JP2009093049A - Toner for electrostatic charge image development, powder toner cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner with a small particle size for electrostatic charge image development, the toner simultaneously satisfying higher picture qualities of images, cleaning property, low temperature fixability and high coloring property even in a recycling system, and to provide a toner for electrostatic charge image development as a color toner, which simultaneously satisfies higher picture qualities of images, low temperature fixability and high coloring property. <P>SOLUTION: The toner contains at least a colorant, a release agent and a binder resin. When a softening temperature and a start temperature of effluence of the toner measured by a Koka flow tester are represented by Ts and Tfb, respectively, a ratio K(Tfb)/K(Ts) of K(Tfb) to K(Ts), defined by formula (1): K(Tfb)=(¾LogG'(Tfb+10°C)-LogG'(Tfb-10°C)¾)/20 and formula (2): K(Ts)=(¾LogG'(Ts)-LogG'(Ts-15°C)¾)/15, respectively, is in a range from 1.0 to 1.3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image, a powder toner cartridge capable of reducing the volume for containing the toner, and an image forming apparatus equipped with the powder toner cartridge.

  In recent years, copying machines are required to be small, high-speed and capable of copying many sheets while maintaining high image quality. However, the current high-speed copying machines are not necessarily downsized. One of the factors is the space after the transfer residual toner is collected. On the other hand, with respect to current environmental problems, the processing of the collected transfer residual toner is a very big problem. That is, by supplying the collected transfer residual toner to the developing device, it is possible to overcome the above-mentioned problems and to achieve a small and high-speed copying machine adapted to environmental problems. Further, since the number of sheets that can be copied increases with respect to the toner to be replenished, the percopy cost is reduced and the cost becomes high.

  In the past, attempts have been made to supply the collected transfer residual toner to a developing device and use it in the developing process. However, as this process is introduced and a large number of copies are repeated, for example, there are various problems such as image quality deterioration and image density reduction, making it difficult to provide stable images over a long period of time. It has the problem of becoming.

Patent Document 1 proposes a developer that regulates the particle size distribution and intends to solve the above-described problems. Specifically, when the volume average particle diameter of the toner was ^{D (μm), D (3} √2) -1 ~ 3 in the range of √2D least 90 wt% of the total toner particles are present, and D ( ³ √2) it is characterized in that ^{the -1} smaller particles using the toner powder is 5 wt% or less. However, the technique is limited to the two-component development method and has the advantage of preventing adverse effects such as fogging and toner scattering during recycling by reducing the proportion of very small particles. On the contrary, since the ratio is too small, it is impossible to obtain a copy faithful to a fine latent image. Patent Document 2 proposes a toner having a specific particle size distribution, but has not yet improved carrier spent and fogging with recycled toner.

  By the way, in image formation by electrophotography, toner is fixed on an image support by a heat fixing method to obtain a permanent visible copy image. In this case, when an overhead projector (OHP) transparency sheet (hereinafter referred to as "OHP sheet") is used as an image support and a copy image is formed on the toner, particularly color toner, the projection image on the OHP is excellent. In order to obtain a good light transmittance, it is required to fix the image surface in a smooth state to prevent scattering or irregular reflection of transmitted light on the image surface during projection.

  In order to achieve this, a color toner that can be rapidly transferred to a molten state having a viscoelasticity lower than that of a conventional black toner at a melting point is used as a general method, and the image surface is heated and pressed. It was designed to be easily smoothed.

  However, lowering the viscoelastic properties of the toner in this way is also accompanied by a decrease in the glass transition temperature, resulting in a decrease in the mechanical strength of the toner at room temperature, that is, when used in an actual machine. Therefore, for example, when mechanical stress such as stirring in the developing device is applied, the external additive on the toner surface is buried and developability and transferability deteriorate. In addition, so-called toner spent occurs in which the toner particles adhere to the carrier particles. Such a problem remarkably occurs particularly when the particle size of the toner is reduced to improve the image quality in recent years. This is due to the fact that the toner becomes more susceptible to mechanical stress as the particle size of the toner becomes smaller.

In order to solve such a problem, in Patent Document 3, a toner having a specific relationship between a volume average particle diameter Dv (μm) and a storage elastic modulus G ′ ₁₇₀ (dyne / cm ² ) at 170 ° C. is used. Has improved. However, in such a toner, theoretically, when the average particle size becomes small, the storage elastic modulus of the toner becomes large, and when the average particle size becomes small, the low-temperature fixability and the glossiness become disadvantageous, thereby reducing the color reproducibility. End up. That is, it is not easy to achieve both high image quality with a small particle size in recent years, low temperature fixability and color reproducibility.

  In Patent Document 4, as a measure for improving the low-temperature fixability, a binder resin for toner containing a conventional amorphous polyester and a crystalline polyester having a significant improvement effect compared with the polyester is proposed. However, when a crystalline polyester and an amorphous polyester are used in combination, the resin composition of the both is close, so that transesterification occurs during melt-kneading and the high crystallinity of the crystalline polyester can be maintained. In other words, the storability of the toner tends to decrease.

  Patent Document 5 and Patent Document 6 describe a binder resin for toner composed of a crystalline polyester having sebacic acid or adipic acid as a carboxylic acid component and a styrene-acrylic resin. Although the fixing property at low speed is evaluated, further improvement in performance is desired.

  Patent Document 7 proposes a toner binder resin containing a specific crystalline polyester and an amorphous hybrid resin, and describes that a toner having a wide fixable temperature range and excellent durability can be provided. However, it has not yet been solved to eliminate fogging and image density unevenness due to poor compatibility of the crystalline polyester with the pigment.

In Patent Document 8, as a binder _{resin, -OCOC-R-COO- (CH} 2) n- ( where in the formula, R represents a straight-chain unsaturated aliphatic group having 2 to 20 carbon atoms, n represents an integer of 2 to 20.) A low-temperature fixability is obtained by using a crystalline polyester containing a structure represented by 60 mol% of the total ester bond in the entire resin. It has not been.

  On the other hand, in recent years, in order to cope with the environment, it has been proposed to collect not only toner but also a toner container by making the container from a flexible material and folding it compactly after use. These containers have a large volume reduction ratio and can be realized at a low cost, and can be automatically supplied by air after being mounted on the machine body so that the toner does not fly into the air. However, since a spiral groove for supplying powder toner cannot be formed in the container, and a supply member such as an agitator cannot be incorporated in the container, (1) the supply of powder toner is not stable. (2) The powder toner may be packed in the container after storage, and the powder toner may not be supplied. (3) Problems such as a large amount of powder toner remaining.

Japanese Patent Laid-Open No. 2-157765 Japanese Patent No. 2896826 Japanese Patent No. 3885241 JP 2001-222138 A JP 11-249339 A JP 2003-302791 A JP 2004-191516 A JP 2005-338814 A

  An object of the present invention is to provide a toner for developing an electrostatic charge image having a small particle diameter that satisfies image quality improvement, cleanability, low-temperature fixability and high colorability simultaneously in a recycling system. Another object of the present invention is to provide a toner for developing an electrostatic image that satisfies both high image quality, low-temperature fixability, and high colorability in a color toner.

  Furthermore, using a toner container that can be collected compactly after use with a flexible material, toner can be automatically supplied from the container to the developing unit stably, and after storage, And a toner container capable of reducing the remaining amount of toner powder in the container and an image forming apparatus equipped with the container.

  In order to solve the above problems, the invention described in claim 1 is a toner containing at least a colorant, a release agent, and a binder resin, and the softening temperature measured by an elevated flow tester is Ts. When the outflow start temperature is Tfb, K (Tfb) / K (Ts) which is a ratio of K (Tfb) represented by the following formula (1) and K (Ts) represented by the following formula (2) Is in the range of 1.0 to 1.3.

[Equation 1]
Formula (1)
K (Tfb) = (┃LogG ′ (Tfb + 10 ° C.) − LogG ′ (Tfb−10 ° C.) ┃) / 20
(In the formula, Log G ′ (Tfb + 10 ° C.) is the logarithm of the storage elastic modulus G ′ at the measurement temperature (Tfb + 10 ° C.) measured by the rheometer, and Log G ′ (Tfb−10 ° C.) is the measurement temperature measured by the rheometer ( (Tfb−10 ° C.) is a logarithm of the storage elastic modulus G ′, and (||) indicates an absolute value.)

[Equation 2]
Formula (2)
K (Ts) = (┃LogG ′ (Ts) −LogG ′ (Ts−15 ° C.) ┃) / 15
(In the formula, Log G ′ (Ts ° C.) is the logarithm of the storage elastic modulus G ′ at the measurement temperature (Ts ° C.) measured by the rheometer, and Log G ′ (Ts−15 ° C.) is the measurement temperature measured by the rheometer ( (Ts−15 ° C.) is a logarithm of the storage elastic modulus G ′, and (||) indicates an absolute value.)

Invention according to claim 2, in the toner for electrostatic image development according to claim 1, as the binder resin comprises a polyvalent alcohol unit and a carboxylic acid unit, -OCOC-R-COO- (CH 2 ) N- (wherein, R represents a linear unsaturated aliphatic group having 2 to 20 carbon atoms, and n represents an integer of 2 to 20). Is included.

  According to a third aspect of the present invention, in the electrostatic image developing toner according to the first or second aspect, K (Tfb) represented by the formula (1) is in the range of 0.070 to 0.080. It is characterized by.

  According to a fourth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to third aspects, a crystalline polyester resin and a styrene acrylic resin are used in combination as the binder resin. It is characterized by that.

  According to a fifth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to fourth aspects, the peak top molecular weight MPT of the toner measured by GPC is in the range of 2000 to 4000. And

  According to a sixth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to fifth aspects, the release agent includes any one of an olefin wax and a paraffin wax. .

  According to a seventh aspect of the present invention, in the electrostatic image developing toner according to any one of the first to sixth aspects, the toner has a number average particle diameter of 3.2 to 4.0 μm, and the number of toners The variation coefficient of distribution (standard deviation of number distribution / number average particle diameter) is 23.0 to 37.0, and toner particles having a particle diameter of 4.0 to 8.0 μm are 20.0 to 39.0 number%. It is contained.

  The invention described in claim 8 is a two-component developer containing the toner according to any one of claims 1 to 7 and a carrier.

  The invention according to claim 9 is a powder toner cartridge in which the toner according to any one of claims 1 to 7 is filled in a powder toner container made of a flexible member capable of reducing volume by 60% or more. It is characterized by being.

  According to a tenth aspect of the present invention, there is provided at least an image carrier, an electrostatic image forming means for forming an electrostatic image on the image carrier, and developing the formed electrostatic image into a visible image using toner. An image forming apparatus comprising: a toner powder-filled toner cartridge; an air inflow unit for injecting air into the cartridge; and an air inflowing the toner. 10. The powder according to claim 9, wherein a pump means for supplying the mixed fluid and a toner supply device having a toner feeding tube for feeding the toner from the cartridge to the developing means are attached. A toner cartridge is mounted.

  According to the present invention, it is possible to provide a toner for developing an electrostatic charge image having a small particle size that satisfies the image quality improvement, cleaning performance, low-temperature fixability and high colorability at the same time even in a recycling system. As the toner, it is possible to provide a toner for developing an electrostatic image having high image quality, low-temperature fixability, OHP permeability, and high colorability.

Hereinafter, the present invention will be described in detail.
In order to obtain toner with good toner replenishment, so-called toner spent in which toner particles adhere to carrier particles, excellent storage stability, good fixability, and high glossiness, a fixing process is required. In the previous toner replenishment, supply, development, and transfer processes, the toner does not soften, and it is necessary for the toner to be melted and fixed instantaneously by the heat energy at the time of fixing. It has been found necessary to have properties.

  That is, according to the present invention, in a toner containing at least a colorant, a release agent, and a binder resin, when the softening temperature measured by an elevated flow tester is Ts and the outflow start temperature is Tfb, the above formula ( Since K (Tfb) / K (Ts), which is the ratio of K (Tfb) represented by 1) and K (Ts) represented by formula (2), is in the range of 1.0 to 1.3, it is described above. In this way, a toner having the above effect is obtained.

  The softening temperature Ts measured by the elevated flow tester corresponds to the temperature at which softening starts through the glass transition point in the solid state in the rheological behavior of the polymer, but is expressed by the formula (2). K (Ts) represents the slope of decrease in the storage elastic modulus G ′ of the toner in the temperature range from the glass transition point to Ts, which is the softening temperature. In this range, the storage elastic modulus G ′ of the toner is large. By being constant and not decreasing, it is possible to prevent so-called toner spent that the toner particles are fixed to the carrier particles with excellent storage stability and toner replenishment properties.

  Further, since toner contamination on the carrier does not occur, it has good charging performance, and there is no occurrence of image fog or density unevenness. Furthermore, although the dot reproducibility tends to deteriorate as the number average particle diameter and the coefficient of variation of the number increase, the toner of the present invention has good charging performance and is advantageous for dot reproducibility.

  Further, the outflow start temperature Tfb measured by an elevated flow tester is a temperature at which the flow starts through a rubbery plateau in the rheological behavior of the polymer, but the toner has a high molecular weight distribution. Since it is a molecular body, it does not flow instantaneously and starts to flow partially from a component having a low molecular weight. (Tfb−10 ° C.) in the formula (1) corresponds to a temperature at which a component having a low molecular weight partially starts to flow. Further, the temperature range until the entire toner moves to the flow region corresponds to (Tfb + 10 ° C.). That is, K (Tfb) represented by the expression (1) represents the slope of the decrease in the storage elastic modulus G ′ when the toner moves to the flow region. In this range, the storage elastic modulus G ′ of the toner is instantaneous. As a result, the toner has good fixability and high gloss.

  That is, it is desirable that K (Tfb) represented by Expression (1) is large and K (Ts) represented by Expression (2) is small, and this ratio K (Tfb) / K (Ts) is 1.0. In the range of ˜1.3, toner replenishability is good, toner particles adhere to carrier particles, so-called toner spent does not occur, storage stability is excellent, fixability is good, and high glossiness Toner can be obtained.

  The fact that K (Tfb) / K (Ts) is less than 1.0 means that the behavior of the polymer as an elastic component is activated by shifting to the flow region, that is, the region on the high temperature side, and the formula (2) Rather than the slope of the decrease in storage elastic modulus G ′ in the temperature range from the glass transition point represented by K (Ts) to the softening temperature Ts, it is represented by K (Tfb) in formula (1). This is a state in which the slope of the decrease in storage elastic modulus G ′ when moving to the flow region becomes smaller, sharp melt property at the time of fixing is deteriorated, fixability is deteriorated, and image of color toner is deteriorated. Glossiness decreases.

  As the molecular structure of the toner when K (Tfb) / K (Ts) is less than 1.0, since the toner has a wide molecular weight distribution from a low molecular weight region to a high molecular weight region, the amount of the high molecular weight component is particularly large. It is presumed that the structure has many branches and a high elastic modulus. On the other hand, if K (Tfb) / K (Ts) exceeds 1.3, the hot offset resistance deteriorates due to a rapid decrease in elastic modulus. When the molecular weight exceeds 1.3, the molecular structure of the toner has many low molecular weight components, and it is presumed that the linear elastic modulus is also low in the high molecular weight region component.

  That is, K (Tfb) / K (Ts) in the range of 1.0 to 1.3 means that the elastic modulus of the toner up to the temperature range when softening starts through the glass transition point which is in a solid state. As a result, storage stability is excellent, toner replenishment property is good, toner particles adhere to the carrier particles, so-called toner spent can be prevented, and toner contamination to the carrier does not occur, so good charging performance It does not cause image fogging or density unevenness, and its thermal modulus drastically decreases due to the application of heat energy during fixing, so that low temperature fixability and high gloss can be obtained, and an appropriate elastic modulus can be obtained. By holding it, both hot offset properties can be achieved.

  In order to have rheological properties in this range, it is necessary that the region having a molecular weight of 100,000 to 1,000,000 in the wide molecular weight distribution of the toner behaves as an elastic body by entanglement with a branched or linear polymer. Even in the region of 100,000 or less, it is necessary to have a branched short polymer chain.

  If the region of 100,000 or less does not contain a branched short polymer chain, the elastic modulus decreases while softening starts through the glass transition point which is in a solid state, and K (Ts) increases. It becomes difficult to obtain a range of K (Tfb) / K (Ts) of 1.0 to 1.3.

  Moreover, K (Ts) can be reduced by lowering the glass transition point of the toner, but this case is disadvantageous in terms of storage stability. In order to contain a branched short polymer chain in the region of 100,000 or less, an active catalyst and a crosslinking agent are added in the process of synthesizing the resin and extending the polymer chain, After synthesizing a short polymer chain, it is preferable to add a crosslinking agent and synthesize more than 100,000 components. The length of the branched polymer chain can be controlled by conditions such as the difference in the activity of the active catalyst at this time and the rate of temperature rise until reaching the synthesis temperature after the monomer is charged. The amount of components in the region of 100,000 or more, the amount of crosslinking components, and the structure can be controlled.

<Measurement method of Ts and Tfb>
In the present invention, Ts and Tfb were measured using an elevated flow tester (manufactured by Shimadzu Corporation) according to the method described in JIS K72101. While heating a sample of 1 cm ^{3 at} a heating rate of 6 ° C./min, a load of 10 kg / cm ² was applied by a plunger and a nozzle having a diameter of 0.5 mm and a length of 1 mm was pushed out. Draw a volume-temperature curve. The flow curve of this flow tester is data as shown in FIG. 5, from which each temperature can be read. In the figure, A is a measurement start temperature, B is Ts (softening temperature), C is Tfb (outflow start temperature), D is a 1/2 outflow temperature, and E is a measurement end temperature.

<Measurement method of storage elastic modulus G '>
The storage elastic modulus G ′ in the present invention is measured using, for example, a viscoelasticity measuring device (rheometer) RDA-II (manufactured by Rheometrics).
Measuring jig: A parallel plate having a diameter of 7.9 mm is used.
Measurement sample: Toner is heated and melted and molded into a cylindrical sample having a diameter of about 8 mm and a height of 3 mm.
Measurement frequency: 1 Hz.
Measurement temperature: 50 ° C to 230 ° C.
Measurement strain setting: The initial value is set to 0.1%, and measurement is performed in the automatic measurement mode.
Sample extension correction: Adjust in automatic measurement mode.

Hereinafter, further preferable points in the toner of the present invention will be described.
[1] As a binder resin, —OCOC—R—COO— (CH ₂ ) n— containing a polyhydric alcohol unit and a carboxylic acid unit (wherein R is a linear non-linear group having 2 to 20 carbon atoms) It is also possible to add a crystalline polyester resin containing a saturated aliphatic group, and n represents an integer of 2 to 20) containing at least 60 mol% of the total ester bond in the entire resin K (Tfb) / K (Ts) is an effective means for obtaining a range of 1.0 to 1.3. This crystalline polyester resin will be described in detail later.

  By adding a crystalline polyester resin having a melting point in the range of −10 ° C. to + 10 ° C. with respect to Tfb, which is the starting temperature of the outflow of the toner, the elastic modulus does not decrease up to the melting point of the crystalline polyester resin. Since the elastic modulus rapidly decreases from the outflow start temperature, the glass transition point of the toner is not lowered, the storage stability is good, and K (Tfb) / K (Ts) is 1.0 to 1.3. Range can be easily obtained.

[2] Further, when K (Tfb) in the formula (1) is in the range of 0.070 to 0.080, the smoothness of the image after fixing is enhanced, and an image with high glossiness can be obtained. If it is less than 0.070, the sharp melt property at the time of fixing is insufficient, and if it exceeds 0.080, the hot offset resistance is insufficient.

  In particular, when a crystalline polyester resin is contained, the crystallinity of the crystalline polyester resin is further impaired by using a styrene acrylic resin having a peak top molecular weight MPT of 2000 to 4000 as measured by GPC. In addition, it is possible to easily obtain a toner in which K (Tfb) / K (Ts) is in the range of 1.0 to 1.3, and excellent in storage and replenishment properties.

[3] As described above, it is preferable to use a crystalline polyester resin and a styrene acrylic resin in combination as the binder resin.
Since the styrene acrylic polymer unit has a resin composition different from that of the crystalline polyester resin, it can maintain the crystallinity of the crystalline polyester even during melt-kneading, and the crystalline polyester resin can be made minute without reducing the physical properties of the crystalline polyester resin. Therefore, it is possible to make use of the advantages of each resin.

[4] Since the peak top molecular weight MPT of the toner is 2000 to 4000, the crystalline polyester does not become a pulverization interface and the styrene acrylic resin becomes a pulverization interface. Further, the toner is not exposed on the toner surface, and the uniformity of the surface dispersion composition can be obtained.

  When the peak top molecular weight MPT of the toner is less than 2,000, the glass transition point is lowered and the storage stability tends to deteriorate. When the MPT exceeds 4000, the grindability deteriorates, so that the number of sites where the wax or crystalline polyester becomes the grinding interface increases, and the fogging and image density unevenness due to the deterioration of the aggregation degree due to the exposure and the uneven dispersion composition. appear. In order to obtain the peak top molecular weight MPT of the toner in the range of 2000 to 4000, the toner can be adjusted to a desired molecular weight according to molecular cutting conditions by shearing during kneading.

<Measurement of peak top molecular weight (MPT)>
The measurement of the peak top molecular weight of the toner in the present invention is performed by stabilizing the column in a heat chamber at 40 ° C. in a GPC measurement apparatus, and flowing THF as a solvent through the column at this temperature at a flow rate of 1 ml / min. Is measured by injecting 100 μl. 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, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and at least about 10 standard polystyrene samples is suitably used. It is.

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 shodexGPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, or manufactured by Tosoh Corporation TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn.
In general, in the measurement of the GPC chromatogram, the high molecular weight side starts from the start point of the rise of the chromatogram from the baseline, and the low molecular weight side measures up to a molecular weight of about 400.

[5] In order to improve image quality, the toner has a number average particle diameter of 3.2 to 4.0 μm, and a variation coefficient of the toner number distribution (standard deviation of number distribution / number average). It is preferable that toner particles having a particle size) of 23.0 to 37.0 and 20.0 to 39.0% by number of toner particles having a particle size of 4.0 to 8.0 μm are contained.

  In general, the improvement in image quality due to the reduction in particle size is accompanied by a deterioration in cleaning properties. In particular, the toner having a number average particle size of 3.5 μm or less becomes difficult to clean. The toner of the present invention has a number average particle diameter of 3.2 to 4.0 μm, thereby ensuring high image quality and sufficient image density, and a number average particle diameter of 3.2 to 4.0 μm. The variation coefficient of the toner number distribution (standard deviation of number distribution / number average particle diameter) is 23.0 to 37.0, and toner particles having a particle diameter of 4.0 to 8.0 μm are 20.0 to 39.0. By containing a few percent, the cleaning property and the low-temperature fixing property can be satisfied at the same time.

  This is because, in the temperature range from the glass transition point to the softening temperature Ts of the toner of the present invention, the storage elastic modulus G ′ of the toner does not greatly decrease and fluctuate. This is due to the fact that the uniform fixation of the additive is enhanced.

  The variation coefficient of the number distribution of the toner (standard deviation of the number distribution / number average particle diameter) is 23.0 to 37.0. This means that the number distribution is not a narrow distribution like a so-called polymerized toner, and is somewhat broad. This means that the distribution has a width.

  The number average particle diameter of 3.2 to 4.0 μm means that the number of so-called small particle diameters is distributed at least 60% or more in 2.0 to 4.0 μm. Since the particles in this range have strong adhesion and high cohesiveness, in the initial mixing stage of the additive mixing, each of the base particles is not uniformly dispersed, and a non-uniform state in which 2-3 particles are lightly aggregated. Become. However, although they are in a lightly aggregated state, they correspond to the size and adhesion that are approximated to particles in the range of 4.0 to 8.0 μm, so that the entire toner has the same state of aggregation. In this state, by continuing mixing, the additive is uniformly fixed to each of the base particles and dispersed in the final final stage of mixing.

  In order to obtain this effect, toner particles having a particle size of 4.0 to 8.0 μm are contained in an amount of 20.0 to 39.0% by number, and the variation coefficient of the toner number distribution (standard deviation of number distribution / number average particle size). ) Must be between 23.0 and 37.0.

  If the toner particle diameter is less than 20.0% by number, the cohesiveness of the base particles becomes very high, so the additive is not uniformly mixed with the additive having high fluidity. The agent is not crushed to the primary particles and remains as aggregates, or the fixed state of the additive becomes non-uniform on the surface of the base particle, and the additive is desorbed in the developing machine. This causes image unevenness, white stripes, and fog.

  Further, the variation coefficient of the toner number distribution being less than 23.0 means that the number distribution is narrow and the number in the range of 2.0 to 4.0 μm with a small particle diameter increases, so that the base particle Since the cohesiveness of the material increases greatly, the same problem occurs.

  If the number of toner particles having a particle size of 4.0 to 8.0 μm exceeds 39.0%, the number of large particles increases with respect to the number average particle size in the range of 3.2 to 4.0 μm. Reproducibility deteriorates and halftone blurring occurs. In particular, in a color image, since a plurality of colors are overlapped, a hue drop occurs due to a deterioration in dot reproducibility.

  Similarly, the variation coefficient of the toner number distribution exceeds 37.0. That is, the variation coefficient of the toner number distribution (standard deviation of the number distribution / number average particle diameter) is 23.0 to 37.0, and 20 toner particles having a particle diameter in the range of 4.0 to 8.0 μm. By containing 0.03 to 39.0% by number, even the highly cohesive base particles having a number average particle diameter of 3.2 to 4.0 μm can be uniformly fixed on the surface of the base particles. An excellent toner can be obtained.

  Since such toner has a good charge rising property and developability, there is no development in non-image areas, and generally the number average particle size is less than 3.5 μm. In such a case, the occurrence of a cleaning failure becomes a problem, but since the transferability is improved, the problem of a cleaning failure does not occur.

  Further, since the toner of the present invention is excellent in uniform fixation of the additive to the surface of the base particle, there is no occurrence of toner scattering, and the additive content can be reduced even with a small particle size, Even a small amount of addition can have sufficient toner fluidity. In particular, in color toners, it is well known that an additive having a surface coverage of toner base particles exceeding 100% is added in order to prevent image voids, but the toner of the present invention is an additive. Even if the surface coverage of the toner base particles is less than 100%, the transferability is improved, so that there is no occurrence of voids in the color image. In addition, since the amount of the additive added can be reduced, the low temperature fixability is not deteriorated by the addition, and it is a great feature that good low temperature fixability can be achieved.

  Furthermore, when mixing a plurality of additives having different fluidity of additives, two-stage mixing is good. Of the plurality of additives, the first additive having the lowest fluidity-imparting effect is first added by 50 to 100% by weight of the total amount of the first additive and mixed by a mixer (first stage). Mixing), and then adding the remaining amount of the first additive and all the other additives and mixing with a mixer (second-stage mixing), so that the toner base is mixed uniformly and moderately. Can be immobilized on the surface. By the first stage mixing, a powder torque between the first additive and the toner base surface is applied, and the first additive is crushed and homogenized. In the toner base particles having a particle size distribution of the present invention, 50% or more of particles having high cohesiveness in the range of 2.0 to 4.0 μm are present, so that the effect of crushing by the powder torque is great, and the additive agglomerates. Aggregation can be reduced.

  When mixing in the first stage, it is effective to add 50 to 100% by weight of the total amount of the first additive. The fluidity and charge amount of the toner change depending on this ratio. Just decide. If it is less than 50% by weight of the total input, the crushing effect at the first stage mixing is insufficient. The first additive is made uniform by the first stage mixing, and the fluidity of the toner is improved. Therefore, the remaining amount of the first additive and all other additives are added and mixed in the second stage mixing. As a result, the additive is uniformly fixed on the surface of the toner base, and a toner free from the surface of the toner base can be obtained in long-term use.

  Examples of the mixing device at this time include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like. In a mixing device having rotating blades, the peripheral speed of the rotating blades is In the first stage mixing, the speed is 3 to 10 m / s, and the second stage mixing is 20 to 60 m / s, so that the most effective crushing and homogenization in the first stage mixing and the toner base in the second stage mixing. Uniform fixation proceeds.

  The lower speed of the first-stage mixing is more advantageous for pulverizing and homogenizing the additive because the powder torque is applied, and 3-10 m / s is preferable because it is low speed and does not impose a load on the toner base. When it is less than 3 m / s, it is not mixed, and when it exceeds 10 m / s, crushing and homogenization are insufficient.

  The second stage mixing is 20-60 m / s. Increasing the peripheral speed is more advantageous because the fixing of the additive to the toner base proceeds and is advantageous, but generally, if it exceeds 40 m / s, the toner is loaded and the toner is fused. It cannot be over 40m / s. However, the toner of the present invention has the property that the elastic modulus of the toner does not decrease up to the temperature range when the softening starts through the glass transition point where the toner base particles are in a solid state. Since the toner base surface is coated with an additive, the adhesion between the toner bases is reduced, and the surface hardness is increased by the inorganic fine particles adhering to the base surface, so even if it is increased to 80 m / s. There is no occurrence of aggregation due to fusion of the toner bases. Thereby, sufficient fixation of the additive to the toner base can be achieved, and a toner having good toner charging performance and fluidity and no fogging can be obtained.

  Since the additive is any one of hydrophobic silica, titanium oxide, alumina oxide, and zirconium oxide, the environmental stability, cleaning property, and transfer property of charging are enhanced.

  The toner of the present invention has a number average particle diameter of 3.2 to 4.0 μm. If the particle size is less than 3.2 μm, the fluidity of the toner deteriorates. Therefore, the additive content must be increased to improve the fluidity, and the low temperature fixability deteriorates or the toner scatters by increasing the additive. It is easy to generate. On the other hand, if the thickness exceeds 4.0 μm, the degree of coloration is lowered, so that the image density is lowered, and thus the toner yield (number of sheets that can be output per toner unit amount) is lowered. The dot reproducibility is excellent when the thickness is preferably in the range of 3.2 to 3.5 μm.

Further, the coefficient of variation (standard deviation of the number distribution / number average particle diameter) of the toner number distribution at this time is 23.0 to 37.0, which is not only advantageous for uniform fixation of the additive. In the recycling system, even when mixed with the recycled toner, the fluidity and charging property of the toner are small and the image is not deteriorated.

  If it is less than 23.0, the distribution is sharp and a good image is obtained in the initial stage. However, when mixed with the recycled toner, the distribution of the initial toner and the distribution of the recycled toner are completely separated. The initial toner is preferentially developed because of the selective developability at the time, and the recycle toner is not developed and continues to accumulate in the developing portion over a long period, which causes carrier spent and developer aggregation.

  If it exceeds 37.0, the distribution is wide, and for the same reason, toner having a certain distribution is selectively developed and the same problem occurs. Accordingly, since the coefficient of variation of the toner number distribution (standard deviation of the number distribution / number average particle diameter) is 23.0 to 37.0, even when the recycled toner is mixed, the selective development is suppressed and the recycled toner is consumed. Therefore, such a malfunction does not occur. The variation coefficient of the toner number distribution (standard deviation of the number distribution / number average particle diameter) is more preferably 24.0 to 35.0.

  Further, the volume average particle diameter (D4) is 4.4 to 5.4 μm, which is advantageous for fixability. If the thickness is less than 4.4 μm, the toner particles are buried between the concaves and convexes of the recording paper, and the nip pressure during fixing is not applied, which tends to cause fixing failure. In addition, particles having a diameter of less than 4.4 μm have high thermal conductivity, and therefore, the particles are crushed after fixing, the granularity of the image is deteriorated, and the sharpness is liable to be lowered. If it exceeds 5.4 μm, the thermal conductivity is deteriorated and disadvantageous to the fixing property, so that the OHP permeability is lowered and the sharpness is also lowered because the particle size is large. In addition, the volume average particle diameter (D4) is in the range of 4.4 to 5.4 μm, and the heat conductivity is appropriate, so that the fixing property is good, and particularly the glossiness of the color toner is improved. OHP permeability is improved. In particular, the sharpness is in the range of 4.4 to 5.0 μm.

  Further, since the toner has a coefficient of variation in the weight distribution (standard deviation of weight distribution / weight average particle diameter) in the range of 26.1 to 30.0, the particles are densely packed without voids in the image formation before fixing. Therefore, the sharpness of the image after fixing is increased. If it is less than 26.1, particles having a large weight diameter increase and a lot of voids are generated, so that the sharpness of the image after fixing is lowered. If it exceeds 30.0, the distribution becomes broad, and fogging and toner scattering occur.

  In addition, as the release agent used in the present invention, all known ones can be used. In particular, by using olefin wax, paraffin wax, and ester wax alone or in combination, transparency is improved and glossiness of an image is improved. Rise. However, when the polyester resin is contained as a binder resin, if ester wax is used, transesterification occurs due to thermal energy during kneading, and the structure of the ester wax is partially destroyed. Don't be. When a styrene acrylic resin is contained as a binder resin, there is no such inconvenience, and since the compatibility with the release agent is high, the release agent can be finely dispersed, which is advantageous.

<Method for measuring particle size distribution of toner particles>
The particle size distribution of the toner particles in the present invention is measured by Coulter Multisizer II (manufactured by Coulter). The measurement method will be described in detail below.
First, 0.1 to 5 ml of a surfactant, preferably (polyoxyethylene alkyl ether) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic aqueous solution is an approximately 1% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used.
Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Volume distribution and number distribution are calculated.
From the obtained distribution, the weight average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained by the following formula.
As channels, 1.26 to less than 1.59 μm; 1.59 to less than 2.00 μm; 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4 0.000 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; Less than 00 μm; 16.00 to less than 20.20 μm; 20.20 to less than 25.40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm; 16 channels less than 40.30 to 50.80 μm And particles having a particle size of 1.26 μm or more and less than 50.80 μm are used.

[6] According to the toner of the present invention, it is possible to supply with a small amount of toner even if the toner container made of a flexible member capable of reducing the volume by 60% or more is used.
Specifically, by filling the toner of the present invention into a powder toner container made of a flexible member capable of reducing the volume by 60% or more, automatic supply from the container to the developing unit can be stably performed. Further, after storage, toner powder packing does not occur in the container, and the remaining amount of toner powder can be further reduced.
Since the toner of the present invention has a low temperature fixability and a small particle size, it has no toner aggregation and excellent flow characteristics. Therefore, as a toner supply means connected to the toner storage means, toner powder and air are mixed. When using a pump means that prevents the fluid from flowing backward, the flexible toner container automatically reduces its volume, and the shape around the container changes, giving a loosening action and the remaining amount of powder toner It has been found that can be reduced particularly effectively.

  Further, a gas such as air is jetted into the toner storage container using a nozzle or the like, and the toner powder layer is allowed to pass through while diffusing, thereby promoting fluidization of the toner as in the present invention. It has also been found that the toner can be supplied more stably and the remaining toner can be reduced even when a supply member such as an agitator cannot be incorporated.

An example of a method for supplying powder toner from a powder toner container that can be used in the present invention will be described below.
In FIG. 1, air is sent from the air inflow unit 30 to the powder toner container 20. The air is ejected into the toner container, and the ejected air passes through the toner layer while diffusing, and then the air ejected from the toner container with the toner into the toner container passes through the toner layer while diffusing. By doing so, fluidization of the toner is promoted. Occurrence of a cross-linking phenomenon or the like is prevented, and toner supply is more reliable.

  In addition to sending air, adding appropriate vibration and impact to the toner storage container is effective for stably sucking and transferring extremely poorly fluid toner, and toner crosslinking. This prevents the toner from being transferred to the toner conduction path stably. As these concrete means, a conventionally known method such as intermittent impact application using a cam and lever or vibration addition using a motor or solenoid may be used.

  As the powder pump means 25, for example, a suction type uniaxial eccentric screw pump (commonly known as MONO pump) is preferable. Its configuration consists of a rotor made in the shape of a screw that is eccentric with a rigid material such as metal, a stator that is made of a rubber material and fixed in the shape of a screw with two insides, and wraps these powders It consists of a holder made of a resin material that forms the transfer path. When the rotor rotates, a strong self-priming force is generated in the pump, and it becomes possible to suck in an airflow containing toner. If an air pump is used in addition to the powder pump means 25, fluidization of the toner is promoted by the supplied air, and toner transfer by the powder pump means 25 becomes more reliable.

  As described above, the powder toner is supplied from the powder toner container 20 to the developing unit 10 together with an air flow that is a carrier medium for the powder toner. The developing unit 10 includes a developing sleeve 11 disposed opposite to the photosensitive member 1 as a latent image carrier and stirring screws 12 and 13. In the developer circulated between the stirring screws 12 and 13, the supplied powder toner is made uniform in toner density and optimized in charge amount. Further, the developer is transferred to the developing sleeve 11 to develop the electrostatic latent image formed on the photoreceptor 1. Of course, this is only an example, and it can be used for other developing devices and developing systems.

  The powder toner container that can be used in the present invention includes a bag portion and a connection portion formed of a flexible single layer or laminated sheet. FIG. 2 shows an example of a powder toner container, and FIG. 3 shows a form when the volume of the powder toner container is reduced. The powder toner storage container 40 includes a rigid mouth portion 41 and a soft and flexible bag portion 42. The mouth part 41 can use a normal molding material such as polyethylene, polypropylene, nylon, ABS resin, NBS resin, and the bag part 42 can use a plastic film or paper such as polyethylene, polypropylene, polyester, polyurethane, In the case of a plastic film, a thickness of about 0.05 to 0.5 mm is preferable.

  If the toner storage container is flexible, the volume of the bag is reduced as the toner suction proceeds, and the introduced air causes toner clogging due to local deformation during volume reduction of the bag-like toner storage container. At the same time as the generation is suppressed, the suction efficiency of the powder pump is increased, and the stored toner is discharged without remaining in the bag.

  As shown in FIG. 1, the toner container 20 to the developing device 10 are connected via a tube 16. The tube 16 is a flexible tube having a diameter of 4 to 10 mm, for example, and is preferably made of a rubber material having toner resistance such as polyurethane, nitrile, EPDM, or silicone.

Next, materials used for the toner of the present invention and a method for producing the toner will be described.
-Binder resin-
The binder resin used in the toner of the present invention can be appropriately selected from known resins according to the purpose. For example, polystyrene, poly-α-still styrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene -Styrene such as maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Resin (monopolymer or copolymer containing styrene or styrene-substituted product), polyester resin, epoxy resin, vinyl chloride resin, rosin-modified maleic acid resin, phenol resin, polyethylene resin, polypropylene resin, petroleum resin, polyurethane resin, Ketone resin, ethylene-ethylene Examples include a acrylate copolymer, a xylene resin, and a polyvinyl butyrate resin. As described above, the range of K (Tfb) / K (Ts) = 1.0 to 1.3 in the present invention is easily obtained. From the viewpoint of becoming, a crystalline polyester resin is preferable, and in order to maintain the advantages of the crystalline polyester resin, a styrene acrylic resin is preferably used as a binder resin to be used together.

  The crystalline polyester resin used in the toner of the present invention undergoes a crystal transition at the glass transition temperature, and at the same time, the melt viscosity suddenly decreases from the solid state, and a fixing function that cannot be obtained with an amorphous polyester resin. Since K (Tfb) / K (Ts) in the present invention can be easily obtained in the range of 1.0 to 1.3.

  However, on the other hand, in the kneading process at the time of toner production, a rapid decrease in melt viscosity occurs due to heat generation during kneading, so that it is difficult to use a crystalline polyester resin alone as a toner. However, when amorphous polyester is mixed, ester bonds are generated between the crystalline polyester and the amorphous polyester due to mechanical energy during kneading, and the crystallinity of the crystalline polyester is destroyed. Therefore, since the glass transition point is lowered at the site where the crystallinity is lost, the cohesiveness due to storage is deteriorated.

  Therefore, by containing a styrene acrylic resin as an amorphous binder resin, the crystalline polyester resin does not collapse, and the crystalline polyester resin undergoes a crystal transition at the glass transition temperature, Since the melt viscosity suddenly decreases from the solid state and K (Tfb) / K (Rs) in the present invention is easily obtained in the range of 1.0 to 1.3, it cannot be obtained with an amorphous polyester resin alone. A fixing function can be exhibited. At the same time, since the storage stability is good and the toner cohesion is good, the supply amount of the powder toner is stable even when filled in a powder toner container made of a flexible member capable of reducing the volume by 60% or more. The powder toner is not packed in the container after storage, and good toner supply is possible.

Crystalline polyester resin used in the present invention include polyhydric alcohol unit and acid _{unit, -OCOC-R-COO- (CH} 2) n- ( In the formula, R represents a straight C2-20 A chain unsaturated aliphatic group, and n represents an integer of 2 to 20.) The structure represented by at least 60 mol% of all ester bonds in the entire resin is contained. In the above formula, R preferably represents a linear unsaturated aliphatic divalent carboxylic acid residue, has 2 to 20 carbon atoms, and more preferably 2 to 4 linear unsaturated aliphatic. It is a group. n is preferably an integer of 2 to 6.

  Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.

The (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic dihydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Those derived from dihydric alcohols can be indicated. Since the crystalline polyester resin uses a linear unsaturated aliphatic dicarboxylic acid unit as the carboxylic acid unit, the crystalline polyester resin has an effect of easily forming a crystal structure as compared with the case of using an aromatic dicarboxylic acid unit. .

  The crystalline polyester resin comprises (1) a polyvalent carboxylic acid unit comprising a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester acid halide having 1 to 4 carbon atoms, etc.). And (2) a polyhydric alcohol unit comprising a linear aliphatic diol can be produced by a polycondensation reaction by a conventional method. In this case, the polyvalent carboxylic acid unit may contain a small amount of other polyvalent carboxylic acid units as necessary.

  In this case, the polyvalent carboxylic acid unit includes (1) an unsaturated aliphatic divalent carboxylic acid unit having a branched chain, (2) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, etc. In addition to aliphatic polyvalent carboxylic acid units, (3) aromatic polyvalent carboxylic acid units such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The content of these polyvalent carboxylic acid units is usually 30 mol% or less, preferably 10 mol% or less, based on the total carboxylic acid, and is suitably added within the range in which the resulting polyester has crystallinity. .

  The non-linear crystalline polyester of the present invention is obtained by using a monomer containing an alcohol component composed of a divalent or higher polyhydric alcohol and a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound. However, in the present invention, in order to form a non-linear polyester, as described above, a trivalent or higher monovalent monomer selected from the group consisting of a trihydric or higher polyhydric alcohol and a trivalent or higher polyvalent carboxylic acid compound. A monomer containing 0.1 to 20 mol, preferably 0.5 to 15 mol, more preferably 1 to 13 mol with respect to 100 mol of all alcohol components is used.

  Divalent polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol. 1,8-octanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-butenediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Among these, from the viewpoint of the softening point and crystallinity of the resin, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6 Hexanediol, preferably a diol having 2 to 6 carbon atoms such as neopentyl glycol, alpha, more preferably ω- linear alkylene glycols, 1,4-butanediol is particularly preferred.

  The diol having 2 to 6 carbon atoms is desirably contained in the alcohol component in an amount of preferably 50 mol% or more, more preferably 60 to 80 mol%, particularly preferably 80 to 100 mol%.

  Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Among these, glycerin is preferable from the viewpoint of the softening point and crystallinity of the resin.

  Examples of the divalent polyvalent carboxylic acid compound include oxalic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid and dodecenyl succinic acid, octyl Aliphatic carboxylic acids such as succinic acid substituted with alkyl groups having 1 to 20 carbon atoms such as succinic acid or alkenyl groups having 2 to 20 carbon atoms; aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; cyclohexane Examples thereof include alicyclic carboxylic acids such as dicarboxylic acids, and anhydrides of these acids, derivatives such as alkyl (1 to 3 carbon atoms) esters, and among these, from the viewpoint of the softening point and crystallinity of the resin, A group carboxylic acid is preferred, and fumaric acid is more preferred.

  The aliphatic carboxylic acid is preferably contained in the carboxylic acid component in an amount of 70 mol% or more, more preferably 80 to 100 mol%.

  Specific examples of polyvalent carboxylic acid units that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid Divalent carboxylic acid units such as: trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid Trivalent or higher polyvalent carboxylic acid units such as acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. Can be mentioned. Among these, trimellitic acid and its acid anhydride are preferable from the viewpoint of the softening point and crystallinity of the resin.

  The alcohol component and the carboxylic acid component can be subjected to polycondensation by reacting at a temperature of 150 to 250 ° C. in an inert gas atmosphere, if necessary, using an esterification catalyst or the like.

In addition, since the styrene acrylic resin used in combination with the crystalline polyester resin has a resin composition different from that of the crystalline polyester resin, the crystallinity of the crystalline polyester can be maintained even during melt-kneading, and the physical properties of the crystalline polyester can be maintained. Since the crystalline polyester is finely dispersed without lowering, it is possible to use the resin by taking advantage of each resin.
As the component, it is preferable to use a styrene acrylic copolymer in which styrene is polymerized by 50 to 100% by weight, preferably 60 to 90% by weight. When the styrene copolymerization amount is less than 50% by weight, the heat melting property of the toner is poor, and as a result, the fixability tends to be insufficient.

  Further, as described above, the binder resin used in the toner of the present invention is such that if the peak top molecular weight MPT of the toner measured by GPC is in the range of 2000 to 4000, the crystalline polyester does not become the pulverized interface but the styrene acrylic resin does not. It is preferable to consider that That is, it is preferable to adjust the peak top molecular weight of the binder resin used in combination with the crystalline polyester so that the peak top molecular weight of the toner falls within such a range.

-Colorant-
The colorant can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), Cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG) ), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu , Permanent Red 4R, Para Red, Faise Red, parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinac Don Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Examples include malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

  The color of the colorant can be appropriately selected according to the purpose, and examples thereof include a black color and a color color. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the black material include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner can be appropriately selected according to the purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, the coloring power decreases, and the electrical characteristics of the toner. May be reduced.

The colorant can also be used as a master batch combined with a resin.
As the resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the binder resin described above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, or a substituted polymer thereof; styrene-p-chlorostyrene Copolymer, Styrene-propylene copolymer, Styrene-vinyltoluene copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate Copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Polymer, styrene-acrylonitrile copolymer Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified Examples include rosin, terpene resin, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type and may use 2 or more types together.

-Charge control agent-
In the toner of the present invention, a charge control agent can be blended in order to control the polarity. Examples of the charge control agent include nigrosine dyes, quaternary ammonium salts, amino group-containing polymers, metal-containing azo dyes, salicylic acid complex compounds, and phenol compounds. These may be used individually by 1 type and may use 2 or more types together.

Next, a method for producing the toner of the present invention will be described.
The toner production method of the present invention includes a step of mechanically mixing a developer component including at least a binder resin, a main charge control agent, and a pigment, a step of melt kneading, a step of pulverizing, and a step of classifying. A method for producing a toner having the above can be applied. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles obtained as a product obtained in the pulverization or classification step is returned and reused.

  The powders (sub-products) other than the particles used as the product referred to here are fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and subsequent classification. It means fine particles or coarse particles other than the components that are produced in the process and have a desired particle size. In the mixing step or the step of melt-kneading such a by-product, it is preferable to mix the raw material and preferably from the other raw material 99 to the sub-product 1 in the weight ratio of the other raw material 50 to the sub-product 50.

  The mixing step of mechanically mixing at least a binder resin, a main charge control agent and a pigment, and a developer component including a by-product may be performed under normal conditions using a normal mixer with a rotating wing, There is no particular limitation.

  When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used.

  It is important that this melt-kneading is performed under appropriate conditions that do not cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize, but the pulverization method for obtaining the particle size distribution of the present invention is preferably produced by pulverization with an opposed airflow pulverizer. Toner. Examples of the counter airflow type pulverizer include those manufactured by Nippon Pneumatic Industry, PJM-I, Hosokawa Micron micron jet mill, counter jet mill, and Kurimoto Seiko cross jet mill.

  By pulverizing with an opposed airflow pulverizer, the circularity of the toner is increased and the surface of the toner is modified very smoothly. The toner thus obtained has good packing between the toner when the isolated dots are filled in the development process, and since there are few gaps, the isolated dots on the photoconductor are not easily collapsed, and the granularity is good and smooth. An image with excellent tonality can be obtained.

  When the pulverization process does not include a pulverization process using an opposed airflow pulverizer, the toner surface is insufficiently modified, and thus the effects of the present invention may not be sufficiently obtained. Furthermore, the toner of the present invention can be further improved in cleaning properties by removing ultrafine powder of 2 μm or less. In order to remove ultrafine powder of 2 μm or less, the weight average diameter and / or the mode value particle diameter is pulverized to 15 μm or less in advance by a mechanical pulverizer, so that the pulverization with the opposed airflow pulverizer is performed. Excessive increase in circularity and generation of ultrafine particles are suppressed.

  If not pulverized in advance with a mechanical pulverizer, not only does it lead to an increase in energy consumption in the process of pulverization to a toner size of 3.7 to 6.5 μm in the number average particle size with an opposed airflow pulverizer, When the circularity is excessively increased, cleaning becomes difficult when used as a toner. In addition, the amount of ultrafine powder generated is large, and if the ultrafine powder of 2 μm or less exceeds 30% in the pulverized product pulverized by the opposed airflow pulverizer, it becomes extremely difficult to remove in the dry classification process, and one pass treatment is performed. In the particle size distribution after classification, it is impossible to reduce the ratio of particles of 0.6 to 2.0 μm to a level of 5% or less.

  Although it is possible to remove particles of 0.6 to 2.0 μm by a wet method such as a decanter type centrifuge, the wet method is not preferable in terms of productivity, and the interface is used for the purpose of dispersing the toner in water. Since an activator is used, dry classification is desirable because there is a concern about the effect on the chargeability of the toner unless sufficient washing is performed.

  In the toner pulverization step, the weight average particle size and / or the mode value particle size is 5 to 15 μm, preferably 5 to 10 μm, and then pulverized by a mechanical pulverizer. The surface of the toner particles can be sufficiently modified while suppressing an excessive increase in circularity and generation of super fine particles during pulverization.

  Examples of the mechanical pulverizer include a kryptron manufactured by Kawasaki Heavy Industries, Ltd., a turbo mill manufactured by Turbo Kogyo Co., Ltd., an ACM pulverizer manufactured by Hosokawa Micron Co., and an inomizer, and the particle size can be arbitrarily adjusted by adjusting the rotational speed of the pulverizing rotor. Can be adjusted.

  As a classification process, a classification cover and a classification plate are provided up and down, and a conical shape is formed with the lower surface of the classification cover and the upper surface of the classification plate raised toward the center, and the classification formed between the conical lower surface and the conical upper surface A plurality of louvers are annularly arranged on the outer periphery of the chamber, an inflow path for secondary air is provided between adjacent louvers, and the powder supplied into the classification chamber is swirled at a high speed into fine powder and coarse powder. Centrifugal airflow classification, in which fine powder is discharged from a fine powder discharge cylinder connected to the center of the classification plate, and coarse powder is discharged from a coarse powder discharge port formed on the outer periphery of the classification plate. This makes it possible to efficiently remove ultrafine powder of 2 μm or less. Examples of such a swirl airflow classifier include a micro spin manufactured by Nippon Pneumatic Industry. Thus, the particle size distribution of the toner of the present invention is obtained.

  The toner produced as described above may be further mixed with inorganic fine particles such as the hydrophobic silica fine powder mentioned above.

  For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.

  Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a lady gemiser, a nauter mixer, and a Henschel mixer.

(Two-component developer)
The two-component developer according to the present invention contains the toner of the present invention and a carrier.
As the carrier, conventionally known carriers can be used, for example, magnetic core particles such as iron powder, ferrite powder, nickel powder, magnetite powder, or the surface of the magnetic core particles treated with a resin. Or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in a resin. Among these, those having a core material and a coating layer on the core material are particularly preferable.

  There is no restriction | limiting in particular as resin which forms the said coating layer, According to the objective, it can select suitably, For example, polyolefin resin, such as polyethylene, a polypropylene, chlorinated polyethylene, chlorosulfonated polyethylene; For example, polymethyl methacrylate), polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polybiliketone, and other polyvinyl or polyvinylidene resins; vinyl chloride-vinyl acetate copolymer, polytetrafluoro Fluorine resins such as ethylene, polyvinyl fluoride, polyvinylidene fluoride and polychlorotrifluoroethylene; polyamides; polyesters; polyurethanes; polycarbonates; Amino resins such as aldehyde resins, epoxy resins, and silicone resins. These may be used individually by 1 type and may use 2 or more types together.

  The average particle diameter of the carrier is preferably 35 μm to 80 μm from the viewpoint of charging ability.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. “Part” is based on weight.

[Example 1]
Synthesis of Resin Composition (1) 60 parts of styrene, 40 parts of n-butyl acrylate, 5 parts of divinylbenzene as a crosslinking agent, 3 parts of benzoyl peroxide and 0.5 part of t-butyl peroxybenzoate were dissolved and desorbed. The mixture was added to a mixture of 200 parts of ionic water and 0.2 part of partially saponified polyvinyl alcohol (“GOHSENOL GH-23” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and stirred. Next, after raising the temperature to 130 ° C. and carrying out suspension polymerization for 1 hour, cooling to room temperature, washing, dehydration and drying, a styrene-based binder for toner having a peak top molecular weight of 3500 and a weight average molecular weight of 23,000 Resin a was obtained.

  Next, 800 g of styrene was placed in the 1 L flask A, 200 g of n-butyl acrylate was placed in the 1 L flask B, and a solution prepared by dissolving 5 g of azobisisobutyronitrile as a polymerization initiator in 100 g of toluene was placed in the 1 L flask C. Next, 250 g of the aforementioned styrene-based binder resin a was placed in a 3 L separable flask, and 300 g of toluene was added and dissolved. And after replacing the inside of a separable flask with nitrogen gas, it heated to the boiling point of toluene. N-Butyl acrylate in Flask B is dropped into Flask A at a dropping rate of 4.44 (g / min), and the contents of Flask A are dropped at a dropping rate of 1.11 (g / min). It was dripped at C. At this time, the flasks A and C were stirred with a stirrer, and each component was sufficiently mixed and dispersed. Ten minutes later, the flask C was dropped into the separable flask at a rate of 6.14 (g / min) over 3 hours to perform solution polymerization. After completion of the dropwise addition, the mixture was further aged for 1 hour while stirring at the boiling point of toluene. Thereafter, while gradually raising the temperature in the separable flask to 190 ° C., toluene was removed from the solvent under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a toner resin composition (1). The resin composition for toner (1) had a peak top molecular weight of 4500 and a THF-insoluble content of 5% by weight.

Synthesis of Resin Composition (2) 80 parts of styrene, 20 parts of n-butyl acrylate, 0.1 part of divinylbenzene and 5 parts of benzoyl peroxide are dissolved, 200 parts of deionized water and partially saponified polyvinyl alcohol (Nippon Synthetic Chemical) The mixture was added to 0.2 parts of “GOHSENOL GH-23” manufactured by Kogyo Co., Ltd. and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization was performed for 3 hours, followed by cooling to room temperature, washing, dehydration, and drying to obtain a toner resin composition (2). The obtained resin composition (2) had a Tg of 58 ° C., a weight average molecular weight (Mw) of 35,000, a THF-insoluble content of 0% by weight, and a peak top molecular weight of 2900.

・ Cyan toner prescription:
Resin composition (1) 60 parts Resin composition (2) 25 parts Cyan pigment (pigment blue 15-3) 5 parts Charge control agent (E-84, manufactured by Orient Chemical Industries) 2 parts Paraffin wax (Nippon Seiwa Co., Ltd.) Product name: HNP-3) 8 parts / Magenta Toner Formulation:
Resin composition (1) 58 parts Resin composition (2) 25 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) 2 parts Paraffin wax (manufactured by Nippon Seiwa Co., Ltd.) Name: HNP-3) 8 parts Yellow toner formulation:
Resin composition (1) 58 parts Resin composition (2) 25 parts Yellow pigment (pigment yellow 180) 7 parts Charge control agent (Orient Chemical Industries, E-84) 2 parts Paraffin wax (Nippon Seiwa Co., Ltd.) Name: HNP-3) 8 parts Black toner formulation:
Resin composition (1) 56 parts Resin composition (2) 24 parts Carbon black (Mogal L:
Cabot Specialty Chemicals, Inc. 10 parts Charge control agent (Orient Chemical Industries, E-84) 2 parts Paraffin wax (Nippon Seiwa Co., Ltd., trade name: HNP-3) 8 parts

Among the above materials, cyan, yellow, and magenta were mixed with pigment, resin composition (2), and pure water at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
For cyan, yellow, and magenta, use the masterbatch that was prepared to be the same as the above recipe, and for black, use a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.) according to the above recipe. After preliminarily mixing, the mixture was kneaded with a biaxial kneader [manufactured by Ikegai, PCM-30].
Next, the mixture was coarsely pulverized using an ACM pulverizer manufactured by Hosokawa Micron Corporation, then pulverized with PJM-I manufactured by Nippon Pneumatic Industry Co., Ltd., and classified with a microspin manufactured by Nippon Pneumatic Industry Co., Ltd., thereby obtaining base toner particles.
Next, using a 30 L super mixer, 100 parts of colloidal silica [H-2000: manufactured by Clariant Co., Ltd.] and 100 parts of titanium oxide P-25 (manufactured by Nippon Aerosil Co., Ltd.) were placed on 100 parts of the base toner particles. The toner of Example 1 was obtained by mixing for 15 minutes while flowing cooling water at a high speed of 40 m / s and then sieving with a 350 mesh (44 μm) sieve.

Ts and Tfb measured by the elevated flow tester measured for the toner of Example 1, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 1.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 1 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

[Example 2]
(Synthesis of resin composition (3))
175 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 815 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 332 g of terephthalic acid, 148 g of maleic anhydride and 22 g of dibutyltin (II) are put in a glass 3 liter-four-necked flask, and a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube are attached, and a nitrogen flow is conducted in an electric mantle heater. The reaction was allowed to proceed with stirring at 210 ° C. for 5 hours under reduced pressure of 5 to 20 mmHg, then returned to normal pressure, and 30 g of tin (II) octylate and 40 g of tri-n-butyl 1,2,4-benzenetricarboxylate were added. Then, the reaction was allowed to proceed with stirring at 210 ° C. for 8 hours under reduced pressure of 5 to 20 mmHg. The polyester resin had a THF insoluble content of 18%, a Tg of 55 ° C., and a peak top molecular weight of 2300. This resin is referred to as “resin composition (3)”.

(Synthesis example of resin composition (4))
1050 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 313 g of fumaric acid, and 50 g of isophthalic acid were placed in a glass 2-liter four-necked flask together with 30 g of tin (II) octylate, A thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen introduction tube were attached, and the reaction was allowed to proceed for 8 hours with stirring at 210 ° C. under reduced pressure of 5-20 mmHg in an electric heating mantle heater. The obtained polyester resin did not contain a THF-insoluble component, had an average weight molecular weight of 12000, a Tg of 60 ° C., and a peak top molecular weight of 2800. This resin is referred to as “resin composition (4)”.

・ Cyan toner prescription:
Resin composition (3) 42 parts Resin composition (4) 43 parts Cyan pigment (pigment blue 15-3) 5 parts Charge control agent (Orient Chemical Industries, E-84) 3 parts Olefin wax (Mitsui Chemicals) , High wax 800P) 7 parts magenta toner formulation:
Resin composition (3) 41 parts Resin composition (4) 42 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemical Industries, E-84) 3 parts Olefin wax (Mitsui Chemicals, High Wax 800P) 7 parts Yellow toner formulation:
Resin composition (3) 41 parts Resin composition (4) 42 parts Yellow pigment (pigment yellow 180) 7 parts Charge control agent (Orient Chemical Industries, E-84) 3 parts Olefin wax (Mitsui Chemicals, High Wax 800P) 7 parts Black toner formulation:
Resin composition (3) 40 parts Resin composition (4) 40 parts Carbon black (Mogal L:
Cabot Specialty Chemicals, Inc.) 10 parts Charge control agent (Orient Chemical Industries, E-84) 3 parts Olefin wax (Mitsui Chemicals, High Wax 800P) 7 parts

Among the above materials, cyan, yellow and magenta were mixed with pigment, resin composition (4) and pure water at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
For cyan, yellow, and magenta, use the master batch that was prepared, and use the same recipe as above. For black, use a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.) as specified above. After preliminary mixing, the mixture was kneaded with a biaxial kneader [manufactured by Ikegai Co., Ltd., PCM-30].
Next, after coarsely pulverizing using an ACM pulverizer manufactured by Hosokawa Micron Co., Ltd., pulverizing using PJM-I manufactured by Nippon Pneumatic Industrial Co., Ltd., and classifying with a microspin manufactured by Nihon Pneumatic Kogyo Co., Ltd. to obtain base toner particles .
Next, a 30 L supermixer was used to mix the additives, cooling water was poured, and 1000 parts of the base toner particles and 3 parts of titanium dioxide (STT-30A, manufactured by Titanium Industry) were added as the first stage mixing. For 5 minutes at a rotational speed of 8 m / s. After mixing 10 parts of hydrophobic silica (H1303VP, manufactured by Wacker) and 2 parts of titanium dioxide (STT-30A, manufactured by Titanium Industry Co., Ltd.) and mixing for 10 minutes at a rotational speed of 60 m / s. The toner of Example 2 was obtained by sieving with a 350 mesh (44 μm) sieve.

Ts and Tfb measured by the elevated flow tester measured for the toner of Example 2, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 1.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 1 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

Example 3
(Synthesis of crystalline polyester resin composition (5))
1,260 g of 1,6-butanediol, 120 g of ethylene glycol, 1400 g of fumaric acid, 350 g of trimellitic acid, 3.5 g of tin octylate and 1.5 g of hydroquinone were equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. After putting into a 5 liter four-necked flask and reacting at 160 ° C. for 5 hours, raising the temperature to 200 ° C. and reacting for 1 hour, and further reacting at 8.3 kPa for 1 hour, a crystalline polyester resin composition (5) was obtained. The crystalline polyester resin composition (5) had a melting point of 105 ° C.

(Synthesis of Resin Composition (6))
380 parts of styrene, 120 parts of butyl methacrylate, 10 parts of divinylbenzene, 5 parts of benzoyl peroxide, 4 parts of 2 liter capacity equipped with a thermometer, a glass air flow introduction tube, a stirring rod with a vacuum-resistant seal device and a water-cooled Jimroth condenser In a one-necked round bottom flask, 500 parts of xylene and all of the above monomers and initiator were charged. Nitrogen gas was introduced from the glass airflow introduction tube to replace the inside of the reactor with an inert atmosphere, and then the contents were gradually heated by a mantle heater with a slider box to 75 ° C. The reaction was carried out while maintaining the temperature at 65 ° C. to 80 ° C. After 10 to 12 hours, the temperature was raised to 130 ° C. in order to complete the polymerization and the polymerization was completed.
Next, the water-cooled condenser and the glass air flow introduction tube were removed from the flask, and a capillary for vacuum distillation and a Claisen fractionation tube were attached instead. A thermometer and a water-cooled Liebig condenser were connected to the Claisen distillation tube, and the outlet of the condenser was connected to the eggplant-shaped flask via a suction adapter. The suction adapter and the vacuum pump were connected with a rubber tube for pressure reduction through a manometer and a trap, and preparation for vacuum distillation was completed. When the mantle heater was heated and the vacuum pump was operated with sufficient stirring of the contents to reduce the pressure to 20 mmHg, xylene or possibly unreacted monomer started to distill at a liquid temperature of 75 ° C. and a distillation temperature of 38 ° C. Finally, the pressure was reduced to 0.5 mmHg at a liquid temperature of 180 ° C. to completely remove the solvent.
The obtained polymer was put in a stainless steel pan in a high-temperature molten state, cooled to room temperature and then crushed to obtain a resin composition (6). Resin composition (6) had a THF insoluble content of 12%, a Tg of 65 ° C., and a peak top molecular weight of 5800.

・ Cyan toner prescription:
Resin composition (6) 31 parts Resin composition (2) prepared in Example 1 17 parts Resin composition (5) 37 parts Cyan pigment (pigment blue 15-3) 5 parts Charge control agent (Orient Chemical Co., Ltd.) E-84) 5 parts Olefin Wax (Mitsui Chemicals, High Wax 1140H) 5 parts Magenta Toner Formula:
Resin composition (6) 30 parts Resin composition (2) prepared in Example 1 16.5 parts Resin composition (5) 36.5 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemistry) 5 parts olefin wax (manufactured by Mitsui Chemicals, high wax 1140H), 5 parts. Yellow toner formulation:
Resin composition (6) 30 parts Resin composition (2) prepared in Example 1 16.5 parts Resin composition (5) 36.5 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemistry) 5 parts olefin wax (manufactured by Mitsui Chemicals, high wax 1140H), 5 parts black toner formulation:
Resin composition (6) 28 parts Resin composition (2) prepared in Example 1 16 parts Resin composition (5) 36 parts Carbon black (Mogal L:
Cabot Specialty Chemicals, Inc. 10 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin wax (Mitsui Chemicals, high wax 1140H) 5 parts

Among the above materials, cyan, yellow, and magenta were mixed with pigment, resin composition (2), and pure water at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
For cyan, yellow, and magenta, using the master batch prepared, the same recipe as above, and for black, using a Henschel mixer [FM10B, made by Mitsui Miike Chemical Co., Ltd.] as prescribed above. After preliminary mixing, the mixture was kneaded with a twin-screw kneader [manufactured by Ikegai, PCM-30].
Next, the mixture was coarsely pulverized using an ACM pulverizer manufactured by Hosokawa Micron Corporation, then pulverized with PJM-I manufactured by Nippon Pneumatic Industry Co., Ltd., and classified with a microspin manufactured by Nippon Pneumatic Industry Co., Ltd., thereby obtaining base toner particles.
Next, a 30 L supermixer was used to mix the additives, cooling water was poured, and as a first stage mixing, 1000 parts of the base toner particles and 3 parts of titanium dioxide (STT-30A, manufactured by Titanium Industry Co., Ltd.) were added. The mixture was mixed for 5 minutes at a rotation speed of / s. As a second stage mixing, 15 parts of hydrophobic silica (H1303VP, manufactured by Wacker) was added, mixed for 10 minutes at a rotational speed of 80 m / s, and then sieved with a 350 mesh (44 μm) sieve. Example 3 Toner was obtained.

Ts and Tfb measured by the elevated flow tester measured for the toner of Example 3, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 1.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 1 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

Example 4
・ Cyan toner prescription:
Resin composition (6) 41 parts Resin composition (2) prepared in Example 1 27 parts Resin composition (5) 17 parts Cyan pigment (pigment blue 15-3) 5 parts Charge control agent (Orient Chemical Co., Ltd.) Manufactured by E-84) 5 parts paraffin wax (trade name: HNP-11, manufactured by Nippon Seiwa Co., Ltd.) 5 parts magenta toner formulation:
Resin composition (6) 40 parts Resin composition (2) prepared in Example 1 26.5 parts Resin composition (5) 16.5 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemistry) 5 parts paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: HNP-11) 5 parts, yellow toner formulation:
Resin composition (6) 40 parts Resin composition prepared in Example 1 (2) 26.5 parts Resin composition (5) 16.5 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Paraffin wax (Nippon Seiwa Co., Ltd., trade name: HNP-11) 5 parts Black toner formulation:
Resin composition (6) 38 parts Resin composition (2) prepared in Example 1 26 parts Resin composition (5) 16 parts Carbon black (Mogal L:
Cabot Specialty Chemicals, Inc. 10 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Paraffin wax (Nippon Seiwa Co., Ltd., trade name: HNP-11) 5 parts

Based on the above formulation, base toner particles were obtained in the same manner as in Example 3.
Next, a 30 L supermixer was used for mixing the additives, cooling water was poured, and 1000 parts of the base toner particles and 3 parts of titanium dioxide (P-25, manufactured by Nippon Aerosil Co., Ltd.) were added as the first stage mixing. The mixture was mixed for 5 minutes at a rotational speed of 8 m / s. As a second stage mixing, 10 parts of hydrophobic silica (R-972: manufactured by Nippon Aerosil Co., Ltd.) was added, mixed for 10 minutes at a rotational speed of 60 m / s, and then sieved with a 350 mesh (44 μm) sieve. A toner of Example 4 was obtained.

Ts and Tfb measured by the elevated flow tester measured for the toner of Example 4, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 1.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 1 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

Example 5
The toner formulation is the same as in Example 4 except that the paraffin wax is changed to Ester Wax WEP-5 manufactured by Nippon Oil & Fats Co., Ltd. in Example 4, and the manufacturing method is adjusted by adjusting the pulverization air pressure and feed, and the classification louver height. A toner of Example 5 was obtained by the same production method as in Example 4 except that toner particles having a particle size distribution of Example 5 were obtained.

Ts and Tfb measured by the elevated flow tester measured for the toner of Example 5, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 1.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 1 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

[Examples 6 to 8]
The same toner formulation as in Example 4 except that the toner particles having the particle size distribution of Examples 6, 7 and 8 were obtained by adjusting the air pressure and feed of pulverization and the louver height of classification in Example 4. The toners of Examples 6, 7, and 8 were obtained in the same manner.

Ts and Tfb by an elevated flow tester measured for the toners of Examples 6, 7, and 8, Log G ′ (Tfb + 10 ° C.), Log G ′ (Tfb−10 ° C.), K (Tfb), Log G ′ (Ts) by a rheometer, Log G ′ (Ts−15 ° C.), K (Ts), and K (Tfb) / K (Ts) are shown in Table 1 (b).
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 2 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

[Comparative Example 1]
(Synthesis of Resin Composition (7))
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1000 g of xylene was added and stirred at 125 ° C. in a nitrogen atmosphere while 1500 g of styrene, 150 g of butyl methacrylate, A mixture of 530 g of acrylic acid and 40 g of dicumyl peroxide was added dropwise from the dropping funnel over 2 hours. Furthermore, after maintaining at 125 ° C. for 1 hour, refluxing was performed at 150 ° C. for 1 hour. The reaction system was maintained at 200 ° C. and 8.0 kPa, and xylene was removed over 2 hours to obtain a styrene-acrylic resin composition (7). The resin composition (7) had a THF insoluble content of 5%, a Tg of 60 ° C., and a peak top molecular weight of 4800.

・ Cyan toner prescription:
Resin composition (7) 45 parts Resin composition (2) 40 parts Cyan pigment (pigment blue 15-3) 5 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin wax (Mitsui Chemicals) , High wax 1140H) 5 parts magenta toner formulation:
Resin composition (7) 44 parts Resin composition (2) 39 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin wax (Mitsui Chemicals, High Wax 1140H) 5 parts yellow toner formulation:
Resin composition (7) 44 parts Resin composition (2) 39 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin wax (Mitsui Chemicals, High Wax 1140H) 5 parts black toner formulation:
Resin composition (7) 40 parts Resin composition (2) 40 parts Carbon black (Mogal L:
Cabot Specialty Chemicals, Inc. 10 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin wax (Mitsui Chemicals, high wax 1140H) 5 parts

Among the above materials, cyan, yellow, and magenta were mixed with pigment, resin composition (2), and pure water at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
For cyan, yellow, and magenta, use the master batch that was prepared, and use the same recipe as above. For black, use a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.) as specified above. After preliminary mixing, the mixture was kneaded with a biaxial kneader [manufactured by Ikegai Co., Ltd., PCM-30].
Next, the mixture was coarsely pulverized using an ACM pulverizer manufactured by Hosokawa Micron Corporation, then pulverized with PJM-I manufactured by Nippon Pneumatic Industry Co., Ltd., and classified with a microspin manufactured by Nippon Pneumatic Industry Co., Ltd., thereby obtaining base toner particles.
Next, a 30 L supermixer was used to mix the additives, cooling water was poured, and as a first stage mixing, 1000 parts of the base toner particles and 3 parts of titanium dioxide (STT-30A, manufactured by Titanium Industry Co., Ltd.) were added. The mixture was mixed for 5 minutes at a rotation speed of / s. As a second stage mixing, 15 parts of hydrophobic silica (H1303VP, manufactured by Wacker) was added, mixed for 10 minutes at a rotational speed of 80 m / s, and then sieved with a 350 mesh (44 μm) sieve, Comparative Example 1 Toner was obtained.

Ts and Tfb measured by the elevated flow tester measured for the toner of Comparative Example 1, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 2.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 2 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

[Comparative Example 2]
・ Cyan toner prescription:
Resin composition (6) 21 parts Resin composition (2) 10 parts Resin composition (5) 54 parts Cyan pigment (pigment blue 15-3) 5 parts Charge control agent (E-84, manufactured by Orient Chemical Industries) 5 Part Olefin wax (Mitsui Chemicals, High Wax 1140H) 5 partsMagenta Toner Formula:
Resin composition (6) 20 parts Resin composition (2) 10 parts Resin composition (5) 53 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin Wax (Mitsui Chemicals, High Wax 1140H) 5 parts Yellow toner formulation:
Resin composition (6) 20 parts Resin composition (2) 10 parts Resin composition (5) 53 parts Magenta pigment (pigment red 122) 7 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin Wax (Mitsui Chemicals, High Wax 1140H) 5 parts Black toner formulation:
Resin composition (6) 18 parts Resin composition (2) 10 parts Resin composition (5) 52 parts Carbon black (Mogal L:
Cabot Specialty Chemicals, Inc. 10 parts Charge control agent (Orient Chemical Industries, E-84) 5 parts Olefin wax (Mitsui Chemicals, high wax 1140H) 5 parts

Among the above materials, cyan, yellow, and magenta were mixed with pigment, resin composition (2), and pure water at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
For cyan, yellow, and magenta, use the master batch that was prepared, and use the same recipe as above. For black, use a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.) as specified above. After preliminary mixing, the mixture was kneaded with a biaxial kneader [manufactured by Ikegai Co., Ltd., PCM-30].
Next, the mixture was coarsely pulverized using an ACM pulverizer manufactured by Hosokawa Micron Corporation, then pulverized with PJM-I manufactured by Nippon Pneumatic Industry Co., Ltd., and classified with a microspin manufactured by Nippon Pneumatic Industry Co., Ltd., thereby obtaining base toner particles.
Next, a 30 L supermixer was used to mix the additives, cooling water was poured, and as a first stage mixing, 1000 parts of the base toner particles and 3 parts of titanium dioxide (STT-30A, manufactured by Titanium Industry Co., Ltd.) were added. The mixture was mixed for 5 minutes at a rotation speed of / s. As a second stage mixing, 15 parts of hydrophobic silica (H1303VP, manufactured by Wacker) was added, mixed for 10 minutes at a rotational speed of 80 m / s, and then sieved with a 350 mesh (44 μm) sieve. Comparative Example 2 Toner was obtained.

Ts and Tfb measured by the elevated flow tester measured for the toner of Comparative Example 2, LogG ′ (Tfb + 10 ° C.), LogG ′ (Tfb−10 ° C.), K (Tfb), LogG ′ (Ts), LogG ′ (Ts) measured by the rheometer −15 ° C.), K (Ts), K (Tfb) / K (Ts) are shown in Table 2.
Further, the number of channels of each particle size measured by Coulter Multisizer II, number average particle size, coefficient of variation of number distribution (standard deviation of number distribution / number average particle size), particle size of 4.0 to 8.0 μm. Table 2 shows the number% of the toner particles and the peak top molecular weight of the toner by GPC.

Evaluation method of Examples 1-8 and Comparative Examples 1-2 <Image evaluation method>
The image forming apparatus Imagio neoC385 manufactured by Ricoh Co., Ltd. has been modified, and the toner supply device shown in FIG. 4 is attached to the developing unit. The toner container 2 is made of polypropylene and has a volume reduction rate by a vacuum pump (100 mmHg). Using a 65% container, each of the toners of Examples 1 to 8 and Comparative Examples 1 and 2 was filled therein and evaluated according to the following image evaluation method. The results are shown in Tables 1 and 2.
Note that the powder pump 26 in the toner supply apparatus of FIG. 4 is a Mono pump.

(Measurement of remaining toner)
Toner storage container filled with toner with 65% volume reduction as described above is stored at 45 ° C. and 80% humidity for 72 hours in a normal temperature / humidity environment (25 ° C., 60%). The image was taken out until the toner end detection was activated (until the amount of supplied toner ceased), and the remaining toner weight remaining in the toner container was measured.

[Equation 4]
Toner remaining weight (%)
= Remaining toner weight (g) / toner filling weight (g) × 100
Calculated with The smaller the remaining amount, the better the replenishment. Furthermore, image evaluation was performed after 10,000 sheets.

(Image density)
The density of a solid solid circle with a diameter of 3 cm was measured at 10 points using a Macbeth densitometer, and the average value was obtained.

(Uneven image density)
The density of a solid solid circle of 3 cm in diameter is measured at 10 points with a Macbeth densitometer, and the difference between the maximum value and the minimum value is determined.

(Image glossiness)
When the paper type 4 of ISO12647-2 (1996) manufactured by Ricoh Co., Ltd. is used as the fixing paper and the A4 solid image is fixed at a toner weight per unit area of 1.0 mg / cm ² , the glossiness is handy gloss. The total gloss checker IG-310 (incident angle 60 degrees: manufactured by Horiba Seisakusho) was used for measurement.

(Fixability)
Using an image 420 made by Ricoh Co., Ltd. as an image output device, copying was performed by changing the heater temperature to obtain a fixed image.
A fixing tape (manufactured by 3M) is applied to the fixed image (toner adhesion amount: 0.85 ± 0.05 mg / cm ² ), and after applying a certain pressure (2 kg), it is slowly peeled off. The image density before and after that was measured with a Macbeth densitometer, and the fixing rate was calculated by the following formula. The temperature of the fixing roller is lowered step by step, and the temperature at which the fixing rate shown by the following formula becomes 80% or less is set as the lower limit fixing temperature.

[Equation 5]
Fixing rate (%) = image density after tape peeling / original image density × 100

(Hot offset generation temperature)
Fixing was evaluated in the same manner as the above-described minimum fixing temperature, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.

  From Tables 1 and 2, the toners of Examples 1 to 8 having specific rheological properties according to the present invention have a small amount of remaining toner and a good toner replenishment property, a high image density, and uneven density. From the fact that it is small, it can be seen that the storage stability is excellent, the fixing minimum temperature is low, the hot offset occurrence temperature is high, that is, the fixing property is good, and the toner is highly glossy.

FIG. 6 is an explanatory diagram illustrating a method of supplying toner from a powder toner container to a developing unit. It is the schematic which shows an example of a powder toner container. It is the schematic when a powder toner container is volume-reduced. FIG. 2 is a schematic view of a toner supply device including a powder toner container, an air supply device, and a powder pump. It is a flow curve by an elevated flow tester.

Explanation of symbols

(About Figure 1)
1 Image carrier or photoreceptor
DESCRIPTION OF SYMBOLS 10 Developing part 11 Developing sleeve 12, 13 Conveying screw 16 Tube 20 Toner storage container 25 Powder pump means 30 Air inflow means (About FIG. 2, FIG. 3)
40 Powder Toner Storage Container 41 Mouth Portion of Powder Toner Storage Container 42 Bag Part of Powder Toner Storage Container (About FIG. 4)
2 Toner container or powder toner cartridge 14 Air supply nozzle 17 Air nozzle tube 20 Air supply tube 21 Air pump 22 Toner supply tube 26 Powder pump

Claims (10)

A toner containing at least a colorant, a release agent, and a binder resin, where Ts is a softening temperature measured by an elevated flow tester, and Tfb is an outflow start temperature. An electrostatic charge characterized in that K (Tfb) / K (Ts), which is a ratio of K (Tfb) to K (Ts) represented by the following formula (2), is in the range of 1.0 to 1.3. Toner for image development.
[Equation 1]
Formula (1)
K (Tfb) = (┃LogG ′ (Tfb + 10 ° C.) − LogG ′ (Tfb−10 ° C.) ┃) / 20
(In the formula, Log G ′ (Tfb + 10 ° C.) is the logarithm of the storage elastic modulus G ′ at the measurement temperature (Tfb + 10 ° C.) measured by the rheometer, and Log G ′ (Tfb−10 ° C.) is the measurement temperature measured by the rheometer ( (Tfb−10 ° C.) is a logarithm of the storage elastic modulus G ′, and (||) indicates an absolute value.)
[Equation 2]
Formula (2)
K (Ts) = (┃LogG ′ (Ts) −LogG ′ (Ts−15 ° C.) ┃) / 15
(In the formula, Log G ′ (Ts ° C.) is the logarithm of the storage elastic modulus G ′ at the measurement temperature (Ts ° C.) measured by the rheometer, and Log G ′ (Ts−15 ° C.) is the measurement temperature measured by the rheometer ( (Ts−15 ° C.) is a logarithm of the storage elastic modulus G ′, and (||) indicates an absolute value.) As the binder resin comprises a polyvalent alcohol unit and a carboxylic acid unit, -OCOC-R-COO- (CH 2) n- ( In the formula, R represents C2-20 straight-chain unsaturated fatty 2. The toner for developing an electrostatic charge image according to claim 1, comprising a crystalline polyester resin having a structure represented by the following formula: n represents an integer group, and n represents an integer of 2 to 20.   3. The electrostatic image developing toner according to claim 1, wherein K (Tfb) represented by the formula (1) is in the range of 0.070 to 0.080. 4.   4. The electrostatic image developing toner according to claim 1, wherein a crystalline polyester resin and a styrene acrylic resin are used in combination as the binder resin.   5. The electrostatic image developing toner according to claim 1, wherein the peak top molecular weight MPT of the toner measured by GPC is in the range of 2000 to 4000.   6. The electrostatic image developing toner according to claim 1, wherein the releasing agent contains any one of olefin wax and paraffin wax.   The toner has a number average particle diameter of 3.2 to 4.0 μm, a coefficient of variation of the toner number distribution (standard deviation of the number distribution / number average particle diameter) of 23.0 to 37.0, and 7. The electrostatic image developing toner according to claim 1, wherein 20.0 to 39.0% by number of toner particles having a particle size of 4.0 to 8.0 [mu] m are contained.   A two-component developer comprising the toner according to any one of claims 1 to 7 and a carrier.   A powder toner cartridge, wherein the toner according to any one of claims 1 to 7 is filled in a powder toner container made of a flexible member capable of reducing volume by 60% or more.   An image forming apparatus comprising at least an image carrier, an electrostatic image forming unit for forming an electrostatic image on the image carrier, and a developing unit for converting the formed electrostatic image into a visible image using toner. The developing means includes a powder toner cartridge filled with toner, an air inflow means for injecting air into the cartridge, and a pump means for supplying the toner as a mixed fluid. And a toner supply device having a toner supply tube for supplying the toner from the cartridge to the developing means, and the powder toner cartridge according to claim 9 is mounted as the cartridge. An image forming apparatus.

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