JP5311845B2 - Toner production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner which, even when low-temperature fixing performance is improved, has good development stability and enables the formation of a high-quality image. <P>SOLUTION: The toner has toner particles including at least a binder resin, a colorant and a wax, and an inorganic fine powder. In a temperature-deformation velocity curve formed by first derivation of a temperature-displacement curve of the toner by thermomechanical measurement under a load of 10.5 mN at a rate of temperature increase of 4&deg;C/min, a temperature (T1) at which deformation velocity first becomes a minimum value is in a range of 30.0-55.0&deg;C, a minimum value (R1) of deformation rate at the T1 is &ge;-0.300%/&deg;C, a temperature (T2) at which deformation velocity becomes the lowest value is in a range of 60.0-90.0&deg;C, and the lowest value (R2) of deformation velocity at the T2 is &le;-0.400/&deg;C. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method.

  Conventionally, an electrophotographic method forms an electrostatic charge image on a photosensitive member by various means, and then develops the electrostatic charge image with toner to form a toner image on the photosensitive member. The toner image is transferred to a transfer material such as paper. Thereafter, the toner image is fixed on the transfer material by heating, pressure, heating pressure, solvent vapor or the like to obtain an image.

  As a process for fixing the toner image, a heat-pressing heating method (hereinafter referred to as a heat roller fixing method) using a heat roller, or a heat fixing method (hereinafter referred to as a heat-fixing method) in which a fixing sheet is fixed to a heating body through a fixing film. The film fixing method has been developed.

  In the heat roller fixing method and the film fixing method, fixing is performed by allowing a toner image on a fixing sheet to pass through the surface of a heat roller or a fixing film while being contacted under pressure by a pressure member that abuts. In this fixing method, the surface of the heat roller or fixing film and the toner image of the fixing sheet are in contact with each other under pressure, so that the thermal efficiency when fusing the toner image on the sheet is extremely high, and quick and good fixing is achieved. It can be carried out. In particular, the film fixing method has a great effect on energy saving, and can also be expected to have an effect such as a short time required until the first print is completed after the electrophotographic apparatus is turned on.

  Electrophotographic devices have received various demands such as high image quality, small size and light weight, high speed and high productivity, and energy saving. Among them, particularly in the fixing process, further speedup, energy saving, and high Development of systems and materials that can achieve reliability is an important technical issue. However, in order to solve these problems by the heat roller fixing method and the film fixing method, it is essential to significantly improve the fixing characteristic ability of the toner, and it can be sufficiently fixed on the fixing sheet at a lower temperature. Performance (hereinafter referred to as low-temperature fixing performance), and the ability to prevent offset, which is a phenomenon of fouling the next fixing sheet by toner contamination adhering to the heating roller or film surface (hereinafter referred to as anti-offset performance) Improvement is necessary. In addition, as performance that tends to be a trade-off relationship with improvement in low-temperature fixing performance, performance that suppresses the phenomenon of toner aggregation and fusion during long-term storage (hereinafter referred to as anti-blocking performance), and a large amount of continuous A performance that suppresses the occurrence of image defects during printing (hereinafter referred to as development stability performance) can be mentioned.

  In addition, with the widespread use of full-color electrophotographic apparatuses, new improvements in image quality have been demanded. In other words, there is a demand for performance (hereinafter referred to as anti-smudge performance) that suppresses the deterioration of the image color gamut due to the toner soaking into the paper in the fixing step. This performance is due to the heating of the first and tenth sheets when the image quality deteriorates due to uneven heating or the output speed is increased in the first half and the second half with respect to the direction of progress of the fixing process. It tends to appear as degradation of image quality due to unevenness. For color toner, an image with a wide image gamut (hereinafter referred to as color gamut performance) is required, and an image with higher image saturation and an image with higher brightness are required even when the image density is the same. It is done. The color gamut performance of such a toner includes (1) color development performance of a colorant contained in the toner, (2) the presence state of the colorant in the toner, (3) binder resin and other components contained in the toner. (4) the surface state of the toner layer formed by fixing on the transfer material, etc., and among them, it is important to form the surface state of the toner layer more uniformly on the transfer material. Become. In recent years, an electrophotographic apparatus has been attracting attention as an alternative technology to a printing machine such as offset printing. When a fixed image after printing is loaded, the image printed on the lower paper is replaced with the upper paper. There is a demand for performance (hereinafter referred to as image stacking performance) that suppresses the phenomenon of being transferred to the back surface.

  Among toners used for heat and pressure fixing, toner having a capsule structure is known as a toner aiming to achieve both low-temperature fixing performance and anti-blocking performance (see Patent Documents 1 and 2). These toners coat the inner core layer having a low glass transition point (Tg) with an outer shell layer having a high Tg, thereby suppressing the seepage of the low Tg material contained in the toner, thereby reducing the low-temperature fixing performance and the resistance to resistance. It is intended to achieve both blocking performance and development stability performance. A toner provided with a coating layer of resin fine particles has good fixing performance, anti-blocking performance and development stability performance (see Patent Documents 3 and 4). As another approach aimed at improving the low-temperature fixing performance of the toner, there is a toner in which a change in thermal physical properties before and after the melting of the toner is controlled (see Patent Document 5). According to this toner, both low-temperature fixing performance and anti-blocking performance can be achieved. However, when these toners are intended to further improve the low-temperature fixing performance, it is difficult to achieve both anti-blocking performance and development stability performance.

JP-A-6-130713 Japanese Patent Laid-Open No. 9-43896 JP 2003-91093 A JP 2004-226572 A JP 2006-84743 A

An object of the present invention is to provide a toner production method capable of solving the above-described problems.

That is, an object of the present invention is to provide a toner production method that has good development stability even when the low-temperature fixing performance is improved in a toner containing wax, and can form a high-quality image. Is.

The present invention provides a core-shell structure containing at least a binder resin containing a styrene acrylic resin having an acid value of 1.0 to 30.0 mg KOH / g, a colorant and a wax, and having a core part and a shell part. A method for producing a toner having toner particles and inorganic fine powder,
The following steps (a) to (c)
(I) Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium metasuccinate, calcium sulfate, barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica The colored particles containing the binder resin, the colorant and the wax are dispersed in an aqueous medium having at least one inorganic dispersant selected from the group consisting of bentonite and alumina, and an aqueous dispersion of colored particles Forming step (a),
(II) An aqueous dispersion of fine resin particles having a volume average particle diameter Dv of 10 to 200 nm and an acid value of 6.0 to 80.0 mgKOH / g is added to the aqueous dispersion of colored particles. Forming a composite dispersion in which particles on which the inorganic dispersant and the resin fine particles are adsorbed are dispersed in water on the surface of the colored particles (b), and
(III) a step of fixing the resin fine particles on the surface of the colored particles (c),
To form toner particles,
The obtained toner has a temperature (T1) at which the deformation speed first reaches a minimum value in a temperature-deformation speed curve obtained by first-order differentiation of a temperature-displacement curve obtained by thermomechanical measurement with a load of 10.5 mN and a heating rate of 4 ° C./min. Is 30.0 to 55.0 ° C., the minimum value (R1) of the deformation rate at T1 is −0.300% / ° C. or more (negatively small), and the temperature at which the deformation rate becomes the minimum value (T2 ) Is 60.0 to 90.0 ° C., and the minimum value (R2) of the deformation rate at T2 is −0.400% / ° C. or less (negatively large).
Further, the present invention provides a core shell having at least a binder resin containing a styrene acrylic resin having an acid value of 1.0 to 30.0 mg KOH / g, a colorant and a wax, and having a core portion and a shell portion. A method for producing a toner having toner particles having a structure and inorganic fine powder,
The following steps (a) to (c)
(I) a step of dispersing the colored particles containing the binder resin, the colorant and the wax in an aqueous medium having tricalcium phosphate to form an aqueous dispersion of colored particles (a);
(II) An aqueous dispersion of fine resin particles having a volume average particle diameter Dv of 10 to 200 nm and an acid value of 6.0 to 80.0 mgKOH / g is added to the aqueous dispersion of colored particles. (B) forming an aqueous dispersion of a composite dispersion in which particles having adsorbed the tricalcium phosphate and the resin fine particles are dispersed in an aqueous medium on the surface of the colored particles;
(III) adding an acid to the composite dispersion to dissolve the tricalcium phosphate, and fixing the resin fine particles to the surface of the colored particles (c);
To form toner particles,
The obtained toner has a temperature (T1) at which the deformation speed first reaches a minimum value in a temperature-deformation speed curve obtained by first-order differentiation of a temperature-displacement curve obtained by thermomechanical measurement with a load of 10.5 mN and a heating rate of 4 ° C./min. Is 30.0 to 55.0 ° C., the minimum value (R1) of the deformation rate at T1 is −0.300% / ° C. or more (negatively small), and the temperature at which the deformation rate becomes the minimum value (T2 ) Is 60.0 to 90.0 ° C., and the minimum value (R2) of the deformation rate at T2 is −0.400% / ° C. or less (negatively large).

  According to the present invention, a toner containing a binder resin, a colorant and a wax has good development stability even when the low-temperature fixing performance is improved, and a high-quality image can be formed.

  The toner of the present invention is a toner having toner particles containing at least a binder resin, a colorant, and a wax, and an inorganic fine powder. The toner has a load of 10.5 mN and a heating rate of 4 ° C./min. In the temperature-deformation rate curve obtained by first-order differentiation of the temperature-displacement curve by thermomechanical measurement, the temperature (T1) at which the deformation rate first reaches a minimum value is 30.0 to 55.0 ° C., and the deformation rate at T1 is The minimum value (R1) is −0.300% / ° C. or more (negatively small), the temperature (T2) at which the deformation rate is the minimum value is 60.0 to 90.0 ° C., and the deformation rate at T2 The minimum value (R2) is −0.400% / ° C. or less (negatively large).

The thermomechanical measurement of toner in the present invention will be described. The toner is compression molded into a cylindrical shape having a diameter of 8 mm and a height of 0.9 mm. A glass cylinder having a cross-sectional area of 1 mm ² is placed on the compression molded toner, and a constant load (10.5 mN) is applied to the cylinder. The whole measurement system is heated at a heating rate of 4 ° C./min in a nitrogen atmosphere, and the moving distance of the cylinder relative to the temperature of the measurement system is measured. The temperature-displacement curve thus obtained is first-order differentiated to create a temperature-deformation speed curve, and each physical property value defined in the present invention is obtained.

As a specific measuring method, assuming that the true density of the toner is ρ (g / cm ³ ), the toner (0.12 × ρ) g is weighed, a 20 kN load is applied for 2 minutes, the diameter is 8 mm, the thickness is The sample is molded into a disk shape of about 0.9 mm.

As a measuring device, TMA / SS150 (manufactured by Seiko Electronics Co., Ltd.) can be used. Set the following conditions and measure the penetration mode. A constant load (10.5 mN) is applied to the sample, and the moving distance of the indenter when heated at a constant speed is measured. The temperature-displacement curve thus obtained is first-order differentiated to obtain a temperature-deformation speed curve.
・ Nitrogen flow rate: 150ml
・ Upper atmospheric load limit: 4.9mN
-Start temperature: 23.0 ° C
・ Measurement load: 10.5mN
・ Limit temperature: 220 ℃
・ Temperature increase rate: 4.0 ° C./min ・ Retention time: 2.0 minutes ・ Sampling: 30 seconds

  The true density of the toner can be measured by, for example, a dry automatic density meter Accupic 1330 (manufactured by Shimadzu Corporation).

  Using the temperature-deformation rate curve obtained in this manner, each physical property value defined in the present invention is obtained. FIG. 1 shows the result of measuring the toner of Example 1 by the thermomechanical measurement. Each physical property value prescribed | regulated by this invention is demonstrated in detail using FIG. In the temperature-deformation rate curve of FIG. 1, the temperature at which the deformation rate first reaches a minimum value is T1 (° C.), and the minimum value of the deformation rate at T1 is R1 (% / ° C.). The temperature at which the deformation speed becomes the minimum value is T2 (° C.), and the deformation speed at T2 is R2 (% / ° C.). The half-value width D2 (° C.) of the deformation rate peak of the toner at T2 is the temperature width at the point where the parallel line of the x axis at the value of 1/2 of R2 intersects the curve in the temperature-deformation rate curve. Show. Further, the deformation speed of the toner at a temperature T3 (° C.) defined by T3 = T1 + 5 is R3 (% / ° C.). Further, in the temperature region above T2, the temperature at which the deformation rate is first 0% / ° C. is defined as T4 (° C.).

  In the thermomechanical measurement, the temperature (T1) at which the deformation rate becomes the minimum value for the first time after the measurement is started is considered to indicate the temperature that should be the first glass transition point of the toner by the thermomechanical measurement. Usually, the glass transition point of a toner is generally measured by a differential scanning calorimeter (DSC). In the DSC measurement, a glass transition behavior in which a resin component changes from a glass state to a fluid state is measured by heat. . For this reason, when heat and mechanical pressure are applied, the behavior of the resin component changing from the glass state to the fluid state may not always match. According to the thermomechanical measurement of the present invention, it is possible to measure a macro toner state change in consideration of heat and mechanical pressure.

  In the present invention, when the toner contains a certain kind of wax and forms a structure that can be said to be a certain kind of core-shell structure, the above-mentioned physical properties are considered to be expressed. That is, the toner of the present invention covers a portion that should be a core portion containing at least a wax and a colorant and has a binder resin having a relatively small glass transition point as a main component, and a surface of the core portion and is relatively glass-coated. It is thought that it has a portion that should be called a shell portion mainly composed of a resin having a large transition point. Whether the core part and the shell part form a phase-separated structure having a clear interface, or a part of the core part and a part of the shell part form a so-called gradient structure is not certain, It is considered that at least the core portion and the shell portion need to exist in different glass states at room temperature. Further, when the content of the shell portion relative to the total amount of toner is relatively small, and the coating state of the shell covering the core is uniform when only one toner is seen, and the uniform state has a small variation between the toners, It is considered that the physical properties defined in the present invention are expressed. In the case where the toner has such physical properties, even when the low-temperature fixing performance is improved, the toner has good development stability performance, and a high-quality image can be formed.

  In the toner of the present invention, the temperature (T1) at which the deformation speed first reaches a minimum value after the start of measurement is 30.0 to 55.0 ° C. When the T1 is in the above range, the low-temperature fixing performance of the toner is exhibited. When T1 exceeds 55.0 ° C., sufficient low-temperature fixing performance of the toner cannot be obtained. When T1 is less than 30.0 ° C., the image loading performance of the toner is degraded. The T1 is considered to contribute greatly to the glass transition point of the binder resin as the main component of the resin contained in the toner. A more preferable range of T1 is more preferably 35.0 to 55.0 ° C, and particularly preferably 35.0 to 50.0 ° C.

  Further, the minimum value (R1) of the deformation rate at T1 is −0.300% / ° C. or more (negatively small). When R1 is within the above range, the development stability of the toner is improved. When R1 is less than −0.300% / ° C. (negatively large), whether the coating state of the shell covering the core is uneven in the toner particles when each toner particle is viewed When the toner is viewed as a whole, the state in which the core covers the shell is considered to have a large variation between the toners. For this reason, even when the addition amount of the resin having a high glass transition point to be added assuming that the shell portion is formed is the same, a change is observed in the value of R1, and the R1 is -0.300. When the temperature is less than% / ° C. (largely negative), the development stability of the toner is lowered.

  On the other hand, even when R1 exceeds -0.030, the development stability of the toner may be deteriorated. It is considered that R1 becomes a larger value (negatively smaller) as the portion to be called a shell portion is as thin and uniform as possible, but it is considered that the shell portion becomes brittle when exceeding a certain state. For this reason, the R1 is more preferably from −0.300 to −0.030% / ° C.

  The R1 can be controlled by the type and amount of resin added assuming that the shell portion is formed, and the presence state of the resin in the toner.

  Further, in the toner of the present invention, the temperature (T2) at which the deformation rate becomes the minimum value is 60.0 to 90.0 ° C., and the minimum value (R2) of the deformation rate at T2 is −0.400% / ° C. The following (negatively large). T2 and R2 indicate the relationship between the ease of fixing of the core portion, which is the main component, and the influence of the shell portion, which is a subcomponent, on the toner fixing property in the fixing step. When the core portion is thermomechanically hard, T2 tends to increase and R2 tends to decrease. Further, when the Tg of the resin constituting the shell portion is high or when the amount of the shell portion is large, T2 tends to increase and R2 tends to decrease. When T2 and R2 are within the above ranges, it is possible to achieve both low-temperature fixing performance, gloss performance, and load resistance performance of the toner. When T2 is less than 60.0 ° C., the offset resistance performance and load resistance performance of the toner are deteriorated. When T2 exceeds 90.0 ° C., sufficient low-temperature fixing performance of the toner cannot be obtained. Similarly, when R2 exceeds −0.400 (when it is negatively small), sufficient gloss performance of the toner cannot be obtained.

  On the other hand, from the viewpoint of gloss performance, R2 is preferably as small as possible (as it is negatively large). However, if R2 is too small, the anti-offset performance of the toner may be reduced. For this reason, from the viewpoint of achieving both the gloss performance and the anti-offset performance, the R2 is preferably −5.000% / ° C. or more (negatively small).

  For this reason, the range of R2 is more preferably -2.500 to -0.400% / ° C, still more preferably -1.500 to -0.500% / ° C, and -1 Particularly preferred is 200 to -0.800% / ° C.

  In the toner of the present invention, the half-value width (D2) of the deformation speed peak of the toner at T2 is preferably 15.0 to 45.0 ° C. A smaller D2 indicates that the viscoelastic change of the toner is larger with respect to the temperature change. In the toner having T1 of 30.0 to 55.0 ° C. and aimed at improving the low-temperature fixing performance, the anti-offset performance and the load-proof performance are further improved. When the D2 is less than 15.0 ° C., the change in the viscoelasticity of the toner with respect to the change in temperature is so large that the toner can easily penetrate into the paper in the fixing step, and the gloss performance of the toner may be deteriorated. In addition, toner load resistance may be reduced. When the D2 exceeds 45.0 ° C., the change in the viscoelasticity of the toner with respect to the change in temperature is small, so that the low-temperature fixing performance and gloss performance of the toner may be deteriorated. The D2 is controlled by the type and amount of resin added assuming that it constitutes a shell part, the coating state of the resin when viewed with a single toner particle, the dispersion state of the resin when viewed as a whole toner, and the like. can do. Further, it can be controlled by the molecular weight distribution of the binder resin contained in the toner, the type and addition amount of the wax, and the like.

  The toner of the present invention preferably has a ratio (R3 / R1) of the deformation rate R3 of the toner at the temperature T3 (° C.) defined by T3 = T1 + 5 to R1 (R3 / R1) of 0.80 to 1.30. When (R3 / R1) is in the above range, the coating state of the shell covering the core when viewed with a single toner particle, and the dispersion state (variation) of the shell amount when the core is viewed as a whole toner are obtained. It will be even better. Thereby, the low-temperature fixing performance and durability stability performance of the toner are further improved. When the (R3 / R1) is less than 0.80, it is considered that the uniformity of the coating state of the shell covering the core in the toner is slightly inferior, or the strength of the shell portion is slightly small, and the development stability and resistance Loading performance may be reduced. When (R3 / R1) exceeds 1.30, the dispersibility of the shell amount when viewed as the whole toner is considered to be slightly non-uniform, and the development stability performance may deteriorate. For the same reason, (R3 / R1) is more preferably 0.90 to 1.20, and particularly preferably 1.00 to 1.20.

  The toner of the present invention preferably has a temperature (T4) at which the deformation speed first becomes 0% / ° C. in the temperature range of T2 or higher, from 100.0 to 180.0 ° C. Low temperature fixing performance, gloss performance, and load resistance performance are further improved. When the T4 is less than 100.0 ° C., the gloss performance and the load resistance performance may be deteriorated. When T4 exceeds 180.0 ° C., the low-temperature fixing performance and the gloss performance may be deteriorated. For the same reason, the T4 is more preferably 110.0 to 170.0 ° C, and particularly preferably 125.0 to 150.0 ° C.

  In the present invention, as a means for controlling T1, R1, T2, R2, D2, and (R3 / R1), it is preferable that the toner contains resin fine particles having a sulfonic acid group. As the resin fine particles, resins such as vinyl resins, polyesters, polyurethanes, polyureas, polyamides, and polyimides can be used. The resin fine particles are preferably contained in an amount of 1.0 to 15.0% by mass based on the total amount of toner. When the content of the resin fine particles is less than 1.0% by mass, R1 may be less than −0.030% / ° C. (negatively small), and development stability performance and load resistance may be reduced. is there. Further, when the content of the resin fine particles exceeds 15.0% by mass, the value of R1 may become a value exceeding −0.300% / ° C. (negatively large). May decrease. In addition, the content of the resin fine particles is more preferably 2.0 to 10.0% by mass, and particularly preferably 3.0 to 8.0% by mass.

  As a method of incorporating the resin fine particles into the toner, (1) a method of forming toner particles after dissolving or dispersing the resin fine particles together with a binder resin, a colorant, a wax, and other additives; There is a method in which after forming colored particles containing a resin, a colorant, a wax, and other additives, a surface layer of resin fine particles is further formed on the surface of the colored particles. Among these, the method (2) is particularly preferable. Further, the colored particles preferably contain a styrene acrylic resin having an acid value in the vicinity of the particle surface.

The resin fine particles have an acid value Av (Av _p ) of 6.0 to 80.0 mgKOH / g, a volume average particle diameter Dv (Dv _p ) of 10 to 200 nm, and the ratio of Av _p to Dv _p (Av _p × Dv _p ) is preferably 200 to 6000. When the acid value of the resin fine particles is within the above range, the acidic group derived from the acid value is likely to interact with the surface of the colored particles, and the particle diameter of the resin fine particles is within the above range, so that the entire toner The amount of the resin fine particles contained in each toner tends to be uniform among the toners while suppressing the amount of the resin fine particles added to the toner. When the Av _p is less than 6.0 mg KOH / g, when the Dv _p exceeds 200 nm, or when (Av _p × Dv _p ) is less than 200, the resin fine particles contained in each toner The amount tends to vary, and δb tends to be a value exceeding 0.60. In this case, the penetration resistance and the offset resistance performance are likely to deteriorate. When the Av _p exceeds 80.0 mgKOH / g, when the Dv _p is less than 10 nm, or when (Av _p × Dv _p ) exceeds 6000, the interaction between the resin fine particles is large. Is likely to exceed 5 × 10 ⁷ Pa, and in the fixing step, the holding power of the heated toner layer is increased, and the low-temperature fixing performance is likely to be deteriorated. Therefore, the Av _p of the resin fine particles is more preferably 10.0 to 55.0 mgKOH / g, and particularly preferably 15.0 to 45.0 mgKOH / g. The Dv _p is more preferably 10 to 150 nm, and particularly preferably 15 to 70 nm. Further, (Av _p × Dv _p ) is more preferably 200 to 3000, further preferably 200 to 1600, and particularly preferably 300 to 1000.

The resin fine particles preferably has a specific 10% particle diameter on a volume distribution and (Dv ₁₀₎ and the _{Dv P (Dv P / Dv 10} ) is 1.0 to 5.0. Even if the amount of the resin fine particles added to the whole toner is not increased, the amount of the resin fine particles contained in each toner tends to be uniform among the toners. In addition, the resin fine particles and the binder resin are easily compatible with each other, and the penetration resistance, color gamut performance, and offset resistance are improved. When the Dv _P / Dv ₁₀ exceeds 5.0, the amount of the resin fine particles contained in each toner particle tends to vary. In this case, the durability stability performance and the offset resistance performance tend to decrease. For this reason, (Dv _P / Dv ₁₀ ) is more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

The fact, for the same reason as described above, the fine resin particles, the ratio of 90% particle diameter on a volume distribution and (Dv ₉₀₎ and the _{Dv P (Dv 90 / Dv P} ) is 1.0 to 5.0 Is preferred. When the (Dv ₉₀ / Dv _P ) exceeds 5.0, the resin fine particles are likely to be released from the toner surface, and the development stability performance tends to be lowered. In addition, the amount of the resin fine particles contained in each toner particle tends to vary. In this case, the penetration resistance and the offset resistance performance may deteriorate. Therefore, the (Dv ₉₀ / Dv _P ) is more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

The volume average particle diameter (Dv _p ), 10% particle diameter (Dv ₁₀ ), and 90% particle diameter (Dv ₉₀ ) of the resin fine particles are, for example, MICROTRAC UPA MODEL: 9232 (manufactured by Lees and Northrup). Can be measured. The measurement conditions are as shown below.
Particle Material: Latex
Transparent Particles: Yes
SPECIAL PARTITICLES: Yes
Particle Refractive Index: 1.59
Fluid: water

  As the resin that can be used for the resin fine particles, resins similar to those exemplified as the resin that can be used for the binder resin described later can be used.

  As a preferred method for producing the toner of the present invention, a step of forming an aqueous dispersion having colored particles containing at least a colorant, a wax, and a binder resin in an aqueous medium having a poorly water-soluble inorganic dispersant. Adding a dispersion of resin fine particles to the aqueous dispersion to form a composite dispersion, heating the composite dispersion, and dissolving the sparingly water-soluble inorganic dispersant of the composite dispersion It is preferable to be formed through a process. Furthermore, the colored particles preferably have a styrene acrylic resin having an acid value. By the interaction with the styrene acrylic resin, the inorganic dispersant is uniformly adsorbed on the surface of the colored particles, and the adsorption amount of the inorganic dispersant is uniformly adsorbed between the colored particles. Furthermore, the adsorption force works due to the interaction between the inorganic dispersant and the resin fine particles, and the resin fine particles can be uniformly contained on the surface of the colored particles, and the resin fine particles can be uniformly contained between the colored particles. It is thought that it becomes. After forming the state in which the inorganic dispersant and the resin fine particles are uniformly adsorbed on the colored particles, the heating step is used to soften the colored particles and the resin fine particles, and further dissolve the inorganic dispersant As a result, the resin fine particles can be uniformly contained on the surface of the colored particles, and the content of the resin fine particles can be uniformly contained between the colored particles.

  The preferable acid value of the styrene acrylic resin having the acid value is preferably 1.0 to 30.0 mgKOH / g. Due to the polar group derived from the acid value, when one colored particle is seen, the styrene acrylic resin is likely to be selectively and uniformly localized near the surface of the colored particle. Also, when the entire colored particles are viewed, the content of the styrene acrylic resin contained in the colored particles tends to be uniform. As a result, the density of polar groups present on the surface of the colored particles tends to be uniform regardless of whether one colored particle or the entire colored particle is viewed. For this reason, the adsorption state of the inorganic dispersant adsorbed on the surface of each colored particle tends to be uniform, and the resin fine particles are easily adsorbed uniformly. As a result, when viewed as a whole toner, the amount of the resin fine particles contained in the toner tends to be uniform, and also when seen as a single toner particle, it is contained in the toner in the lateral and depth directions. The amount of the resin fine particles tends to be uniform. In addition, the range of the acid value of the styrene acrylic resin having the acid value is more preferably 3.0 to 20.0 mgKOH / g, and particularly preferably 5.0 to 16.0 mgKOH / g.

  As a vinyl monomer that can be used for the styrene acrylic resin, a vinyl monomer that can be used for a binder resin described later can be used.

  The styrene acrylic resin preferably has a maximum value (Mp) at a molecular weight of 4000 to 100,000 in a molecular weight distribution in terms of polystyrene (St) by gel permeation chromatography (GPC). When the styrene acrylic resin has Mp in the above range, the adhesion between the colored particles and the resin fine particles is further improved. When the Mp is less than 4000, the resin fine particles are likely to be embedded in the colored particles, and the blocking resistance of the toner may be lowered. When the Mp exceeds 100,000, the adhesiveness between the resin fine particles and the colored particles is lowered, and the durability stability performance of the toner may be lowered. The Mp range is more preferably a molecular weight of 50000 to 50000, and particularly preferably a molecular weight of 6000 to 25000.

  For the same reason, the styrene acrylic resin preferably has a weight average molecular weight (Mw) of 4000 to 200000. When the Mw is less than 4000, the resin fine particles are likely to be embedded in the colored particles, and the blocking resistance of the toner may be reduced. When the Mw exceeds 200,000, the adhesiveness between the resin fine particles and the colored particles is lowered, and the durability stability performance of the toner may be lowered. The range of Mw is more preferably 5000 to 100,000, and particularly preferably 7000 to 30000.

  In order to have the Mp and Mw of the styrene acrylic resin in the above range, it is possible to control the composition and production conditions of the styrene acrylic resin.

  The step of forming the aqueous dispersion having the colored particles preferably has a poorly water-soluble inorganic dispersant. Examples of inorganic dispersants include trivalent calcium phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metasuccinate and calcium sulfate And inorganic salts such as barium sulfate; inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina. These inorganic dispersants are preferably used in an amount of 0.2 to 20 parts by mass alone or in combination of two or more with respect to 100 parts by mass of the colored particles.

  The colored particles have a glass transition point (Tt) at 25.0 to 60.0 ° C., a melting point (Tw) at 65.0 to 95.0 ° C., and the resin particles have a temperature of 40.0 to 90.0 ° C. It has a glass transition point (Ts), the difference between Tt and Tw (Tw−Tt) is 10.0 to 50.0 ° C., and the difference between Tt and Ts (Ts−Tt) is 5 It is preferably from 0 to 50.0 ° C.

  When the (Tw−Tt) is less than 10.0 ° C., the colored particles become too soft in the heating step, and the resin fine particles are immediately immobilized on the surface of the colored particles. Variations are likely to occur. As a result, the development stability of the toner may be reduced. When the (Tw−Tt) exceeds 50.0 ° C., the resin fine particles are easily released from the toner, and the development stability of the toner may be deteriorated. Similarly, when the (Ts−Tt) is less than 5.0 ° C., the colored particles become sufficiently soft in the heating step, and the resin fine particles are immediately fixed on the surface of the colored particles. Variations in the content of the resin fine particles are likely to occur. As a result, the development stability of the toner may be reduced. When (Ts−Tt) exceeds 50.0 ° C., the resin fine particles are likely to be released from the toner, and the development stability of the toner may be deteriorated. For this reason, (Tw−Tt) is more preferably 15.0 to 50.0 ° C., and particularly preferably 25.0 to 45.0 ° C. The (Ts−Tt) is more preferably 10.0 to 40.0 ° C., and particularly preferably 15.0 to 35.0 ° C.

  If the Tt is less than 25.0 ° C., the colored particles may be easily fused. In addition, the toner penetration resistance tends to decrease. When the Tt is 65 ° C. or more, the low-temperature fixing performance of the toner tends to be lowered. When the Tw is less than 65.0 ° C., the colored particles are easily fused in the heating step. In addition, the anti-offset performance of the toner may be reduced. When the Tw exceeds 95.0 ° C., the colored particles may not be sufficiently soft in the heating step, and the resin fine particles may be easily released from the toner, and the development stability of the toner may be deteriorated. If the Ts is less than 40.0 ° C., the resin fine particles are immediately immobilized on the surface of the colored particles in the heating step, and therefore the content of the resin fine particles tends to vary among the toners. As a result, the development stability of the toner may be reduced. When the Ts exceeds 90.0 ° C., the resin fine particles are easily released from the toner, and the development stability performance of the toner may be deteriorated. Therefore, the Tt is more preferably 25.0 to 48.0 ° C, further preferably 30.0 to 48.0 ° C, and particularly preferably 33.0 to 45.0 ° C. . The Tw is more preferably 65.0 to 90.0 ° C, more preferably 70.0 to 90.0, and particularly preferably 70.0 to 85.0 ° C. The Ts is more preferably 50.0 to 85.0 ° C, still more preferably 55.0 to 80.0 ° C, and particularly preferably 60.0 to 78.0 ° C.

  The toner of the present invention contains 55.0 to 97.0% by mass of a component soluble in tetrahydrofuran (THF) by a Soxhlet extraction method, and the THF-soluble component contains 0.005 elemental sulfur derived from a sulfonic acid group. It is preferable to contain 0.150 mass%. In the present invention, the sulfonic acid group is considered to be a sulfonic acid group contained in the resin fine particles added to the toner assuming that it constitutes a shell portion. According to the present invention, when the content of the sulfonic acid group is in the above range, the adsorptivity between the core portion and the shell portion is improved. For this reason, even if the addition amount of the resin fine particles to be contained in the toner is reduced, the physical property values defined in the present invention can be expressed well, and while maintaining good durability stability performance and load resistance performance, The fixing performance can be further improved.

  When the content of the THF soluble component exceeds 97.0% by mass, the resin fine particles are likely to be embedded in the colored particles, so that the toner blocking performance and development stability performance may be deteriorated. In addition, the anti-offset performance of the toner tends to decrease. When the content of the THF-soluble component is less than 55.0% by mass. Since the adhesion between the resin fine particles and the colored particles tends to be lowered, the development stability performance of the toner may be lowered. Further, since the low-temperature fixing performance of the toner tends to be lowered, the content of the THF soluble component is more preferably 60.0 to 90.0% by mass, and 65.0 to 85.0% by mass. It is particularly preferable that The content of the THF-soluble component can be controlled by the types and addition amounts of the binder resin and the crosslinking agent, toner production conditions, and the like.

  The content of the THF-soluble component is specifically defined by a value measured by the Soxhlet extraction method shown below. Further, the THF-soluble component contained in the toner refers to a component recovered as follows.

A cylindrical filter paper (for example, Toyo Filter Paper No. 86R can be used) is vacuum-dried at 40 ° C. for 24 hours, and then left in an environment adjusted to a temperature and humidity of 25 ° C. and 60% RH for 3 days. When the true density of the toner is ρ (g / cm ³ ), the toner (1 × ρ) g is weighed (W1 g), put into this cylindrical filter paper, subjected to a Soxhlet extractor, and 200 ml of THF is used as a solvent at 90 ° C. Extract in an oil bath for 24 hours. Then, after cooling the Soxhlet extractor at a cooling rate of 1 ° C. per minute, the cylindrical filter paper is gently taken out and vacuum-dried at 40 ° C. for 24 hours. After leaving this in an environment adjusted to a temperature and humidity of 25 ° C. and 60% RH for 3 days, the amount of solid content remaining on the cylindrical filter paper is weighed (W2 g).

The content of the THF soluble component of the toner is calculated from the following formula.
Content (mass%) of THF soluble component of toner = 100− (W2 / W1) × 100

  The THF-soluble component contained in the toner is filtered using the quantitative filter paper (for example, ADVANTEC quantitative filter paper No. 5A can be used). After the volatile matter was distilled off from the obtained solution using an evaporator set at 40 ° C., the solid content obtained by vacuum drying at 40 ° C. for 24 hours is defined as a THF-soluble component.

  The THF-soluble component contained in the toner preferably has a maximum value (Mp) at a molecular weight of 8000 to 200,000 in a molecular weight distribution in terms of polystyrene (St) by gel permeation chromatography (GPC). When the THF soluble component has Mp in the above range, the balance between the sharp melting of the toner and the viscosity retention at the time of melting is improved, and the low-temperature fixing performance, penetration resistance, color gamut performance, and offset resistance are improved. The performance becomes even better. When the Mp is less than 8000, the offset resistance performance and the penetration resistance performance may be deteriorated. When the Mp exceeds 200,000, the low-temperature fixing performance and the penetration performance may deteriorate. The Mp range is more preferably a molecular weight of 10,000 to 100,000, and particularly preferably a molecular weight of 15,000 to 35,000.

  For the same reason, the THF-soluble component preferably has a weight average molecular weight (Mw) of 10,000 to 500,000. When the Mw is less than 10,000, the offset resistance performance and the penetration resistance performance may be deteriorated. When the Mw exceeds 500,000, the low-temperature fixing performance and the penetration performance may be deteriorated. The Mw range is more preferably 30000 to 200000, and particularly preferably 50000 to 150,000.

  In order to have the Mp and Mw within the above ranges, it is possible to control the types and addition amounts of the binder resin and the crosslinking agent, the toner production conditions, and the like.

  The toner of the present invention preferably has an average circularity in the range of 0.945 to 0.995 by FPIA3100. More preferably, it is 0.965 to 0.995, and particularly preferably 0.975 to 0.990. When the average circularity is less than 0.945, the toner easily breaks from the concave and convex portions of the toner in the developing device, and the broken toner is deposited on the charging member and the like, and the development stability performance tends to be lowered. In the toner containing resin fine particles as in the present invention, if the resin fine particle content is not uniform between the toners, the resin fine particles form concave and convex portions of the toner, and the average circularity becomes a small value. The resin fine particles are easily broken in the developing device. When the average circularity is larger than 0.995, the toner is easily packed in an excessively dense manner, and when the low temperature fixing performance is aimed at, the development stability performance may be lowered. Further, in the cleaning of the photosensitive drum, since the shape is too spherical, an image defect such as a cleaning defect such as slipping through the cleaning blade may appear. The average circularity of the toner of the present invention can also be adjusted by using a surface modifying device described later.

  The toner of the present invention preferably has a content of particles of 1 μm or less in a number distribution by FPIA 3000 of 20.0% by number or less. When the content of the particles exceeds 20% by number, the particles are accumulated in the charging member or the like in the developing device, and the development stability performance tends to be lowered. In the toner containing resin fine particles as in the present invention, if the resin fine particle content is not uniform on the toner surface, the resin fine particles are likely to be detected as particles having a size of 1 μm or less, and the development stability performance tends to be lowered. In addition, the transferability of the toner is lowered, the graininess in the low density region is poor, and an image with a feeling of roughness may be obtained. The content of the particles is more preferably 15.0% by number or less, still more preferably 10.0% by number or less, and particularly preferably 5.0% by number or less.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 3.0 to 7.0 μm. If the D4 is less than 3.0 μm, the toner may be overfilled during long-term storage, and storage stability performance may deteriorate. Further, in the cleaning of the photosensitive drum, since the shape is too spherical, an image defect such as a cleaning defect such as slipping through the cleaning blade may appear. In addition, the transferability of the toner is lowered, the graininess in the low density region is poor, and an image with a feeling of roughness may be obtained. When the D4 is 7.0 μm or more, the development stability performance may be lowered when the low temperature fixing performance is aimed at. In the present invention, the preferable range of D4 is more preferably 3.5 to 6.5 μm, and particularly preferably 4.0 to 6.0 μm.

  Next, materials used for the toner of the present invention and a method for producing the same will be described.

  As the binder resin used in the toner of the present invention, various resins conventionally known as binder resins for electrophotography can be used. Among them, (a) a polyester, (b) a hybrid resin having a polyester and a vinyl polymer, (c) a resin selected from a vinyl polymer and a mixture thereof may be a main component. preferable. The polyester preferably has a urethane bond or a urea bond.

  Specific examples of the monomer that can be used for the binder resin of the present invention include the following compounds.

  As the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane , Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxy) Phenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and other bisphenol A alkylene oxide adducts, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1 , 3-propylene glycol, 1,4-butanediol, neopentylglyco 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogen Added bisphenol A, following formula (VII)

（式中、Ｒはエチレンまたはプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数を示し、且つｘ＋ｙの平均値は２乃至１０を示す。）
で示されるビスフェノール誘導体、または下記式（ＶＩＩＩ）

(In the formula, R represents an ethylene or propylene group, x and y each represents an integer of 1 or more, and the average value of x + y represents 2 to 10.)
Or a bisphenol derivative represented by the following formula (VIII)

で示される化合物等が挙げられる。

And the like.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; carbon Succinic acid or anhydride thereof substituted with an alkyl group of several 6 to 12; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof; n-dodecenyl succinic acid, isododecenyl succinic acid, tri And merit acid.

  Among them, in particular, a bisphenol derivative typified by the general formula (VIII) and an alkyldiol having 2 to 6 carbon atoms as a diol component, a divalent carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof (For example, fumaric acid, maleic acid, maleic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, alkyl dicarboxylic acid having 4 to 10 carbon atoms, and acid anhydrides of these compounds) And the like, and polyester obtained by polycondensation of these with an acid component is preferable as a toner because it has good charging characteristics.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 1,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof.

  The use amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomers. Furthermore, as a binder resin, a polyester unit that has an ester bond in the main chain and is a polycondensate of polyhydric alcohol and polybasic acid, and a vinyl polymer unit that is a polymer having an unsaturated hydrocarbon group In the case of using a hybrid resin having the above, it is possible to expect further improved wax dispersibility, low-temperature fixability, and offset resistance. The hybrid resin used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, it is a resin formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester, preferably a vinyl polymer. A graft copolymer (or block copolymer) having a trunk polymer and a polyester unit as a branch polymer.

  Examples of the vinyl monomer for producing the vinyl polymer include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2, 4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn -Styrene such as dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof; ethylene, propylene, butylene, isobutylene Styrene unsaturated monoolefins such as butadiene and isoprene Saturated polyenes; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, acrylate acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, dodecyl acrylate Acrylates such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl Vinyl ketones such as hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile, acrylamide Examples thereof include acrylic acid or methacrylic acid derivatives.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Furthermore, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate and 1,3-butylene glycol diene. Acrylates, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene. Examples include lenglycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate; diacrylates linked by chains containing aromatic groups and ether bonds Examples of the compounds include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the like The thing which replaced the acrylate of the compound of this with the methacrylate is mentioned.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  The hybrid resin used in the present invention preferably contains a monomer component capable of reacting with both resin components in one or both of the vinyl polymer unit component and the polyester unit. Examples of the monomer constituting the polyester unit that can react with the vinyl polymer unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer unit, those that can react with the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a reaction product of a vinyl polymer unit and a polyester unit, a polymer containing a monomer component capable of reacting with each unit is present, and a polymerization reaction of one or both resins is performed. The method obtained by

  Examples of the polymerization initiator used for producing the vinyl polymer of the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl -4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclo Ketone peroxides such as xanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl Peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy Oxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhex Hydro terephthalate, di -t- butyl peroxy azelate and the like.

  As a manufacturing method which prepares the said hybrid resin, the manufacturing method shown to the following (1)-(6) can be mentioned, for example.

  (1) A method in which a vinyl polymer unit, a polyester unit and a hybrid resin component are blended after production, and the blended product is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The For the hybrid resin component, a vinyl polymer and a polyester resin are separately manufactured, dissolved and swollen in a small amount of an organic solvent, an esterification catalyst and an alcohol are added, and the ester exchange reaction is performed by heating. Synthesized ester compounds can be used.

  (2) A method for producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer after the production thereof. The hybrid resin component is produced by a reaction between a vinyl polymer (a vinyl monomer can be added if necessary) and any one of a polyester monomer (alcohol, carboxylic acid) and polyester, or a reaction with both. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer and a hybrid resin component in the presence of a polyester unit after the production thereof. The hybrid resin component is produced by a reaction between one or both of a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer.

  (4) After the production of the vinyl polymer unit and the polyester unit, the hybrid resin component is produced by adding one or both of the vinyl monomer and the polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Is done. Also in this case, an organic solvent can be appropriately used.

  (5) After producing the hybrid resin component, one or both of a vinyl monomer and a polyester monomer (alcohol, carboxylic acid) are added, and at least one of addition polymerization and polycondensation reaction is performed, thereby producing a vinyl resin. Polymer units and polyester units are produced. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate.

  (6) A vinyl polymer unit, a polyester unit, and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate.

  In the above production methods (1) to (5), a polymer unit having a plurality of different molecular weights and crosslinking degrees can be used for the vinyl polymer unit and the polyester unit.

  The binder resin contained in the toner of the present invention includes a mixture of the polyester resin and a vinyl polymer, a mixture of the hybrid resin and a vinyl polymer, the polyester resin and the hybrid resin. A mixture of vinyl polymers may be used.

  The toner of the present invention contains one kind or two or more kinds of waxes. Examples of the wax that can be used in the present invention include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; fats such as oxidized polyethylene wax Oxides of aliphatic hydrocarbon waxes; block copolymers of aliphatic hydrocarbon waxes; waxes based on fatty acid esters such as carnauba wax and montanic acid ester wax; and partially or partially fatty acid esters such as deoxidized carnauba wax The thing which deoxidized all is mentioned. For example, examples of the ester wax include behenyl behenate and stearyl stearate.

  Examples thereof include partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 350 to 2400, more preferably in the region of molecular weight 400 to 2000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.

  The wax content is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the binder resin. In the toner of the present invention, a part of the wax contained in the toner is used as a plasticizer by being compatible with a binder resin when the toner is produced. Further, in the fixing step, a part of the wax contained in the toner is compatible with the binder resin and used as a plasticizer. For this reason, since all of the wax contained in the toner does not act as a release agent, it is preferable to contain more wax than usual. If the wax content is less than 3 parts by mass, the anti-offset performance tends to decrease. When the wax content exceeds 30 parts by mass, the endothermic amount of the wax in the fixing process becomes too large, and the low-temperature fixing performance tends to be lowered. The wax content of the toner of the present invention is more preferably 5 to 20 parts by mass, and particularly preferably 6 to 14 parts by mass.

  When the above physical properties are required, the extraction method is not particularly limited and any method can be used when the wax needs to be extracted from the toner.

  For example, a predetermined amount of toner is Soxhlet extracted with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained.

  Thereafter, identification analysis is performed by IR method or the like.

  In addition, quantitative analysis is performed by DSC.

  Among these wax components, those having a maximum endothermic peak in the region of 60 to 140 ° C. in the DSC curve measured by a differential scanning calorimeter are preferable, and those having the maximum endothermic peak in the region of 60 to 90 ° C. Further preferred. By having the maximum endothermic peak in the above temperature range, it is possible to effectively exhibit releasability while greatly contributing to low-temperature fixing. When this maximum endothermic peak is less than 60 ° C., the self-aggregation force of the wax component becomes weak, and as a result, the high temperature offset resistance deteriorates. On the other hand, when the maximum endothermic peak exceeds 140 ° C., the fixing temperature increases and low temperature offset tends to occur. Furthermore, when the toner is obtained directly by a polymerization method in which polymerization is carried out in an aqueous medium, if this maximum endothermic peak temperature is high, problems such as precipitation of wax components mainly during granulation, such as when adding a large amount, occur. There is.

  The toner of the present invention may use a charge control agent.

  Examples of the charge control agent for controlling the toner to be negatively charged include, for example, organometallic compounds, chelate compounds, monoazo metal compounds, acetylacetone metal compounds, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, and quaternary ammonium. Examples thereof include salts, calixarene, silicon compounds, nonmetal carboxylic acid compounds and derivatives thereof.

  Examples of the charge control agent for controlling the toner to be positively charged include modified products of nigrosine and fatty acid metal salts, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate and the like. Quaternary ammonium salts, and onium salts such as phosphonium salts and analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten) Molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyls Borate, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; and the like, can be used in combination singly or two or more kinds. Among these, a charge control agent such as a nigrosine-type quaternary ammonium salt is particularly preferably used.

  The charge control agent may be contained in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin in the toner.

  The toner of the present invention contains a colorant. As the black colorant, carbon black, a magnetic material, or a color toned to black using a yellow / magenta / cyan colorant shown below is used.

  As the colorant for cyan toner, magenta toner, and yellow toner, for example, the following colorants can be used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12 to 15, 17, 23, 24, 60, 62, 74, 75, 83, 93 to 95, 99, 100, 101, 104, 108 to 111, 117, 123, 128, 129,138,139,147,148,150,166,168-177,179,180,181,183,185,191: 1,191,192,193,199 are preferably used. Examples of the dye system include C.I. l. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 can be mentioned.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5-7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. And CI Pigment Bio Red 19.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 0.4 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  Furthermore, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Examples include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  The magnetic material has a coercive force (Hc) of 1.59 to 23.9 kA / m (20 to 300 oersted), saturation magnetization (σs) of 50 to 200 emu / g when 796 kA / m (10 koersted) is applied. A magnetic material having a remanent magnetization (σr) of 2 to 20 emu / g is preferable.

  In the toner of the present invention, it is preferable that an inorganic fine powder or a hydrophobic inorganic fine powder is externally added to the toner particles and mixed as a fluidity improver. For example, titanium oxide fine powder, silica fine powder, and alumina fine powder are preferably added and used, and silica fine powder is particularly preferred.

The inorganic fine powder used in the toner of the present invention has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, and particularly in the range of 50 to 400 m ² / g gives good results. Is preferable.

  Furthermore, the toner of the present invention may have an external additive other than the fluidity improver mixed with the toner particles as necessary.

For example, for the purpose of improving the cleaning property, etc., the primary particle diameter exceeds 30 nm (preferably the specific surface area is less than 50 m ^{2 /} g), more preferably the primary particle diameter is 50 nm or more (preferably the specific surface area is 30 m ^2). It is also a preferable form to add inorganic particles or organic particles that are nearly spherical at less than / g) to the toner particles. For example, spherical silica particles, spherical polymethylsilsesquioxane particles, and spherical resin particles are preferably used.

  Still other additives such as lubricant powders such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; or abrasives such as cerium oxide powder, silicon carbide powder, strontium titanate powder; anti-caking agent; or carbon, for example Conductivity imparting agents such as black powder, zinc oxide powder and tin oxide powder; organic fine particles having opposite polarity and inorganic fine particles can also be added in small amounts as developability improvers. These additives can also be used after hydrophobizing the surface.

  The external additive as described above may be used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) with respect to 100 parts by mass of the toner.

  When the toner of the present invention is produced by a pulverization method, a known method can be used. As a known method, for example, components necessary as a toner such as a binder resin, a release agent, and a charge control agent and other additives are sufficiently mixed in a mixer such as a Henschel mixer and a ball mill, and then heated rolls. Then, they are melt-kneaded using a heat kneader such as a kneader or an extruder so that the resins are mutually melted. Toner particles are obtained by a multi-step process in which other toner materials such as magnetite are dispersed or dissolved, and after cooling and solidification and pulverization, classification and surface treatment with resin particles and the like. A toner can be obtained by adding and mixing fine powder or the like to the obtained toner particles as necessary. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.

  The pulverization step can be performed using a known pulverizer such as a mechanical impact type or a jet type. In order to obtain a developer having a specific circularity according to the present invention, it is preferable to further pulverize by applying heat or to add a mechanical impact in an auxiliary manner. Further, a hot water bath method in which finely pulverized (classified as necessary) toner particles are dispersed in hot water, a method of passing in a hot air stream, or the like may be used.

  As a method of applying a mechanical impact force, for example, there is a method using a mechanical impact type pulverizer such as a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industry. Also, like devices such as Hosokawa Micron's Mechano-Fusion System and Nara Machinery's Hybridization System, the toner is pressed against the inside of the casing by centrifugal force with high-speed rotating blades, and the force of compression force, friction force, etc. A method of applying a mechanical impact force to the toner may be used.

  When processing with mechanical impact is applied, setting the ambient temperature during processing to a temperature near the glass transition point Tg of the toner (that is, a temperature range of ± 30 ° C. with respect to the glass transition point Tg) prevents aggregation. From the viewpoint of productivity. More preferably, the treatment at a temperature in the range of ± 20 ° C. with respect to the glass transition point Tg of the toner is particularly effective for improving the transfer efficiency.

  Furthermore, the toner of the present invention is a method of obtaining a spherical toner by atomizing a molten mixture into air using a disk or a multi-fluid nozzle, or a water-based organic solvent that is soluble in a monomer and insoluble in a polymer obtained. The toner is produced using a dispersion polymerization method in which toner is directly produced by using emulsion, or an emulsion polymerization method represented by a soap-free polymerization method in which toner is produced by direct polymerization in the presence of a water-soluble polar polymerization initiator. It can also be produced by a method such as a dissolution suspension method or an emulsion aggregation method.

  A particularly preferred production method is a suspension polymerization method obtained by directly polymerizing a polymerizable monomer in an aqueous medium.

  In the production of toner by suspension polymerization, generally, a polymerizable monomer, a colorant, a wax, a charge control agent, a cross-linking agent, etc. are uniformly distributed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. Dissolve or disperse. The monomer composition thus obtained is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size distribution of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size at a stretch. The polymerization initiator may be added in advance to the monomer composition, or may be added after the monomer composition is suspended in an aqueous medium.

  After the suspension, stirring may be performed using an ordinary stirrer to such an extent that the particle state is maintained and the floating / sedimentation of the particles is prevented. In the present invention, the pH is preferably 4 to 10.5 when suspended. If the pH is less than 4, the toner may have a wide particle size distribution. On the other hand, if the pH exceeds 10.5, the charging performance of the toner may deteriorate.

  In the suspension polymerization method, known surfactants and organic / inorganic dispersants can be used as dispersion stabilizers. Among these, inorganic dispersants can be preferably used because their stability is not easily lost even when the reaction temperature is changed. Examples of such inorganic dispersants include trivalent calcium phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metasuccinate and sulfuric acid. Inorganic salts such as calcium and barium sulfate; inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina.

  These inorganic dispersants are preferably used alone or in combination of two or more, with respect to 100 parts by weight of the polymerizable monomer. When aiming at a more finely divided toner having an average particle diameter of 5 μm or less, 0.001 to 0.1 parts by mass of a surfactant may be used in combination.

  Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, and potassium stearate.

  When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, it is preferable to produce the inorganic dispersant in an aqueous medium. Specifically, for example, in the case of tricalcium phosphate, it is possible to produce a poorly water-soluble tricalcium phosphate by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution with high-speed stirring. Distribution becomes possible. The inorganic dispersant can be almost completely removed by dissolving with an acid or alkali after completion of the polymerization.

  In the polymerization step, the polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. When the polymerization is performed within this temperature range, the binder resin and the wax are phase-separated with the progress of the polymerization, and a toner in which the wax is encapsulated is obtained. It is also preferable to raise the reaction temperature to 90 to 150 ° C. at the end of the polymerization reaction.

  The toner of the present invention can be used as a toner for a one-component developer, and can also be used as a toner for a two-component developer having a carrier.

  When used as a two-component developer, it is used as a developer in which the toner of the present invention and a carrier are mixed. The carrier is composed of an element selected from iron, copper, zinc, nickel, cobalt, manganese, and chromium element alone or a composite ferrite. The carrier has a spherical shape, a flat shape, or an indeterminate shape, any of which can be used. Moreover, it is preferable to control the fine structure (for example, surface unevenness) of the carrier surface.

  Examples of the method for producing the carrier include a method in which the ferrite core is fired and granulated to previously generate a carrier core and then the surface thereof is coated with a resin. From the viewpoint of reducing the load on the toner of the carrier, a method of obtaining a low-density dispersion carrier by kneading and classifying ferrite and resin, and further, directly kneading the ferrite and monomer in an aqueous medium A method of obtaining a true spherical carrier by suspension polymerization can also be used.

  A coated carrier in which the surface of the carrier core is coated with a resin is particularly preferably used. Examples of the production method include a method in which a resin is dissolved or suspended in a solvent, and the solution or suspension is applied and adhered to a carrier, or a method in which a resin powder and a carrier core are simply mixed and adhered. It is done.

  The substance that covers the surface of the carrier core varies depending on the material of the toner, for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, Examples thereof include polyamide, polyvinyl butyral, and amino acrylate resin. These can be used alone or in plural.

As the magnetic characteristics of the carrier, the magnetization intensity (σ1000) at 79.6 kA / m (1 k Oersted) after magnetic saturation is preferably 30 to 300 emu / cm ³ . In order to achieve higher image quality, it is more preferably 100 to 250 emu / cm ³ . When the magnetization intensity is greater than 300 emu / cm ^3, it becomes difficult to obtain a high-quality toner image. On the other hand, if it is less than ³⁰ emu / cm ³ , the magnetic binding force also decreases, and carrier adhesion is likely to occur.

  Regarding the shape of the carrier, SF-1 indicating the degree of roundness is preferably 180 or less, and SF-2 indicating the degree of unevenness is preferably 250 or less. SF-1 and SF-2 are defined by the following formulas and are measured by Luzex III manufactured by Nireco.

  When the two-component developer is prepared by mixing the toner of the present invention and the carrier, the mixing ratio is preferably 2 to 15% by mass, more preferably 4 to 13% by mass as the toner concentration in the developer. .

<Measurement of Glass Transition Point (Tg) and Melting Point (Tm) of Toner and Materials Used by DSC>
The peak temperature of the maximum endothermic peak of the wax and toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 6 mg of toner is precisely weighed and placed in an aluminum pan. Use an empty aluminum pan as a reference. Measurement is performed at a temperature rising rate of 1.0 ° C./min within a measurement range of 0 to 200 ° C. In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection point between the line of the midpoint of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the binder resin.

  In the present invention, the glass transition point (Tg) and melting point (Tm) of the toner and the material used are measured using a differential scanning calorimeter (DSC). As the DSC, Q1000 (manufactured by TA Instruments) can be used. In the measurement method, about 6 mg of a sample is precisely weighed on an aluminum pan, an empty aluminum pan is used as a reference pan, and measurement is performed in a nitrogen atmosphere with a modulation amplitude of 1.0 ° C. and a frequency of 1 / min. The measurement temperature is maintained at 10 ° C. for 1 minute, and then Tg is determined by a midpoint method using a reversing heat flow curve obtained by scanning from 10 ° C. to 200 ° C. at a heating rate of 1 ° C./min. The glass transition point determined by the midpoint method is the glass transition point at the intersection of the baseline before the endothermic peak and the baseline after the endothermic peak in the DSC curve at elevated temperature and the rising curve. (See FIG. 2).

  In the measurement of the melting point of the toner, the melting point is the temperature at which the melting peak becomes maximum in the reversing heat flow curve obtained by the same measurement as described above. The melting point onset value and offset value are defined as the melting point onset value at the intersection of the tangent line drawn at the maximum slope of the peak of the melting peak and the extrapolated baseline before the peak. The temperature at the intersection of the tangent drawn at the point of maximum slope before the end of the melting peak and the extrapolated baseline after the peak is taken as the offset value of the melting point.

  The endothermic amount is a straight line connecting the point where the peak rises from the extrapolated baseline before the melting peak and the point where the extrapolated baseline and the peak touch after the melting peak in the reversing heat flow curve obtained by the above measurement. Obtained from the area surrounded by the melting peak.

<Measurement of molecular weight in terms of styrene by GPC>
In the present invention, a method for measuring the molecular weight in terms of styrene (St) by gel permeation chromatography (GPC) will be described.

The column is stabilized in a 40 ° C. heat chamber, and THF (tetrahydrofuran) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml per minute, and 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, one having a molecular weight of about 10 ^{2 to} 10 ⁷ is used, and it is appropriate to use a standard polystyrene sample having at least about 10 points. Specifically, for example, standard polystyrene Easy PS-1 manufactured by Polymer Laboratories (a mixture of molecular weights 7500000, 841700, 148000, 28500, 2930 and a mixture of molecular weights 2560000, 320000, 59500, 9920, 580) and PS-2 (A mixture of molecular weights 377400, 96000, 19720, 4490, 1180 and a mixture of molecular weights 188700, 46500, 9920, 2360, 580) can be used in combination. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko, A combination of TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn is given.

  The maximum value (Mp) and the weight average molecular weight (Mw) of the molecular weight distribution of the THF-soluble component of the toner of the present invention are determined from the molecular weight distribution obtained by the above measurement.

  A sample used for the GPC apparatus is manufactured as follows.

  The sample to be measured is placed in THF, mixed well, and allowed to stand for 18 hours. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.) can be used. Is a GPC sample. The concentration of the sample to be measured with respect to THF is 5 mg / ml.

  The weight average molecular weight (Mw), number average molecular weight (Mn), etc. of the wax and other resins used in the present invention can also be measured in the same manner as described above.

<Measurement of acid value of resin>
The acid value of the resin is determined as follows. Basic operation conforms to JIS-K0070.

  The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample is called an acid value, and is measured by the following method.

(1) Reagent (a) Preparation of solvent As a sample solvent, an ethyl ether-ethyl alcohol mixture (1 + 1 or 2 + 1) or a benzene-ethyl alcohol mixture (1 + 1 or 2 + 1) is used. These solutions are neutralized with a 0.1 mol / liter potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use.
(B) Preparation of phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) Preparation of a 0.1 mol / liter potassium hydroxide-ethyl alcohol solution

  Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to 1 liter, leave it for 2 to 3 days, and filter. The standardization is performed according to JISK 8006 (basic matters concerning titration during the reagent content test).

(2) Operation Weigh correctly 1 to 20 g of sample, add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this was titrated with a 0.1 mol / liter potassium hydroxide-ethyl alcohol solution, and the neutralization end point was reached when the indicator was slightly red for 30 seconds.

(3) Calculation formula The acid value is calculated by the following formula.
A = B × f × 5.661 / S
A: Acid value (mgKOH / g)
B: 0.1 mol / liter-amount of potassium hydroxide ethyl alcohol solution used (ml)
f: 0.1 mol / liter-factor of potassium hydroxide ethyl alcohol solution S: sample (g)

<Measurement of average circularity of toner>
The average circularity of the toner can be measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation).

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) is used for measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, The projected area S, the peripheral length L, and the like are measured.

Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

<Measurement of weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set in the dedicated software, the “average diameter” on the “Analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the graph / number% in the dedicated software. The “average diameter” on the “analysis / number statistics (arithmetic mean)” screen is the number average particle diameter (D1).

  EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention concretely, these do not limit this invention at all.

(Production Example 1 of Resin Fine Particles)
The following raw materials were put in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, reacted at 260 ° C. under normal pressure for 8 hours, cooled to 240 ° C., and reduced in pressure to 1 mmHg over 1 hour. Furthermore, it was made to react for 3 hours and the polyester which has a sulfonic acid group was obtained.

(Alcohol monomer)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (BPA-PO): 40 mol%
Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (BPA-EO): 5 mol%
・ Ethylene glycol: 70 mol%
(Acid monomer)
・ Terephthalic acid: 95 mol%
-Trimellitic acid: 5 mol%
-5-sodium sulfoisophthalic acid: 4.8 mol%
(catalyst)
Tetrabutyl titanate: 0.1 mol%
(Styrene acrylic monomer)
Styrene: 20 mol%
-Methacrylic acid: 5 mol%

  The polyester: 100 parts by mass, methyl ethyl ketone: 50 parts by mass, and tetrahydrofuran: 50 parts by mass were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and heated to 75 ° C. while stirring. To this, 400 parts by mass of 75 ° C. water was added and stirred for 1 hour. The mixture was heated to 95 ° C., stirred for 4 hours, and cooled to 30 ° C. to obtain resin fine particles 1. A part was taken out and dried in a hot air dryer at 40 ° C. for 3 days, and then the physical properties of the resin fine particles 1 were measured. The physical properties of the resin fine particles 1 are shown in Table 1.

(Production Examples 2 and 3 of resin fine particles)
Except for those shown in Table 2, resin fine particles 2 and 3 were obtained in the same manner as in Production Example 1 of resin fine particles. The physical properties of the resin fine particles 2 and 3 were measured in the same manner as in Production Example 1 of resin fine particles. The physical properties of the resin fine particles 2 and 3 are shown in Table 1.

(Production Example 1 of Styrene Acrylic Resin)
The following raw materials were put in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and after sufficient nitrogen substitution, the reaction was carried out at 90 ° C. for 8 hours. After completion of the reaction, the reaction solution was added to 1000 parts by mass of methanol, and the precipitate was collected and dried to obtain styrene acrylic resin 1. Table 3 shows the physical properties.
Styrene: 70 parts by mass n-butyl acrylate: 10 parts by mass Acrylic acid: 5 parts by mass Methacrylic acid: 15 parts by mass t-Butylperoxy-2-ethylhexanoate: 6 parts by mass

(Production Example 2 of Styrene Acrylic Resin)
In Styrene Acrylic Resin Production Example 1, a styrene acrylic resin 2 was obtained in the same manner as in Styrene Acrylic Resin Production Example 1 except that the pressure was reduced to 1 mmHg over 1 hour after the reaction was completed, and the residual monomer was distilled off. . Table 3 shows the physical properties.

(Production example of amorphous polyester)
The following raw materials were put in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, reacted at 260 ° C. under normal pressure for 8 hours, cooled to 240 ° C., and reduced in pressure to 1 mmHg over 1 hour. The mixture was further reacted for 3 hours to obtain amorphous polyester. Table 3 shows the physical properties.

(Alcohol monomer)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (BPA-PO): 25 mol%
・ Ethylene glycol: 105 mol%
(Acid monomer)
・ Terephthalic acid: 100 mol%
(catalyst)
Tetrabutyl titanate: 0.1 mol%

[Example 1]
-Styrene 55 parts by mass-n-butyl acrylate 45 parts by mass-Pigment Blue 15: 3 6 parts by mass-Aluminum salicylate compound 1 part by mass (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
-0.14 parts by mass of divinylbenzene-1 part by mass of styrene acrylic resin 1 obtained in Production Example 1 of styrene acrylic resin-10 parts by mass of Fischer-Tropsch wax (melting point 78 ° C, half-width of melting point 3.6 ° C)
A mixture of monomers consisting of 15 mm ceramic beads were put in this, and dispersed for 2 hours using an attritor to obtain a monomer composition.

  850 parts by mass of ion-exchanged water and 3.5 parts by mass of tricalcium phosphate are added to a container equipped with a high-speed agitator TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.), and the rotational speed is adjusted to 12000 rpm. The dispersion medium was heated to 70 ° C.

  To the monomer composition, 6 parts by mass of t-butylperoxy-2-ethylhexanoate (TBEH) as a polymerization initiator was added, and this was put into the dispersion. The granulation process was performed for 3 minutes while maintaining 12000 revolutions / minute with the high-speed stirring device. Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, and polymerization was performed at 150 rpm for 10 hours. Cooling to 50 ° C. gave a colored particle dispersion.

The resin fine particles 1: 16.8 parts by mass (solid content: 4.2 parts by mass) were added to the colored particle dispersion. After stirring for 30 minutes, 0.2 mol / liter hydrochloric acid was added, and the pH of the reaction system was adjusted to 1.8 over 2 hours. After further stirring for 1 hour, the mixture was cooled to 20 ° C., filtered, washed and dried to obtain toner particles.
The above mentioned toner particles 1: 100 parts by mass _{· n-C 4 H 9 Si} (OCH 3) 3 treated with hydrophobic titanium oxide (BET specific surface area: 120 m ² / g): 1 part by weight,
-Hydrophobic silica treated with hexamethyldisilazane and then treated with silicone oil (BET specific surface area of 160 m ² / g): A mixture of 1 part by mass was mixed with a Henschel mixer to obtain toner 1. Table 5 and Table 6 show the physical properties of Toner 1.

  Using the toner 1, the following evaluation was performed. Table 7 shows the evaluation results.

[Examples 2 to 5]
Toners 2 to 5 were obtained in the same manner as in Example 1 except that the amount of raw materials used was changed to the conditions shown in Table 4. The toners 2 to 5 were evaluated in the same manner as in Example 1. The physical properties of each toner are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

[Comparative Example 1]
A toner 6 was obtained in the same manner as in Example 1 except that the dispersion liquid of the resin fine particles 1 was not added. The toner 6 was evaluated in the same manner as in Example 1. The physical properties of the toner 6 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

[Comparative Example 2]
A toner 7 was obtained in the same manner as in Example 1 except that the concentration of hydrochloric acid added after adding the resin fine particles 1 in Example 1 was changed from 0.2 mol / liter to 2.0 mol / liter. The toner 7 was evaluated in the same manner as in Example 1. The physical properties of the toner 7 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

[Comparative Example 3]
Toner 8 was obtained in the same manner as in Example 1 except that 0.2 mol / liter of hydrochloric acid added after addition of resin fine particles 1 was not added. The toner 8 was evaluated in the same manner as in Example 1. The physical properties of the toner 8 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

[Comparative Example 4]
In Example 2, the toner 9 was prepared in the same manner as in Example 2 except that 6.0 parts by mass of styrene acrylic resin was changed to 25.0 parts by mass of amorphous polyester and the resin fine particles 1 were not added. Obtained. The toner 9 was evaluated in the same manner as in Example 2. The physical properties of the toner 9 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Evaluation method of anti-blocking performance>
5 g of toner was weighed into a 100 ml polycup, placed in a warm air dryer adjusted to 50 ° C. and a room adjusted to 25 ° C., and allowed to stand for 1 week. The fluidity of the toner when the polycup was gently taken out and rotated slowly was compared between the toner left at 50 ° C. and the toner left at 25 ° C., and evaluated visually.

Evaluation criteria A of anti-blocking performance: The fluidity of the toner set at 50 ° C. is equivalent to that of the toner set at 25 ° C. (the anti-blocking performance is excellent).
B: Although the fluidity of the toner standing at 50 ° C. is slightly inferior to that of the toner standing at 25 ° C., the fluidity gradually recovers with the rotation of the polycup (good anti-blocking performance).
C: The toner left standing at 50 ° C. shows agglomerated and fused lump. (Inferior blocking resistance)
D: Toner left at 50 ° C. does not flow (particularly anti-blocking performance is inferior)

<Evaluation methods for low-temperature fixing performance, anti-offset performance, gloss performance, penetration resistance, and image storage performance>
A commercially available color laser printer (LBP-5500, manufactured by Canon Inc.) was used to take out the toner from the cyan cartridge, and 80 g of toner 1 was filled therein. The cartridge is mounted on a cyan station, and an unfixed toner image (0.6 mg / cm ² ) of 2.0 cm in length and 15.0 cm in width is passed on an image receiving paper (Canon office planner 64 g / m ² ). It formed in the part of 2.0 cm from the upper end part and 2.0 cm from the lower end part with respect to the direction. Subsequently, the fixing unit removed from the commercially available color laser printer (LBP-5500, manufactured by Canon) was remodeled so that the fixing temperature and the process speed could be adjusted, and a fixing test of an unfixed image was performed using this. Under normal temperature and humidity, the process speed was set to 220 mm / second, and the toner image was fixed at each temperature while changing the set temperature every 10 ° C. in the range of 120 ° C. to 220 ° C. According to the following evaluation criteria, low-temperature fixing performance, anti-offset performance, and color gamut performance were evaluated.

Evaluation criteria A for low-temperature fixing performance: A low-temperature offset does not occur at 120 ° C. or higher, and toner does not peel off even when rubbed with a finger (low-temperature fixing performance is particularly excellent)
B: Low temperature offset does not occur at 130 ° C. or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is good)
C: Low temperature offset does not occur at 140 ° C. or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is at a level where there is no problem)
D: Low temperature offset does not occur at 150 ° C or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is slightly inferior)
E: At 160 ° C. or higher, no low temperature offset occurs, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is inferior)

Evaluation criteria A for anti-offset performance: High temperature offset does not occur in the temperature range of + 70 ° C or higher, which is the evaluation criteria for low-temperature fixing performance (particularly excellent anti-offset performance)
B: High temperature offset does not occur in the temperature range of + 60 ° C. or higher, which is an evaluation standard for low temperature fixing performance (offset resistance is good)
C: High temperature offset does not occur in a temperature range of + 50 ° C. or higher, which is an evaluation standard for low temperature fixing performance (offset resistance is at a level where there is no problem).
D: High-temperature offset does not occur in the temperature range of + 40 ° C. or higher, which is the evaluation standard for low-temperature fixing performance (offset resistance is slightly inferior)
E: High temperature offset does not occur in the temperature range of + 30 ° C. or higher, which is the evaluation standard for low temperature fixing performance (offset resistance is inferior)

Evaluation criteria for gloss performance Low-temperature offset and fixed images in which high-temperature offset did not occur were measured using a handy gloss meter, PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.) at a light incident angle of 75 °. The evaluation was based on the following criteria.
A: The maximum glossiness of the solid image portion is 45 or more (the gloss performance is particularly excellent).
B: The maximum glossiness of the solid image portion is 40 or more and less than 45 (excellent gloss performance)
C: The maximum glossiness of the solid image portion is 35 or more and less than 40 (the gloss performance is at a level where there is no problem).
D: The maximum glossiness of the solid image portion is 30 or more and less than 35 (the gloss performance is slightly inferior)
E: The maximum glossiness of the solid image portion is less than 30 (gross performance is inferior)

Evaluation standard for penetration resistance Change between the gloss value (t1) of the image having the highest glossiness and the gloss value (t2) of the image created at the fixing device temperature + 10 ° C. when the image was created The rate [change rate (%) = (t1−t2) × 100 / t1] was evaluated according to the following criteria.
A: The rate of change in glossiness is less than 5% (particularly excellent in penetration resistance)
B: The rate of change in glossiness is 5% or more and less than 10% (excellent penetration resistance)
C: The change rate of the glossiness is 10% or more and less than 15% (the level of impregnation resistance is not a problem)
D: The change rate of glossiness is 15% or more and less than 20% (smear resistance is slightly inferior)
E: Change rate of glossiness is 20% or more (impregnation performance is poor)

Evaluation of image storage performance In the evaluation of gloss performance, the following evaluation was performed on the fixing paper of the image having the highest glossiness. The image was placed on 500 sheets of unused paper of the same type with the image portion of the fixing paper facing downward. Furthermore, 500 sheets of the same kind of unused paper were placed on the fixing paper, and the fixing paper was sandwiched. This was left still in a 40 degreeC thermostat. After leaving still for 1 day as it was, each was taken out from the thermostat. The manner in which the toner of the fixing paper adheres to unused paper in contact with the image portion of the fixing paper was evaluated according to the following criteria.
A: No adhesion of toner from the fixing paper is observed (image storage performance is particularly excellent)
B: A very small amount of toner adheres to the area of the image area (the image storage performance is excellent).
C: A slight amount of toner is attached to the area of the image area (the image storage performance is at a level where there is no problem).
D: Although toner adheres to the entire area of the image area, the color of the adhered area is light (the image storage performance is slightly inferior)
E: A dark portion is seen on unused paper, and clear toner adhesion is observed (image storage performance is inferior)

<Evaluation of durability and stability>
A commercially available color laser printer (LBP-5500, manufactured by Canon Inc.) was used to take out the toner from the cyan cartridge, and 50 g of toner 1 was filled therein. The cartridge was mounted on a cyan station, and continuous printing with a printing rate of 1% was performed on image-receiving paper (Canon office planner 64 g / m ² ), and a solid image was formed once every 500 sheets. When the toner in the cartridge became 25 g or less, the operation of adding 50 g of toner 1 and performing continuous printing in the same manner was repeated. The durability stability performance was evaluated according to the following evaluation criteria.

Evaluation criteria A for durability stability performance: When the total amount of added toner is 200 g or more, an image defect occurs in an image with a printing rate of 1%. Alternatively, no image defect occurs when the total amount of added toner is 250 g. (Excellent durability and stability)
B: When the total amount of added toner is 150 g, an image defect occurs in an image with a printing rate of 1%. (Durable and stable performance is good)
C: When the total amount of added toner is 100 g, an image defect occurs in an image with a printing rate of 1%. (Durable and stable performance is at a level where there is no problem)
D: When the total amount of added toner is 50 g, an image defect occurs in an image with a printing rate of 1%. (Stable durability performance is slightly inferior)
E: An image defect occurs in an image with a printing rate of 1% without adding toner. (The durability stability performance is inferior)

It is a figure which shows the temperature-deformation rate curve obtained by measuring the toner of Example 1 by the thermomechanical measurement of this invention. In the figure, an example in which each physical property value defined in the present invention is obtained is shown. It is a figure which shows an example of the measuring method of the glass transition point (Tg) and melting | fusing point (Tm) by DSC.

Claims (6)

Toner particles having a core-shell structure containing at least a binder resin containing a styrene acrylic resin having an acid value of 1.0 to 30.0 mg KOH / g, a colorant and a wax, and having a core part and a shell part; A method for producing a toner having an inorganic fine powder,
The following steps (a) to (c)
(I) Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium metasuccinate, calcium sulfate, barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica The colored particles containing the binder resin, the colorant and the wax are dispersed in an aqueous medium having at least one inorganic dispersant selected from the group consisting of bentonite and alumina, and an aqueous dispersion of colored particles Forming step (a),
(II) An aqueous dispersion of fine resin particles having a volume average particle diameter Dv of 10 to 200 nm and an acid value of 6.0 to 80.0 mgKOH / g is added to the aqueous dispersion of colored particles. (B) forming a composite dispersion in which particles on which the inorganic dispersant and the resin fine particles are adsorbed are dispersed in an aqueous medium on the surface of the colored particles;
(III) a step of fixing the resin fine particles on the surface of the colored particles (c),
To form toner particles,
The obtained toner has a temperature (T1) at which the deformation speed first reaches a minimum value in a temperature-deformation speed curve obtained by first-order differentiation of a temperature-displacement curve obtained by thermomechanical measurement with a load of 10.5 mN and a heating rate of 4 ° C./min. Is 30.0 to 55.0 ° C., the minimum value (R1) of the deformation rate at T1 is −0.300% / ° C. or more (negatively small), and the temperature at which the deformation rate becomes the minimum value (T2 ) Is 60.0 to 90.0 ° C., and the toner has a minimum deformation rate (R2) at T2 of −0.400% / ° C. or less (negatively large).   2. The toner production method according to claim 1, wherein the toner has a full width at half maximum (D2) of the deformation speed peak of the toner at T2 of 15.0 to 45.0 ° C. 3.   The toner has a ratio (R3 / R1) of a deformation rate R3 of the toner at a temperature T3 (° C.) defined by T3 = T1 + 5 and R1 (R3 / R1) of 0.80 to 1.30. 3. A method for producing a toner according to 1 or 2.   4. The toner according to claim 1, wherein the toner has a temperature (T4) at which the deformation rate becomes 0% / ° C. in a temperature range of T2 or higher, from 100.0 to 180.0 ° C. 5. The method for producing the toner according to item. The resin fine particles have a sulfonic acid group,
The toner contains 55.0 to 97.0% by mass of a component soluble in tetrahydrofuran (THF), and the THF soluble component contains 0.005 to 0.150% by mass of a sulfur element derived from a sulfonic acid group. The toner manufacturing method according to claim 1, wherein the toner is contained. Toner particles having a core-shell structure containing at least a binder resin containing a styrene acrylic resin having an acid value of 1.0 to 30.0 mg KOH / g, a colorant and a wax, and having a core part and a shell part; A method for producing a toner having an inorganic fine powder,
The following steps (a) to (c)
(I) a step of dispersing the colored particles containing the binder resin, the colorant and the wax in an aqueous medium having tricalcium phosphate to form an aqueous dispersion of colored particles (a);
(II) An aqueous dispersion of fine resin particles having a volume average particle diameter Dv of 10 to 200 nm and an acid value of 6.0 to 80.0 mgKOH / g is added to the aqueous dispersion of colored particles. A step (b) of forming a composite dispersion in which particles of the tricalcium phosphate and the resin fine particles adsorbed on the surface of the colored particles are dispersed in an aqueous medium; and
(III) adding an acid to the composite dispersion to dissolve the tricalcium phosphate, and fixing the resin fine particles to the surface of the colored particles (c);
To form toner particles,
The obtained toner has a temperature (T1) at which the deformation speed first reaches a minimum value in a temperature-deformation speed curve obtained by first-order differentiation of a temperature-displacement curve obtained by thermomechanical measurement with a load of 10.5 mN and a heating rate of 4 ° C./min. Is 30.0 to 55.0 ° C., the minimum value (R1) of the deformation rate at T1 is −0.300% / ° C. or more (negatively small), and the temperature at which the deformation rate becomes the minimum value (T2 ) Is 60.0 to 90.0 ° C., and the toner has a minimum deformation rate (R2) at T2 of −0.400% / ° C. or less (negatively large).

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