JP2005274963A - Electrostatic developing toner, electrostatic developing color toner, production method of them and developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic developing color toner having excellent oilless fixing strippability, brilliance and OHP transparency, to provide a production method of the electrostatic developing color toner and to provide a developer using the electrostatic developing color toner. <P>SOLUTION: The electrostatic developing color toner which comprises binder resin, a colorant and a releasing agent and has a shape factor SF1 of 110 to 140 satisfies the following conditions (1)-(4). In the colorant, the number proportion of primary particles of which the minor axis is 15 to 80 nm is ≥95%, the major axis is ≤150 nm and the ratio of the minor axis to the major axis is 1/1 to 1/3. (1) Frequency of magenta toner is 6.28 rad/s and storage modulus G1'm determined from dynamic viscoelastic measurement at 160°C is 200 to 400 Pa. (2) Storage modulus G1'y, G1'c and G1'k of yellow toner, cyan toner and black toner determined from the dynamic viscoelastic measurement is 90 to 200 Pa. (3) (G1'c/G1'm), (G1'y/G1'm) and (G1'k/G1'm) falls into the range of 0.22 to 0.96 and the relation of G2'm>G2'k>G2'y≥G2'c holds. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention includes an electrostatic charge developing toner used when developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, and toners of cyan, magenta, yellow, and black. The present invention also relates to a color toner for electrostatic charge development, a production method thereof, and a developer.

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

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

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

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

In recent years, as a means for intentionally enabling control of the toner shape and surface structure, a toner production method using an emulsion polymerization aggregation method has been proposed (see, for example, Patent Documents 1 and 2).
In general, a resin dispersion is prepared by emulsion polymerization or the like. On the other hand, a colorant dispersion in which a colorant is dispersed in a solvent is prepared, and then mixed to form an aggregate corresponding to the toner particle size, and heated. In this way, the toner is fused and united to obtain a toner.
The shape can be controlled to some extent by this method, and the chargeability and durability can be improved. However, since the internal structure is almost uniform, the peelability of the fixing sheet at the time of fixing, when OHP is output Problems remain in the stabilization of transparency and the existence of a difference in color between charges.

As described above, in the electrophotographic process, in order to stably maintain the performance of the toner even under various mechanical stresses, the surface hardness can be maintained without suppressing the exposure of the release agent to the surface or the fixing property. In addition, it is necessary to improve the mechanical strength of the toner itself and to achieve both sufficient charging and fixing properties.
Further, in recent years, the demand for higher image quality has increased, and in particular for color image formation, there has been a significant tendency to reduce the diameter of toner in order to achieve high-definition images. However, with the simple reduction in size while maintaining the conventional particle size distribution, the presence of fine powder side toner causes significant problems of carrier and photoconductor contamination and toner scattering, making it difficult to achieve high image quality and high reliability at the same time. It is. For this purpose, it is necessary that the particle size distribution can be sharpened and the particle size can be reduced.

In recent years, in digital full-color copiers and printers, color image originals are separated by B (blue), R (red), and G (green) filters, and then the dot diameter is 20 to 70 μm corresponding to the original original. The latent image is developed using Y (yellow), M (magenta), C (cyan), and Bk (black) developers using a subtractive color mixing effect, but a larger amount of developer than conventional black and white machines. Uniform chargeability, sustainability, toner strength, and sharpness of particle size distribution are becoming more and more important because it is necessary to transfer the toner and to cope with a smaller dot diameter. Further, in view of speeding up and energy saving of these machines, further low temperature fixability is required. In view of these points, the agglomerated and coalesced toner suitable for the production of a small particle size with a sharp particle size distribution has excellent characteristics.
The toner mounted on the full color machine needs to be sufficiently mixed with a large amount of toner, and improvement of color reproducibility and OHP transparency are essential at this time. In particular, this tendency becomes conspicuous in a reproduction region that is an intermediate color such as skin color and has a low toner paste amount per unit area.

  Generally, a polyolefin-based wax is internally added to the release agent component for the purpose of preventing low temperature offset during fixing. Along with this, a small amount of silicone oil is uniformly applied to the fixing roller to improve the high temperature offset property. For this reason, silicone oil adheres to the output transfer material that is output, and there is an unpleasant feeling of stickiness when it is handled, which is not preferable.

For this reason, an oilless fixing toner in which a large amount of a release agent component is included in the toner has been proposed (for example, see Patent Document 3).
However, in this case, the releasability can be improved to some extent by adding a large amount of the release agent, but the compatibility of the binder component and the release agent occurs, and the bleeding of the stable release agent is not uniform. Therefore, it is difficult to obtain the stability of peeling. Furthermore, since the means for controlling the cohesive force of the binder resin of the toner depends on the Mw and Tg of the binder, it is difficult to directly control the spinnability and cohesiveness at the time of fixing the toner. Furthermore, the free component of the release agent may cause charging inhibition.

  As a method for solving these problems, a method of obtaining the rigidity of the binder resin by adding a high molecular weight component (see, for example, Patent Documents 4 and 5), or compensating by introducing chemical cross-linking, and as a result, There has been proposed a method for improving the releasability in oilless fixing that reduces the spinnability at the fixing temperature (see, for example, Patent Documents 6 and 7).

  On the other hand, regarding the release agent, an approach to the problems of the oilless fixability, particularly oilless peelability, OHP transparency in a full color image, or toner powder fluidity inhibition caused by the release agent has been studied and proposed. (For example, Patent Document 8). Specifically, for the purpose of improving oil releasability, the melt viscosity is lowered by setting the melting point of the release agent to a medium temperature range and applying an amorphous or low crystalline release agent such as ester wax. This suppresses oilless peelability, and suppresses OHP transparency inhibition of full-color images by this low crystal structure.

  However, in this case, the release agent component often causes plasticization in the binder resin component, and as a result, the rheology of the resin at the time of fixing is lowered, so that the oilless releasability of the toner is lowered. For this reason, it is necessary to introduce a cross-linking structure on the surface of the binder resin itself, to increase the molecular weight and Tg, to suppress a decrease in peelability due to plasticization, and to introduce a large amount of release agent. In particular, the image gloss is lowered and the transparency of the OHP is often impaired. Furthermore, since a large amount of release agent is required, not only is it disadvantageous in cost, but the amount of the release agent on the fixed image increases, and as a result, contact occurs when it is discharged after being fixed on the machine. Due to the roll, contact marks are generated in the release agent layer, and the image quality is impaired. This becomes more conspicuous as the image has a higher glossiness.

  Further, in order to have good transparency, it is important that the volume average particle diameter of the colorant in the toner is small. If the pigment itself is agglomerated or agglomerated in the toner, such as when the volume average particle diameter of the colorant is large or the colorant has a large number of coarse particles, the transparency of the toner is deteriorated due to the deterioration of the light transmittance of the toner. Becomes worse. In order to ensure color reproducibility and transparency, many regulations have been made in the pigment treatment process. For example, in the kneading and pulverizing method, a master batch method in which the pigment concentration is increased and pre-kneading is generally used, and a flushing method in which the aqueous medium of the pigment cake is replaced with a resin or a method using a three-roll mill is known. It has been. When the flushing method is used, since the water-containing cake before drying the pigment is used, the pigment can be finely dispersed as a whole without aggregation occurring during drying.

It is generally difficult to use a release agent such as wax in order to achieve moderate gloss in color image reproduction and transparency for obtaining an excellent OHP image. For this reason, a large amount of oil is applied to the fixing roll to assist in releasing the mold, so that not only the sticky feeling of a copy image containing OHP and the addition of the image to the image with a pen are difficult, but also a non-uniform gloss. It often creates a feeling. Waxes such as polyethylene, polypropylene, and paraffin that are commonly used in normal black-and-white copying are more difficult to use because they impair OHP transparency.
Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP-A-5-061239 JP-A-4-69666 Japanese Patent Laid-Open No. 9-258481 JP 59-218460 A JP 59-218459 A JP-A-6-337541

The present invention provides a toner for developing an electrostatic charge, a color toner for developing an electrostatic charge, a method for producing the same, and a developer that have solved the above-mentioned problems in the conventional toner.
That is, the object of the present invention is to maintain excellent releasability and good glossiness in oilless fixing, excellent fixing characteristics such as fixed image surface glossiness and OHP transparency, and a discharge roll for discharging a fixed image. The present invention provides a toner for developing an electrostatic charge, a color toner for developing an electrostatic charge, a method for producing the same, and a developer that exhibit fine image quality without any contact mark of the roll.

The above problems have been solved by the present invention described below.
<1> A yellow toner, a magenta toner, a cyan toner, and a black toner, each of which is an electrostatic charge developing color toner including at least a binder resin, a colorant, and a release agent, and the following (1) A color toner for developing electrostatic charge, which satisfies the conditions (4) to (4).
(1) The storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement of the magenta toner at a frequency of 6.28 rad / s and a temperature of 160 ° C. is 200 to 400 Pa (2000 to 4000 dyn / cm ² ).
(2) The storage elastic moduli G1′y, G1′c, and G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. for yellow toner, cyan toner, and black toner are 90 to 200 Pa. (900 to 2000 dyn / cm ² ).
(3) (G1′c / G1′m), (G1′y / G1′m) and (G1′k / G1′m) are in the range of 0.22 to 0.96, respectively.
(4) Storage elastic modulus G2′y, G2′m, G2′c and G2 obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 180 ° C. for yellow toner, magenta toner, cyan toner and black toner. “k” has a relationship of G2′m>G2′k> G2′y ≧ G2′c.

<2> In at least one of the yellow toner, magenta toner, cyan toner, and black toner, the release agent is polyalkylene, and a temperature of 85 ° C. obtained from measurement of dynamic viscoelasticity of the polyalkylene. The complex viscosity η * a at a measurement frequency of 6.28 rad / s is 0.1 to 1.0 Pa · s, and the complex viscosity η * a and a temperature of 85 ° C. determined from dynamic viscoelasticity measurement, The ratio (η * a) / (η * b) to the complex viscosity η * b at a measurement frequency of 62.8 rad / s is 1.0 to 3.5, as described in <1> Color toner for electrostatic charge development.

<3> The maximum value of the endothermic peak obtained from the differential thermal analysis of the polyalkylene is 85 to 95 ° C., and the total endothermic area of the component at 85 ° C. or less obtained from the area of the endothermic peak of the polyalkylene. 3. The electrostatic charge according to claim 2, wherein the ratio is 5 to 15%, and the amount of polyalkylene in the toner determined from the peak height of the endothermic maximum value is 6 to 9% by mass. Color toner for development.

<4> Viscosity ηs140 obtained from an E-type viscometer equipped with a cone plate having a cone angle of 1.34 ° at 140 ° C. of the polyalkylene is 1.5 to 5.0 mPa · s. The color toner for electrostatic charge development according to 2> or <3>.

<5> The polyalkylene includes at least a rod-like polyalkylene and a massive polyalkylene, and the size of the rod-like polyalkylene and the massive polyalkylene is 200 to 1500 nm. <2> The color toner for electrostatic charge development according to any one of to <4>.

<6> The electrostatic charge developing color toner according to any one of <2> to <5>, wherein the area ratio of the polyalkylene bulk crystals is 10 to 30%.

<7> At least one of the yellow toner, magenta toner, cyan toner, and black toner has a coating layer, has a thickness of 0.1 to 0.3 μm, and is obtained from XPS. The color toner for electrostatic charge development according to any one of <1> to <6>, wherein the amount of polyalkylene present on the surface is 11 to 30 atm%.

<8> A developer composed of an electrostatic charge developing color toner having a yellow toner, a magenta toner, a cyan toner, and a black toner, and a carrier, and each toner in the electrostatic charge developing color toner is at least bound A developer comprising a resin, a colorant and a release agent and satisfying the following conditions (1) to (4):
(1) The storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement of the magenta toner at a frequency of 6.28 rad / s and a temperature of 160 ° C. is 200 to 400 Pa (2000 to 4000 dyn / cm ² ).
(2) The storage elastic moduli G1′y, G1′c, and G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. for yellow toner, cyan toner, and black toner are 90 to 200 Pa. (900 to 2000 dyn / cm ² ).
(3) (G1′c / G1′m), (G1′y / G1′m) and (G1′k / G1′m) are in the range of 0.22 to 0.96, respectively.
(4) Storage elastic modulus G2′y, G2′m, G2′c and G2 obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 180 ° C. for yellow toner, magenta toner, cyan toner and black toner. “k” has a relationship of G2′m>G2′k> G2′y ≧ G2′c.

<9> An electrostatic charge developing toner containing a binder resin, a colorant and a release agent, and having a shape factor SF1 of 110 to 140, wherein the colorant is a primary particle having a minor axis in the range of 15 to 80 nm. The electrostatic charge developing toner is characterized in that the number ratio is 95% or more of all particles, the major axis is 150 nm or less, and the ratio of the minor axis to the major axis is 1: 1 to 1: 3.

<10> The colorant is composed of one or more organic pigments, has a dispersed particle diameter D50 of 50 to 250 nm, and a pigment content in the toner of 3 to 10% by mass. <9> The electrostatic charge developing toner according to <9>.

<11> The release agent is a polyalkylene, and the maximum value of the endothermic peak obtained by differential thermal analysis of the polyalkylene is 85 to 95 ° C., and from the height of the peak of the endothermic maximum value. The toner for electrostatic charge development according to <9> or <10>, wherein the amount of polyalkylene in the toner is 6 to 9% by mass.

<12> The polyalkylene includes at least a rod-like polyalkylene and a massive polyalkylene, and the size of the rod-like polyalkylene and the massive polyalkylene is 200 to 1500 nm. <9> -The toner for electrostatic charge development according to any one of <11>.
<13> The electrostatic charge developing toner according to any one of <9> to <12>, wherein the colorant has a structure partially or entirely covered with a resin.

<14> At least one electrostatic charge developing toner among yellow toner, magenta toner, cyan toner and black toner among the electrostatic charge developing color toners according to any one of <1> to <7>, And a method for producing an electrostatic charge developing toner according to any one of <9> to <13>, wherein a binder resin particle dispersion in which binder resin particles are dispersed, and a colorant particle The dispersed colorant particle dispersion liquid and the release agent dispersion liquid in which the release agent particles are dispersed are mixed, and at least one metal salt polymer is added to the binder resin particles and the colorant particles. And an aggregating step for forming an agglomerated particle dispersion in which agglomerated particles containing release agent particles are dispersed, and fusing and coalescing by heating the agglomerated particle dispersion to a temperature above the glass transition point of the binder resin. A process for producing a toner for developing an electrostatic charge, comprising: Method.

  The present invention maintains excellent releasability and good glossiness in oilless fixing, has excellent fixing characteristics such as fixed image surface glossiness and OHP transparency, and roll contact with a discharge roll when discharging a fixed image It is possible to provide a toner for developing an electrostatic charge, a color toner for developing an electrostatic charge, a production method thereof, and a developer that show fine image quality without a mark.

The color toner for electrostatic charge development of the present invention has a yellow toner, a magenta toner, a cyan toner and a black toner, and each toner contains at least a binder resin, a colorant and a release agent. The condition (4) is satisfied. Hereinafter, the color toner for electrostatic charge development of the present invention having the above-mentioned yellow toner, magenta toner, cyan toner and black toner is referred to as “color toner of the present invention”.
(1) The storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement of the magenta toner at a frequency of 6.28 rad / s and a temperature of 160 ° C. is 200 to 400 Pa (2000 to 4000 dyn / cm ² ).
(2) The storage elastic moduli G1′y, G1′c, and G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. for yellow toner, cyan toner, and black toner are 90 to 200 Pa. (900 to 2000 dyn / cm ² ).
(3) (G1′c / G1′m), (G1′y / G1′m) and (G1′k / G1′m) are in the range of 0.22 to 0.96, respectively.
(4) The storage elastic moduli G2′y, G2′m, G2′c and G2′k at a frequency of 6.28 rad / s and a temperature of 180 ° C. of yellow toner, magenta toner, cyan toner and black toner are G2′m>G2′k> G2′y ≧ G2′c.

  The electrostatic charge developing toner of the present invention contains a binder resin, a colorant, and a release agent, has a shape factor SF1 of 110 to 140, and the colorant has a minor axis in the range of 15 to 80 nm. The number ratio of primary particles is 95% or more of all particles, the major axis is 150 nm or less, and the ratio of minor axis to major axis is 1: 1 to 1: 3. Hereinafter, the electrostatic charge developing toner of the present invention containing the colorant having the specific shape described above is referred to as “the electrostatic charge developing toner of the present invention”.

First, the toner of the present invention will be described in detail.
The toner of the present invention contains a colorant having a specific primary particle size as a colorant at a high ratio, thereby suppressing aggregation of the colorant generated in the toner due to a low share, a good color reproduction range, It achieves both high peelability and good gloss, and maintains fine image quality.
More specifically, in the step of adjusting the colorant dispersion, the primary particles of the colorant are colored over time and resistant to pH changes by including a material that suppresses the occurrence of aggregation such as a polyphosphate compound. By adjusting the agent dispersion, a color toner for electrostatic charge development that maintains a good color gamut and fine image quality is obtained.

As described above, in the colorant used in the toner of the present invention, the number ratio of primary particles having a minor axis in the range of 15 to 80 nm is 95% or more of all particles, and the major axis is 150 nm or less. Further, the ratio of the minor axis to the major axis is 1: 1 to 1: 3. By satisfying these requirements, not only a good color gamut and color developability but also transparency when an image is formed on OHP. It will be excellent.
Here, the short diameter in the colorant means a diameter that minimizes the distance connecting points having the same normal line on the surface of the colorant particle, and the long diameter means the same method on the surface of the colorant particle. The diameter that maximizes the distance connecting points with lines.
The minor axis and major axis of the colorant used in the toner of the present invention are values observed with a transmission electron microscope.

If the minor axis of the colorant is less than 15 nm, the toner has good transparency, but the color developability is impaired. If it exceeds 80 nm, the transparency of the toner is impaired.
The minor axis of the colorant is preferably 25 to 60 nm, and more preferably 28 to 55 nm.

If the number ratio of primary particles having a minor axis in the range of 15 to 80 nm is less than 95%, variations in color developability and transparency between toner particles are likely to occur.
The number ratio of primary particles having a minor axis in the range of 15 to 80 nm is preferably 97% or more, and more preferably 98% or more.

When the major axis of the colorant exceeds 150 nm, the transparency of the toner is impaired.
The major axis of the colorant is preferably 130 nm or less, and more preferably 125 nm or less.

When the ratio of the major axis to the minor axis in the colorant exceeds 3, the dispersibility in the toner particles is deteriorated, and transparency and charging stability are likely to be impaired.
The ratio of the minor axis to the major axis is preferably 1: 1 to 1: 2.5, and more preferably 1: 1 to 1: 2.

The toner of the present invention is preferably produced by the following emulsion polymerization aggregation method.
The emulsion polymerization aggregation method includes a binder resin particle dispersion in which binder resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent dispersion in which release agent particles are dispersed. And agglomeration step of forming an aggregated particle dispersion in which aggregated particles containing binder resin particles, colorant particles, and release agent particles are dispersed. And aggregating step of fusing and coalescing the agglomerated particle dispersion by heating to a temperature equal to or higher than the glass transition point of the binder resin, and the agglomerated particles between the aggregating step and the fusing step It is preferable to have an adhesion step in which a fine particle dispersion in which fine particles are dispersed is added and mixed in the dispersion to form fine particles on the aggregated particles to form adhered particles.
The binder resin particles are preferably fine particles having a particle size of 1 μm or less.

  Preparation of the toner by the emulsion polymerization aggregation method is preferable in that it can be incorporated as one of the constituent elements without limiting fine particles having an arbitrary function, but has a disadvantage that the particles are likely to aggregate. However, when the colorant used in the present invention having the above-mentioned particle diameter is used, the aggregation of particles can be prevented, and the disadvantage that the particles are easily aggregated can be overcome.

In the adhesion step, the fine particle dispersion is added to and mixed with the aggregated particle dispersion prepared in the aggregation step, and the fine particles are adhered to the aggregated particles to form adhered particles. Corresponds to particles newly added to the aggregated particles as viewed from the aggregated particles, and may be referred to as “additional fine particles” in this specification. As the additional fine particles, in addition to the resin fine particles, release agent fine particles, colorant fine particles and the like may be used singly or in combination.
The method of additionally mixing the fine particle dispersion is not particularly limited, and may be performed gradually, for example, or may be performed stepwise by dividing into a plurality of times.

  Thus, by adding and mixing the fine particles (additional fine particles), the generation of fine particles can be suppressed, and the particle size distribution of the resulting electrostatic image developing toner can be sharpened, resulting in higher image quality. Contribute. Also, by providing the adhesion step, a pseudo shell structure can be formed, and the toner surface exposure of internal additives such as a colorant and a release agent can be reduced, and as a result, the chargeability and the life can be improved. In addition, it is possible to maintain the particle size distribution during fusion in the fusion process, to suppress fluctuations, and to add a stabilizer such as a surfactant or base or acid to enhance stability during fusion. This is advantageous in that the cost can be reduced and the quality can be improved.

  Therefore, when using a release agent, it is more preferable to add additional fine particles mainly composed of resin fine particles. If this method is used, the toner shape can be easily controlled by adjusting the temperature, the number of stirring, the pH and the like in the fusing step. After completing the fusing process, the toner particles are washed and dried to obtain a toner. In consideration of the chargeability of the toner, it is preferable to sufficiently perform substitution washing with ion-exchanged water, and the degree of washing is generally monitored by the conductivity of the filtrate. You may include the process of neutralizing ion with an acid or an alkali at the time of washing | cleaning. The solid-liquid separation after washing is not particularly limited, but suction filtration, pressure filtration, etc. are preferably used from the viewpoint of productivity. Further, the drying method is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The binder resin particles used in the toner of the present invention are not particularly limited, but a binder resin particle dispersion containing an ionic surfactant is generally prepared by an emulsion polymerization method or the like. The binder resin particle dispersion is mixed with a colorant particle dispersion and a release agent particle dispersion, and heteroaggregation is caused by an ionic surfactant having a polarity opposite to that of the ionic surfactant. Then, aggregated particles having a toner diameter are formed, and then heated to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce the aggregated particles, and are washed and dried to obtain a toner. The toner shape is preferably from irregular to spherical.

In the agglomeration step, in the initial stage of mixing the binder resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion, the balance of the amount of the ionic dispersant of each polarity is shifted in advance. , Neutralize ionically by adding a polymer of metal salt, and then form the first-stage aggregated mother particles at a temperature below the glass transition point, stabilize, and then shift the ionic balance as the second stage. A resin fine particle dispersion treated with an ionic dispersant having a polarity and quantity so as to compensate for the resin is added, and if necessary, below the glass transition point of the resin fine particles in the aggregated particles and the resin contained in the additional resin fine particles. After slightly heating and stabilizing at a higher temperature, the particles added in the second stage of the agglomeration formation were coalesced while adhering to the surface of the base agglomerated particles by heating above the glass transition point. It may be a thing.
Further, the stepwise operation of aggregation may be repeated a plurality of times. This two-stage method is effective for improving the inclusion of the release agent and the colorant.
The metal salt polymer is preferably an inorganic metal salt polymer, and more preferably polyaluminum chloride.

  The binder resin used in the toner of the present invention is not particularly limited. For example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Esters having a vinyl group such as n-butyl acid, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, methacrylate Vinyl nitriles such as ronitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Polyols such as ethylene, propylene and butadiene Homopolymer consisting of a monomer, such fins acids, or copolymers obtained by combining two or more of these, and further can be mixtures thereof. In addition, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, etc., non-vinyl condensation resin, or a mixture of these with the vinyl resin, or a vinyl monomer in the presence of these resins Examples thereof include a graft polymer obtained by polymerizing a polymer.

  When a vinyl-based monomer is used as the binder resin, a binder resin particle dispersion can be prepared by carrying out emulsion polymerization using an ionic surfactant or the like. In addition, in the case of other resins, if the resin is soluble in an oily solvent with relatively low solubility in water, the resin is dissolved in those solvents and a homogenizer together with an ionic surfactant or polymer electrolyte in water. The resin fine particle dispersion can be prepared by dispersing as fine particles in water using a disperser and then evaporating the solvent by heating or decompressing.

The binder resin particles preferably have a center diameter of 1 μm or less, more preferably 50 to 400 nm, and even more preferably 70 to 350 nm.
In addition, when the center diameter of the binder resin particles exceeds 1 μm, the particle size distribution of the finally obtained toner of the present invention may be widened, or free particles may be generated, leading to deterioration of performance and reliability. is there. On the other hand, when the center diameter of the binder resin particles is less than 50 nm, the solution viscosity at the time of toner production becomes high, and the particle size distribution of the finally obtained toner may be wide.
When the center diameter of the binder resin particles is 1 μm or less and 70 nm or more, the uneven distribution between the toners is reduced, the dispersion in the toner is good, and the variation in performance and reliability is advantageous.
The volume average particle diameter of the resin fine particles can be measured by, for example, a Doppler scattering type particle size distribution measuring device (Nikkiso Co., Ltd., Microtrac UPA 9340) or a laser diffraction type particle size distribution measuring device (Horiba, Ltd., LA-700).

  In the colorant used in the toner of the present invention, the ratio of the number of primary particles having a minor axis in the range of 15 to 80 nm is 95% or more of all particles, the major axis is 150 nm or less, and the minor axis and major axis are further reduced. If the requirement that the ratio is 1: 1 to 1: 3 is not particularly limited, for example, in the case of a yellow pigment, C.I. I. Pigment Yellow (hereinafter abbreviated as “PY”)-74, PY-83, PY-93, PY-94, PY-95, PY-97, PY-109, PY-110, PY-120, PY-128, PY-138, PY-139, PY-147, PY-150, PY-151, PY-154, PY-155, PY-166, PY-175, PY-180, PY-181, PY-185, PY- 191 and the like are C.I. I. Pigment Orange (hereinafter abbreviated as “PO”)-61, PO-64, PO-71, PO-73, etc.

  For red pigments, C.I. I. Pigment Red (hereinafter abbreviated as “PR”)-4, PR-5, PR-23, PR-48: 2, PR-48: 4, PR-57: 1, PR-112, PR-122, PR- 144, PR-146, PR-147, PR-150, PR-166, PR-170, PR-177, PR-184, PR-185, PR-202, PR-207, PR-214, PR-220, PR-221, PR-238, PR-242, PR-254, PR-255, PR-264, PR-272, etc.

  For blue pigments, C.I. I. Pigment Blue (hereinafter abbreviated as “PB”)-15: 1, PB-15: 2, PB-15: 3, PB-15: 4, PB-15: 5, PB-15: 6, PB-16, PB-17: 1, PB-60, etc. are green pigments such as C.I. I. Pigment Green (hereinafter abbreviated as “PG”)-7, PG-36 and the like are purple pigments such as C.I. I. Pigment violet (hereinafter abbreviated as “PV”)-19, PV-23, PV-37 and the like are preferable.

  Further, these colorants can be used alone or mixed and further in a solid solution state. These colorants are dispersed by a known method. For example, a media type dispersing machine such as a rotary shear type homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.

  Furthermore, when preparing a colorant dispersion, a small amount of a dispersion stabilizer can be added to prevent aggregation of the colorant after dispersion. Although the action of the dispersion stabilizer is not clear, it is considered that it has the effect of suppressing static electricity generated between each material (colorant, water, surfactant, etc.) in the dispersion liquid, It is presumed that aggregation can be prevented.

  Preferred dispersion stabilizers include antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, phosphoric acid esters, polyphosphates such as sodium polyphosphate, zinc borate and the like. Among them, polyphosphate is a colorant. It is more preferable in that the aggregation of can be suppressed for a long time.

  Moreover, it is preferable that the addition amount of a dispersion stabilizer is 0.1 to 10% with respect to a coloring agent, it is more preferable that it is 0.2 to 2%, and it is about 0.3 to 1%. Is more preferable. If the amount of the dispersion stabilizer added is less than 0.1%, the effect for preventing aggregation may be reduced. On the other hand, when the amount of the dispersion stabilizer added exceeds 10%, the amount of the dispersant remaining in the toner increases, and the chargeability and powder fluidity of the toner may be reduced.

  The dispersion stabilizer may be added immediately after the colorant is dispersed, but in the case of a colorant whose aggregation progresses relatively quickly with time, it is added to the colorant before the colorant is dispersed, A method of dispersing is preferred.

The colorant is preferably dispersed in a number average particle diameter D50 of 50 to 250 nm. When the colorant is contained in the electrostatic charge developing toner in a range of 3 to 10% by mass, not only color developability but also OHP permeability. Will also be excellent. When the number average particle diameter D50 is less than 50 nm, the ratio of the surface area to the colorant volume becomes large, so that the dispersant is insufficient, the storage stability of the colorant dispersion is lowered, and other raw materials are used during toner production. Abnormal aggregation may occur due to shock when mixed with. On the other hand, if the number average particle diameter D50 exceeds 250 nm, the transparency and color developability of the toner may be impaired.
The number average particle size can be measured with a Doppler scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac UPA 9340) or a laser diffraction type particle size distribution measuring device (manufactured by Horiba, LA-700).

The colorant used in the toner of the present invention preferably has a structure in which it is partially or wholly covered with a resin. By having this structure, the dispersibility in the toner particles is improved.
Although there is no restriction | limiting in particular as said resin, For example, styrenes, such as styrene, parachlorostyrene, alpha-methylstyrene; Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid Esters having vinyl groups such as lauryl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; single quantities of polyolefins such as ethylene, propylene and butadiene Homopolymer consisting of, or copolymers obtained by combining two or more of these, and further can be mixtures thereof. In addition, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, etc., non-vinyl condensation resin, or a mixture of these with the vinyl resin, or a vinyl monomer in the presence of these resins And a graft polymer obtained by polymerizing the polymer.

  The release agent used in the toner of the present invention is preferably a substance having a main maximum peak measured in accordance with ASTM D3418-8 at 85 to 95 ° C., more preferably 85 to 93 ° C. . When the main maximum peak is less than 85 ° C., the melt viscosity becomes low and the dissolution property at the time of oilless fixing is improved, but the release agent melts when the toner is produced by the emulsion polymerization aggregation method. Therefore, the encapsulating property of the release agent is deteriorated at the time of producing the toner, and the particle size controllability is impaired, or the amount of the surface release agent is increased, so that the powder fluidity of the toner may be impaired. On the other hand, when the main maximum peak exceeds 95 ° C., the production stability is improved, but the melt viscosity is increased. There may be a temperature that decreases.

  In addition, as the release agent used in the toner of the present invention, the ratio of the component at 85 ° C. or less obtained from the endothermic peak area to the total endothermic area is preferably 5 to 15%, more preferably 7 ~ 13%. When the amount of the component at 85 ° C. or less is less than 5%, the compatibility between the release agent component and the binder resin may be poor, and the fixability may be deteriorated. In some cases, the elution property of the release agent at the time of fixing is lowered, and as a result, the oilless releasability is impaired.

  Further, the amount of the release agent in the toner obtained from the peak of the endothermic maximum value in the differential thermal analysis of the release agent is preferably 6 to 9% by mass, and preferably 6.5 to 8.5%. % Is more preferable. If the amount of the release agent is less than 6%, a sufficient amount of elution cannot be obtained during oilless fixing, and the peelability is impaired and the surface becomes rough. There is. On the other hand, when the amount of the release agent exceeds 9%, the releasability is improved, but the amount of the release agent on the toner surface and the fixed image increases, so that the powder flowability of the toner is reduced. In addition, when the fixed image is discharged, a contact mark such as a discharge roll is generated, which may impair the image quality.

  In the present invention, for example, DSC-7 manufactured by Perkin Elmer is used for measurement of the main maximum peak. The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

As examples of the release agent used in the toner of the present invention, minerals such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, petroleum wax, and polyalkylene which is a modified product thereof can be used. Alkylene is preferable from the viewpoint of releasability and transparency of a fixed image.
As said polyalkylene, the maximum value of endotherm calculated | required from differential thermal analysis is 80-95 degreeC, and the ratio with respect to the total endothermic area of the 85 degrees C or less component calculated | required from the area of the said endothermic peak is 5-15%. Preferably there is.

  The polyalkylene preferably has a viscosity ηs140 determined by an E-type viscometer equipped with a cone plate having a cone angle of 1.34 ° at 140 ° C. of 1.5 to 5.0 mPa · s. More preferably, it is 5 to 4.0 mPa · s. When the viscosity ηs140 is lower than 1.5 mPa · s, the elution property at the time of fixing is good, but the release agent layer formed on the fixed image becomes non-uniform, causing uneven peeling, and visually May cause uneven image gloss. On the other hand, when the viscosity ηs140 is higher than 5.0 mPa · s, the elution property is lowered, so that a release agent sufficient for releasing the image and the fixing roll at the time of oilless fixing is not supplied, and the peeling is performed. Defects may occur.

  In the present invention, the viscosity of the release agent is measured with an E-type viscometer. For the measurement, an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with an oil circulation type thermostat is used. The cone plate uses a cone angle of 1.34 °. Put the material in the cup, set the temperature of the circulation device to 140 ° C, set the empty measurement cup and cone to the measurement device, and keep the temperature constant while circulating the oil. When the temperature is stabilized, 1 g of the sample is put in the measuring cup, and the cone is allowed to stand still for 10 minutes. After stabilization, rotate the cone and measure. The rotational speed of the cone is 60 rpm. The measurement is performed three times, and the average value is taken as the viscosity η.

  The release agent is dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, and is heated to a temperature higher than the melting point and is subjected to strong shearing by a homogenizer or pressure discharge type disperser. And a dispersion of particles less than 1 micron can be made. The particle size of the obtained release agent particle dispersion is measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

Further, when the release agent is a polyalkylene, it is preferable that the shape of the polyalkylene includes a rod shape and a lump shape in a transmission electron microscope observation of the toner, and the size thereof is 200 to 1500 nm. More preferably, it is 200 nm to 1000 nm. When the size of the polyalkylene is less than 200 nm, sufficient elution cannot be obtained even when melted at the time of fixing, and peeling stability may be insufficient. On the other hand, if it exceeds 1500 nm, crystal grains having a size in the visible light range may remain in the image after fixing and / or on the image surface, and the transparency to transmitted light may be deteriorated.
The shape of the rod means that the major axis is larger than three times the minor axis,
The shape of the block means that the major axis is 1 to 3 times the minor axis.
The size of the polyalkylene refers to the major axis.

  In the toner of the present invention, a charge control agent can be blended in order to further improve and stabilize the chargeability of the toner. As the charge control agent, quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used. However, aggregation, fusion, and temporary stability are possible. In order to control the ionic strength that affects the properties and reduce the contamination of wastewater, materials that are difficult to dissolve in water are better.

  Further, inorganic fine particles can be added to the toner of the present invention in a wet manner in order to stabilize the chargeability of the toner. Examples of inorganic fine particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, all of which are usually used as external additives on the toner surface, such as ionic surfactants and polymer acids. It can be used by dispersing in a polymer base.

  In the toner of the present invention, for the purpose of imparting fluidity and improving the cleaning property, after the toner is dried, inorganic fine particles such as silica, alumina, titania, calcium carbonate, etc. Resin fine particles such as resin, polyester, and silicone can be applied to the toner surface by applying a shearing force in a dry state and used as a fluidity aid or a cleaning aid.

  In the toner production method of the present invention, a surfactant is used for the purpose of emulsion polymerization of the binder resin, dispersion of the colorant, addition dispersion of resin fine particles, dispersion of the release agent, aggregation thereof, or stabilization thereof. Can be used. Examples of the surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap, and cationic surfactants such as amine salt type and quaternary ammonium salt type. Can be used. It is also effective to use a nonionic surfactant such as polyethylene glycol, alkylphenol ethylene oxide adduct, and polyhydric alcohol.

  In the toner manufacturing method of the present invention, a desired toner can be obtained through an arbitrary washing step, solid-liquid separation step, and drying step after the fusion step, but the washing step develops and maintains chargeability. For this reason, it is preferable to sufficiently perform substitution cleaning with ion-exchanged water. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

The toner of the present invention has a volume average particle size D50V in the range of 2 to 9 μm, its volume average particle size distribution index GSDv (D84V / D16V) is 1.30 or less, its volume average particle size distribution index GSDv and number average particle size distribution. The ratio with respect to the index GSDp (GSDv / GSDp) is preferably 0.95 or more. A more preferable range is such that D50V is 3 to 8 μm, GSDv is 1.0 to 1.28, and the ratio of (GSDv / GSDp) is 0.95 to 1.2.
When the volume average particle diameter D50V of the toner is less than 2 μm, the chargeability of the toner becomes insufficient and the developability may be lowered. On the other hand, if it exceeds 9 μm, the resolution of the image may deteriorate. On the other hand, when the volume average particle size distribution index GSDv exceeds 1.30, the resolution may decrease, and the ratio of the volume average particle size distribution index to the number average particle size distribution index (GSDv / GSDp) is less than 0.95. In other words, the toner chargeability may be reduced, which may cause image defects such as fogging due to toner scattering in the developing machine and toner adhesion to non-image areas.

The particle size distribution measurement other than the colorant in the toner of the present invention will be described.
A Coulter counter TA-II type (manufactured by Beckman Coulter, Inc.) is used as a measuring apparatus, and ISOTON-II (manufactured by Beckman Coulter, Inc.) is used as an electrolyte.
As a measuring method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. This is added to 100 to 150 ml of the electrolytic solution.

  The electrolyte solution in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser, and the particle size distribution of particles of 2.0 to 60 μm is measured using the Coulter counter TA-II type with an aperture diameter of 100 μm. Thus, a volume average distribution and a number average distribution are obtained. The number of particles to be measured is 50,000. From these volume average distribution and number average distribution, a volume average particle diameter is obtained. In the particle size distribution, the cumulative distribution is drawn from the small diameter side to the divided particle size range (channel), and the particle size that becomes 16% cumulative is defined as the volume average particle size D16v and the number average particle size D16p. In addition, the particle size which is 84% cumulative is defined as the volume average particle size D84v and the number average particle size D84p, and using these, the volume average particle size distribution index GSDv is obtained from D84v / D16v. / D16p.

  The toner of the present invention has a shape factor SF1 in the range of 110 to 140, preferably SF1 in the range of 110 to 138. Thereby, an electrostatic charge developing toner excellent in developability and transferability can be provided. The shape factor SF1 is an average value of shape factors (perimeter length squared / projected area), and is calculated by the following method. The optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and the square of perimeter / projection area (ML2 / A) of 50 or more toners is calculated to obtain the average value. It was obtained.

The charge amount of the toner of the present invention is preferably in the range of 20 to 40 μC / g, more preferably in the range of 20 to 35 μC / g in absolute value. If the charge amount is less than 20 μC / g, background stains (fogging) may occur easily, and if it exceeds 40 μC / g, the image density may decrease.
The ratio of the charge amount in the summer (high temperature and high humidity) of the electrostatic charge developing toner to the charge amount in the winter (low temperature and low humidity) is preferably in the range of 0.5 to 1.5, preferably 0.7 to A range of 1.3 is more preferable. If the charge amount ratio is outside the range of 0.5 to 1.5, the environmental dependency of the charging property becomes strong, and the charging stability may be lacking.

  In the present invention, the molecular weight distribution is performed under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” THF (tetrahydrofuran) was used as an eluent. As experimental conditions, the sample concentration was 0.5%, and the flow rate was 0.6 ml / min. The experiment was conducted using a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

As described above, the color toner of the present invention includes a yellow toner, a magenta toner, a cyan toner, and a black toner, and each toner includes at least a binder resin, a colorant, and a release agent. ) To (4) are satisfied.
Generally, the toner reproduction range is determined by the pigment dispersion diameter, and the smaller the dispersion diameter, the larger the reproduction range. However, even if the reproduction range is widened, the reproducibility is not always improved, and is particularly noticeable in a low toner paste amount region where a color mixing property such as skin color is required. The reason is not necessarily clear, but is estimated as follows. The colorant dispersion diameter in the toner often depends on the characteristics of the colorant, and yellow is poorly dispersed compared to cyan and magenta, and is easily affected by the colorant dispersion diameter. It's easy to do. Therefore, yellow has a narrow reproduction range and is easily recognized as a color with high density. On the other hand, cyan is not easily affected by this, and magenta in the middle is easily recognized as a color having a lower density than yellow and cyan. Even if the amount of toner paste is high or it is not a problem if it is a single color, it is likely to be affected by color mixing such as skin color and a low amount of paste.
Therefore, in the present invention, the reproducibility is improved by increasing the storage elastic modulus G1′m of the magenta toner more than other colors, thereby increasing the reflected light and increasing the density recognized as yellow and cyan. It was.
In the measurement of the dynamic viscoelasticity in the present invention, the storage elastic moduli G1 ′ and G2 ′ obtained from the dynamic viscoelasticity at a frequency of 6.28 rad / s, temperatures of 160 ° C. and 180 ° C. by the sinusoidal vibration method are used. Use.
For the measurement of the dynamic viscoelasticity, for example, a rheometric scientific ARES measuring device is used.

In the dynamic viscoelasticity measurement, a normal toner is formed into a tablet, then set on a parallel plate having a diameter of 25 mm, the thickness of the sample is adjusted to 20 mm, and the normal force is set to 0, and then a vibration frequency of 6.28 rad / sec. Gives a sine wave vibration. The measurement starts at 130 ° C. for the purpose of eliminating the strain response error at the start of measurement, continues to 200 ° C., and uses storage elastic moduli G1 ′ and G2 ′ calculated at 160 ° C. and 180 ° C.
The temperature is adjusted by controlling the temperature in the measurement system using liquefied nitrogen. The measurement time interval is preferably 30 seconds, and the temperature adjustment accuracy after the start of measurement is preferably ± 1.0 ° C. or less from the viewpoint of measurement accuracy. Further, during the measurement, the strain amount is appropriately maintained at each measurement temperature, and is adjusted as appropriate so that an appropriate measurement value can be obtained.

In general, the dynamic elasticity and viscosity of a toner depend on the frequency at the time of dynamic viscoelasticity measurement. When the frequency is high, not only the binder resin component constituting the toner but also the presence of internal additives such as a color material and magnetic metal fine particles in the toner are increased and tend to be hardened. On the other hand, when the frequency is low, these contributions are reduced, resulting in a soft behavior, resulting in a lower measured storage modulus.
Further, a polymer material such as toner usually changes into a glass region, a transition region, a rubber upper region, and a fluid region as the temperature rises from the state, that is, the motion state of the molecular chain. The glass region is in a state where the movement of the main chain of the polymer is frozen at a temperature below the glass transition temperature (Tg), but gradually becomes softer from the glass state as the temperature rises and the movement of the molecule increases. Eventually, it will show a fluid state.
These properties are also affected by the measurement frequency as described above, and the magnitude of the properties is the structure of the toner, that is, the thickness (volume) in the vicinity of the surface composed only of the binder resin, and the abundance of the internal additive of the toner. -It is also influenced by the position of existence, the state of existence, that is, the dispersed state and the affinity with the binder resin.

In the color toner of the present invention, the core-shell structure is formed in the toner particle preparation process, and the difference in the presence state of the coloring material, magnetic metal fine particles, or release agent particles inside the toner particles is These differences are detected as differences in responsiveness when the dynamic viscoelastic frequency is changed.
The inventors of the present invention have excellent releasability and good glossiness in oilless fixing by satisfying the above conditions (1) to (4) when the yellow toner, magenta toner, cyan toner and black toner in the color toner are satisfied. It has been found that it is a color toner that has excellent fixing characteristics such as surface glossiness of the fixed image and transparency of OHP, and has a fine image quality with no trace of contact with the discharge roll when discharging the fixed image. It was.

When the G1′m is less than 200 Pa, or when at least one of the G1′c, G1′y, and G1′k is less than 90 Pa, the spinnability at the time of melting the toner becomes high, and the oilless peelability Not only decreases, but also the high temperature offset property deteriorates.
Also, when G1′m is greater than 400 Pa, or when at least one of G1′c, G1′y, and G1′k is greater than 200 Pas, there is no spinnability due to high elasticity and hardness, and HOT property In addition, the oil-less peelability is improved, but the adhesiveness with a material such as paper, that is, the fixing property is lowered.
The G1′m is preferably 200 to 350 Pa, and more preferably 200 to 320 Pa.
The G1′c, G1′y, and G1′k are preferably 110 to 200 Pa, and more preferably 120 to 200 Pa.

  As described above, in the color toner of the present invention, G1′m is set to a larger value than G1′c, G1′y, and G1′k. This improves the reproducibility of intermediate colors such as skin color.

Further, G1′c, G1′y, and G1′k divided by G1′m, G1′c / G1′m, G1′y / G1′m, and G1′k / G1′m, Each of 0.22 to 0.96, magenta toner, yellow toner, cyan toner and black toner frequency 6.28 rad / s, storage elastic modulus G2′m, G2′k, G2′y at a temperature of 180 ° C., and When G2′c satisfies the relationship of G2′m>G2′k> G2′y ≧ G2′c, there is no intercolor difference in fixability and peelability, and a good image surface is obtained. On the other hand, at least one of G1′c / G1′m, G1′y / G1′m, G1′k / G1′m is less than 0.22 or more than 0.96, or G2′m>G2′k> When the relationship of G2′y ≧ G2′c is not satisfied, fixing property is deteriorated and peeling unevenness occurs.
G1′c / G1′m, G1′y / G1′m, and G1′k / G1′m are preferably 0.30 to 0.96, and preferably 0.40 to 0.96. More preferred.

Further, it is generally known that the characteristics of the release agent greatly change with the melting point. However, in consideration of the melting of the release agent in a short time in the fixing step, the release agent is changed from the solid in the toner. These characteristics are greatly influenced in the temperature range where the molten state and the solid state coexist near the melting point. Theoretically, the melting point is a temperature at which the crystal melts. However, since these crystalline substances have a distribution, there actually exists a state in which the crystal and the melting coexist within the melting point ± 10 ° C. For this reason, in this invention, the dynamic viscoelasticity measurement at the temperature of 85 degreeC is also performed. The dynamic viscoelasticity measurement in this case is performed at a temperature of 85 ° C. At this time, the complex viscosity η * is measured at measurement frequencies of 6.28 and 62.8 rad / s, and at this time, the complex viscosity η * a is preferably 0.1 to 1.0 Pa · s. More preferably, it is 0.15-0.8 Pa.s.
If the dynamic viscoelasticity at a temperature of 85 ° C. is less than 1 mPa · s, the release agent layer eluted at the time of fixing and heating is not uniform on the image but is heated and pressed by a fixing roll. In this case, the release agent layer may become non-uniform (film breakage), and peeling unevenness may occur. On the other hand, if it exceeds 1.0 Pa · s, not only the elution property is lowered and the peelability is deteriorated, but also the fixing property is sometimes deteriorated.

Further, the release agent is polyalkylene, and the complex viscosity η * a at a temperature of 85 ° C. and a measurement frequency of 6.28 rad / s determined from the dynamic viscoelasticity measurement of the polyalkylene is 0.1 to 1. It is preferably 0 Pa · s, and the ratio of the complex viscosity η * a to the complex viscosity η * b at a temperature of 85 ° C. and a measurement frequency of 62.8 rad / s determined from dynamic viscoelasticity measurement (η * a) / (η * b) is preferably from 1.0 to 3.5, preferably from 1.0 to 3.5, and more preferably from 1.0 to 3.3.
If η * a / η * b is less than 1.0, the elution property at the time of fixing is good, but the release agent layer is non-uniform (film breakage) and peeling at the time of oilless fixing. Unevenness may occur. On the other hand, when it exceeds 3.3, the elution property is lowered and peeling inhibition may occur.

  The magenta toner, yellow toner, cyan toner and black toner (hereinafter sometimes referred to as “each toner in the color toner of the present invention”) in the color toner of the present invention satisfying the above-described conditions are those of the present invention described above. In the toner, the ratio of the number of primary particles having a minor axis in the range of 15 to 80 nm is 95% or more of all particles, the major axis is 150 nm or less, and the ratio of minor axis to major axis is 1: 1. It is obtained by using a colorant which is ˜1: 3 and setting the shape factor SF1 to 110 to 140.

  The preferred embodiment of each toner in the color toner of the present invention is the same as the preferred embodiment of the toner of the present invention. Specifically, at least one of the toners in the color toner of the present invention preferably satisfies the requirements as a preferred embodiment of the toner of the present invention, and all the toners in the color toner of the present invention It is more preferable to satisfy the prescribed requirements as a preferred embodiment of the toner.

Further, as the colorant used for each toner in the color toner of the present invention, in addition to the colorant used for the toner of the present invention described above, the following colorants are also preferably used.
For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Is mentioned.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

  Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C Rose Bengal, Eoxin Red, Alizarin Lake and the like.

  Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, indanthrene blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate.

  Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

The developer of the present invention comprises an electrostatic charge developing color toner and a carrier. As the electrostatic charge developing color toner, the yellow toner, magenta toner, cyan toner, and the like in the electrostatic charge developing color toner of the present invention described above. It is characterized by using black toner.
There is no restriction | limiting in particular as said carrier, A well-known carrier can be used and the resin coat carrier which has a resin coating layer on the core material surface can be mentioned. Further, a resin-dispersed carrier in which a magnetic material or the like is dispersed in a matrix resin may be used.
Examples of the coating resin and matrix resin used in the carrier include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone, and vinyl chloride-vinyl acetate. Copolymer, Styrene-acrylic acid copolymer, Straight silicone resin composed of organosiloxane bond or modified product thereof, Fluorine resin, Polyester, Polyurethane, Polycarbonate, Phenol resin, Amino resin, Melamine resin, Benzoguanamine resin, Urea resin, Amide Examples thereof include, but are not limited to, resins and epoxy resins. These may be used alone or in combination.

  In order to adjust the electric resistance of the carrier, a conductive material may be added in the coating resin or on the surface of the coating resin. Examples of the conductive material include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black. It is not limited.

Furthermore, examples of the carrier core material include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, the carrier is a magnetic material for use in the magnetic brush method. It is preferable.
The volume average particle size of the carrier core material is preferably 10 to 500 μm, and more preferably 30 to 100 μm.
Further, the addition amount of the coating resin is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the core material.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
A toner is prepared by the following method.
The following resin fine particles, colorant particle dispersion, release agent particle dispersion, and inorganic fine particle dispersion are prepared. Next, while a predetermined amount of these are mixed and stirred, a polymer of an inorganic metal salt is added thereto and ionically neutralized to form aggregates of the above particles. Resin fine particles are additionally added before reaching the desired toner particle diameter to obtain the toner particle diameter. Next, after adjusting the pH of the system from a weakly acidic to a neutral range with an inorganic hydroxide, the mixture is heated to a temperature higher than the glass transition temperature of the resin fine particles, and united and fused. After completion of the reaction, a desired toner is obtained through sufficient washing, solid-liquid separation, and drying processes.

(Preparation of binder resin particle dispersion)
Oil layer styrene (manufactured by Wako Pure Chemical Industries): 32 parts by mass n-butyl acrylate (manufactured by Wako Pure Chemical Industries): 8 parts by mass β-carboethyl acrylate (manufactured by Rhodia Nikka): 1.2 parts by mass dodecanethiol (manufactured by Wako Pure Chemical Industries) : 0.5 parts by mass / water layer 1
Ion-exchanged water: 17.0 parts by mass Anionic surfactant (manufactured by Rhodia): 0.50 parts by mass Aqueous layer 2
Ion-exchanged water: 40 parts by mass Anionic surfactant (manufactured by Rhodia): 0.06 parts by mass ammonium persulfate (manufactured by Wako Pure Chemical Industries): 0.4 parts by mass

  The oil layer component and the water layer 1 component were placed in a flask and mixed by stirring to obtain a monomer emulsified dispersion. The components of the aqueous layer 2 were put into a reaction vessel, and the inside of the vessel was sufficiently substituted with nitrogen and stirred, and then heated in an oil bath until the temperature in the reaction system reached 75 ° C. The monomer emulsion dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropwise addition, the polymerization was further continued at 75 ° C., and the polymerization was terminated after 3 hours.

The obtained binder resin particles were 240 nm when the number average particle diameter D _50n of the resin fine particles was measured with a laser diffraction particle size distribution measuring device (Horiba, LA-700). When the glass transition point of the resin was measured at a temperature rising rate of 10 ° C./min using a DSC-50 manufactured by Tokosha Co., Ltd., it was 52 ° C., and a THF was used using a molecular weight measuring instrument (HLC-8020, manufactured by Tosoh Corporation). It was 12500 when the number average molecular weight (polystyrene conversion) was measured as a solvent.
As a result, an anionic resin dispersion having a center diameter of 240 nm, a solid content of 42%, a glass transition point of 52 ° C., and an Mw of 28000 was obtained.

(Preparation of colorant dispersion 1)
Magenta pigment (ECR186Y, manufactured by Dainichi Seika Kogyo Co., Ltd.): 80 parts by mass anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.): 8 parts by mass ion-exchanged water: 200 parts by mass (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and then using an ultrasonic disperser, irradiation with 28 kHz ultrasonic waves for 10 minutes gives a colorant dispersion 1 having a volume average particle diameter of 132 nm. It was.
Note that ECR186Y has a ratio of the number of primary particles in which 95% or more of the particles are in the range of 15 to 80 nm, the major axis is 150 nm or less, and the ratio of minor axis to major axis is 1: 1 to 1: 3. It is.

(Preparation of colorant dispersion 2)
Carbon black (R330, manufactured by Cabot): 80 parts by weight anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku): 8 parts by weight ion-exchanged water: 200 parts by weight The above components are mixed and dissolved, and a homogenizer (Ultra (Talax T50: manufactured by IKA Co., Ltd.) for 10 minutes, and then using an ultrasonic disperser, 28 kHz ultrasonic waves were irradiated for 10 minutes to obtain a colorant dispersion 2 having a volume average particle diameter of 125 nm.
R330 is a ratio of the number of primary particles, in which 95% or more of the particles are in the range of 15 to 80 nm, the major axis is 150 nm or less, and the ratio of minor axis to major axis is 1: 1 to 1: 3. It is.

(Preparation of colorant dispersion 3)
Yellow pigment (5GX03, Clariant): 80 parts by mass Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku): 8 parts by mass ion-exchanged water: 200 parts by mass The above components are mixed and dissolved, and a homogenizer (Ultrata (Lux T50: manufactured by IKA) was used for 10 minutes, and then using an ultrasonic disperser, 28 kHz ultrasonic waves were applied for 20 minutes to obtain a colorant dispersion 3 having a volume average particle size of 108 nm.
5GX03 has a primary particle number ratio of 95% or more of the particles in a range of 15 to 80 nm, a major axis of 150 nm or less, and a ratio of minor axis to major axis of 1: 1 to 1: 3. It is.

(Preparation of colorant dispersion 4)
Cyan pigment (ECB301, manufactured by Dainichi Seika Kogyo): 80 parts by weight anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku): 8 parts by weight ion-exchanged water: 200 parts by weight The above components are mixed and dissolved. Disperse for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), then irradiate ultrasonic waves of 28 kHz for 10 minutes using an ultrasonic disperser to obtain a colorant dispersion 4 having a volume average particle diameter of 120 nm. Obtained.
ECB301 has a primary particle number ratio in which 95% or more of the particles are in the range of 15 to 80 nm, the major axis is 150 nm or less, and the ratio of minor axis to major axis is 1: 1 to 1: 3. It is.

(Preparation of colorant dispersion 5)
Yellow pigment (5GX03, Clariant): 80 parts by mass Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku): 8 parts by mass ion-exchanged water: 200 parts by mass The above components are mixed and dissolved, and a homogenizer (Ultrata (Lux T50: manufactured by IKA Co., Ltd.) was used for 10 minutes, and then using an ultrasonic disperser, 28 kHz ultrasonic waves were applied for 5 minutes to obtain a colorant dispersion 5 having a volume average particle diameter of 252 nm.
In addition, 5GX03 has a ratio of the number of primary particles, the range of 15 to 80 nm of the particles is 93%, the average major axis is 175 nm, and the ratio of minor axis to major axis is 1: 3.

(Preparation of inorganic fine particle dispersion)
ST-OL (Nissan Chemical Co., Ltd., center particle size 40 nm) is used as colloidal silica A, and ST-OS (Nissan Chemical Co., Ltd., center particle size 20 nm) is used as colloidal silica B. Then, 15 g of 0.3 mol / l HNO ₃ nitric acid was added, 0.3 g of polyaluminum chloride was added thereto, and the mixture was allowed to stand at room temperature for 20 minutes to be aggregated to prepare an inorganic fine particle dispersion.

(Adjustment of release agent dispersion 1)
Polyalkylene wax (FNP92, melting point 92 ° C, manufactured by Nippon Seiwa Co., Ltd.): 45 parts by weight anionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 5 parts by weight ion-exchanged water: 200 parts by weight And then sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion 1 having a center diameter of 210 nm and a solid content of 18%.
The viscosity of the FNP92 at 140 ° C. by an E-type viscometer is 4.7 mPas, the complex viscosity η * at a measurement frequency of 6.28 rad / s at 85 ° C. is 0.1 Pa · s, and the frequency is 62.8 rad. The ratio (η * a) / (η * b) between the complex viscosity η * b at the time of / s and this was 1.0. The maximum endothermic peak in the suggested thermal analysis was 92 ° C., and the ratio of the endothermic area of 85 ° C. or lower was 11%.

(Preparation of release agent dispersion 2)
Polyalkylene wax (FNP0085, melting point 85 ° C., manufactured by Nippon Seiwa Co., Ltd.): 45 parts by mass anionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 5 parts by mass ion-exchanged water: 200 parts by mass And then sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion 2 having a solid diameter of 180% and a solid content of 18%.
The viscosity of the FNP0085 at 140 ° C. by an E-type viscometer is 4.3 mPa, the complex viscosity η * at a measurement frequency of 6.28 rad / s at 85 ° C. is 0.1 Pa · s, and the frequency is 62.8 rad. The ratio (η * a) / (η * b) between the complex viscosity η * b at the time of / s and this was 2.8. The maximum endothermic peak in the suggested thermal analysis was 85 ° C., and the ratio of the endothermic area at 85 ° C. or lower was 10%.

(Preparation of release agent dispersion 3)
Polyalkylene wax (FNP0100, melting point 100 ° C., manufactured by Nippon Seiwa Co., Ltd.): 45 parts by mass anionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 5 parts by mass ion-exchanged water: 200 parts by mass And then sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure-discharge type gorin homogenizer to obtain a release agent dispersion 3 having a center diameter of 220 nm and a solid content of 18%.
The viscosity of the FNP0100 measured by an E-type viscometer at 140 ° C. is 3.8 mPas, the complex viscosity η * at a measurement frequency of 6.28 rad / s at 85 ° C. is 1.0 Pa · s, and the frequency is 62.8 rad. The ratio (η * a) / (η * b) of the complex viscosity η * b to / s at this time was 3.5. The maximum endothermic peak in the suggested thermal analysis was 100 ° C., and the ratio of the endothermic area of 85 ° C. or lower was 5%.

(Preparation of release agent dispersion 4)
Polyalkylene (FT100, melting point 98 ° C., manufactured by Nippon Seiwa Co., Ltd.): 45 parts by mass Cationic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 5 parts by mass Ion-exchanged water: 100 parts by mass The mixture was heated and sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion 4 having a center diameter of 280 nm and a solid content of 18%.
Note that the viscosity of the FT100 measured by an E-type viscometer at 140 ° C. is 6.5 mPas, the complex viscosity η * at a measurement frequency of 6.28 rad / s at 85 ° C. is 0.7 Pa · s, and the frequency is 62.8 rad. The ratio (η * a) / (η * b) of the complex viscosity η * b at the time of / s and 2.3 was 2.3. The maximum endothermic peak in the suggested thermal analysis was 98 ° C., and the ratio of the endothermic area of 85 ° C. or lower was 13%.

(Preparation of Toner 1)
Binder resin dispersion: 70 parts by weight Colorant dispersion 1: 14 parts by weight Colloidal silica A (ST-OL) / Colloidal silica B (ST-OS) pre-aggregate: 13.0 parts by weight release agent dispersion 1:22 parts by mass of polyaluminum chloride: 0.14 parts by mass The above components were sufficiently mixed and dispersed in a round stainless steel flask using Ultra Turrax T50. Next, 0.32 parts by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 47 ° C. with stirring in an oil bath for heating. After maintaining at 47 ° C. for 60 minutes, 30 parts by mass of the binder resin dispersion was slowly added thereto.

Thereafter, the pH of the system is adjusted to 6.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask is sealed and heated to 96 ° C. while continuing stirring using a magnetic seal. Hold for 5 hours. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate was 7.01, the electric conductivity was 9.7 μS / cm, and the surface tension was 71.2 Nm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. It was. Next, vacuum drying was continued for 12 hours to produce toner 1.

When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.7 microns, and the particle size distribution coefficient GSD was 1.20. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 134, and it was potato-like.
When the toner 1 was observed with a transmission electron microscope, the shape of the release agent present in the toner was in the form of a rod and a lump, and the area ratio of the lump was 28%. Furthermore, the average diameter of the release agent was 620 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.3 μm.
Further, the amount of the surface release agent of the toner measured by X-ray photoelectron spectroscopic analysis was 29 atm%.
Furthermore, the storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 260 Pa.

(Preparation of Toner 2)
In the production of the toner 1, the addition amount of the binder resin dispersion is changed to 71 parts by mass, the addition of 14 parts by mass of the colorant dispersion 1 is changed to 13 parts by mass of the colorant dispersion 2, and the temperature is 47 ° C. Toner 2 was prepared in the same manner as toner 1 except that the addition amount of the binder resin dispersion after holding for 60 minutes was changed to 30.4 parts by mass.
The particle diameter of the toner 2 was measured with a Coulter counter. The volume average diameter D50 was 5.6 microns and the particle size distribution coefficient GSD was 1.21. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 131, and it was potato-like.

When the toner 2 was observed with a transmission electron microscope, the shape of the release agent present in the toner was in the form of a rod and a lump, and the area ratio of the lump was 28%. Furthermore, the average diameter of the release agent was 530 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.3 μm.
Further, the amount of the surface release agent of the toner measured by X-ray photoelectron spectroscopic analysis was 19 atm%.
Furthermore, the storage elastic modulus G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 190 Pa.

(Preparation of Toner 3)
In the production of the toner 1, the amount of the binder resin dispersion added was changed to 72 parts by mass, the addition of 14 parts by mass of the colorant dispersion 1 was changed to 11 parts by mass of the colorant dispersion 3, and the temperature was 47 ° C. Toner 3 was prepared in the same manner as toner 1 except that the amount of binder resin dispersion added after holding for 60 minutes was changed to 30.7 parts by mass.
When the particle diameter of the toner 3 was measured with a Coulter counter, the volume average diameter D50 was 5.6 microns and the particle size distribution coefficient GSD was 1.21. In addition, the particle shape factor SF1 obtained by shape observation with Luzex was 133.4, and it was observed that the particles were potato-like.

When the toner 3 was observed with a transmission electron microscope, the shape of the release agent present in the toner was in the form of a rod and a lump, and the area ratio of the lump was 28%. Furthermore, the average diameter of the release agent was 480 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.3 μm.
Further, the amount of the surface release agent of the toner measured by X-ray photoelectron spectroscopic analysis was 23 atm%.
Furthermore, the storage elastic modulus G1′y obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 175 Pa.

(Preparation of Toner 4)
In the production of the toner 1, the amount of the binder resin dispersion added was changed to 73 parts by mass, the addition of 14 parts by mass of the colorant dispersion 1 was changed to 9 parts by mass of the colorant dispersion 4, and the temperature was 47 ° C. Toner 4 was prepared in the same manner as toner 1 except that the amount of the binder resin dispersion added after holding for 60 minutes was changed to 31 parts by mass.
When the particle diameter of the toner 4 was measured with a Coulter counter, the volume average diameter D50 was 5.6 microns, and the particle size distribution coefficient GSD was 1.21. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 131, and it was potato-like.

When the toner 4 was observed with a transmission electron microscope, the release agent present in the toner had a rod-like shape and a lump shape, and the lump area ratio was 28%. Furthermore, the average diameter of the release agent was 700 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.3 μm.
Further, the amount of the surface release agent of the toner was measured by X-ray photoelectron spectroscopic analysis and found to be 21 atm%.
Furthermore, the storage elastic modulus G1′c obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 170 Pa.

(Preparation of Toner 5)
In the production of the toner 1, the addition amount of the binder resin dispersion was changed to 73 parts by mass, the addition of 14 parts by mass of the colorant dispersion 1 was changed to the addition of 5 parts by mass of the colorant dispersion 2, and the release agent. The addition amount of the dispersion resin 1 was changed to 25 parts by mass, the addition amount of polyaluminum chloride was further changed to 0.41 parts by mass, and the addition amount of the binder resin dispersion after being kept at 47 ° C. for 60 minutes A toner 5 was produced in the same manner as in the production of the toner 1 except that the toner was changed to 31 parts by mass.
When the particle diameter of the toner 5 was measured with a Coulter counter, the volume average diameter D50 was 5.4 microns and the particle size distribution coefficient GSD was 1.2. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 128, and it was potato-like.

When the toner 5 was observed with a transmission electron microscope, the release agent present in the toner had a rod-like shape and a lump shape, and the lump area ratio was 28%. Furthermore, the average diameter of the release agent was 240 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.3 μm.
Further, the amount of the surface release agent of the toner was measured by X-ray photoelectron spectroscopic analysis and found to be 11 atm%.
Furthermore, the storage elastic modulus G1′k obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 200 Pa.

(Production of Toner 6)
In the preparation of the toner 1, 14 parts by mass of the colorant dispersion 1 is added to 18 parts by mass of the colorant dispersion 4, and 22 parts by mass of the release agent dispersion 1 is 17 parts by mass of the release agent dispersion 3. The same procedure as in the preparation of Toner 1 was performed except that However, when the pH in the system was adjusted to 6.0 with a 0.5 mol / L sodium hydroxide aqueous solution, the pH was changed to 7.0 to prepare toner 6.
When the particle diameter of the toner 6 was measured with a Coulter counter, the volume average diameter D50 was 5.8 microns, and the particle size distribution coefficient GSD was 1.18. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 124, and it was potato-like.

When the toner 6 was observed with a transmission electron microscope, the shape of the release agent present in the toner was a stick and a lump, and the area ratio of the lump was 27%. Furthermore, the average diameter of the release agent was 1100 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.2 μm.
Further, the amount of the surface release agent of the toner was measured by X-ray photoelectron spectroscopic analysis and found to be 25 atm%.
Furthermore, the storage elastic modulus G1′c obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 90 Pa.

(Preparation of Toner 7)
In the production of the toner 1, the addition amount of the binder resin dispersion is changed to 95 parts by mass, the addition of 14 parts by mass of the colorant dispersion 1 is changed to 21 parts by mass of the colorant dispersion 5, and the temperature is 47 ° C. Toner 7 was prepared in the same manner as toner 1 except that the binder resin dispersion was not added after holding for 60 minutes.
When the particle diameter of the toner 7 was measured with a Coulter counter, the volume average diameter D50 was 5.4 microns and the particle size distribution coefficient GSD was 1.21. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 129 with 129.

When the toner 7 was observed with a transmission electron microscope, the release agent present in the toner had a rod-like shape and a lump shape, and the lump area ratio was 26%. Furthermore, the average diameter of the release agent was 980 nm. Moreover, the presence of a shell layer (coating layer) could not be confirmed.
Further, the amount of the surface release agent of the toner was measured by X-ray photoelectron spectroscopic analysis and found to be 33 atm%.
Furthermore, the storage elastic modulus G1′y obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 360 Pa.

(Production of Toner 8)
In the production of the toner 1, the addition amount of the binder resin dispersion is changed to 64 parts by mass, the addition of 22 parts by mass of the release agent dispersion 1 is changed to the addition of 42 parts by mass of the release agent dispersion 2, and 47 Toner 8 was prepared in the same manner as toner 1 except that the addition of the binder resin dispersion after holding at 60 ° C. for 60 minutes was changed to 28 parts by mass.
When the particle diameter of the toner 8 was measured with a Coulter counter, the volume average diameter D50 was 5.4 microns and the particle size distribution coefficient GSD was 1.21. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by shape observation by Luzex was 142, and it was potato-like.

When the toner 8 was observed with a transmission electron microscope, the release agent present in the toner had a rod-like shape and a lump shape, and the lump area ratio was 31%. Furthermore, the average diameter of the release agent was 1700 nm. In addition, the presence of a shell layer (coating layer) was observed, and the thickness was 0.08 μm.
Further, the amount of the surface release agent of the toner was measured by X-ray photoelectron spectroscopic analysis and found to be 35 atm%.
Furthermore, the storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. was 180 Pa.

  After adding 0.2 g of hydrophobic silica (manufactured by Cabot, TS720) to each of 60 g of the produced toners 1 to 8 and blending them with a sample mill, coarse particles were removed using a sieve of 45 μm mesh. Next, 5 parts of this toner and 100 parts of a ferrite carrier having a volume average particle size of 50 μm coated with 1% of a methacrylate resin (manufactured by Soken Chemical Co., Ltd .: weight average molecular weight 80000) were stirred and mixed using a V blender. Developers 1 to 8 were obtained by sieving with a sieve of 177 μm mesh.

<Example 1>
The fixing property of toners 1 to 4 was adjusted to 3.0 g / m ² on the OHP sheet (Fuji Xerox Co., Ltd .: V507) by using a modified Docu Center Color 400 manufactured by Fuji Xerox Co., Ltd. Then, an image composed of toners 1 to 4 was obtained and fixed using an external fixing device at a fixing speed of 100 mm / sec under Nip 6.5 mm.
The peelability between the external fixing device and the fixed image after fixing was good, it was confirmed that they were peeled without any resistance, and no offset occurred. Also, no image defect was observed when the fixed image was folded in two and stretched again. Further, the surface gloss of these fixed images was good, the transparency of the OHP sheet was excellent, and a transmission image without turbidity was confirmed.

The storage elastic modulus obtained from the dynamic viscoelasticity measurement of yellow toner, magenta toner, cyan toner and black toner at a frequency of 6.28 rad / s and a temperature of 180 ° C. is G2′y = 152 Pa, G2′m = 200 Pa, G2′c = 150 Pa and G2′k = 160 Pa satisfy the relationship of G2′m>G2′k> G2′y ≧ G2′c.
Furthermore, the human image was copied on J paper manufactured by Fuji Xerox Co., and the reproducibility of the skin color was visually evaluated. The obtained image reproduced the skin color without problems.

<Example 2>
In Example 1, an image was obtained and fixed in the same manner as in Example 1 except that the toner 2 was replaced with the toner 5.
The peelability between the external fixing device and the fixed image after fixing was good, it was confirmed that they were peeled without any resistance, and no offset occurred. Also, no image defect was observed when the fixed image was folded in two and stretched again. Further, the surface gloss of these fixed images was good, the transparency of the OHP sheet was excellent, and a transmission image without turbidity was confirmed.

The storage elastic modulus obtained from the dynamic viscoelasticity measurement of yellow toner, magenta toner, cyan toner and black toner at a frequency of 6.28 rad / s and a temperature of 180 ° C. is G2′y = 152 Pa, G2′m = 200 Pa, G2′c = 150 Pa and G2′k = 190 Pa satisfy the relationship of G2′m>G2′k> G2′y ≧ G2′c.
Furthermore, the human image was copied on J paper manufactured by Fuji Xerox Co., and the reproducibility of the skin color was visually evaluated. The obtained image reproduced the skin color without problems.

<Example 3>
In Example 1, an image was obtained and fixed in the same manner as in Example 1 except that the toner 4 was replaced with the toner 6.
The peelability between the external fixing device and the fixed image after fixing was good, it was confirmed that they were peeled without any resistance, and no offset occurred. Also, no image defect was observed when the fixed image was folded in two and stretched again. Further, the surface gloss of these fixed images was good, the transparency of the OHP sheet was excellent, and a transmission image without turbidity was confirmed.

The storage elastic modulus obtained from the dynamic viscoelasticity measurement of yellow toner, magenta toner, cyan toner and black toner at a frequency of 6.28 rad / s and a temperature of 180 ° C. is G2′y = 152 Pa, G2′m = 200 Pa, G2′c = 148 Pa and G2′k = 160 Pa satisfy the relationship of G2′m>G2′k> G2′y ≧ G2′c.
Furthermore, the human image was copied on J paper manufactured by Fuji Xerox Co., and the reproducibility of the skin color was visually evaluated. The obtained skin color image was slightly yellowish.

<Comparative Example 1>
In Example 1, an image was obtained and fixed in the same manner as in Example 1 except that the toner 3 was replaced with the toner 7.
The peelability between the external fixing device and the fixed image after fixing was poor, and image gloss unevenness due to the poor peeling from the roll occurred during discharge. Further, contact marks such as pinch rolls at the time of discharge were observed. Furthermore, although the surface glossiness of these fixed images was high, roll contact marks were also visually recognized on the OHP sheet, and the image quality was low.

The storage elastic modulus obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 180 ° C. for yellow toner, magenta toner, cyan toner and black toner is G2′y = 180 Pa, G2′m = 200 Pa, With G2′c = 150 Pa and G2′k = 160 Pa, the relationship of G2′m>G2′k> G2′y ≧ G2′c is not satisfied.
Furthermore, the human image was copied on J paper manufactured by Fuji Xerox Co., and the reproducibility of the skin color was visually evaluated. The obtained skin color image was yellowish.

<Comparative example 2>
In Example 1, an image was obtained and fixed in the same manner as in Example 1 except that the toner 1 was replaced with the toner 8.
The peelability between the external fixing device and the fixed image after fixing was poor, and image gloss unevenness due to the poor peeling from the roll occurred during discharge. Further, contact marks such as pinch rolls at the time of discharge were observed. Furthermore, although the surface glossiness of these fixed images was high, roll contact marks were also visually recognized on the OHP sheet, and the image quality was low.
The storage elastic modulus obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 180 ° C. for yellow toner, magenta toner, cyan toner and black toner is G2′y = 152 Pa, G2′m = 158 Pa, With G2′c = 150 Pa and G2′k = 160 Pa, the relationship of G2′m>G2′k> G2′y ≧ G2′c is not satisfied.
Furthermore, the human image was copied on J paper manufactured by Fuji Xerox Co., and the reproducibility of the skin color was visually evaluated. The obtained skin color image was yellowish.

From the above results, by using yellow toner, magenta toner, cyan toner and black toner that satisfy the following conditions (1) to (4), the peelability between the external fixing device after fixing and the fixed image is good. Separation was confirmed without resistance, and no offset occurred. Also, no image defect was observed when the fixed image was folded in two and stretched again. Further, it can be seen that the surface gloss of these fixed images is good, the transparency of the OHP sheet is excellent, and a transmission image without turbidity can be obtained. In addition, the skin color reproducibility is also excellent.
(1) The storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement of the magenta toner at a frequency of 6.28 rad / s and a temperature of 160 ° C. is 200 to 400 Pa (2000 to 4000 dyn / cm ² ).
(2) The storage elastic moduli G1′y, G1′c, and G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. for yellow toner, cyan toner, and black toner are 90 to 200 Pa. (900 to 2000 dyn / cm ² ).
(3) (G1′c / G1′m), (G1′y / G1′m) and (G1′k / G1′m) are in the range of 0.22 to 0.96, respectively.
(4) The storage elastic moduli G2′y, G2′m, G2′c, and G2′k at a frequency of 6.28 rad / s and a temperature of 180 ° C. of yellow toner, magenta toner, cyan toner, and black toner are G2′m. >G2′k> G2′y ≧ G2′c.

Claims (7)

The toner includes a yellow toner, a magenta toner, a cyan toner, and a black toner, and each toner is an electrostatic charge developing color toner including at least a binder resin, a colorant, and a release agent, and the following (1) to (4) The color toner for electrostatic charge development characterized by satisfying the following conditions:
(1) The storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement of the magenta toner at a frequency of 6.28 rad / s and a temperature of 160 ° C. is 200 to 400 Pa (2000 to 4000 dyn / cm ² ).
(2) The storage elastic moduli G1′y, G1′c, and G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. for yellow toner, cyan toner, and black toner are 90 to 200 Pa. (900 to 2000 dyn / cm ² ).
(3) (G1′c / G1′m), (G1′y / G1′m) and (G1′k / G1′m) are in the range of 0.22 to 0.96, respectively.
(4) Storage elastic modulus G2′y, G2′m, G2′c and G2 obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 180 ° C. for yellow toner, magenta toner, cyan toner and black toner. “k” has a relationship of G2′m>G2′k> G2′y ≧ G2′c.   In at least one of the yellow toner, magenta toner, cyan toner and black toner, the release agent is polyalkylene, and a temperature of 85 ° C. and a measurement frequency of 6 obtained from dynamic viscoelasticity measurement of the polyalkylene. The complex viscosity η * a at .28 rad / s is 0.1 to 1.0 Pa · s, the complex viscosity η * a and the temperature obtained from dynamic viscoelasticity measurement are 85 ° C., and the measurement frequency is 62. The electrostatic charge development according to claim 1, wherein the ratio (η * a) / (η * b) to the complex viscosity η * b at .8 rad / s is 1.0 to 3.5. Color toner.   The maximum value of the endothermic peak obtained from the differential thermal analysis of the polyalkylene is 85 to 95 ° C., and the ratio of the component at 85 ° C. or less obtained from the endothermic peak area of the polyalkylene to the total endothermic area is 5 3. The color for electrostatic charge development according to claim 2, wherein the polyalkylene content in the toner is 6 to 9% by mass calculated from the peak of the endothermic maximum value. toner.   At least one of the yellow toner, magenta toner, cyan toner, and black toner has a coating layer, has a thickness of 0.1 to 0.3 μm, and exists on the surface required by XPS. The color toner for electrostatic charge development according to any one of claims 1 to 3, wherein the amount of the polyalkylene is 11 to 30 atm%. A developer comprising an electrostatic charge developing color toner having a yellow toner, a magenta toner, a cyan toner and a black toner, and a carrier, wherein each toner in the electrostatic charge developing color toner includes at least a binder resin, a colored toner A developer comprising an agent and a release agent and satisfying the following conditions (1) to (4):
(1) The storage elastic modulus G1′m obtained from the dynamic viscoelasticity measurement of the magenta toner at a frequency of 6.28 rad / s and a temperature of 160 ° C. is 200 to 400 Pa (2000 to 4000 dyn / cm ² ).
(2) The storage elastic moduli G1′y, G1′c, and G1′k obtained from the dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 160 ° C. for yellow toner, cyan toner, and black toner are 90 to 200 Pa. (900 to 2000 dyn / cm ² ).
(3) (G1′c / G1′m), (G1′y / G1′m) and (G1′k / G1′m) are in the range of 0.22 to 0.96, respectively.
(4) Storage elastic modulus G2′y, G2′m, G2′c and G2 obtained from dynamic viscoelasticity measurement at a frequency of 6.28 rad / s and a temperature of 180 ° C. for yellow toner, magenta toner, cyan toner and black toner. “k” has a relationship of G2′m>G2′k> G2′y ≧ G2′c. An electrostatic charge developing toner comprising a binder resin, a colorant and a release agent, and having a shape factor SF1 of 110 to 140;
In the colorant, the ratio of the number of primary particles having a minor axis in the range of 15 to 80 nm is 95% or more of all particles, the major axis is 150 nm or less, and the ratio of minor axis to major axis is 1: 1. A toner for developing electrostatic charge, which is ˜1: 3. The yellow toner, the magenta toner, the cyan toner, and the black toner among the electrostatic toners for developing electrostatic charge according to any one of claims 1 to 4, and the toner for developing electrostatic charges of at least one of the toners for black and black. Or a method for producing the electrostatic charge developing toner according to 6, wherein
The binder resin particle dispersion in which the binder resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the release agent dispersion in which the release agent particles are dispersed are mixed, and at least this An aggregation step of adding a polymer of one kind of metal salt to form an aggregated particle dispersion in which aggregated particles including binder resin particles, colorant particles and release agent particles are dispersed; and the aggregated particle dispersion A method for producing an electrostatic charge developing toner comprising a fusing step of fusing and coalescing by heating to a temperature above the glass transition point of the binder resin.