to measure the toner, not the toner base particles.
The control means of TP2 / TP1 includes the following. In order to increase TP2 / TP1, for example, the polarity difference between the core component and the high heat-resistant resin fine particle component is increased (when the high heat-resistant resin fine particle and the core component are adhered in water, Designed with a large polarity to make it more hydrophilic), increase the molecular weight of high heat resistant resin fine particles, increase the crosslink density of high heat resistant resin fine particles, increase the amount of high heat resistant resin fine particles added, The coverage of the core component in (component) is increased (the polarity difference between the core component and the high heat-resistant resin fine particle component so as to make it a thin film or not enter the core component even with the same added amount). In order to reduce TP2 / TP1, the reverse design may be performed.

The TP1 of the black toner indicating the formation state of the structure is preferably 1.37 or more, more preferably 1.46 or more, and further preferably 1.55 or more from the viewpoint of blocking resistance. The TP1 of the black toner is preferably 1.70 or less, more preferably 1.63 or less, from the viewpoint of fixability.
The TP1 of the magenta toner is preferably 1.29 or more from the viewpoint of blocking resistance, more preferably 1.41 or more, and further preferably 1.53 or more. Further, the TP1 of the magenta toner is preferably 1.90 or less, more preferably 1.74 or less from the viewpoint of fixability.

Further, if TP2 / TP1 of the black toner is within the above range with respect to TP2 / TP1 of the magenta toner, the output picture (especially in terms of performance such as fixing property and gloss property) is magenta and black. An original beautiful color gamut without difference can be expressed, and an excellent output image can be obtained.

2.2. BETN, BETF, “BETN-BETF”
“BETN-BETF” is obtained by removing the external additive from the toner to expose the surface of the toner base particles, and then measuring the specific surface area of the toner base particles. The BET specific surface area represented by BETN is a numerical value that captures all of the particle size and circularity of the toner base particles and the minute irregularities on the surface. On the other hand, the specific surface area measured by the flow type particle analyzer represented by BETF is calculated because the particle size and circularity of the toner base particles are calculated by image analysis taken at a coarse resolution, and the surface area is calculated from these values. The surface area excluding the minute unevenness value. Therefore, the difference between BETN and BETF is estimated to represent the minute irregularities on the surface of the toner base particles, and the larger the “BETN−BETF”, the larger the minute irregularities.

A small BETN-BETF indicates that the surface of the toner base particles is almost smooth. In this case, the low temperature fixability is not impaired by the heat insulating action of the air intervening in the minute irregularities, and the high heat resistant resin fine particles are unnecessarily formed on the outer side of the toner. Therefore, low-temperature fixability and high gloss properties are improved because less heat energy is required to melt the portion.
On the other hand, when BETN-BETF is large, it indicates that fine irregularities are formed on the surface of the toner base particles, and the high heat-resistant resin fine particles (components) do not become too thin and can maintain heat resistance, or Further, since the high heat-resistant resin fine particles (components) have a structure in which they do not excessively sink into the central portion of the toner, the blocking resistance is improved.
Therefore, in order to balance “blocking resistance” with “high gloss and low temperature fixability” in an advanced region, it is particularly preferable that “BETN-BETF” is in an appropriate range.

The BET specific surface area and the specific surface area measured with a flow particle analyzer are measured using the toner base particles obtained by removing the external additive from the toner after the external addition, not the toner base particles before the external addition. It has been found in the present invention that it is important to control the difference. As will be described later, since the shape of the high heat-resistant resin fine particles is changed by the external addition, the toner used in the printer and the copying machine is an external addition product. Therefore, the surface structure of the toner base particles after the external addition is the toner performance. Estimated to be related.

Black toner, BETN-BETF toner comprising magenta toner of the present invention is preferably at least 0.54 m ² / g, more preferably not less than ^{^{0.77m 2 / g, 0.99m 2 /}} g or more is particularly preferable. Further, BETN-BETF is preferably 1.56 ² / g or less, more preferably 1.51 m ² / g, and particularly preferably 1.45 m ² / g.
When BETN-BETF is small, low-temperature fixability and high gloss tend to be improved. When BETN-BETF is large, the blocking resistance tends to be improved.

The means for controlling BETN-BETF include the following. In order to increase BETN-BETF, it is necessary to increase the minute surface irregularities. For example, in order to prevent the embedding of the high heat-resistant resin fine particles, the core component that increases the particle diameter of the high heat-resistant resin fine particles Increase the polarity difference between the high heat-resistant resin fine particle components (when attaching the high heat-resistant resin fine particles and the core component in water, the polarity of the high heat-resistant resin fine particles is designed to be more hydrophilic than the core component). For example, it is not heated above the Tg of the fine particles.

Further, when externally adding to the toner base particles, the temperature is lowered, the time is shortened, the rotational speed of the stirring blade is decreased, and so on, so that the high heat-resistant resin fine particles are embedded in the core component and / or excessively. It is also effective to prevent stretching. Also, the BETN-BETF can be increased by increasing the addition amount of the high heat-resistant resin fine particles. On the other hand, when BETN-BETF is reduced, the reverse design may be performed.

2.3. Glass transition temperature (Tg)
Furthermore, Tg measured with a differential scanning calorimeter (DSC) of the toner is also important from the viewpoint of realizing excellent fixability even during low-temperature fixing or high-speed printing while maintaining blocking resistance. The glass transition temperature (Tg) range of the black toner and the magenta toner is preferably 44 ° C. or less, more preferably 43 ° C. or less, and further preferably 42 ° C. or less. The Tg range is preferably 34 ° C. or higher, more preferably 36 ° C. or higher, and still more preferably 38 ° C. or higher. “Glass transition temperature (Tg)” may be simply abbreviated as “Tg”. Tg in the present invention is measured by the method described in Examples. It is detected by the second heating measurement of DSC.

By adjusting the Tg of the black toner and the magenta toner within this range, a more preferable low-temperature fixability is obtained while maintaining blocking resistance within the range in which the TP2 / TP1 of the obtained toner is adjusted to the above-described suitable range. be able to.
This is because the anti-blocking property can be supplemented by increasing the Tg of the toner, and the low-temperature fixability can be adjusted to a more preferable range by decreasing the Tg of the toner.

As a method for increasing the Tg of the toner, the copolymerization ratio of the monomer component having a high Tg is increased, the molecular weight (Mc) component that is not more than twice the molecular weight between the entanglement points is decreased (the molecular weight modifier or the like is decreased, And a plasticizer having a melting point of 100 ° C. or lower (for example, wax or crystalline resin) for plasticizing the binder resin. On the other hand, in order to lower the Tg of the toner, the reverse design may be performed. The “monomer component having a high Tg” refers to a monomer having a high Tg of a homopolymer produced using the same.

2.4. Composition of toner base particles 2.4.1. Core (central part) component The toner base particles are formed by coating high-heat-resistant resin fine particles on "a core component containing at least a binder resin (for example, polymer primary particles) and a colorant".
The high heat-resistant resin fine particles may contain a charge control agent or the like if necessary, and it is preferable that a wax is contained from the viewpoint of preventing offset on the high temperature side. It is more preferable that it is contained in a state of being substantially encapsulated with components since problems caused by wax release such as filming can be solved.

In order to make the wax substantially encapsulated with the high heat resistant resin component, there is a method of polymerizing, precipitating or agglomerating the binder resin on the surface of the wax in the presence of wax particles in water and / or an organic solvent. Can be mentioned.
The binder resin is not particularly limited as long as it is generally used as a binder resin in the production of toner. For example, polystyrene resin, poly (meth) acrylic resin, polyolefin resin, epoxy resin Examples thereof include thermoplastic resins such as resins and polyester resins, and mixtures of these resins.

As the monomer component used for producing the binder resin, a monomer generally used in producing a toner binder resin can be appropriately used.
For example, a polymerizable monomer having an acidic group (hereinafter sometimes simply referred to as an acidic monomer), a polymerizable monomer having a basic group (hereinafter simply referred to as a basic monomer). Any polymerizable monomer of a polymerizable monomer having neither an acidic group nor a basic group (hereinafter sometimes referred to as other monomer) can be used.

When a polystyrene resin and a poly (meth) acrylic resin are used as the binder resin, the following monomers are exemplified.
Examples of the acidic monomer include a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid; a polymerizable monomer having a sulfonic acid group such as sulfonated styrene; Polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide; and the like.

Examples of basic monomers include aromatic vinyl compounds having an amino group such as aminostyrene; nitrogen-containing heterocyclic-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone; amino acids such as dimethylaminoethyl acrylate and diethylaminoethyl methacrylate. (Meth) acrylic acid ester having a group; These acidic monomers and basic monomers contribute to the dispersion stabilization of the toner base particles. It may be used singly or as a mixture of plural kinds, and may exist as a salt with a counter ion.

Further, the acidic monomer and the basic monomer may be contained in one or both of the central part (core) component of the toner base particles and the high heat-resistant resin fine particles. The "resin component consisting of a binder resin and an acidic or basic monomer" and the "resin component consisting of a binder resin and an acidic or basic monomer" that constitute the high heat-resistant resin fine particles have the same composition. Preferably not.
This is because the high heat-resistant resin fine particle component and the core component described above need to be configured with an exquisite balance that the second measurement is more compatible than the first measurement of tan δ. This is particularly important in the present invention in the sense of adjusting to an appropriate affinity.

In addition, regarding the acid value (base value) depending on the addition amount of the acidic (or basic) monomer, in the case where toner base particles are produced by adhering highly heat-resistant resin fine particles to the core component in water, the toner It is preferable to increase the acid value (base number) of the high heat-resistant resin fine particles compared to the core (center part) component of the mother particle. Specifically, the acid value (base number) of the high heat-resistant resin fine particles is set to the acid of the core component. It is preferable to adjust it to 1.1 times or more and 2.8 times or less of the valence (base number). If this magnification is too small, the high heat resistant resin fine particles may be buried in the core component, and satisfactory blocking resistance may not be obtained. If this magnification is too large, the high heat resistant resin in water compared to the core component. This is because the fine particles are too stable and do not adhere.

Other monomers include styrenes such as styrene, methyl styrene, chlorostyrene, dichlorostyrene, pt-butyl styrene, pn-butyl styrene, pn-nonyl styrene; methyl acrylate, acrylic acid Acrylic esters such as ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate Methacrylic acid esters such as isobutyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl methacrylate; acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N, - acrylamides such as dibutyl acrylamide; and the like. “Other monomers” may be used alone or in combination.

When the binder resin is a cross-linked resin, a polyfunctional monomer is used together with the above-mentioned polymerizable monomer. For example, divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Examples include dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, diallyl phthalate, and the like.

Among them, a bifunctional polymerizable monomer is preferable, and divinylbenzene, hexanediol diacrylate, and the like are particularly preferable. These polyfunctional polymerizable monomers may be used alone or as a mixture of plural kinds.
In addition, a polymerizable monomer having a reactive group in a pendant group, for example, glycidyl methacrylate, methylol acrylamide, acrolein, or the like can be used.

A known chain transfer agent can be used as necessary. Specific examples of the chain transfer agent include t-dodecyl mercaptan, dodecanethiol, diisopropyl xanthogen, carbon tetrachloride, trichlorobromomethane and the like. The chain transfer agent may be used alone or in combination of two or more kinds, and is preferably 0 to 5% by mass with respect to the polymerizable monomer.

When polystyrene resin and poly (meth) acrylic resin are used as the binder resin, the number average molecular weight in gel permeation chromatography (hereinafter referred to as GPC) is preferably 5000 or more, more preferably 8000 or more, More preferably, it is 10,000 or more, preferably 40,000 or less, more preferably 30,000 or less, and still more preferably 20,000 or less. The weight average molecular weight is preferably 30,000 or more, more preferably 50,000 or more, preferably 300,000 or less, more preferably 250,000 or less.

When a polyester resin is used as the binder resin, examples of the divalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Diols such as neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A Bisphenol A alkylene oxide adducts such as;

Examples of the divalent acid include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malon Acids, anhydrides or lower alkyl esters of these acids; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid and n-dodecyl succinic acid; and other divalent organic acids.

When the binder resin is a cross-linked resin, a polyfunctional monomer is used together with the above-described dihydric alcohol and acid. For example, as a trihydric or higher polyhydric alcohol, for example, sorbitol, 1, 2, 3, 6 -Hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, and the like.

Examples of the trivalent or higher acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7, Examples include 8-octanetetracarboxylic acid, anhydrides thereof, and the like.

In addition, regarding the acid value of the polyester-based resin, when the high heat-resistant resin fine particles are adhered to the core component in water, the acid value of the high heat-resistant resin fine particles is higher than that of the core (center) component of the toner base particles. More preferably, the acid value of the high heat-resistant resin fine particles is preferably adjusted to 1.1 times or more and 2.8 times or less of the acid value of the core component.
If this magnification is large, the high heat-resistant resin fine particles are less likely to be embedded in the core component, so that satisfactory blocking resistance is obtained. If this magnification is small, the high heat-resistant resin fine particles are more stable in water than the core component. It does not become too much, and the high heat-resistant resin fine particles tend to adhere well to the core component.

These polyester resins can be synthesized by a usual method. Specifically, conditions such as reaction temperature (170 to 250 ° C.), reaction pressure (5 mmHg to normal pressure) and the like are determined according to the reactivity of the monomer, and the reaction is terminated when predetermined physical properties are obtained. .
When a polyester resin is used as the binder resin, the number average molecular weight in GPC is preferably 2000 to 20000, and more preferably 3000 to 12000.

It is preferable to use a wax as an anti-offset agent and to improve low-temperature fixability.
As the wax used in the toner of the present invention, known waxes can be arbitrarily used. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and copolymerized polyethylene; paraffin wax; behenic acid Ester wax having a long chain aliphatic group such as behenyl, montanate ester, stearyl stearate; plant wax such as hydrogenated castor oil, carnauba wax; ketone having a long chain alkyl group such as distearyl ketone; Silicone having higher fatty acid such as stearic acid; long chain fatty acid (pentaerythritol, trimethylolpropane, glycerin, etc.) polyhydric alcohol ester or partial ester thereof; higher fatty acid amide such as oleic acid amide, stearic acid amide, etc. Exemplified
Preferred examples include hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax; ester waxes; silicone waxes. Among them, ester waxes are more preferable, monoester waxes mainly containing hydrocarbons having 18 and / or 22 carbon atoms are more preferable, behenyl behenate, stearyl behenate, behenyl stearate, and the like. The inclusion is most preferred. Waxes may be used alone or in combination.

The melting point peak of wax (the endothermic peak top at the time of DSC second heating of the toner) is preferably 90 ° C. or less, more preferably 80 ° C. or less, further preferably 75 ° C. or less, preferably 50 ° C. or more, and more preferably 60 ° C. or more. Preferably, 65 degreeC or more is more preferable. When the melting point peak temperature of the wax is high, blocking resistance tends to be improved, and when the melting point peak of the wax is low, low temperature fixability and high gloss property tend to be improved.

The difference between the melting point peak of the wax and the onset temperature of the wax (intersection temperature of the tangent at the first inflection point appearing before the endothermic peak and the baseline before the endothermic peak in the second DSC of the toner) is 10 ° C. or less. Preferably, it is 8 ° C. or lower, more preferably 4 ° C. or lower.
The onset temperature of the wax is preferably 86 ° C. or lower, more preferably 76 ° C. or lower, still more preferably 71 ° C. or lower, 46 ° C. or higher, more preferably 56 ° C. or higher, and even more preferably 61 ° C. or higher. When the onset temperature is low, the low-temperature fixability and the high gloss property tend to improve, and when the onset temperature is high, the blocking resistance tends to improve.

The amount of wax is preferably 1 part by mass or more with respect to 100 parts by mass of toner, more preferably 2 parts by mass or more, and still more preferably 5 parts by mass or more. Moreover, it is preferable that it is 35 mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 25 mass parts or less.

A known colorant can be arbitrarily used as the colorant. Specific examples of the colorant include carbon black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dye, chrome yellow, quinacridone dye, benzidine yellow, rose bengal, triallylmethane dye, Known arbitrary dyes such as monoazo dyes, disazo dyes, and condensed azo dyes can be used alone or in combination.

In the case of a full-color toner, yellow is a benzidine yellow, monoazo and / or condensed azo dye; magenta is a quinacridone and / or monoazo dye; cyan is a phthalocyanine dye; black Is preferably carbon black;

Specifically, as cyan, C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15: 4, yellow includes C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, a C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 185 and magenta include C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment Red 5 and C.I. I. Pigment red 122, C.I. I. Pigment Red 209, C.I. I. And CI Pigment Red 269 (238).
Examples of magenta toner include C.I. I. Pigment red 269 (238) and / or C.I. I. It is preferable to use CI Pigment Red 122.

In this embodiment, the black toner preferably contains carbon black, and the magenta toner preferably contains at least one of a quinacridone dye or pigment.

The colorant is preferably used in an amount of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner.

Any known charge control agent can be used. Specific examples of charge control agents include nigrosine dyes, amino group-containing vinyl copolymers, quaternary ammonium salt compounds, polyamine resins and the like for positive chargeability, and chromium, zinc, iron and cobalt for negative chargeability. And metal-containing azo dyes containing metals such as aluminum, salts of salicylic acid or alkylsalicylic acid with the aforementioned metals, metal complexes, and the like.
The amount of the charge control agent is preferably 0.1 to 25 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the toner.
The charge control agent may be mixed inside the toner base particles, or may be used in a form adhered to the surface of the toner base particles.

2.4.2. Components of high heat resistant resin fine particles The toner base particles are preferably composed of the core and high heat resistant resin fine particles present around the core.
In addition, if necessary, the core and / or the high heat-resistant resin fine particles may contain a wax, a charge control agent and the like. The core and / or the high heat resistant resin fine particles preferably contain a wax.
Examples of the type of “high heat resistant resin fine particle component” that is a component of the high heat resistant resin fine particles include the above-mentioned resins that are generally used as a binder resin when a toner is produced. Although the kind of resin is not specifically limited, For example, thermoplastic resins, such as a polystyrene-type resin, a poly (meth) acrylic-type resin, a polyolefin-type resin, an epoxy-type resin, a polyester-type resin, the mixture of these resins, etc. are mentioned. Detailed resin selection will be described later.

2.5. Toner Form The lower limit of the volume average particle diameter of the toner of the present invention is preferably 3 μm or more, and more preferably 5 μm or more. The upper limit is preferably 8 μm or less, and more preferably 6 μm or less.
Further, the shape is such that the average circularity measured using a flow particle image analyzer FPIA-3000 is preferably 0.92 or more, more preferably 0.95 or more, still more preferably 0.97 or more, Is 0.99 or less.
When the average circularity is large, it is difficult to cause a decrease in image density due to deterioration of charging due to poor adhesion of the external additive to the toner base particles.

3. Production of Toner for Developing Electrostatic Image The toner of the present invention may be produced by any known method in a large production method classification, and is not particularly limited.

3.1. Preparation method of toner mother particles 3.1.1. Method of aggregating particles smaller than toner base particles to produce toner base particles A method of preparing toner base particles by preparing each raw material as particles smaller than the toner base particle size, and mixing and aggregating them can be used. .

3.1.1.1. Emulsion polymerization A method of preparing a binder resin as “polymer primary particles” smaller than the toner base particle size and obtaining a dispersion of the polymer primary particles is described below.
Also, the same method can be used for the production of the high heat-resistant resin fine particles.
Polymer primary particles having a styrene or (meth) acrylic monomer as a constituent element can be obtained by emulsion polymerization of the monomer composition and, if necessary, a chain transfer agent using an emulsifier. Known emulsifiers can be used, but one or more emulsifiers selected from cationic surfactants, anionic surfactants, and nonionic surfactants can be used in combination.

Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.
Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.

Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose Etc.

The amount of the emulsifier used is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. When the amount of the emulsifier used is increased, the particle size of the obtained polymer primary particles is reduced, and when the amount used is reduced, the particle size of the obtained polymer primary particles is increased. Moreover, 1 type, or 2 or more types, such as partially or fully saponified polyvinyl alcohol, such as polyvinyl alcohol, cellulose derivatives, such as a hydroxyethyl cellulose, can be used together with these emulsifiers as a protective colloid.

Further, a known polymerization initiator can be used alone or in combination of two or more as required. For example, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and redox initiators combining these persulfates as a component with a reducing agent such as acidic sodium sulfite, hydrogen peroxide, 4, 4 ′ -Water-soluble polymerization initiators such as azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydroperoxide, etc., and redox initiators combining these water-soluble polymerization initiators with reducing agents such as ferrous salts Benzoyl peroxide, 2,2′-azobis-isobutyronitrile and the like are used. These polymerization initiators may be added to the polymerization system before, simultaneously with, or after the addition of the polymerizable monomer, and these addition methods may be combined as necessary.

In order to disperse the wax with a suitable dispersed particle size in the toner, it is preferable to use so-called seed polymerization in which the wax is added as a seed during emulsion polymerization. By adding as a seed, the wax is finely and uniformly dispersed in the toner, so that deterioration of the chargeability and heat resistance of the toner can be suppressed.
Also, a wax / long-chain polymerizable monomer dispersion prepared by previously dispersing a wax in a water-based dispersion medium with a long-chain polymerizable monomer such as stearyl acrylate is prepared. The polymerizable monomer can also be polymerized in the presence of.
Emulsion polymerization is possible using a colorant as a seed, but if a polymerizable monomer is polymerized in the presence of the colorant, the metal in the colorant affects radical polymerization, making it difficult to control the molecular weight and rheology of the resin. Therefore, it is preferable to add the colorant dispersion in the next step without adding the colorant during the emulsion polymerization.

3.1.1.2. Method of emulsifying resin After obtaining the resin by a method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., the resin is mixed with an aqueous medium, and the temperature is higher than either the melting point of the resin or the glass transition temperature. The polymer primary particles are obtained by heating to a low viscosity and emulsifying by applying shearing force.
Examples of the emulsifier for applying a shearing force include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. If the viscosity of the resin during emulsification is high and does not decrease to the desired particle size, increase the temperature using an emulsifier capable of pressurization to atmospheric pressure or higher, and emulsify with the resin viscosity lowered to obtain the desired particle size. Polymer primary particles having a diameter can be obtained.

As another method, a method of reducing the viscosity of the resin by mixing an organic solvent in advance with the resin may be used. The organic solvent to be used is not particularly limited as long as it dissolves the resin, but a ketone solvent such as tetrahydrofuran (THF), methyl acetate, ethyl acetate, and methyl ethyl ketone, and a benzene solvent such as benzene, toluene, and xylene. Etc. can be used. Furthermore, an alcohol solvent such as ethanol or isopropyl alcohol may be added to water or resin for the purpose of improving the affinity with an aqueous medium and controlling the particle size distribution. When an organic solvent is added, it is necessary to remove the organic solvent from the emulsion after the emulsification is completed. As a method of removing the organic solvent, there is a method of volatilizing the organic solvent while reducing the pressure at room temperature or under heating. Further, for the purpose of controlling the particle size distribution, a salt such as sodium chloride or potassium chloride, ammonia or the like may be added.

Emulsifiers and dispersants may be added for the purpose of controlling the particle size distribution. Examples include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; the emulsifiers described above; inorganic compounds such as tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, and barium carbonate. . The amount used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin.

When a resin containing an acidic group or a basic group is used, the amount of emulsifier or dispersant added can be reduced, but the hygroscopicity of the resin increases and the chargeability may deteriorate.
Further, a phase inversion emulsification method may be used. In the phase inversion emulsification method, an organic solvent, a neutralizing agent, and a dispersion stabilizer are added to the resin as necessary, and an aqueous medium is added dropwise with stirring to obtain emulsified particles. In this method, an organic solvent is removed to obtain an emulsion. As the organic solvent, the same organic solvents as those described above can be used. As the neutralizing agent, general acids such as nitric acid, hydrochloric acid, sodium hydroxide and ammonia, and alkalis can be used.

3.1.1.3. Formation of toner mother particles by aggregation and ripening In any of the above preparation methods for emulsion polymerization and resin emulsification, the volume average particle diameter of the obtained polymer primary particles is usually 0.02 μm or more, preferably 0.05 μm. Above, particularly preferably 0.1 μm or more, usually 3 μm or less, preferably 2 μm or less, particularly preferably 1 μm or less.
When the volume average particle diameter of the polymer primary particles is equal to or more than the lower limit value, it is easy to control the aggregation speed in the aggregation process. On the other hand, if it is not more than the above upper limit value, the particle size of the toner base particles obtained by agglomeration is hardly increased, and it becomes easy to obtain the toner base particles having a target particle size.

In the aggregation step, the polymer primary particles, the colorant particles, the charge control agent to be blended as necessary, and the wax are mixed simultaneously or sequentially. First, a dispersion of each component, that is, a polymer primary particle dispersion, a colorant particle dispersion, a charge control agent dispersion and a wax fine particle dispersion, if necessary, are mixed and mixed to obtain a dispersion mixture. It is preferable from the viewpoint of the uniformity of the composition and the uniformity of the particle diameter.

The colorant is preferably used in the state of being dispersed in water in the presence of an emulsifier, and the volume average particle diameter of the colorant particles is preferably 0.01 μm or more, particularly preferably 0.05 μm or more, preferably 3 μm. Hereinafter, it is particularly preferably 1 μm or less.
In the aggregating step, agglomeration is usually performed in a tank equipped with a stirrer, and there are a heating method, a method of adding an electrolyte, and a method of combining them. When polymer primary particles are aggregated with stirring to obtain particle aggregates of the desired size, the particle size of the particle aggregate is controlled from the balance between the cohesive force between the particles and the shearing force by stirring. However, the cohesive force can be increased by heating or adding an electrolyte.

In the case of performing aggregation by adding an electrolyte, the electrolyte may be any of acid, alkali, and salt, and may be either organic or inorganic. Specifically, the acid may be hydrochloric acid, nitric acid, sulfuric acid, citric acid, or the like. Acid, etc .; alkali, sodium hydroxide, potassium hydroxide, ammonia water, etc .; salt, NaCl, KCl, LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO ₄ , MgCl ₂ , CaCl ₂ , MgSO ₄ , CaSO ₄ , ZnSO ₄ , Al ₂ (SO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , CH ₃ COONa, C ₆ H ₅ SO ₃ Na, and the like.
Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

The amount of electrolyte added varies depending on the type of electrolyte, the target particle size, etc., but is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the solid component of the mixed dispersion. preferable. Further, it is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less.

When the amount of the electrolyte added is large, the progress of aggregation is accelerated, fine particles of 1 μm or less do not remain even after aggregation, and the average particle size of the obtained particle aggregate easily reaches the target particle size. On the other hand, when the addition amount is small, rapid agglomeration hardly occurs and the particle size can be easily controlled, and the obtained agglomerated particles do not easily contain coarse powder or irregular shapes.
The aggregation temperature in the case of performing aggregation by adding an electrolyte is preferably 20 ° C. or higher, particularly preferably 30 ° C. or higher, preferably 70 ° C. or lower, particularly preferably 60 ° C. or lower.

The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale. In order to reach the target particle size, the toner base particles must be held at the predetermined temperature for at least 30 minutes. Is preferred. The temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.
The timing of adding the high heat-resistant resin fine particles may be any timing, may be charged simultaneously with the raw material of the core component (for example, polymer primary particles, pigment, wax, etc.), or a part of the raw material of the core component or You may add, after making all aggregate.

When the core component and the high heat-resistant resin fine particles are charged at the same time, if the polarity of the high heat-resistant fine particles is designed to be thermodynamically intermediate between the core component and the medium (for example, water), High heat-resistant resin fine particles are attached around.
When the high heat-resistant resin fine particles are adhered in a wet medium such as water and / or an organic solvent, the composition of the raw material of the core component is determined (the toner base particles are produced by aggregating particles smaller than the toner base particles) In some cases, it is preferable to add the high heat-resistant resin fine particles after agglomerating a part or all of the core component) from the viewpoint of arranging the high heat-resistant fine particles on the surface of the core component.

Examples of the composition and preparation method of the high heat-resistant resin fine particles include those described above. The addition may be performed once or a plurality of times. The first heat-resistant resin fine particles and the high heat-resistant resin fine particles from the next time may be different or any combination.
In order to increase the stability of the particle aggregate obtained in the aggregation step, it is preferable to perform fusion in the aggregated particles in the aging step after the aggregation step. The temperature of the ripening step is preferably not less than Tg of the polymer primary particles, more preferably not less than 5 ° C higher than Tg of the polymer primary particles, and preferably not more than Tg of the high heat-resistant resin fine particles, more preferably high The temperature is 5 ° C. or lower than the Tg of the heat-resistant resin fine particles. The time required for the ripening step varies depending on the shape of the intended toner base particles, but preferably reaches 0.1 to 10 hours, particularly preferably 0.5 to 5 after reaching the Tg or more of the polymer primary particles. It is desirable to keep the time.

It is preferable to add a surfactant, adjust pH, or use both in combination after the agglomeration step, preferably before the aging step or during the aging step. As the surfactant used here, one or more emulsifiers that can be used in producing the polymer primary particles can be selected and used, and particularly used when the polymer primary particles are produced. It is preferable to use the same emulsifier.

The addition amount in the case of adding the surfactant is not limited, but is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably with respect to 100 parts by mass of the solid component of the mixed dispersion. Is 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.
After the aggregation process, before the completion of the aging process, by adding a surfactant or adjusting the pH, aggregation of the particle aggregates obtained in the aggregation process can be suppressed. The generation of coarse particles may be suppressed.
By controlling the time of the aging process, various types of toner can be used depending on the purpose, such as a cocoon shape that maintains the shape of the aggregated polymer primary particles, a potato type that has advanced fusion, and a spherical shape that has undergone further fusion. Mother particles can be produced.

3.1.2. Method for producing particles of toner mother particle size by atomization After mixing the respective raw materials, the mixture is atomized to the size of toner mother particles, and high heat resistant resin fine particles are added before and after the atomization, thereby adding toner mother particles. A method of obtaining particles can be used.

3.1.2.1. Method for preparing toner mother particles by suspension polymerization In the same styrene-based or (meth) acrylic monomer as described above, a colorant, a polymerization initiator, and, if necessary, a wax, a polar resin, a charge control agent, An additive such as a cross-linking agent is added to prepare a monomer composition that is uniformly dissolved or dispersed.
This monomer composition is dispersed in an aqueous medium containing a suspension stabilizer or the like as necessary. Granulation is performed by adjusting the stirring speed and time so that the droplets of the monomer composition have the desired toner base particle size. Thereafter, by the action of the dispersion stabilizer, the toner base particles can be obtained by performing polymerization by stirring to such an extent that the particle state is maintained and the sedimentation of the particles is prevented.

Specific examples of the suspension stabilizer include calcium phosphate, magnesium phosphate, calcium hydroxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more, and an amount of 1 part by mass or more and 10 parts by mass or less is preferable with respect to 100 parts by mass of the polymerizable monomer. The suspension stabilizer may be added to the polymerization system before, simultaneously with, or after the addition of the polymerizable monomer, and these addition methods may be combined as necessary.

When the monomer composition contains a polar resin such as polyester resin or carboxyl group-containing styrene resin, the monomer composition is dispersed in an aqueous medium to form droplets. Easy to move to the vicinity of the droplet surface. By carrying out the polymerization in this state, toner mother particles having a difference in composition between the inside and the surface can be obtained. For example, if a polar resin having a Tg higher than the Tg after polymerization of the monomer is selected, a structure in which the Tg inside the toner base particles is low and a high Tg resin exists on the surface is obtained. . In the present invention, the blocking resistance of the toner obtained by coating the core component with the high heat-resistant resin fine particles is enhanced. However, if this method is used in combination, it becomes easier to obtain good blocking resistance.

The timing for adding the high heat-resistant resin fine particles may be any timing. For example, the high heat-resistant resin fine particles are dissolved in the monomer composition and then dispersed in an aqueous medium so that the high heat-resistant resin fine particles are thermodynamic. In particular, the polarity of the high heat-resistant resin fine particles can be designed so as to come to the interface between the core component and water.
Further, after dispersing the monomer composition of the core component, high heat-resistant resin fine particles may be added, or the monomer composition of the core component may be dispersed and the polymerizable monomer of the core component may be dispersed. The high heat-resistant resin fine particles may be added after polymerizing part or almost all. From the viewpoint of disposing the high heat-resistant fine particles on the surface of the core component, it is preferable to polymerize a part of the polymerizable monomer and then add the high heat-resistant resin fine particles. It is more preferable to add the high heat-resistant resin fine particles after polymerizing all.

Examples of the composition and preparation method of the high heat resistant resin fine particles include those described above. The addition may be performed once or a plurality of times. The first high heat-resistant resin fine particles and the next high heat-resistant resin fine particles may be different or any combination. In addition, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

3.1.2.2. Method for producing toner mother particles by dissolution suspension An oil-based dispersion in which at least a binder resin and a colorant and, if necessary, a wax and a charge control agent are dissolved or dispersed in an organic solvent is prepared, and this is used as an aqueous medium. Disperse in. Thereafter, the organic solvent is removed from the dispersion to obtain toner mother particles. The high heat-resistant fine particles may be added in advance to the oil-based dispersion, may be added after being dispersed in an aqueous medium, or may be added after removing the organic solvent.

Examples of the composition and preparation method of the high heat-resistant resin fine particles include those described above. The addition of the high heat-resistant resin fine particles may be performed once or a plurality of times. The first heat-resistant resin fine particles and the high heat-resistant resin fine particles from the next time may be different or any combination.
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. If necessary, a dispersant can be used. The use of a dispersant is preferable because the particle size distribution becomes sharp and the dispersion is stable. As the dispersant, the same emulsifiers as those used in the above emulsion polymerization can be used. In addition, various hydrophilic polymer substances that form a polymeric protective colloid in an aqueous medium can be present.

In addition, in order to control the particle size of the high heat-resistant resin fine particles, inorganic fine particles and / or polymer fine particles can be used. As the inorganic fine particles, various conventionally known inorganic compounds that are insoluble or hardly soluble in water are used. Examples of such materials include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite. Here, the polymer fine particles may be regarded as the high heat-resistant resin fine particles.

When the oil dispersion is dispersed in an aqueous medium, a known dispersing machine such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, or an ultrasonic wave can be applied as a dispersing device.
An oil-based dispersion liquid may be prepared using a prepolymer having a reactive group instead of the binder resin, and after dispersing in an aqueous medium, the reactive group may be reacted to extend the resin. In this method, since the prepolymer has a relatively low molecular weight, it is difficult to increase the viscosity of the oil-based dispersion, and the dispersion in an aqueous medium becomes easy.

In order to facilitate the uniform dispersion of the colorant in the oily dispersion, the colorant may be prepared in advance as a master batch combined with a resin, and this may be dispersed in an organic solvent.
As a method of removing the organic solvent, there is a method of volatilizing the organic solvent while reducing the pressure at room temperature or under heating.
When a highly polar resin and a low polarity resin are used in combination as the binder resin, after the monomer composition is dispersed in the aqueous medium to form droplets, the highly polar resin is in the vicinity of the droplet surface, The resin with low polarity moves to the vicinity of the droplet center. Thereafter, by removing the organic solvent, toner mother particles having a difference in composition between the inside and the surface can be obtained.

When preparing an oily dispersion using a prepolymer capable of reacting with an active hydrogen group-containing compound such as a hydroxyl group, amino group, or carboxyl group, the active hydrogen group-containing compound is dispersed after dispersing the oily dispersion in an aqueous medium. And an extension reaction or a cross-linking reaction between the two from the surface of the droplet in the aqueous medium, whereby a stretched or cross-linked resin is preferentially generated on the surface of the droplet. Thereafter, by removing the organic solvent, toner mother particles having a difference in composition between the inside and the surface can be obtained.

In these methods, by selecting the raw material in consideration of the Tg of the obtained resin, a structure in which the ratio of the resin having a high Tg is higher on the surface than on the inside of the toner base particles can be obtained. Further, the polymer fine particles used for the dispersant are regarded as the high heat-resistant resin fine particles and adjusted to the physical properties of the high heat-resistant resin fine particles, whereby the high heat-resistant resin fine particles (polymer fine particles) are present on the surface of the toner base particles. May be made.

3.1.3. Cleaning and drying of toner base particles As described above, “method of aggregating particles smaller than toner base particles to prepare toner base particles”, “method of preparing toner base particles by suspension polymerization”, “toner base by dissolution suspension” The toner base particles produced by the “method for producing particles” and the like are separated from the aqueous solvent, washed, dried, subjected to an external addition treatment, and supplied to an electrostatic charge image developing toner.

The liquid used for cleaning includes water, but it can also be cleaned with an acid or alkali aqueous solution. Moreover, it can also wash | clean with warm water or hot water, and these methods can also be used together. Through such a washing step, suspension stabilizers, emulsifiers, unreacted monomers and the like can be reduced and removed.
In the washing step, for example, the toner base particles are made into a thick slurry or wet cake by filtration, decantation, etc., and a liquid for newly washing is added thereto to disperse the toner base particles. preferable. The toner base particles after washing are preferably collected in the form of a wet cake in terms of handling in the subsequent drying process.

In the drying process, a vibration type fluid drying method, a fluidized drying method such as a circulation type fluid drying method, an air flow drying method, a vacuum drying method, a freeze drying method, a spray drying method, a flash jet method or the like is used. The operating conditions such as temperature, air volume, and degree of reduced pressure in the drying process are appropriately optimized based on the Tg of the toner base particles, the shape, mechanism, size, etc. of the apparatus used.

3.1.4. Method for preparing toner mother particles by melt-kneading pulverization method Melt-kneading pulverization method is a method in which a charge control agent, a release agent, a magnetic material and the like are dry-mixed with a binder resin and a colorant as necessary, and then an extruder. In this method, toner base particles are obtained by melt-kneading and the like, and then pulverized and classified. In the external addition step after obtaining the toner base particles, high heat-resistant resin fine particles may be added and adhered to the surface of the core component.

3.1.5. Timing of adding high heat-resistant resin fine particles When preparing toner base particles in a wet medium (in water and / or in an organic solvent), the high heat-resistant resin fine particles are added at the same time as the core component (dissolved / dispersed / suspended). The heat resistant resin fine particles may be thermodynamically disposed on the surface of the core component and the wet medium, or after the composition and / or shape of the core component is determined, Resin fine particles may be added to physically and / or discontinuously cover the surface of the core component with the high heat resistant resin fine particles.

Furthermore, when the toner base particles are prepared in a wet medium (in water and / or in an organic solvent), the high heat-resistant resin fine particles may be added before and after the cleaning of the core component, or before and after the drying of the core component. High heat-resistant resin fine particles may be added. In addition, the high heat resistant resin fine particles may be added in the external addition step. When the high heat resistant resin fine particles are adhered in the external addition step, it is better to add the high heat resistant resin fine particles and fix them before adding the external additive. preferable.
In the melt-kneading pulverization method for producing toner base particles by dry method, it is preferable to add the high heat-resistant resin fine particles before and after the external addition step after the pulverization and classification to adhere the high heat-resistant resin fine particles.
From the viewpoint of firmly fixing the core component and the high heat-resistant resin fine particles, it is particularly preferable to add the high heat-resistant resin fine particles in water and / or an organic solvent.

3.2. Production of toner satisfying parameters of the present invention 3.2.1. About “TP2 / TP1” In order for TP2 / TP1 measured with a rheometer to satisfy a specific value range, a high heat-resistant resin fine particle component is widely present on the surface of the toner base particles, and the outside is coated with an external additive. Covering, adjusting the particle size and amount of the high heat resistant resin fine particles, and adhering in water, it is necessary to adjust the polarity balance between the core component and the high heat resistant resin fine particles, and further adjust the composition ratio of the entire toner base particles. is there.

The volume median diameter (Dv ₅₀ ) of the high heat-resistant resin fine particles is preferably 50 nm or more, more preferably 70 nm or more, preferably 300 nm or less, and more preferably 250 nm or less. The “volume median diameter (Dv ₅₀ )” in the present invention is defined as a value measured by the method described in the examples according to the size and measured as such.
When the particle diameter of the high heat-resistant resin fine particle is 100 nm or more, it is preferable to spread the high heat-resistant resin fine particle thinly on the surface of the toner base particle by externally adding the high heat-resistant resin fine particle by impact. When high heat-resistant resin fine particles having a particle diameter of 100 nm or more are expanded by impact of external addition operation, a toner having a BETN-BETF of 0.54 or more and 1.56 or less is obtained. It becomes easy.

On the other hand, when the particle size of the high heat-resistant resin fine particles is smaller than 100 nm, there is a tendency that the change in which the high heat-resistant resin fine particles are expanded by the external addition operation tends to hardly occur. Therefore, it is preferable that the toner satisfy the parameters of the present invention.
When determining the addition amount of the high heat-resistant resin fine particles, it is preferable to determine based on the coverage. It can be calculated from the ratio of the surface area obtained from the target particle diameter when the toner base particles are assumed to be spherical and the projected area obtained from the average particle diameter when the high heat-resistant resin fine particles are assumed to be spherical. Specifically, the coverage is AR / (4r (1-A)) where R is the toner base particle radius, r is the high heat resistant resin fine particle radius, and A is the weight ratio of the high heat resistant resin fine particles in the resin component. expressed.

When the particle size of the high heat-resistant resin fine particles is 100 nm or more, the coverage is preferably 25% or more and 85% or less, more preferably 35% or more and 70% or less, and 40% or more and 60% or less. It is particularly preferred.
When the particle size of the high heat-resistant resin particles is smaller than 100 nm, the coverage is preferably 55% or more and 120% or less, more preferably 65% or more and 105% or less, and 70% or more and 95% or less. It is particularly preferred.

It is desirable that the high heat-resistant resin fine particle component is disposed in the vicinity of the surface when it is in the form of toner. As long as it does not deviate from the present invention, the shape may be particulate or spherical or may be a thin film.
In order to adjust the TP2 / TP1 measured by the rheometer so as to be a value suitable for each color toner as described above, the composition is combined so that the binder resin and the high heat-resistant resin fine particles have appropriate compatibility. Is desirable.

In the first measurement of the tan δ maximum value with a rheometer, the binder resin and the high heat-resistant resin fine particles are in contact with each other without melting. When the first measurement is completed, the binder resin and the high heat-resistant resin fine particles are melted together by the heating during the measurement. Therefore, in the second measurement, the measurement is started in a melted state. This difference appears in the difference between TP2 / TP1.
Therefore, it is desirable to adjust the compatibility by selecting the type of resin contained in the high heat-resistant resin fine particles according to the type of the binder resin. Hereinafter, although the adjustment method is illustrated, the numerical value quoted in the example is not limited.

That is, for example, if the binder resin is a styrene acrylic resin that is a kind of poly (meth) acrylic resin, the resin contained in the high heat-resistant resin fine particles is also a styrene acrylic resin, and the ratio of styrene monomer to acrylic monomer. For example, when the binder resin is 70:30, the resin contained in the high heat-resistant resin fine particles is 95: 5; or the number of hydrophilic monomers relative to 100 parts by mass of other monomers is When the resin is 1 part, the resin contained in the high heat-resistant resin is 1.5 parts; using a hybrid resin of styrene acrylic resin and polyester as the binder resin; It is done.

Since appropriate compatibility between the core component and the high heat resistant resin fine particle component can be obtained, the difference between the solubility parameter (SP value) of the binder resin and the SP value of the high heat resistant resin fine particle component is 0.5 to 1. 0 is preferable, and 0.6 to 0.8 is more preferable.

Further, from the viewpoint of increasing the adhesive strength with a recording medium such as paper and reducing member contamination, it is particularly preferable that there is no shadow difference between the core component and the high heat-resistant resin fine particle component when measured with a transmission electron microscope. The “core component” contains at least a binder resin and a colorant, and the “high heat-resistant resin fine particle component” is present in the vicinity thereof. It is preferable that there is no shadow difference for all color toners including black toner and magenta toner.
The measurement conditions of the transmission electron microscope are measured as described in the examples, and the “shadow difference” is the “shadow difference” when a photograph of such a measurement is viewed with the naked eye.
Here, “there is no shadow difference” means that there is no difference in the dyeing degree (black and white degree) between the core component and the high heat resistant resin fine particle component, and the edge of the high heat resistant resin fine particle component (that is, the core component and the high heat resistant resin). This means that the boundary of the fine particle component is not visible. However, “there is no shadow difference” does not exclude an aspect in which the shadow difference is not clear and the shadow difference is hardly visible.

It is important to have a certain degree of affinity so that the high heat-resistant resin fine particles do not leave the core component, so the monomer component of the binder resin constituting the core component and the high heat-resistant resin fine particles are configured. It is preferable that at least one of the monomer components is the same. By doing so, the interface between the core component and the high heat-resistant resin fine particles becomes seamless, and the adhesive strength is increased. For example, the high heat-resistant resin is adhered to the surface of the core component by wet processing, and then the external addition process increases the strength. When stretching the heat-resistant resin, a part of the high heat-resistant resin can be anchored to the core component, and the portion protruding from the core component can be stretched to increase the coverage, and the preferred high heat-resistant resin fine particle component coating A form can be obtained.

Further, if the binder resin is a polyester resin, the resin contained in the high heat resistant resin fine particles is also a polyester resin, and if the binder resin is 3 mgKOH / g or less, the resin contained in the high heat resistant resin fine particles May be 4 mg KOH / g or more and 20 mg KOH / g or less; the binder resin should not have a hydroxyl group, and the resin contained in the high heat-resistant resin fine particles should have a hydroxyl group;

If the resin contained in the binder resin and the high heat-resistant resin fine particles are the same, the compatibility between the binder resin and the high heat-resistant resin fine particles proceeds at the time of toner mother particle production, and therefore TP2 and TP1 measured by the rheometer are almost equal. Take the same value. Further, if the compatibility between the binder resin and the high heat-resistant resin fine particles is extremely poor, the toner structure is not melted by the heat of the first measurement and the toner structure is maintained, so that TP2 and TP1 take almost the same value. The high heat-resistant resin fine particles contain a resin, but may contain other components such as wax, a charge control agent and the like.

The number average molecular weight by GPC of the resin contained in the high heat-resistant resin fine particles is preferably 8000 or more, more preferably 10,000 or more, still more preferably 13,000 or more, preferably 50,000 or less, more preferably 4 10,000 or less, more preferably 35,000 or less.
The weight average molecular weight by GPC of the resin contained in the high heat-resistant resin fine particles is preferably 20,000 or more, more preferably 30,000 or more, preferably 300,000 or less, more preferably 200,000 or less.

The Tg of the high heat-resistant resin fine particles is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably 100 ° C. or lower, and more preferably 90 ° C. or lower. Further, it is necessary to be higher than Tg of the binder resin, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher.
In order to adjust the TP2 / TP1 of the toner measured by the rheometer so that it falls within the range of the present invention, it is necessary to dispose the high heat-resistant resin fine particles in the vicinity of the surface of the toner base particles.

Therefore, as an effective composition of the high heat-resistant resin fine particles, when the toner base particles are prepared in a wet medium (water and / or an organic solvent), it is preferable to make the composition more compatible with the medium than the binder resin. For example, when the medium is water, the ratio of the acidic monomer or the basic monomer is higher than that of the binder resin and 1.0 part by mass or more with respect to 100 parts by mass of the other monomers; A suitable polymerization initiator is used.

3.2.2. About “BETN-BETF” When BETN-BETF is too small, the surface of the toner base particles is low in heat-resistant resin fine particles; the deformation due to the impact of the external addition operation is excessive; When BETN-BETF is too large, high heat-resistant resin fine particles are excessive; deformation due to impact of external addition operation is insufficient; particle diameter of high heat-resistant resin fine particles is very large;

The core component particles before adding the high heat-resistant resin fine particles have an uneven shape, and when the high heat-resistant resin fine particles are attached with the same charge (plus or minus) in water, There is a tendency to selectively adhere to the convex portions of the core component particles, which is a preferable tendency. In conventional toners, the polarity difference between the core component and the high heat-resistant resin fine particles was small, so even after the addition of the high heat-resistant resin fine particles, the high heat-resistant resin fine particles do not stay near the surface of the toner base particles, but are embedded deeply inside the toner. It will be crowded.

In the present invention, the high heat-resistant resin fine particles remain near the surface of the toner base particles. Further, in the case of being spread by an external addition operation, the high heat-resistant resin fine particle component is thinly spread on the surface of the toner base particles.
Therefore, the high heat-resistant resin fine particles are not uniformly distributed over the entire surface of the toner base particles, but have a tendency that the adhesion rate to the convex portions is higher than the adhesion rate to the concave portions. The anti-blocking property is deteriorated by fusing toners in a heating environment, but the convex portions of the toner come in contact with each other stochastically. Therefore, it becomes a preferable form that the heat resistance of a convex part is high.
Therefore, the value of “BETN-BETF” is a parameter that clearly distinguishes the difference between the preferred form and the unfavorable form, and the toner in which “BETN-BETF” is in a suitable range is effective for the present invention ( Particularly good blocking resistance) is exhibited.

4). External attachment 4.1. External Additive In the present invention, an external additive is added in order to obtain the physical properties of the toner of the present invention and in order to improve the fluidity and charge control properties of the toner. Since the external additive adheres to the entire surface of the toner base particles, it is preferable that the portion where the high heat-resistant resin fine particles do not exist is also coated with the external additive. The external additive can be appropriately selected from various inorganic or organic fine particles. Two or more kinds of external additives may be used in combination.

Inorganic fine particles include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and other carbides, boron nitride, titanium nitride. , Various nitrides such as zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, titanium Various titanate compounds such as calcium oxide, magnesium titanate, strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearyl Calcium, zinc stearate, various metal soaps such as magnesium stearate, talc, bentonite, various carbon black or conductive carbon black, magnetite, can be used ferrite.

As the organic fine particles, fine particles such as styrene resin, acrylic resin, epoxy resin, and melamine resin can be used. In addition, charging stability can be improved by using fine particles containing fluorine atoms. Among these external additives, silica, titanium oxide, alumina, zinc oxide, various carbon blacks and the like are particularly preferably used.
In addition, the external additive is prepared by applying the surface of the inorganic or organic fine particles to a silane coupling agent such as hexamethyldisilazane (HMDS) or dimethyldichlorosilane (DMDS), a titanate coupling agent, silicone oil, or dimethyl silicone oil. Hydrophobic by treating agents such as silicone oil treating agents such as modified silicone oil and amino-modified silicone oil, silicone varnish, fluorine-based silane coupling agent, fluorine-based silicone oil, coupling agent having amino group or quaternary ammonium base Those subjected to surface treatment such as chemical conversion can also be used. Two or more kinds of the treatment agents can be used in combination.

The amount of the external additive added is preferably 1.0 part by mass or more, particularly preferably 1.5 parts by mass or more, and preferably 6.5 parts by mass or less with respect to 100 parts by mass of the toner base particles. Part or less is particularly preferable.
In the toner of the present invention, conductive fine particles may be used as an external additive from the viewpoint of charge control. Examples of the conductive fine particles include metal oxides such as conductive titanium oxide, silica, and magnetite or those doped with a conductive substance, and conjugated double bonds such as polyacetylene, polyphenylacetylene, and poly-p-phenylene. Examples thereof include organic fine particles obtained by doping a conductive material such as a metal into the polymer, carbon typified by carbon black and graphite, etc., but from the viewpoint that conductivity can be imparted without impairing the fluidity of the toner, conductive titanium oxide. Or the metal oxide and organic fine particle which doped the electroconductive substance are more preferable.

The lower limit of the content of the conductive fine particles is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the toner base particles. It is particularly preferred. On the other hand, the upper limit of the content of the conductive fine particles is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less.

4.2. External Addition Method of External Additive Examples of the external additive addition method include a method using a high-speed stirrer such as a Henschel mixer and a method using an apparatus capable of applying a compressive shear stress. The toner can be prepared by a one-stage external addition method in which all external additives are added to the toner base particles simultaneously and externally added, but can also be prepared by a separate external addition method in which each external additive is externally added.

In order to prevent a temperature rise during external addition, a cooling device is installed in the container, and external addition is performed. By adjusting the temperature, rotation speed, time, etc. of the external addition, the toner TP2 / TP1 obtained can be adjusted to be within the numerical range of the present invention. For example, when stirring for a long time (for example, 25 minutes or more) at 3000 rpm with a Henschel mixer, TP2 / TP1 increases, and when stirring for a short time (for example, 5 minutes or less) under the same conditions, TP2 / TP1 decreases.

5). Other (use etc.)
The toner for developing an electrostatic charge image of the present invention may be used in any form of a two-component developer using a toner together with a carrier, or a magnetic or non-magnetic one-component developer not using a carrier.
When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder or ferrite powder, or a known material such as a resin coating on the surface thereof or a magnetic carrier. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

The toner cartridge and the image forming apparatus containing the toner set of the present invention have the excellent effects exhibited by the toner set of the present invention. Further, if an image forming method for forming an image using the toner set of the present invention described above is used, the above excellent output image can be provided.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely with a manufacture example, an Example, a comparative example, and an estimation example, this invention is not limited to the following examples, unless the summary is exceeded.
In the following examples, “parts” and “%” simply mean “parts by mass” and “mass%”, respectively, in terms of mass.
Volume median diameter (Dv ₅₀ ), number median diameter (Dn ₅₀ ), particle diameter distribution (Dv ₅₀ / Dn ₅₀ ), average circularity, weight average molecular weight (Mw), and the like were measured as follows. In the present invention, each numerical value is defined as measured as follows.

<Medium diameter measurement 1>
The volume median diameter (Dv ₅₀ ) of particles having a volume median diameter (Dv ₅₀ ) of less than 1 micron is determined by the Nikkiso Co., Ltd. model Microtrac Nanotrac 150 (hereinafter abbreviated as “Nanotrack”) and its analysis software MicrotracParticle. Analyzer Ver10.1.2-019EE, ion-exchanged water with electric conductivity of 0.5 μS / cm as solvent, solvent refractive index: 1.333, measurement time: 120 seconds, number of measurements: 5 measurement conditions Then, it was measured by the method described in the instruction manual, and the average value was obtained.
Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.04.

<Medium diameter measurement 2>
1 micron or more volume median diameter volume median diameter of the particles having a _{_{(Dv 50)} (Dv 50)} and the number median diameter _{(Dn 50)} is Beckman Coulter Multisizer III (aperture diameter 100 [mu] m) (Hereinafter, abbreviated as “Multisizer”), and using the company's Isoton II as a dispersion medium, the dispersion was dispersed to a concentration of 0.03% by mass. The particle size distribution was a value obtained by dividing Dv ₅₀ by Dn ₅₀ .

<Average circularity>
The average circularity is determined by dispersing the dispersoid in a dispersion medium (Cell Sheath: Sysmex) at 5720-7140 / μL, and using a flow particle analyzer (FPIA 3000: Sysmex) to perform HPF analysis. The amount was measured in the HPF mode under the condition of 0.35 μL and HPF detection amount of 2000 to 2500.

<Weight average molecular weight (Mw)>
The THF-soluble component of the polymer primary particle dispersion was measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8320 manufactured by Tosoh Corporation, column: TOSOH TSKgel SuperHM-H (diameter 6 mm × length 150 mm × 2), solvent: THF, column temperature 40 ° C., flow rate 0.5 mL / min, sample concentration: 0.1% by mass, calibration curve: standard polystyrene

<Emulsion solid content concentration>
The emulsion solid content concentration was determined by evaporating water by heating a 2 g sample at 195 ° C. for 90 minutes using an infrared moisture meter FD-610 manufactured by Kett Science Laboratory.

<Measurement method with transmission electron microscope, measurement method of shadow difference>
After the toner was embedded in an epoxy resin and cured, the shell and the core were subjected to differential dyeing by gas exposure with ruthenium tetroxide for 5 minutes. Next, the cross section was cut out with a knife, and an ultrathin section of toner having a thickness of 200 nm was prepared using an ultramicrotome. Furthermore, using a TEM (transmission electron microscope) H7500 (manufactured by Hitachi High-Tech), an ultrathin section of the toner was observed at an acceleration voltage of 100 kV, and the shadow difference was confirmed with the naked eye.

Production Example 1
<Preparation of Wax Dispersion A1: Emulsification Process>
Ester wax 1 (manufactured by NOF Corporation, product name: WEP-3, DSC second measurement melting point peak: 71.0 ° C., DSC second measurement onset temperature: 68.6 ° C., DSC second measurement inflection point: 69. 9 ° C., catalog acid value 0.1 mg KOH / g, catalog hydroxyl value 3 mg KOH / g or less) 30.00 parts (1440 g), decaglycerin decabehenate (Mitsubishi Chemical Foods, Inc., product name: B100D, hydroxyl value 27, 0.24 parts of 20% sodium dodecylbenzenesulfonate aqueous solution (hereinafter abbreviated as “20% DBS aqueous solution”) 1.93 parts and 67.83 parts of demineralized water were heated to 90 ° C. The mixture was mixed for 20 minutes in a CSTR type stirring layer equipped with a 45 ° C. inclined three-stage paddle blade.

Next, while this dispersion was heated to 90 ° C., circulation emulsification was started under a pressure of 25 MPa using a valve homogenizer (manufactured by Gorin Co., Ltd., 15-M-8PA type), and the particle size was measured with Nanotrac. the volume median diameter _{(Dv 50)} is dispersed until 245 nm, to prepare a wax dispersion A1 (emulsion solid content concentration = 31.2%, a wax component concentration 30.8%).

<Preparation of Wax Dispersion A2: Emulsification Process>
22.50 parts of the ester wax 1 as a raw material, ester wax 2 (manufactured by NOF Corporation, product name: WEP-5, catalog melting point 82 ° C., catalog acid value 0.1 mgKOH / g, catalog hydroxyl value 3 mgKOH / g or less) Using a method similar to that of the wax dispersion A1, using 7.50 parts (1080 g), 0.24 parts decaglycerin decabehenate, 1.93 parts 20% DBS aqueous solution, 67.83 parts demineralized water, A2 (emulsion solid content concentration = 31.4%) was prepared.

<Production of polymer primary particles: polymerization step>
10.7 parts of wax dispersion A1 (as a wax component), 252 parts of demineralized water, 0.5% in a reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device 0.02 part of iron (II) sulfate heptahydrate aqueous solution was charged, and the temperature was raised to 90 ° C. under a nitrogen stream while stirring.

Thereafter, with the stirring continued, the following mixture of monomers and emulsifier solution, which was previously stirred for 30 minutes with a homogenizer, was added over 240 minutes.
The time when the addition of the monomer / emulsifier aqueous solution started to be added was set as the polymerization start, and the following initiator aqueous solution was added over 0 to 480 minutes from the start of the polymerization. The following iron sulfate aqueous solution was added 240 minutes after the start of polymerization. The temperature was raised to 95 ° C. 300 minutes after the start of polymerization. Heating and stirring were continued until 540 minutes from the start of polymerization.

[Monomers]
Styrene 70.9 parts Butyl acrylate 29.1 parts Acrylic acid 0.85 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.95 parts [Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part Demineralized water 66.9 parts [Initiator aqueous solution]
8% aqueous hydrogen peroxide solution 28.0 parts 8% L-(+) ascorbic acid aqueous solution 28.0 parts [iron sulfate aqueous solution]
0.5% iron (II) sulfate heptahydrate aqueous solution 0.08 parts

After 540 minutes from the start of polymerization, the mixture was cooled to 30 ° C. to obtain milky white primary polymer particles. The volume median diameter (Dv ₅₀ ) measured using Nanotrac was 239 nm. The weight average molecular weight (Mw) was 67,000. Solid content concentration was 24.1 mass% and Tg was 38 degreeC.

<Preparation of high heat-resistant resin fine particles: polymerization step>
In a reactor equipped with a stirrer, heating / cooling device, concentrating device, and each raw material / auxiliary charging device, 50.6 parts of wax dispersion A2 and 20% DBS as a particle size adjusting emulsifier (DBS SP) 2.96 parts of an aqueous solution and 350 parts of demineralized water were charged, and the temperature was raised to 75 ° C. under a nitrogen stream while stirring.

5 minutes after adding the following initiator aqueous solution 1, the mixture of the following monomers / emulsifier aqueous solution previously stirred for 30 minutes with a homogenizer was added over 180 minutes while continuing stirring.
The time when the addition of the monomer / emulsifier aqueous mixture was started was set as the polymerization start, and the following initiator aqueous solution 2 was continuously added over a period of 240 minutes to 60 minutes from the start of the polymerization. The following initiator aqueous solution 3 was continuously added over a period of 240 minutes to 120 minutes from the start of polymerization. The following iron sulfate aqueous solution was added 180 minutes after the start of polymerization. The temperature was raised to 93 ° C. 180 minutes after the start of polymerization. Heating and stirring were continued until 480 minutes from the start of polymerization.

[Monomers]
Styrene 97.9 parts Butyl acrylate 2.1 parts Acrylic acid 1.5 parts 1-Dodecanethiol 1.0 part [Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part Demineralized water 66.7 parts [Initiator aqueous solution 1]
20% ammonium persulfate aqueous solution 6.0 parts [initiator aqueous solution 2]
14.2 parts of 8% aqueous hydrogen peroxide solution [Initiator aqueous solution 3]
21.3 parts of 8% L-(+) ascorbic acid aqueous solution [iron sulfate aqueous solution]
0.05% aqueous solution of 0.5% iron (II) sulfate heptahydrate

480 minutes after the start of polymerization, the mixture was cooled to 30 ° C. to obtain milky white high heat-resistant resin fine particles. The volume median diameter (Dv ₅₀ ) measured using Nanotrac was 158 nm. The weight average molecular weight (Mw) was 59000. The solid content concentration was 20.0% and the Tg was 80 ° C.

<Preparation of Bk (black) colorant dispersion>
The container stirrer equipped with a propeller blade, Mitsubishi Chemical Co., Ltd. Carbon black # 44 (catalog properties: particle size 24 nm, a nitrogen adsorption specific surface area 110m ² / g, coloring power 129%, granular 77cm ^3/100 g, volatile content 0.8%, pH value 8, PVC blackness 10) 20 parts, anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S-20D) 1 part, nonionic surfactant (manufactured by Kao Corporation, 4 parts of Emulgen 120) and 75 parts of ion-exchanged water having an electrical conductivity of 1 μS / cm were added, and the mixture was predispersed until the volume median diameter Dv ₅₀ was about 90 μm, to obtain a pigment premix solution.

The pigment premix solution was supplied as a raw material slurry to a wet bead mill and subjected to one-pass dispersion. Note that zirconia beads (true density of 6.0 g / cm ³ ) having a diameter of 120 mmφ, a separator having a diameter of 60 mmφ, and a diameter of 50 μm were used as a dispersion medium. Since the effective internal volume of the stator is about 2L and the filling volume of the media is 1.4L, the media filling rate is 70%.

When the rotational speed of the rotor is constant (the peripheral speed at the tip of the rotor is about 11 m / sec), the pigment premix liquid is supplied from the supply port by a non-pulsating metering pump at a supply speed of about 40 L / hr, and reaches a predetermined particle size. The product was acquired from the outlet. During operation, cooling water of about 10 ° C. is circulated from the jacket, and the volume median diameter (Dv ₅₀ ) is 157 nm, the number median diameter (Dn ₅₀ ) is 106 nm, and the solid content concentration is 2k% Bk (black). A colorant dispersion was obtained.

<Preparation of Ma (magenta) colorant dispersion>
Into a container having an internal volume of 300 L equipped with a stirrer (propeller blade), P.I. R. 20 parts (40 kg) of 238 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-4-[{2-methoxy-5-[(phenylamino) carbonyl] phenyl} azo] naphthalene-2-carboxamide ), 1 part of 20% sodium dodecylbenzenesulfonate aqueous solution, 4 parts of polyoxyethylene lauryl ether of HLB15.3, and 75 parts of ion-exchanged water having an electric conductivity of 1.5 μS / cm or less are preliminarily dispersed. Thus, a pigment premix solution was obtained.

The pigment premix solution was supplied as a raw material slurry to a wet bead mill and circulated and dispersed. The inner diameter of the stator was φ75 mm, the separator diameter was φ60 mm, the distance between the separator and the disk was 15 mm, and zirconia beads having a diameter of 50 μm (true density of 6.0 g / cm ³ ) were used as a dispersion medium.
Since the effective internal volume of the stator is 0.5 L and the filling volume of the media is 0.35 L, the media filling rate is 70% by mass.
The rotation speed of the rotor is constant (the peripheral speed of the rotor tip is about 11 m / sec), and the pigment premix liquid is continuously supplied from the supply port at a supply speed of 50 L / hr by a non-pulsating metering pump, and continuously from the discharge port. The Ma colorant dispersion was obtained when it reached a predetermined particle size by being repeatedly discharged and repeatedly circulated.
The volume median diameter (Dv ₅₀ ) of the Ma (magenta) colorant dispersion measured with Nanotrac was 153 nm, the pH was 5.8, and the solid content concentration was 25.5% by mass.

<Preparation of Bk (Black) Toner Base Particle 1 Dispersion: Aggregation Step>
In a mixer equipped with a stirrer, a heating / cooling device, and each raw material / auxiliary charging device, 89.1 parts (as solids) of the polymer primary particles obtained above, 0.45 part of 20% DBS aqueous solution, Add 75.8 parts of deionized water, 11.5 parts of 5% iron (II) sulfate heptahydrate aqueous solution, and 7.38 parts of Bk colorant dispersion (as solids) in order and stir uniformly. Mixed.

Thereafter, the internal temperature was raised to 40 ° C., and the temperature was raised stepwise until the volume median diameter became 5.5 μm. This temperature (primary aggregation temperature) was 45 ° C.
As soon as the temperature was lowered by 1 ° C. from the primary aggregation temperature, 9.90 parts of polymer primary particles (as solids) were added. After 180 minutes, 3.33 parts of high heat-resistant resin fine particles (as a solid content) were added. After 30 minutes, 20.1 parts of 20% DBS aqueous solution and 22.9 parts of deionized water were added, and then the temperature was raised to 65 ° C. over 50 minutes, and then stepwise until the circularity reached 0.975. The temperature rose.
The temperature (final circularization temperature) when the circularity reached 0.975 was 70 ° C. Thereafter, it was immediately cooled to 30 ° C. to obtain a Bk (black) toner base particle 1 dispersion.

<Preparation of Bk (Black) Toner Base Particle 1: Cleaning and Drying Step>
The obtained Bk (black) toner base particle 1 dispersion was extracted and suction filtered with an aspirator using 5 types C (Toyo Roshi Kaisha, Ltd., No. 5C) filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), and ion-exchanged water having an electric conductivity of 1 μS / cm was added and stirred uniformly, and then stirred for 30 minutes.
After repeating this process until the electric conductivity of the filtrate reaches 2 μS / cm, the obtained cake is dried in a blow dryer set at 40 ° C. for 48 hours, whereby Bk (black) toner base particles are obtained. 1 was obtained.

<Manufacture of Bk (Black) Toner 1: External Addition Step>
Polymer / silica composite particles (ATLAS100: manufactured by Cabot Corporation: silica / polymer ratio = 70/30, true specific gravity = 1.7 g / cm) with respect to Bk (black) toner base particles 1 (100 parts) obtained above. ³ ), 4 parts of octahydropentalene), 0.5 part of titania and silica composite oxide particles (STX501: manufactured by Nippon Aerosil Co., Ltd.), small particle size silica (RY200L: manufactured by Nippon Aerosil Co., Ltd.) Was added, and the mixture was stirred and mixed at 3000 rpm for 15 minutes with a Henschel mixer and sieved to obtain Bk (black) toner 1.

Production Examples 2-3
In the preparation step (aggregation step) of the Bk (black) toner mother particle 1 dispersion in Production Example 1, the addition amount as the solid content of the polymer primary particles, and the addition as the solid content of the polymer primary particles after the completion of the primary aggregation Bk (black) toner 2 and Bk shown in Production Examples 2 and 3 in the same manner as Production Example 1, except that the amount and the addition amount of the high heat-resistant resin fine particles as solids were changed as shown in Table 1. (Black) Toner 3 was produced.

Production Examples 4-6
In the preparation step (aggregation step) of the Bk (black) toner mother particle 1 dispersion in Production Example 1, the amount of the polymer primary particles added as the solid content, the type of the pigment dispersion, the number of pigment parts (as the solid content), the primary Production Example as in Production Example 1 except that the addition amount as the solid content of the polymer primary particles after completion of the aggregation and the addition amount as the solid content of the high heat-resistant resin fine particles were changed as shown in Table 1. Ma (magenta) toners 1 to 3 shown in 4 to 6 were produced.
However, only the Ma (magenta) toner 3 of Production Example 6 was immediately cooled to 30 ° C. after the circularity reached 0.965 in the aggregation step, and the Ma (magenta) toner mother particles 3 were removed in the external addition step. 100 parts of silica with a particle size of 110 nm, 1 part of silica with a particle diameter of 30 nm, 0.4 part of titania with a particle diameter of 15 nm, 0.4 part of silica with a particle diameter of 10 nm are added and stirred at 5500 rpm for 10 minutes. By mixing and sieving, Ma (magenta) toner 3 was obtained.

High heat-resistant resin fine particles coat the toner base particles (the toner base particles are assumed to be 5.6 μm). Table 1 also shows the diameter (Dv ₅₀ ), the number median diameter (Dn ₅₀ ), the particle size distribution (Dv ₅₀ / Dn ₅₀ ), and the average circularity.
Further, TP1 and TP2 of the toners obtained in Production Examples 1 to 6 were measured by the following method, and TP2 / TP1 was obtained by dividing the value of TP2 by TP1, and is shown in Table 1.

[Measurement method of TP2 and TP1 and definition of TP2 / TP1]
TP2 / TP1 measured with a rheometer was determined by the following procedure.
The measurement was performed by the following method using a rheometer ARES (measurement control software TA Orchestrator V7.2.0.2) manufactured by TA Instruments.

<8mm cylindrical pellet measurement>
About 0.3 g of a sample was put in a jig for 8 mm diameter, and the clamping force was 1.25 tons (gauge 25 kg / cm ² ) by a press machine (5 ton press PE-5Y manufactured by Kodaira Seisakusho Co., Ltd.). ) For 15 minutes and molded into pellets. In the present invention, this may be abbreviated as “molded body”.

On the surface of an aluminum 8 mm disposable plate used for the measurement, scratches were formed in a lattice shape with 12 in each direction, width and width of the opening 50 to 100 μm, and depth 1 to 10 μm (average 3 to 5 μm).

First temperature rise measurement: The pellet (molded body) was set in a measuring apparatus equipped with a circular parallel plate having an upper and lower diameter of 8 mm, and the upper plate was lowered while the temperature was raised to 40 ° C. to adjust the force “Force” to 200 g. Then, it measured on condition of the following.

Fixture compliance 'Fixture compliance' 0
Plate inertia 'Tool inertia' 0
Measurement frequency 'Frequency' 6.28rad / sec
Initial temperature 'Initial Temp.' 40.0 ℃
Final temperature 'Final Temp.' 120.0 ℃
Temperature rising rate 'Ramp Rate' 4.0 ℃ / min
Holding time after temperature rise 'Soak Time After Ramp' 20s (seconds)
Measurement cycle time 'Time Per Measure' 10s (seconds)
Strain 'Strain' 0.025%
Option 'Option'
Holding time before measurement after reaching initial temperature 'Delay Before Test' Not set Automatic tension adjustment 'Auto Tension Adjustment'
Automatic tension adjustment 'Auto Tension Adjustment' setting Automatic tension direction 'Auto Tension Direction' Compression
Initial Force 'Initial Static Force' 204.0g
Automatic tension sensitivity 'Auto Tension Sensitivity' 2.0g
Automatic tension switching 'Switch Auto Tension to Programmed Extension'
Sample modulus setting 'When Sample Modulus'<3.00e + 05Pa
Maximum automatic tension rate 'Max Auto Tension Rate' 0.01mm / s (mm per second)
Automatic strain adjustment 'Auto Strain Adjustment'
Automatic strain adjustment 'Auto Strain' setting Maximum strain 'Max Applied Strain' 40.0%
Maximum allowable torque 'Max Allowed Torque' 100.0gf ・ cm
Minimum allowable torque 'Min Allowed Torque' 0.2gf ・ cm
Distortion adjustment 'Strain Adjustment' 20.0%
Measurement end setting 'End of Test'
Temperature control off 'Turn OFF Temp Controller' No
Set temperature after measurement 'Set End of Test Temp' Yes
Temperature after measurement 'Set End of Test Temp to' 40.0 ℃
Motor off 'Turn OFF Motor' No
Hold 'Turn Hold ON' Yes

Second temperature increase measurement: When the temperature decreased to 40 ° C., the second temperature increase measurement was performed under the same conditions as the first time. However, the settings at the end of measurement were as follows. When the first measurement was completed, the system was automatically air-cooled. When the temperature reached 40 ° C., the pellet (molded body) was not taken out, and the measurement at the second temperature increase was started immediately.

Measurement end setting 'End of Test'
Temperature control off 'Turn OFF Temp Controller' No
Set temperature after measurement 'Set End of Test Temp' Yes
Temperature after measurement 'Set End of Test Temp to' 120.0 ℃
Motor off 'Turn OFF Motor' No
Hold 'Turn Hold ON' No

By dividing the loss elastic modulus (G ″) obtained by the first temperature rise measurement by the storage elastic modulus (G ′), tan δ (= G ″ / G ′) is obtained and appears in the range of 40 ° C. to 80 ° C. The maximum value TP1 (see FIG. 2) of tan δ was determined.
Similarly, the maximum value TP2 (see FIG. 2) of tan δ appearing in the range of 40 ° C. to 80 ° C. in the second measurement was obtained, and TP2 / TP1 was obtained by dividing TP2 by TP1. Further, Tg of the toner obtained in the production example was measured by the following method and listed in Tables 1 and 4.

[Measurement and definition of Tg]
Tg measurement by a differential scanning calorimeter (DSC) was performed as follows using Q20 manufactured by TA Instruments.
3 ± 1 mg of toner is put in an aluminum pan and precisely weighed to the order of 0.1 mg. The aluminum pan filled with 3 mg of aluminum oxide is used as a reference, and the temperature is increased from 0 ° C. to 120 ° C. at 10 ° C./min. Warm up.
After holding at 120 ° C. for 10 minutes, the temperature was lowered to 0 ° C. at 10 ° C./minute, held for 5 minutes, and then heated again to 120 ° C. at 10 ° C./minute.

The glass transition temperature (Tg) was defined as the temperature at the intersection of the baseline before the endothermic peak at the second temperature rise and the tangent at the first inflection point appearing at 30 to 55 ° C. after the end of the endothermic peak.
The Tg when the sample of the polymerized primary particles and the high heat-resistant resin fine particles was an aqueous dispersion was measured by the above method after freeze-drying to remove moisture.

Example 1
“Bk (TP2 / TP1) /” is a value obtained by dividing the TP2 / TP1 value of each toner and the TP2 / TP1 value of the Bk toner by the TP2 / TP1 value of the Ma toner when the Bk toner and the Ma toner are combined. Ma (TP2 / TP1) ", the collapse load / determination / score as a proking resistance A of each toner, the score as a combination of Bk toner and Ma toner, the remaining rate / determination / score as a fixing test A, In addition, the total score A was obtained by adding the combination score of blocking resistance A to the score of the fixing test A, and the following comprehensive judgment A was performed based on the total score A. The results are shown in Table 2. However, in the evaluation of each color of the blocking resistance A and the fixing test A, if there is an item determined to be “×” (0 points) even in one item, the total score A is 0 because the toner cannot be set and withstand actual use. Points.

[Comprehensive judgment A]
The total score A is less than 10 points: × (actually unavailable, rejected)
Total score A is 10 points or more and less than 15 points: △ (actual use, pass)
The total score A is 15 points or more and less than 18 points: ○ (Actual use possible, pass in the preferred range)
The total score A is 18 points or more: ◎ (Available, pass within a more preferable range)

In addition, the blocking resistance A and the fixing test A were carried out as follows, and were judged and scored.

[Measurement method of blocking resistance A]
10 g of toner is put in a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, and a load of 20 g is put on it and left in an environment of a temperature of 50 ° C. and a humidity of 55% for 48 hours, and then the toner is taken out of the container and the load is applied from above. The degree of aggregation was confirmed by applying.
The collapse load is described in Table 2, and further judged according to the following criteria, and the results are shown in Table 2.

[Judgment criteria and points for blocking resistance A]
It will not collapse unless a load exceeding 1800 g is applied: ×
(0 points cannot be used or rejected)
It collapses with a load exceeding 1300 g and not exceeding 1800 g:
(3 points available, pass)
Collapses with a load of 1300 g or less: ◎
(5 points pass in the preferred range)

[Combined score]
The combination score was obtained by summing the scores of Bk toner and Ma toner. If either one is 0, even if one color is not usable or rejected, it cannot be used as a combination as the same set. Therefore, the score was 0.

[Measurement Method of Fixing Test A]
The fixability A was measured, judged and scored by the following method.
A developer was obtained by stirring and mixing 10 parts of toner and 100 parts of a ferrite carrier having a volume average particle size of 35 μm. This developer is a non-magnetic two-component (using organic photoreceptor) development method, roller (PCR) charging, mag roller development method, development speed A4 horizontal conversion 50 sheets / minute, 4-color tandem method, commercially available with IH fixing device Using a full-color printer, each color was printed as a single color, and an image with an image density of about 1.7 was printed.

The obtained fixed image surface is subjected to a peeling test using a mending tape (manufactured by Sumitomo 3M Co., Ltd.), the image density before and after peeling is divided by the image density before peeling and multiplied by 100 to remain fixed. Rate (%). That is, the larger the remaining ratio number, the stronger the fixing strength and the better the toner.

[Judgment criteria and points for fixing test A]
Remaining rate less than 20%: × (actual use failure 0 points)
Remaining rate 20% or more and less than 30%: △ (Acceptable use 2 points)
Residual rate of 30% or more and less than 40%: ○ (Acceptable 3 acceptable points for actual use)
Residual rate 40% or more: ◎ (Acceptable 5 points in a more preferable range)

Examples 2 to 4 and Comparative Examples 1 to 3 were also evaluated, judged and scored in the same manner as in Example 1 except that the combination of Bk toner and Ma toner was changed. The results are shown in Table 2.

[Explanation of Estimation Examples 1 and 2]
FIG. 3 shows the relationship between blocking resistance (collapse load) and TP2 / TP1 for Bk toners 1 to 3 and

Ma toners

1 and 2 having the same external addition. FIG. 3 shows data for each color toner. The regression equation expressed in a linear form using the least square method is shown. In FIG. 3, the TP2 / TP1 of the Bk toner with a collapse load of 1800 g or less that is acceptable is 1.45 or more from the regression equation, and the TP2 of the Bk toner that has a collapse load of 1300 g or less with a preferable range. / TP1 is found to be 1.52 or more from the regression equation, and further, TP2 / TP1 of Ma toner having a collapse load of 1800 g or less that passes is 1.22 or more from the regression equation. It can be seen from the regression equation that the TP2 / TP1 of the Ma toner that is 1300 g or less that passes the load in the preferred range is 1.32 or more.

FIG. 4 shows the relationship between fixability (residual rate) and TP2 / TP1 of Bk toners 1 to 3 and

Ma toners

1 and 2 with the same external addition. FIG. 4 shows the minimum data for each color toner. The regression equation expressed in a linear form using the square method is shown.
In FIG. 4, TP2 / TP1 of Bk toner having a remaining rate of 20% or more, which is an index of fixability, is 1.77 or less from the regression equation, and the collapse load is acceptable within a preferable range. TP2 / TP1 of the Bk toner that is at least% is 1.69 or less, and TP2 / TP1 of the Bk toner that is 40% or more that is acceptable in a more preferable range is 1.60 or less. The TP2 / TP1 of the Ma toner with a remaining rate of 20% or more that passes is 1.62 or less from the regression equation, and the TP2 / TP1 of the Bk toner that passes 30% or more with a collapse load within a preferable range. It can also be seen that TP1 is 1.54 or less, and TP2 / TP1 of Bk toner with a collapse load of 40% or more that passes within a more preferable range is 1.46 or less.

From these relationships, the TP2 / TP1 of the Bk toner is preferably 1.45 or more and 1.77 or less, and the median of the upper and lower limits of the TP2 / TP1 is 1.61. This toner assuming 1.61 toner is referred to as Bk toner [4]. Further, the Ma toner having the minimum TP2 / TP1 value (1.21), in which the collapsing load, which is an index of anti-blocking property, exceeds 1800 g and is rejected in the Ma toner combined therewith is defined as Ma toner [4]. A combination with Bk toner [4] is estimation example 1 in Table 3.

Further, the Ma toner having the maximum TP2 / TP1 value (1.22) at which the collapse load, which is an index of anti-blocking property, is 1800 g or less in the Ma toner combined with the Bk toner [4] is defined as Ma toner [5]. A combination with Bk toner [4] is an estimation example 2 in Table 3.
From estimation examples 1 and 2 shown in Table 3, when the value obtained by dividing TP2 / TP1 of Bk toner by TP2 / TP1 of Ma toner is 1.32 or less, both Bk toner and Ma toner have blocking resistance and fixing. It turns out that both tests are satisfied.

<Result>
From Table 2, in the combination of Bk toner and Ma toner of Examples 1 to 4, the overall judgment was “◎” and “○”, and the anti-blocking property was good and the result of the fixing test was also good. (Although both the blocking resistance and the low-temperature fixability were compatible with both toners), it can be seen that the toners of Comparative Examples 1 to 3 could not achieve this.

Production Example 11
<Preparation of Ma (Magenta) Toner Base Particle 11 Dispersion: Aggregation Step>
In a mixer equipped with a stirrer, a heating / cooling device, and each raw material / auxiliary charging device, 90.2 parts (as solids) of the polymer primary particles obtained above, 0.45 part of a 20% DBS aqueous solution, Add 75.8 parts of deionized water, 11.5 parts of 5% iron (II) sulfate heptahydrate aqueous solution, 6.38 parts of Ma colorant dispersion (as solids) in order and stir uniformly. Mixed.

Thereafter, the internal temperature was raised to 40 ° C., and the temperature was raised stepwise until the volume median diameter became 5.5 μm. This temperature (primary aggregation temperature) was 44 ° C.
As soon as the temperature was lowered by 1 ° C. from the primary aggregation temperature, 10.0 parts of polymer primary particles (as a solid content) were added. After 180 minutes, 2.18 parts (as solid content) of high heat-resistant resin fine particles were added. After 30 minutes, 20.1 parts of 20% DBS aqueous solution and 22.9 parts of deionized water were added, and then the temperature was raised to 65 ° C. over 50 minutes, and then stepwise until the circularity reached 0.975. The temperature rose. The temperature when the circularity reached 0.975 (final circularization temperature) was 71 ° C. Thereafter, it was immediately cooled to 30 ° C. to obtain a Ma (magenta) toner mother particle 11 dispersion.

<Preparation of Ma (Magenta) Toner Base Particles 11: Cleaning and Drying Step>
The obtained toner mother particle 11 dispersion was extracted, and suction filtered with an aspirator using 5 types C (manufactured by Toyo Roshi Kaisha, Ltd., No. 5C) filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), and ion-exchanged water having an electric conductivity of 1 μS / cm was added and stirred uniformly, and then stirred for 30 minutes.
After repeating this process until the electric conductivity of the filtrate reaches 2 μS / cm, the obtained cake is dried in an air dryer set at 40 ° C. for 48 hours to obtain Ma (magenta) toner base particles. 11 was obtained.

<Manufacture of Ma (Magenta) Toner 11: External Addition Step>
Polymer / silica composite particles (ATLAS100: manufactured by Cabot Corporation: silica / polymer ratio = 70/30, true specific gravity = 1.7 g / cm) with respect to Ma (magenta) toner base particles 11 (100 parts) obtained above. ³ ), 4 parts of octahydropentalene), 0.5 part of titania and silica composite oxide particles (STX501: manufactured by Nippon Aerosil Co., Ltd.), small particle size silica (RY200L: manufactured by Nippon Aerosil Co., Ltd.) Was added, and the mixture was stirred and mixed at 3000 rpm for 15 minutes with a Henschel mixer and sieved to obtain Ma (magenta) toner 11.

Production Example 12
In the preparation step (aggregation step) of the Ma (magenta) toner base particle 11 dispersion in Production Example 11, the addition amount as the solid content of the polymer primary particles described in Table 4, the polymer primary particles after the completion of the primary aggregation Production Example 12 in the same manner as in Production Example 11 except that the addition amount as a solid content and the addition amount as a solid content of the high heat-resistant resin fine particles were changed and the coverage was changed as shown in Table 4. Ma toner 12 shown in FIG.

Production Example 13 and Production Example 14
In the preparation process (aggregation process) of the Ma (magenta) toner base particle 11 dispersion, the amount of the polymer primary particles added as the solid content, the pigment dispersion liquid type, the number of pigments as the solid content, and the primary polymer after completion of the primary aggregation The amount of addition as a solid content of the particles, the addition amount as a solid content of the high heat resistant resin fine particles, and the high heat resistant resin fine particles coat the toner base particles (the toner base particles are assumed to be 5.6 μm). Cy (cyan) toners 11 and 12 shown in Production Examples 13 and 14 were produced in the same manner as in Production Example 11 except that the procedure was changed as described above.
In addition, as a pigment dispersion liquid type, as a Cy (cyan) colorant dispersion liquid, Daiichi Seika Kogyo Co., Ltd. EP700 (PB15: 3, copper phthalocyanine pigment, pigment concentration 24.0%, solid content 34.3%) )It was used.

Production Example 15 and Production Example 16
In the preparation process (aggregation process) of the Ma (magenta) toner base particle 11 dispersion, the amount of the polymer primary particles added as the solid content, the pigment dispersion liquid type, the number of pigments as the solid content, and the primary polymer after completion of the primary aggregation The amount of addition as a solid content of the particles, the addition amount as a solid content of the high heat resistant resin fine particles, and the high heat resistant resin fine particles coat the toner base particles (the toner base particles are assumed to be 5.6 μm). Ye (yellow) toners 11 and 12 shown in Production Examples 15 and 16 were produced in the same manner as in Production Example 11 except that the procedure was changed as described above.
For the pigment dispersion type, a dispersion prepared as follows was used as the Ye (yellow) colorant dispersion.

<Preparation of Ye (yellow) colorant dispersion>
2-[(2-methoxy-4-nitrophenyl) azo] -N- (2-methoxyphenyl) -3-oxobutanamide as PY-74 in a 300 L internal volume container equipped with a stirrer (propeller blade) 32 parts (64 kg), 1.0 part of 20% sodium dodecylbenzenesulfonate aqueous solution, 5.5 parts of polyoxyethylene lauryl ether of HLB15.3, and ion exchange with an electric conductivity of 1.5 μS / cm or less 61.5 parts of water was added and predispersed to obtain a pigment premix solution.

The pigment premix solution was supplied as a raw material slurry to a wet bead mill and circulated and dispersed. The inner diameter of the stator was φ75 mm, the separator diameter was φ60 mm, the distance between the separator and the disk was 15 mm, and zirconia beads having a diameter of 50 μm (true density of 6.0 g / cm ³ ) were used as a dispersion medium. Since the effective internal volume of the stator is 0.5 L and the filling volume of the media is 0.35 L, the media filling rate is 70%.
The rotation speed of the rotor is constant (the peripheral speed of the rotor tip is 11 m / sec), and the pigment premix liquid is continuously supplied from the supply port by a non-pulsating metering pump at a supply speed of 50 L / hr and continuously from the discharge port. The yellow (Y) colorant dispersion was obtained when a predetermined particle size was reached by repeatedly discharging and repeating this. The volume median diameter (Dv ₅₀ ) of the Ye (yellow) colorant dispersion measured with Nanotrac was 159 nm, the pH was 6.6, and the solid content concentration was 38.7% by mass.

Production Examples 17 to 19
In the preparation process (aggregation process) of the Ma (magenta) toner base particle 11 dispersion, the amount of the polymer primary particles added as the solid content, the pigment dispersion liquid type, the number of pigments as the solid content, and the primary polymer after completion of the primary aggregation The amount of addition as a solid content of the particles, the addition amount as a solid content of the high heat resistant resin fine particles, and the high heat resistant resin fine particles coat the toner base particles (the toner base particles are assumed to be 5.6 μm). Bk (black) toners 11, 12 and 13 shown in Production Examples 17 to 19 were produced in the same manner as in Production Example 11 except that the procedure was changed as described above.
As the pigment dispersion liquid type, a dispersion liquid prepared as follows was used as a Bk (black) colorant dispersion liquid.

<Preparation of Bk (black) colorant dispersion>
The container stirrer equipped with a propeller blade, manufactured by Mitsubishi Chemical Corporation Carbon black # 44 (catalog properties: particle size 24 nm, a nitrogen adsorption specific surface area 110m ² / g, coloring power 129%, granular 77cm ^3/100 g, volatile content 0 0.8%, pH value 8, PVC blackness 10) 20 parts, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20D) 1 part, nonionic surfactant (Kao Co., Emulgen 120) 4 parts and 75 parts of ion-exchanged water having an electric conductivity of 1 μS / cm were added, and the mixture was predispersed until the volume median diameter Dv ₅₀ was about 90 μm to obtain a pigment premix solution.

The rotation speed of the rotor is constant (the peripheral speed at the tip of the rotor is about 11 m / sec), and the pigment premix solution is supplied from the supply port at a supply speed of about 40 L / hr by a non-pulsating metering pump, and the product is obtained from the discharge port. did. During operation, cooling water of about 10 ° C. was circulated from the jacket to obtain a Bk (black) colorant dispersion having a volume median diameter (Dv ₅₀ ) of 147 nm and a solid content concentration of 24.6%. .

Primary aggregation temperature / final rounding temperature in the aggregation process, volume median diameter (Dv ₅₀ ), number median diameter (Dn ₅₀ ), particle diameter distribution (Dv ₅₀ / Dn ₅₀ ) The average circularity is also shown in Table 4.
Further, for the toners obtained in Production Examples 11 to 19, TP1 and TP2 were measured by the above-described method, and TP2 / TP1 was obtained by dividing the value of TP2 by TP1, and is shown in Table 4.

For the toners obtained in Production Examples 11 to 19, blocking resistance B was measured, judged and scored by the following method, and listed in Table 4.

[Measurement method of blocking resistance B]
10 g of toner is put in a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, and a load of 20 g is put on it and left in an environment of a temperature of 50 ° C. and a humidity of 55% for 48 hours, and then the toner is taken out of the container and the load is applied from above. The degree of aggregation was confirmed by applying.
The collapse load is described in Table 4, and further, determined and scored according to the following criteria, and the results are shown in Table 4.

[Decision criteria and points for blocking resistance B]
It will not collapse unless a load exceeding 1500 g is applied: ×
(0 points, 3 colors can be overlaid, color machine cannot be used)
It collapses with a load exceeding 1300 g and 1500 g or less:
(3 points, 3 colors can be overlaid, can be used with color machines)
Collapses with a load of 1300 g or less: ◎
(5 points can be used with a color machine that can superimpose three colors. Can be used even at low-temperature fixing and high-speed printing.)

The toners obtained in Production Examples 11 to 19 were measured, judged, and scored according to the following method, and listed in Table 4.

[Measurement method of fixing test B]
10 parts of toner and 100 parts of a volume median particle size 35 μm ferrite carrier were stirred and mixed to obtain a developer. This developer is a non-magnetic two-component (using organic photoreceptor) development method, roller (PCR) charging, mag roller development method, development speed A4 horizontal conversion 50 sheets / minute, 4-color tandem method, commercially available with IH fixing device Using a full-color printer, each color was printed as a single color, and an image with an image density of about 1.7 was printed.

Even when three or more colors of toner were developed at the same time and had a high adhesion amount, the following determination / score was given as an index that low-temperature fixability could withstand in practical use.
[Judgment criteria and points for fixing test B]
Residual rate less than 35%: ×
(Can not be used with 3 color superimposing color machines. Fail 0 points)
Remaining rate 35% or more and less than 45%: ○
(Three colors can be overlaid. Can be used on a color machine. Pass even at low temperature fixing. 3 points)
Residual rate 45% or more: ◎
(Available with 3 color superimposing color machines. 5 points for low temperature fixing and high speed printing)

Example 11
When the Ma toner 11, the Cy toner 12, the Ye toner 11, and the Bk toner 12 are combined, the TP2 / TP1 value of each color toner and the TP2 / TP1 value of the Ma toner are three colors other than the Ma toner. The value divided by the average value of TP2 / TP1, the collapse load / determination / score as blocking resistance B of each toner, and the remaining rate / determination / score of fixing test B as fixability B, and further as a toner set Table 5 shows the results of scoring and determination based on the following criteria as the overall judgment B.

[Determined as total score B as toner set]
The total score B as a combination of the four colors is obtained by adding the score B as the fixing test B of each color to the total score of the blocking resistance B of each color as a total score B. B was carried out and is shown in Table 5. However, in the evaluation of each color of the blocking resistance B and the fixing test B, if there is an item judged as “×” (0 points) even in one item, the total score B is 0 because the toner cannot be set and can withstand actual use. Points.

[Comprehensive judgment B]
Total score less than 24 points: ×
(Three color stackable color machines cannot be used or rejected)
Total score 24 points or more and less than 32 points:
(Acceptable for use with 3 color superimposing color machines)
Total score 32 points or more and less than 39 points: ○
(It can be used with a color machine that can superimpose three colors.
Total score 39 points or more: ◎
(It can be used with a color machine that can superimpose three colors, and passes even when fixing at low temperatures and at high speeds.)

Comparative Example 11
In Comparative Example 11, the numerical values of the respective items were measured and calculated in the same manner as in Example 11 except that the toners of the respective colors were changed to the combinations shown in Table 5 as a toner set, and determination / comprehensive determination was performed. It was shown to.

Explanation of Estimation Examples 11 to 21 FIG. 5 plots the collapse load (g), which is an index of blocking resistance of each color, on the Y axis with TP2 / TP1 as the X axis for the experimental results in Table 5. Furthermore, a thick line represents a 1500 g line that is a critical point in practical use on the Y axis and a 1300 g line that passes the blocking resistance within a preferable range.
Furthermore, since it was confirmed that the correlation between Bk (black circles) in FIG. 5 shows good linearity between X and Y, the regression equation expressed in a linear form using the least square method for each color is shown. Indicated.

In FIG. 6, with respect to the experimental results shown in Table 5, TP2 / TP1 is plotted on the X axis, and the residual ratio (%), which is an index of fixability of each color, is plotted on the Y axis. Further, the bold line represents the line of 35%, which is a critical point in practical use, and 45% where the fixability is acceptable in a preferable range on the Y axis.
Furthermore, when the correlation of Bk (black circle) in FIG. 6 is confirmed, it is confirmed that a good linearity is shown between X and Y. Therefore, the regression equation expressed in a linear form using the least square method for each color. showed that.

Table 6 shows the lower limit and preferred lower limit of TP2 / TP1 for each color derived from the intersection of 1500 g and 1300 g of the primary line form and blocking resistance of FIG. 5, and the primary line form and fixability of FIG. 6. The upper limit and the preferable upper limit value of TP2 / TP1 derived from the intersections of 45% and 35% of the remaining ratio are shown.
Moreover, as the most preferable TP2 / TP1, an average value of a preferable lower limit and a preferable upper limit is shown as a median value.

The TP2 / TP1 of the Ma toner 11 of Production Example 11 used in Example 11 is 1.39, and both the blocking resistance and the fixing property are both excellent, but the Bk toner 11 of Production Example 17 used in Comparative Example 11 Although TP2 / TP1 is 1.40, which is almost the same TP2 / TP1 as Ma toner 11, it is clear from Table 6 that the blocking resistance is out of the actual use range. As is clear, the lower limit / preferable lower limit, the center, the preferable upper limit, and the upper limit of TP2 / TP1 are different for each color, and TP2 / TP1 needs to be different for each color. I understand.

In the estimation examples 11 to 21 shown in Table 7, these correlations are analyzed and explained in more detail, and for the purpose of clarifying each critical point, anti-blocking resistance using TP2 / TP1 shown in FIG. 5 as an explanatory variable. 6 is calculated based on the primary line format, and the remaining rate regarding the fixability with TP2 / TP1 shown in FIG. 6 as an explanatory variable is based on the assumption of TP2 / TP1 based on the primary line format. Based on the calculated result, the result of each determination / score is shown.
Further, the value obtained by dividing the TP2 / TP1 value of the Ma toner by the average value of the three colors TP2 / TP1 other than the Ma toner, the collapse load / determination / score as the blocking resistance of each toner, and the fixing property Table 7 also shows the remaining rate / determination / score, as well as the results of scoring and determination based on the following criteria as the overall determination B as the toner set.

The estimation example 11 shows an example in which four colors are manufactured with 1.37 which is the median value of the preferable TP2 / TP1 range as the performance of the Ma toner alone, but blocking resistance of the Bk toner (4) and the Cy toner (3) is shown. It can be seen that the characteristic is out of the actual use range and out of the actual use range as a four-color set.
Estimation Example 12 shows an example in which four colors are manufactured at 1.62 which is the median value of the TP2 / TP1 range preferable as the Cy toner single unit performance. However, the fixability of Ma toner (4) is out of the actual use range. It turns out that it is out of the actual use range as a four-color set.

The estimation example 13 shows an example in which four colors are manufactured at 1.54 which is the median value of the TP2 / TP1 range preferable as the single performance of each of the Ye toner and the Bk toner. However, the fixability of the Ma toner (5) is shown. It can be seen that it is outside the actual use range and out of the actual use range as a four-color set.

Therefore, it can be seen that, even if four colors are adjusted to the preferred TP2 / TP1 value of any color, the actual color is out of the usable range as a four-color set.

Further, in the estimation examples 14 to 21, in the four-color set, if the value obtained by dividing the TP2 / TP1 value of the Ma toner by the average value of the three colors TP2 / TP1 other than the Ma toner is in any range, The result of analyzing whether the color set is actually usable or actually usable within a preferable range is shown.
Specifically, when Cy, Ye, and Bk toners have the most preferable median value (TP2 / TP1), any TP2 / TP1 value that Ma toner takes can be used as a four-color set. It was analyzed whether it could be used in the preferred range.

As a result, when the value obtained by dividing the TP2 / TP1 value of the Ma toner by the average value of TP2 / TP1 of the three colors other than the Ma toner is 0.817 or more and 0.951 or less, it can be actually used. When the value obtained by dividing the TP2 / TP1 value of the toner by the average value of TP2 / TP1 of the three colors other than the Ma toner is 0.849 or more and 0.900 or less, it is understood that the four-color set is preferable.

<Result>
From Tables 5 and 7, when the value obtained by dividing the TP2 / TP1 value of the Ma toner by the average value of TP2 / TP1 of the three colors other than the Ma toner is 0.817 or more and 0.951 or less, the comprehensive determination is made. “◎”, “◯”, “△”, the anti-blocking property remains good, and the result of the fixing test is also good, but the TP2 / TP1 value of Ma toner is TP2 / TP1 of three colors other than Ma toner. When the value divided by the average value is less than 0.817 or exceeds 0.951, the overall judgment is “x”, and it is understood that it cannot be achieved.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on June 22, 2016 (Japanese Patent Application No. 2016-1223827) and a Japanese patent application filed on July 15, 2016 (Japanese Patent Application No. 2016-140670). Incorporated herein by reference.

1 Structure composed of high heat resistant resin fine particles and external additives (may have discontinuous parts)
2 Core component (component constituting the central part of the toner)
3 tan δ curve of the first measurement and TP1
4 Tan δ curve and TP2 of the second measurement
A Convex part of toner surface with many thin heat-resistant resin fine particle components B Concave part of toner surface with few thin heat-resistant resin fine particle components

Claims

A toner set including at least an electrostatic charge image developing black toner and an electrostatic charge image developing magenta toner, wherein a first measured value of a tan δ maximum value observed at 40 ° C. or more and 80 ° C. or less by a rheometer is TP1, When the second measured value of the tan δ maximum value observed between 40 ° C. and 80 ° C. is TP2, TP2 / TP1 of the electrostatic charge image developing black toner is TP2 / TP1 of the electrostatic charge image developing magenta toner. 1.03 times or more and 1.32 times or less of the toner set.
The toner set according to claim 1, wherein the electrostatic charge image developing black toner and the electrostatic charge image developing magenta toner include at least a binder resin, a colorant, a release agent, and an external additive.
3. The toner set according to claim 1, wherein TP2 / TP1 of the electrostatic charge image developing magenta toner and the electrostatic charge image developing black toner is 1.20 or more and 2.50 or less.
The toner set according to any one of claims 1 to 3, wherein TP2 / TP1 of the magenta toner for developing an electrostatic charge image is 1.28 or more and 1.49 or less.
The toner set according to any one of claims 1 to 4, wherein TP2 / TP1 of the black toner for developing an electrostatic charge image is 1.45 or more and 1.77 or less.
The black toner for developing electrostatic images contains carbon black, and the magenta toner for developing electrostatic images contains at least one of quinacridone dyes and pigments and monoazo dyes. 6. The toner set according to any one of items 5.
A toner cartridge containing the toner set according to any one of claims 1 to 6.
An image forming apparatus containing the toner set according to any one of claims 1 to 6.
An image forming method for forming an image using the toner set according to any one of claims 1 to 6.
A toner set including at least a magenta toner for developing an electrostatic image, a cyan toner for developing an electrostatic image, a yellow toner for developing an electrostatic image, and a black toner for developing an electrostatic image. When the first measured value of the tan δ maximum value observed below is TP1, and the second measured value of the tan δ maximum value observed at 40 ° C. or more and 80 ° C. or less is TP2, the magenta toner for developing the electrostatic charge image is used. TP2 / TP1 is 0.817 times or more and 0.951 times or less of the average value of TP2 / TP1 of the cyan toner for developing electrostatic images, the yellow toner for developing electrostatic images, and the black toner for developing electrostatic images. A toner set characterized by
A tan δ maximum value observed in a rheometer at 40 ° C. or higher and 80 ° C. or lower, wherein the electrostatic image developing black toner is used in a toner set including at least an electrostatic image developing black toner and an electrostatic image developing magenta toner. The first measured value of TP1 is TP1, and the second measured value of the tan δ maximum value observed between 40 ° C. and 80 ° C. is TP2, and TP2 / TP1 of the black toner for developing electrostatic images is the electrostatic charge. A black toner for developing an electrostatic charge image, which is 1.03 times or more and 1.32 times or less of TP2 / TP1 of magenta toner for image development.
12. The electrostatic charge image development according to claim 11, wherein TP2 / TP1 of the electrostatic charge image developing black toner is 1.13 times or more and 1.20 times or less of TP2 / TP1 of the electrostatic charge image development magenta toner. For black toner.
The toner comprises toner base particles containing at least a core component containing a binder resin and a colorant and a high heat-resistant resin fine particle component present around the core component, and the core component and the high component when measured with a transmission electron microscope. The black toner for developing an electrostatic charge image according to claim 11, wherein the heat-resistant resin fine particle component has no shadow difference.
An electrostatic image developing magenta toner used in a toner set including at least an electrostatic image developing magenta toner, an electrostatic image developing cyan toner, an electrostatic image developing yellow toner, and an electrostatic image developing black toner, When the first measured value of the tan δ maximum value observed at 40 ° C. or higher and 80 ° C. or lower with a rheometer is TP1, and the second measured value of the tan δ maximum value observed at 40 ° C. or higher and 80 ° C. or lower is TP2, TP2 / TP1 of the electrostatic image developing magenta toner is 0.817 times the average value of TP2 / TP1 of the electrostatic image developing cyan toner, electrostatic charge image developing yellow toner, and electrostatic charge image developing black toner. A magenta toner for developing an electrostatic charge image, wherein the magenta toner is 0.951 times or more.
TP2 / TP1 of the electrostatic image developing magenta toner is 0.849 of an average value of TP2 / TP1 of the electrostatic image developing cyan toner, electrostatic image developing yellow toner, and electrostatic image developing black toner. The magenta toner for developing an electrostatic charge image according to claim 14, which is not less than twice and not more than 0.900 times.
The toner comprises toner base particles containing at least a core component containing a binder resin and a colorant and a high heat-resistant resin fine particle component present around the core component, and the core component and the high component when measured with a transmission electron microscope. The magenta toner for developing an electrostatic charge image according to claim 14 or 15, wherein the heat-resistant resin fine particle component has no shadow difference.