JP2003131418A - Electrostatic latent image developing toner, method for manufacturing the same, developer, image forming method and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic latent image developing toner adaptable to oilless fixation, excellent in anti-offsetting property and stably forming images of high image quality having no image stain as well as a moderate gloss on the image surface over a long period of time and to provide a method for manufacturing the toner, a developer, an image forming method and an image forming apparatus. SOLUTION: In the electrostatic latent image developing toner comprising at least a resin a colorant and a crystalline compound, toner particles have a sea-island structure and the islands are a specified crystalline compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic latent image developing toner used in copiers, printers and the like, and a method for manufacturing the same.
The present invention relates to a developer, an image forming method, and an image forming apparatus.

[0002]

2. Description of the Related Art In recent years, in an image forming method using an electrophotographic method, digital image forming has become mainstream due to the progress of digital technology. The digital image forming method is 1200 dpi (dpi is 1 inch or 2.
It is basically based on visualizing a small dot image of 1 pixel (such as the number of dots per 54 cm), and a high image quality technique for faithfully reproducing these small dot images is required.

From the viewpoint of improving the image quality as described above, the particle size of the electrostatic latent image developing toner (sometimes simply referred to as toner) is being reduced. In the past, a so-called pulverized toner has been mainly used for forming an electrophotographic image, in which a toner powder obtained by mixing a binder resin and a pigment, kneading and pulverizing the mixture is classified in a classification step. However, the toner obtained through such a manufacturing process has a limitation in reducing the toner particle size and homogenizing the particle size distribution. Therefore, it is difficult to achieve a sufficiently high image quality in an electrophotographic image using such a pulverized toner.

In recent years, a polymerized toner obtained by a suspension polymerization method or an emulsion polymerization method has attracted attention as a means for achieving a reduction in the particle size of the toner particles and a uniform particle size distribution and shape.
The polymerized toner is a technology of uniformly dispersing a raw material polymerizable monomer in an aqueous system and then polymerizing it to produce a toner. Usually, resin particles and a colorant obtained by a suspension polymerization method or an emulsion polymerization method are used. Since it is necessary to associate (aggregate / fuse) the particles, the technology in that direction has been actively developed.

On the other hand, as a method of fixing a toner image formed on an image support such as paper (also called a transfer material or transfer paper), the image support on which the toner image is formed is pressed against a heating roller. A heat roller fixing method in which fixing is performed by passing between rollers is widely used. However, the heat roller fixing method has a drawback that image contamination is likely to occur due to an offset phenomenon in which molten toner adheres to the heating roller.

Therefore, as a means for preventing the occurrence of the offset phenomenon, it is known to apply silicone oil to the surface of the heating roller of the fixing device so as to impart releasability to toner to the heating roller. Is advantageous in that the type of toner used is not limited.

However, in such a method, since the transfer paper is coated with the silicone oil, it is not possible to write with a writing instrument such as a ballpoint pen, which is not suitable for a business document. Further, there is also a problem that the volatile component contained in the silicone oil is volatilized by the heat of the surface of the heating roller and adheres to the optical system, the band electrode and the like to contaminate them, thereby causing a defective image quality.

[0008] Further, there is an increasing number of devices equipped with a finisher such as a bookbinding mechanism for closing a book in which a large amount of copying is performed by speeding up the apparatus and supporting print-on-demand.

From the above viewpoint, there is a daily demand for the development of an oilless fixing technique in which the silicone oil is not supplied to the fixing device (heating roller) or the amount of the silicone oil supplied to the fixing device is extremely low. It is in an increasing situation.

Further, devices equipped with a finisher such as a large amount of copying and a bookbinding mechanism for closing the inside have become widespread, and in these devices, the sheets bundled by bookbinding etc. come into contact with each other, and the toner on the paper becomes a white background on the next page. There is a problem that stains are generated by transfer or rubbing.

In response to such demands, it has been widely practiced to add a releasing agent such as wax to the toner to impart releasability to the toner itself. A toner (polymerized toner) obtained by a polymerization method is also added with release agent particles, and a method is known in which resin particles and release agent particles are associated with each other during the polymerization step. However, in the toner obtained by this method, a sufficient amount of the release agent cannot be introduced into the associated particles, and the content of the release agent varies among the formed associated particles, Sufficient releasability (offset resistance) for the entire toner
I have not been able to demonstrate.

To solve these problems, Japanese Patent Laid-Open No. 8-414
As in the invention described in Japanese Patent No. 68, a technique for improving the compound used in the release agent and increasing the amount of addition to the associated particles (toner particles) has been investigated. However, due to the structural reason that the toner particles are composed of the resin particles, the release agent, and the associated particles of the colorant, the release agent is released from the associated particles, and the released release agent is developed. There are problems that the carrier constituting the agent is contaminated and deteriorated, the fluidity of the toner is lowered, and the filming problem of the photoconductor occurs.

Further, paying attention to the toner particle structure, a toner having a sea-island structure in which a releasing agent phase is phase-separated into a binder resin phase in the toner particle structure is disclosed in JP-A-3-2960.
No. 67, JP-A-10-161338, and JP-A-5-88409. However, in these inventions, there is no mention of variations in the amount of the release agent added in the toner particles, and these variations are not mentioned. There was no suggestion of having sufficient control of the. Further, the toners disclosed in these patents have a structure in which the release agent is phase-separated, but the release agent phase exists as a lump in the center of the toner particles. It is a structure in which it is difficult to effectively exude toner outside the toner particles. There is no choice but to increase the amount of release agent added to the toner particles, and since the distance until the release agent oozes out of the toner is long, it is difficult for the release agent to sufficiently ooze out during image fixing,
It was not possible to achieve a sufficient offset property.

[0014]

The present invention has been made based on the above circumstances.

That is, the first object of the present invention is to have excellent offset resistance corresponding to oilless fixing, have an appropriate gloss on the image surface, and stably obtain a high-quality image free from image stains for a long period of time. An object of the present invention is to provide an electrostatic latent image developing toner that can be formed and a method for producing the same.

A second object of the present invention is to provide a toner for developing an electrostatic latent image which prevents occurrence of toner filming on a photoconductor and has good cleaning property, and a method for producing the same.

Further, a third object of the present invention is that the paper is strong against rubbing or contact between papers, and the paper is not contaminated even when printed materials are piled up and stored at the time of bookbinding. To provide a latent electrostatic latent image developing toner and a method for producing the same.

Further, a fourth object of the present invention is to develop an electrostatic latent image capable of stably forming a high-quality image for a long period of time, which is excellent in developability and fine dot reproducibility and is excellent in fine line reproducibility. To provide a toner for toner and a manufacturing method thereof.

A fifth object of the present invention is to provide a developer, an image forming method and an image forming apparatus using the above excellent toner.

[0020]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have made diligent studies, and as a result, polymerization having a sea-island structure obtained by associating the resin particles of the present invention with particles of a crystalline compound. It has been found that the object of the present invention can be achieved by focusing on the structure of the toner and specifying the shape of the crystalline compound region in the toner particles.

That is, the object of the present invention is achieved by adopting any one of the following configurations.

[1] An electrostatic latent image developing toner containing at least a resin, a colorant and a crystalline compound, which satisfies the following conditions. The toner particles have a sea-island structure, and the average horizontal ferret diameter of the islands of the crystalline compound is 200.
~ 900 nm, and the ferret horizontal diameter variation coefficient is 4
It is 0% or less. The crystalline compound is n (normal) -paraffin 9
It contains 2% by mass or more and a plurality of n-paraffin components having different carbon numbers, and the peak end temperature of the maximum endothermic peak in the endothermic curve measured by DSC is 70 to 1
20 ° C., the peak half width of the maximum endothermic peak is 12
℃ or less, and the penetration is 4 or less.

[2] A toner for developing an electrostatic latent image containing at least a resin, a colorant and a crystalline compound, which satisfies the following conditions. The toner particles have a sea-island structure, and the toner having 5 to 40 crystalline compound islands per toner particle accounts for 99% or more of the total. The crystalline compound is molecularly distilled Fischer-Tropsch wax or polyethylene using a metallocene catalyst.

[3] A toner for developing an electrostatic latent image containing at least a resin, a colorant and a crystalline compound, which satisfies the following conditions. The toner particles have a sea-island structure, an average value of the island shape factor of the crystalline compound is 110 to 200, the variation coefficient is 35% or less, and the island shape factor is 100.
The proportion of islands in the range of from 110 to 30 is 30% by number or less of all the islands present in the toner particles, and the shape factor is 200.
The ratio of the above islands is 10% by number or less of all the islands present in the toner particles. The crystalline compound is n (normal) -paraffin 9
It contains 2% by mass or more and a plurality of n-paraffin components having different carbon numbers, and the peak end temperature of the maximum endothermic peak in the endothermic curve measured by DSC is 70 to 1
20 ° C., the peak half width of the maximum endothermic peak is 12
℃ or less, and the penetration is 4 or less.

[4] In an electrostatic latent image developing toner containing at least a resin, a colorant, and a crystalline compound, the toner particles have a sea-island structure, and the resin constitutes a sea part to form crystals. The toner for developing an electrostatic latent image according to any one of [1] to [3], which comprises islands of a polymerizable compound and islands of a colorant.

[5] The electrostatic latent image developing toner according to any one of [1] to [4], wherein the number average particle size is 3 to 9 μm. Toner for electrostatic latent image development.

[6] The method for producing a toner for developing an electrostatic latent image according to any one of [1] to [5], wherein at least the polymerizable monomer is polymerized in an aqueous medium. A method for producing a toner for developing an electrostatic latent image.

[7] The method for producing a toner for developing an electrostatic latent image according to any one of [1] to [5], characterized in that at least resin particles are aggregated / fused in an aqueous medium. A method for producing a toner for developing an electrostatic latent image.

[8] In the method for producing the electrostatic latent image developing toner according to any one of [1] to [5], the composite resin fine particles obtained by the multi-stage polymerization method and the colorant particles are aggregated. / A method for producing a toner for developing an electrostatic latent image, which is obtained by fusing.

[0030]

[9] An electrostatic latent image developing toner produced by the method for producing an electrostatic latent image developing toner according to any one of [6] to [8].

[10] A developer comprising the electrostatic latent image developing toner according to any one of [1] to [5].

[11] An electrostatic latent image developing toner produced by the method for producing an electrostatic latent image developing toner according to any one of [6] to [8]. Developer.

[12] In the image forming method, which comprises a step of visualizing the electrostatic latent image formed on the photoconductor, transferring the visible image onto recording paper, and fixing the image by heating, the visible image is formed by [1]. ~ [5] and

An image forming method, which is performed using the electrostatic latent image developing toner according to any one of [9].

[13] An image forming apparatus using the image forming method described in [12], characterized in that imagewise irradiation of the photosensitive member is performed by digital exposure.

The term "penetration" as used in the present invention refers to JIS
It refers to the degree of penetration at 25 ° C. measured by K-2235.
A penetration of more than 4 is not preferable because the fluidity of the toner is lowered, and fusion with a frictional charging member such as a carrier is promoted to accelerate its deterioration.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The toner particles of the present invention have a sea-island structure. The sea-island structure means an island-like phase having a closed interface (boundary between phases) in a continuous phase. Is a structure in which exists. That is, in the toner of the present invention, the resin, the colorant, and the crystalline compound constituting the toner particles do not mutually compatibilize with each other and independently form a phase, so that the toner particles have a sea-island structure. Will have. Further, the present invention has a structure in which islands of the crystalline compound and islands of the colorant are present in the continuous phase of the resin which is the sea due to the nature of the toner.

In this way, the toner particles of the present invention have a structure in which the phases of the other constituents are present in an island shape in the continuous phase. In the present invention, the amount of the crystalline compound liberated from the toner particles can be drastically reduced by making the average diameter of the ferret horizontal diameter of the island portion constituting the toner particles and the value of the horizontal diameter within a specific range. Found.
As a result, the crystalline compound added to the toner particles effectively exhibits its function at the time of image formation, so that the offset property is improved, and the above-mentioned problems such as suppressing the occurrence of toner filming on the photoconductor are achieved. is there.

That is, in the prior art, the crystalline compound added to the polymerized toner tends to be released more easily than the toner particles, but the present invention solves this problem. In the present invention, the definite reason for effectively preventing the release of the crystalline compound has not been clarified. Presumably, in the prior art, the added crystalline compound has a spherical shape or a shape close to a spherical shape. Therefore, small particles of the added crystalline compound easily move in the toner particles and have large particles. However, since the contact area in the toner particles is small, the crystalline compound is not firmly held in the toner particles, and it is presumed that the crystalline compound easily comes out on the surface of the toner particles and is easily desorbed. It

On the other hand, in the toner particles of the present invention, the islands of the crystalline compound in the toner particles are firmly held in the particles, so that they are free from the toner particles except during the heat fixing step. Therefore, it is presumed that the function of leaching out of the toner particles quickly and surely was imparted during the heat fixing. Further, the problem of smearing is solved by forming a protective layer of a crystalline compound having a small friction coefficient on the surface of the fixed toner image by a crystalline compound having an appropriately exuding and releasing function on the surface of the toner particles. It also achieves the prevention of stains that occur when sheets of paper with image information are bundled and piled up, such as in bookbinding.

The structure of the toner particles of the present invention having a sea-island structure means that the toner particles have areas of different brightness according to a cross-sectional photograph of the toner particles taken by a transmission electron microscope. It can be confirmed that it is present. That is, in the toner particles of the present invention, granular islands (phase of crystalline compound and phase of colorant) having different brightness are present in the continuous phase (phase of binder resin) by the transmission electron microscope. Is confirmed. Further, based on the result obtained from the observation result of the electron microscope, the number of islands in one toner particle, the shape factor of the island, the ferret horizontal diameter of the island, and other factors that specify the sea-island structure in the toner particle are obtained as numerical values. It is what is done.

The brightness in the transmission electron micrograph means the difference in electron beam transmittance caused by the difference in the crystal state of each element constituting the toner particles, that is, the binder resin, the colorant, and the crystalline compound. This is caused by visualization, and since the colorant generally has a lower electron beam transmittance than the binder resin, it is photographed at a low luminance, and the crystalline compound is photographed at a higher luminance than the binder resin.

In the electron micrograph, low brightness means 0 when the brightness signal of a pixel is divided into 256 gradations.
~ 99 gradations, and medium brightness is 80 ~ 160
The range of gradation and the high brightness mean the range of 127 to 255 gradations, but in the present invention, as long as they are relative, that is, the above-mentioned toner particle constituents can be discriminated by a photograph, respectively. Well, it is not necessarily limited to the above range. For example, with respect to islands of a crystalline compound, when a section for observation with a transmission electron microscope is placed in an environment of 80 to 120 ° C., they flow out and are observed as vacancies, so that they can be easily distinguished from the islands of colorant. .

As described above, in the present invention, by identifying each constituent element in the toner particles based on the brightness, it is possible to visually judge and identify the sea as the sea and the island as the island by the electron micrograph. The information on the luminance is converted into image information that can be visually identified by the image analysis device installed in the electron microscope device.

Further, the toner particles (a) and (b) of FIG.
FIG. 2 is a schematic view showing an example of toner particles each having a sea-island structure. In an electron micrograph, the toner particles of the present invention are composed of a continuous phase and island portions having different brightness as shown in this schematic view. It is observed to be one. Further, there is a region having no island portion of length a and depth b along the outer circumference of the toner particle.

In the present invention, the crystalline compound forming the island portion is an organic compound having a melting point and is a hydrocarbon compound. The melting point of the crystalline compound in the toner particles of the present invention is lower than the softening point of the toner, specifically 12
It is 0 ° C. or less.

In the toner of the present invention, a method for confirming that the crystalline compound forming the island portion has a melting point can be confirmed by a differential scanning calorimeter (DSC), and the crystallinity can be confirmed. It can be confirmed that it is possessed by a means such as an X-ray diffractometer. Further, the crystalline compound contained in the toner of the present invention also contains a compound that exhibits a function as a release agent during image formation.

The melting point of the crystalline compound is 70 to 120.
C. is preferable, and more preferably 80 to 110.
℃ In a toner containing a crystalline compound having a melting point in the range of 70 to 120 ° C., it is possible to reduce the melt viscosity, improve the adhesiveness to paper and the like, and further, the crystalline compound is present. However, since the elastic modulus on the high temperature side is maintained in the preferable range, good offset resistance is exhibited.

When the melting point of the crystalline compound is less than 70 ° C., the fixability itself is improved, but the storability is deteriorated, causing a problem in practical use. On the other hand, when the melting point exceeds 120 ° C., the melting start temperature becomes high, so that the contribution to the improvement of the fixability is low, and the effect of improving the fixability is reduced.

Here, the melting point of the crystalline compound means a value measured by DSC, and specifically, the temperature is raised from 0 ° C. to 200 ° C. under the condition of 10 ° C./min (first temperature rising process). The temperature at which the maximum endothermic peak that is sometimes measured is the melting point. The melting point is in agreement with the “endothermic peak (P1) in the first temperature rising process by DSC” described later.

The transmission electron microscope apparatus capable of observing the structure of the toner particles of the present invention is usually well observed by a model well known to those skilled in the art, and for example, "LEM-2".
000 type (manufactured by Topcon) "and the like are used. In the present invention, the value obtained from the result of the transmission electron micrograph of the number of islands in the toner particles, which is the feature of the present invention, is calculated from the projection surface of 1,000 or more toner particles at a magnification of 10,000. It is calculated.

In the present invention, the photographing method using a transmission electron microscope is a commonly known method used when measuring toner particles. That is, as a specific method for measuring the tomographic plane of the toner, the toner may be sufficiently dispersed in a room temperature curable epoxy resin and then embedded and cured, or dispersed in styrene fine powder having a particle diameter of about 100 nm. After pressure molding, the resulting block was dyed with ruthenium tetroxide or osmium tetroxide in combination and cut into flaky samples using a microtome equipped with diamond teeth. The tomographic morphology of the toner was photographed using a microscope (TEM).
From the photograph, the shape of the crystalline compound region in the toner particles is visually confirmed, and the photographed image information is calculated by the image processing apparatus "Luzex F" (manufactured by Nireco Corporation) provided in the electron microscope apparatus. Depending on the processing
The values of the Feret diameter, the number, and the shape factor of the island portion in the toner particle can be obtained.

The structure of the toner particles of the present invention is specified by the above method. Hereinafter, the factors that specify the structure of the toner particles of the present invention will be described in detail.

The average value of the ferret horizontal diameter of the island portion present in the toner particles of the toner of the present invention is 200 to 900 nm, preferably 300 to 750 nm, and particularly preferably 450 to 700 nm. If the average value of the horizontal Feret diameter in the toner particles is less than 200 nm, the amount of the crystalline compound exuding from the toner particles is too small, which is not preferable for image formation. Further, the average Feret horizontal diameter exceeds 900 nm. If this happens, the charge density on the surface of the toner particles becomes uneven, which is not preferable for image formation.

The ferret horizontal diameter used in the present invention represents the horizontal length of the toner particles when the toner particles are horizontally placed in an arbitrary state, and the ferret horizontal diameter of the island portion is In this way, the horizontal length of each island existing inside the toner particles arbitrarily placed is shown.

The variation coefficient of the ferret horizontal diameter of the island portion in the toner particles of the present invention is 40% or less, preferably 35% or less, and particularly preferably 30% or less. The variation coefficient of the ferret horizontal diameter of the island portion in the toner particles of the toner of the present invention is obtained by the following formula.

Variation coefficient of ferret horizontal diameter = (S2 / K2)
X100 (%) [In formula, S2 shows the standard deviation of the ferret horizontal diameter of 100 island parts, K2 shows the average value of the ferret horizontal diameter. In the present invention, the variation coefficient of the ferret horizontal diameter of the island portion in the toner particles represents the variation of the average value of the ferret horizontal diameter, that is, the variation of the size of each island of the crystalline compound. If the coefficient of variation of the ferret horizontal diameter exceeds 40%, the size of the island will vary greatly,
The crystalline compound cannot form a uniform release agent layer on the fixing member (roller or belt), and toner that causes offset occurs, which is not preferable.

Further, in the present invention, the present invention is achieved when the coefficient of variation is 40 or less, and when the value of the coefficient of variation is 0, that is, there is no variation in the horizontal diameter of the ferret. There is no need to be.

The toner of the present invention contains one toner particle,
It has 1 to 20 islands of 99% or more. This means that in the toner of the present invention, the particles of the crystalline compound are always contained and present in the toner particles. That is, in the conventional toner, not only the pulverized toner but also the suspension-polymerized toner disclosed in JP-A-5-88409 contains an additive such as a release agent in the toner particles in the order of several%. It has been confirmed that there is a toner that has not been released, and it cannot be asserted that the toners up to now always contain an additive such as a release agent in each toner particle.

The toner of the present invention contains 1 in 1 toner particle.
Those having ~ 20 islands are 99% by number or more. Island (crystalline compound) present in each toner particle, as seen from a transmission electron micrograph of 1000 toner particles.
Is calculated, and the average value of the required number is calculated. In the present invention, the number of crystalline compound islands present in one toner particle is 1 to 40, preferably 8 to 18, and particularly preferably 10 to 16. It should be noted that one having no island in one toner particle does not have a sea-island structure and is outside the scope of the present invention. Further, when the number of islands exceeds 40, the amount of the crystalline compound added in the toner particles is too large, which is not preferable in image formation.

In the toner of the present invention, the shape factor of the islands in the toner particles has an average value within the range of 110 to 200. Here, the shape factor of islands is a numerical value of the shape of islands existing in the toner particles, and the value is calculated by the following formula.

Shape factor of island = [(maximum length of island) ² × π /
(Area of island) × 4] × 100 The shape factor defined by the above equation is a numerical representation of the shape of the island, and an island having a shape factor of 100 is a true sphere. The larger the shape factor value is, the longer the island shape is, and the shape factor value is 100.
It is shown that as the number increases, the shape of the island changes from true sphere to ellipse to needle.

Further, in the present invention, the variation of the shape of the island is quantified by the variation coefficient of the shape. The coefficient of variation of the island shape is defined by the following equation.

Coefficient of variation of shape coefficient = (S3 / K3) × 100 (%) [In the formula, S3 represents the standard deviation of the shape coefficient of 100 islands, and K3 represents the average value of the shape coefficients. In the present invention, when the average value of the shape factors is 110 to 200, the value of the variation coefficient is 35% or less, and the ratio of the average value of the shape factors in the range of 100 to 110 is 30 number% or less. The ratio of those with an average coefficient of 200 or more is 10
The number is less than or equal to%. That is, the present invention is based on the finding that the bleeding rate of the crystalline compound to the outside of the toner particles can be controlled by the shape factor having a specific distribution. In the present invention, if the average value of the shape factors is 110 to 200, the variation coefficient may be 35% or less, but the variation coefficient is 0%, that is, the average value of the shape factors is 110 to 2
In the case of No. 00, there is no need for the islands to have a uniform shape with no variation in shape.

In the present invention, the island shape factor is 110 to 20.
It was found that the islands of 0 are those which firmly hold the toner particles without spilling out from the toner particles, and effectively exude the crystalline compound at the time of heat fixing. If the shape factor is less than 110, as the shape becomes closer to a sphere, the island is more likely to spill out than the toner particles.
When the value exceeds 0, the shape becomes elongated, so that it tends to be difficult for the crystalline compound to effectively exude out of the toner particles during heat fixing.

However, the average value of the shape factors is 110 to 200.
The coefficient of variation of the thing exceeds 35%, 100
If the proportion of those in the range of 110 to 110 exceeds 30% by number, and the proportion of those of 200 or more exceeds 10% by number, they are not detached from the toner particles, and moreover the crystalline compound is effectively exuded. Even though it can be done, the shape of the island becomes too ununiform,
Since the proportion of islands detached from the toner particles or islands where the crystalline compound cannot be effectively exuded increases, it becomes difficult to exert the effect as a release agent on image formation, and the effect found in the present invention Is difficult to obtain, which is not preferable.

The shape of the islands in the toner particles of the present invention is as described above, but more preferably, when the average value of the shape factors of the islands is 110 to 200, the variation coefficient is 25% or less. , The average shape factor of the island is 10
The proportion of those in the range of 0 to 110 is 10% or less, and the proportion of those in which the average value of the island shape factor is 200 or more is 7% or less.

The toner particles having a sea-island structure of the present invention are
In addition to the above-mentioned crystalline compound components, what constitutes the island part,
Some colorant components also form colorant islands in the toner particles and are present in the toner particles. The island of the colorant component is shown as island B in FIG. Since the islands of the crystalline compound component and the islands of the colorant component have different luminances, they can be easily identified in an electron micrograph. The present invention specifies the island portion in the sea-island structure in the toner particles by various parameters. For the island of the crystalline compound component, the ferret horizontal diameter, the number, and the shape factor of the island described above are used. The island of the colorant component is specified based on the area of the Voronoi polygon described below.

In the present invention, various numerical characteristic values are calculated for the island portion in the sea-island structure of the toner particles. These values are attached to the electron microscope apparatus based on the image information observed by the electron microscope apparatus. It is calculated by the image analysis device.

Further, in the toner of the present invention, the toner particles have a sea-island structure, but have areas where no island exists in the area along the outer periphery of the toner particles. In the schematic view of the toner particles (a) and (b) in FIG. 1, the region indicated by the length a and the depth b along the outer periphery of the toner particle cross section is a region not including islands. That is, in the toner of the present invention, the depth is 100 to 200 nm and the length is 500 to 6000 in the region along the outer periphery of the toner particle cross section.
It has been confirmed to have a region that does not include any nm island portion.

In the toner of the present invention, by preventing the islands from existing in the specific region along the outer periphery of the toner particles, it is possible to effectively prevent the islands from being detached from the toner particles. It is presumed that the crystalline compound or colorant added to the toner particles is appropriately dispersed in the particles, and the crystalline compound is effectively exuded at the time of heat fixing. It is supposed to be.

The toner of the present invention is confirmed to have a sea-island structure by the above-mentioned transmission electron microscope, but the crystalline compound added to the toner particles forms crystalline compound islands. The colorant is such that islands of the colorant are formed, and thus a plurality of types of islands are formed for each kind of additive. The properties described so far are of the same type, namely between islands of crystalline compounds,
Alternatively, it is a characteristic of the colorant between islands and not between different types of islands.

Since the islands of different additives, that is, the islands of the crystalline compound and the islands of the colorant have different luminances, they can be easily identified in the electron micrograph and the image analysis apparatus for calculating the above-mentioned characteristics can be obtained. Is set so that the characteristic values between different types of islands will not be calculated by mistake. Regarding the island in the toner particle of the present invention, the island of the crystalline compound is
It is specified by the Feret diameter, the shape factor of islands, and the number of islands present in each toner particle, and the island of the colorant is specified by the area of the Voronoi polygon.

The sea part of the toner particles having the sea-island structure of the present invention is made of resin.

Next, the particle size of the toner of the present invention will be described. The toner used in the present invention has a number average particle diameter of 3 to 9 μm, preferably 4.5 to 8.5 μm, and more preferably 5 to 8 μm. This particle size is
In the toner production method, it can be controlled by the concentration of the aggregating agent (salting out agent), the addition amount of the organic solvent, the fusing time, and the composition of the polymer.

When the number average particle size is 3 to 9 μm, the transfer efficiency is improved, the halftone image quality is improved, and the image quality of fine lines, dots, etc. is improved. To calculate the particle size distribution of the toner and measure the number average particle size, Coulter Counter TA
-II, Coulter Multisizer (both manufactured by Coulter, Inc.), SLAD1100 (laser diffraction particle size analyzer manufactured by Shimadzu Corporation), and the like can be used for measurement. In the present invention, a Coulter Multisizer is used, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting a particle size distribution and a personal computer are connected and measured and calculated.

Next, the method for producing the toner of the present invention will be described. The toner of the present invention is preferably obtained by polymerizing at least a polymerizable monomer in an aqueous medium. In this production method, a polymerizable monomer is polymerized by a suspension polymerization method to prepare resin particles, or a monomer is added in a liquid (in an aqueous medium) containing an emulsion of necessary additives. By emulsion polymerization to prepare fine resin particles, after adding charge controllable resin particles as necessary, an organic solvent, aggregating agents such as salts and the like to agglomerate the resin particles, by a method of fusing It is manufactured.

<Suspension Polymerization Method> As an example of the method for producing the toner of the present invention, a charge control resin is dissolved in a polymerizable monomer, and a colorant and, if necessary, a release agent, and further polymerization are used. Various constituent materials such as an initiator are added, and the various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser or the like.
The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in an oil droplet having a desired size as a toner in a water-based medium containing a dispersion stabilizer by using a homomixer or a homogenizer. After that, the stirring mechanism is moved to a reaction device (stirring device) which is a stirring blade described later, and the polymerization reaction is advanced by heating. After completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the toner of the present invention. The “aqueous medium” as referred to in the present invention means one containing at least 50% by mass of water.

<Emulsion Polymerization Method> Further, as a method for producing the toner of the present invention, a method of aggregating / fusing resin particles in an aqueous medium to prepare may be mentioned. This method is not particularly limited, but for example, the methods described in JP-A-5-265252, JP-A-6-329947, and JP-A-9-15904 can be mentioned. That is, a method of salting out, aggregating, and fusing a plurality of fine particles composed of resin particles and a constituent material such as a colorant, or fine particles composed of a resin and a colorant, etc., particularly by dispersing them in water using an emulsifier After that, a coagulant having a critical coagulation concentration or more is added for salting out, and at the same time, the particles are gradually grown while forming fused particles by heat fusion at a temperature not lower than the glass transition temperature of the formed polymer itself. When the desired particle size is reached, a large amount of water is added to stop the particle size growth, and the particle surface is smoothed while heating and stirring to control the shape, and the particles are heated in a fluid state while still containing water. By drying, the toner of the present invention can be formed. Here, a solvent such as alcohol, which is infinitely soluble in water, may be added together with the coagulant.

In the method for producing a toner of the present invention, the composite resin fine particles and the colorant particles formed through at least the step of dissolving the crystalline compound in the polymerizable monomer and then polymerizing the polymerizable monomer are prepared. It is obtained by aggregating / fusing. The toner of the present invention is one in which a crystalline compound is dissolved in a polymerizable monomer, but it may be one which is dissolved and dissolved or one which is melted and dissolved.

Further, the method for producing the toner of the present invention involves aggregating / fusing the composite resin fine particles obtained by the multi-stage polymerization method and the colorant particles. The multi-stage polymerization method will be described below.

<Production Method of Composite Resin Particles Obtained by Multistage Polymerization Method> The production method of the toner of the present invention comprises the following steps.

1: multi-stage polymerization step 2: aggregation / fusion of composite resin particles and colorant particles to obtain toner particles Aggregation / fusion step 3: filtering of the toner particles from a dispersion system of toner particles,
A filtration / washing step for removing a surfactant and the like from the toner particles, a drying step for drying the washed toner particles, and a step for adding an external additive to the dried toner particles.

Each step will be described in detail below. [Multistage Polymerization Step] The multistage polymerization step is a polymerization method carried out in order to expand the molecular weight distribution of the resin particles in order to obtain a toner in which offset generation is prevented. That is, the polymerization reaction is performed in multiple stages in order to form a phase having different molecular weight distributions in one resin particle, and the obtained resin particle has a molecular weight gradient from the center of the particle toward the surface layer. It is intended to be formed. For example, a method of forming a low molecular weight surface layer by first adding a polymerizable monomer and a chain transfer agent after obtaining a high molecular weight resin particle dispersion liquid is adopted.

In the present invention, it is preferable to employ a multi-step polymerization method of three or more steps from the viewpoint of stability of production and crushing strength of the obtained toner. The two-step polymerization method and the three-step polymerization method, which are typical examples of the multi-step polymerization method, will be described below. In the toner obtained by such a multi-step polymerization reaction, a toner having a lower molecular weight on the surface layer is preferable from the viewpoint of crushing strength.

<Two-Step Polymerization Method> The two-step polymerization method is a central part (nucleus) formed from a high molecular weight resin containing a crystalline compound.
And a method for producing composite resin particles composed of an outer layer (shell) formed of a low molecular weight resin.

To explain this method in detail, first, a crystalline compound is dissolved in a monomer to prepare a monomer solution,
This monomer solution is dispersed in an aqueous medium (for example, an aqueous surfactant solution) as oil droplets, and then this system is subjected to a polymerization treatment (first-stage polymerization) to obtain high-molecular-weight resin particles containing a crystalline compound. To prepare a dispersion liquid.

Then, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the dispersion liquid of the resin particles, and the monomer is subjected to a polymerization treatment in the presence of the resin particles (second-stage polymerization). Is a method of forming a coating layer made of a low molecular weight resin (polymer of monomer) on the surface of the resin particles.

<Three-Step Polymerization Method> The three-step polymerization method comprises a central portion (nucleus) formed of a high molecular weight resin, an intermediate layer containing a crystalline compound, and an outer layer (shell) formed of a low molecular weight resin. It is a method for producing composite resin particles.
The toner of the present invention exists as the composite resin particles as described above.

This method will be described in detail. First, the dispersion liquid of resin particles obtained by a polymerization treatment (first-stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). Along with the addition of the above, in the above aqueous medium, a monomer solution obtained by dissolving a crystalline compound in a monomer is dispersed in oil droplets, and then the system is subjected to a polymerization treatment (second-stage polymerization) to obtain a resin. Coating layer (intermediate layer) made of a resin (monomer polymer) containing a crystalline compound on the surface of particles (core particles)
To form a dispersion liquid of composite resin particles (high molecular weight resin-intermediate molecular weight resin).

Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the obtained dispersion liquid of the composite resin particles, and the monomer is subjected to a polymerization treatment in the presence of the composite resin particles ( By three-step polymerization), a coating layer made of a low molecular weight resin (polymer of monomer) is formed on the surface of the composite resin particles. In the above method, by incorporating an intermediate layer, the crystalline compound can be finely and uniformly dispersed, which is preferable.

One feature of the method for producing a toner according to the present invention is to polymerize a polymerizable monomer in an aqueous medium. That is, when forming the resin particles (nucleus particles) or the coating layer (intermediate layer) containing the crystalline compound,
This is a method of obtaining latex particles by dissolving a crystalline compound in a monomer, dispersing the resulting monomer solution in oil droplets in an aqueous medium, and adding a polymerization initiator to this system for polymerization. .

The aqueous medium referred to in the present invention means water 50 to 10
A medium composed of 0 mass% and a water-soluble organic solvent of 0 to 50 mass%. As the water-soluble organic solvent, for example, methanol, ethanol, isopropanol, butanol,
Acetone, methyl ethyl ketone, tetrahydrofuran and the like can be exemplified, and an alcohol-based organic solvent that does not dissolve the obtained resin is preferable.

Here, the disperser for dispersing oil droplets by mechanical energy is not particularly limited, and for example, an agitator "CLEARMIX" (M -Technique Co., Ltd.), ultrasonic disperser, mechanical homogenizer,
Menton Gorin, a pressure type homogenizer, etc. can be mentioned. Further, as the dispersed particle size, 10 to
1000 nm, preferably 50-1000 nm,
More preferably, it is 30 to 300 nm. Here, the phase separation structure of the crystalline compound in the toner particles, that is, the Feret diameter, the shape coefficient, and the variation coefficient thereof may be controlled by giving a distribution to the dispersed particle diameter.

The particle size of the composite resin particles obtained in this polymerization step is 10 to 10 in terms of the weight average particle size measured by using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.).
It is preferably in the range of 1000 nm.

Further, the glass transition temperature (T
g) is preferably in the range of 48 to 74 ° C, more preferably 52 to 64 ° C.

The softening point of the composite resin particles is 95-14.
It is preferably in the range of 0 ° C. The toner of the present invention is
It is obtained by forming a resin layer formed by fusing resin particles by aggregating / fusing on the surfaces of the resin and the colored particles, which will be described below.

[Aggregating / Fusing Step] In this aggregating / fusing step, the composite resin particles obtained by the multi-step polymerization step and the colorant particles are agglomerated / fused (simultaneous salting out and fusing occur. Is performed) to obtain amorphous (non-spherical) toner particles.

The term "aggregation / fusion" used in the present invention means that salting-out (aggregation of particles) and fusion (disappearance of the interface between particles) occur at the same time, or the action of causing salting-out and fusion at the same time. Say. In order to perform salting out and fusion at the same time, particles (composite resin particles, colorant particles) are formed under the temperature condition of the glass transition temperature (Tg) of the resin constituting the composite resin particles or higher.
Need to be aggregated.

In this aggregating / fusing step, internal additive particles (fine particles having a number average primary particle diameter of about 10 to 1000 nm) such as a charge control agent are aggregated / fused together with the composite resin particles and the colorant particles. Good. Also, the colorant particles are
The surface may be modified, and as the surface modifier, a conventionally known one can be used.

The colorant particles are agglomerated / fused in a state of being dispersed in an aqueous medium. The aqueous medium in which the colorant particles are dispersed is preferably an aqueous solution in which the surfactant is dissolved at a concentration equal to or higher than the critical micelle concentration (CMC).

The disperser used to disperse the colorant particles is not particularly limited, but preferably a stirring device "CLEARMIX (CLEAR) equipped with a rotor rotating at high speed.
MIX) "(manufactured by M-Technique Co., Ltd.), ultrasonic disperser,
Examples thereof include a pressure homogenizer such as a mechanical homogenizer, Manton-Gaulin, a pressure homogenizer, and a medium type homogenizer such as a Getzman mill and a diamond fine mill.

In order to coagulate / fuse the composite resin particles and the colorant particles, a salting agent (coagulant) having a critical coagulation concentration or more is added to the dispersion liquid in which the composite resin particles and the colorant particles are dispersed. It is necessary to heat the dispersion to a temperature not lower than the glass transition temperature (Tg) of the composite resin particles as well as to add.

A temperature range suitable for aggregation / fusion is (Tg + 10) to (Tg + 50 ° C.), and particularly preferably (Tg + 15) to (Tg + 40 ° C.). In addition, an organic solvent infinitely soluble in water may be added in order to effectively carry out the fusion.

[Aging Step] The aging step is a step subsequent to the aggregating / fusing step, in which the temperature is kept near the melting point of the crystalline compound, preferably ± 20 ° C., even after the resin particles are fused.
In this step, the crystalline compound is phase-separated by continuing stirring at a constant intensity. In this step, it is possible to control the Feret's diameter of the crystalline compound, the shape factor and the coefficient of variation thereof.

In the present invention, the resin particles and the colorant are salted out, aggregated and fused in an aqueous medium to obtain colored particles (in the present invention, referred to as toner particles), and then the toner particles are water-based. When separated from the medium, it is preferably carried out at a temperature not lower than the Kraft point of the surfactant present in the aqueous medium, and more preferably at a temperature range of Kraft point to (Craft point + 20 ° C.). is there.

The Kraft point is the temperature at which the aqueous solution containing the surfactant begins to turn cloudy, and the Kraft point is measured as follows.

<Measurement of Kraft Point> An aqueous medium used in the steps of salting out, aggregating, and fusing is prepared by adding a coagulant in an amount actually used to the solution, and the solution is prepared at 1 ° C. Stored for 5 days. The solution was then gradually heated with stirring until clear. The temperature at which the solution became clear is defined as the Kraft point.

From the viewpoint of suppressing excessive charging of the toner particles and imparting uniform charging properties, the toner for electrostatic latent image development according to the present invention is used in order to stabilize and maintain the charging properties especially against the environment. , The metal element described above (as a form, metal,
250 to 20 in the toner)
The content is preferably 000 ppm, more preferably 800 to 5000 ppm.

In the present invention, the total value of the divalent (trivalent) metal element used as the aggregating agent and the monovalent metal element added as the aggregating terminator described later is 350 to 35,000 pp.
It is preferably m.

The amount of residual metal ions in the toner was measured by using a fluorescent X-ray analyzer "System 3270" (manufactured by Rigaku Denki Kogyo Co., Ltd.) to determine the metal species of the metal salt used as the aggregating agent (eg calcium chloride). Derived from calcium, etc.)
It can be determined by measuring the intensity of the fluorescent X-ray emitted from As a specific measuring method, a plurality of toners having a known content ratio of the coagulant metal salt are prepared, and 5 g of each toner is used.
Pelletized, and the content ratio of the coagulant metal salt (mass pp
The relationship (calibration curve) between m) and the fluorescent X-ray intensity (peak intensity) from the metal species of the metal salt is measured. Next, the toner (sample) whose content ratio of the aggregating agent metal salt is to be measured is pelletized in the same manner, and the fluorescent X-ray intensity from the metal species of the aggregating agent metal salt is measured to determine the content ratio, that is, "metal ion remaining in the toner You can ask for the "quantity".

[Filtration / Washing Step] In this filtration / washing step, a filtering treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above step, and the filtered toner particles (cake-shaped A cleaning process is performed to remove deposits such as surfactants and salting-out agents from the aggregate. Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using a Nutsche or the like, or a filtration method using a filter press or the like.

[Drying Step] This step is a step of drying the washed toner particles.

Examples of the dryer used in this step include a spray dryer, a vacuum freeze dryer, a vacuum dryer, a stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, and a rotary dryer. It is preferable to use a dryer or a stirring dryer.

The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

The toner particles that have been dried are
When the aggregates are aggregated by the weak attraction between particles, the aggregates may be crushed. Here, as the disintegration processing device,
A mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill or a food processor can be used.

The toner of the present invention forms composite resin particles in the absence of a colorant, adds the dispersion of the colorant particles to the dispersion of the composite resin particles, and mixes the composite resin particles and the colorant particles. It is preferably prepared by aggregating / fusing.

Thus, by carrying out the preparation of the composite resin particles in a system in which no colorant is present, the polymerization reaction for obtaining the composite resin particles is not hindered. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the contamination of the fixing device and the image stain due to the accumulation of the toner do not occur.

Further, as a result of the polymerization reaction being surely performed to obtain the composite resin particles, no monomer or oligomer remains in the obtained toner particles, and the image forming method using the toner can be used. No offensive odor is generated in the heat fixing step.

Further, the obtained toner particles have uniform surface characteristics and a sharp charge amount distribution, so that an image having excellent sharpness can be formed for a long period of time. Such a toner having a uniform composition, molecular weight, and surface characteristics among toner particles maintains good adhesiveness (high fixing strength) to an image support in an image forming method including a fixing step by a contact heating method. However, it is possible to improve the anti-offset property and the wrapping prevention property, and it is possible to obtain an image having an appropriate gloss.

Next, each constituent factor used in the toner manufacturing process will be described in detail. (Polymerizable Monomer) As the polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is used as an essential constituent component, and a crosslinkable monomer is added as necessary. Used. Further, it is desirable to contain at least one kind of monomer having an acidic polar group or basic polar group in the structure as described below. (1) Hydrophobic Monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and conventionally known monomers can be used. Further, one kind or a combination of two or more kinds can be used so as to satisfy the required characteristics.

Specifically, a monovinyl aromatic monomer,
(Meth) acrylic acid ester-based monomer, vinyl ester-based monomer, vinyl ether-based monomer, monoolefin-based monomer, diolefin-based monomer, halogenated olefin-based monomer, etc. may be used. it can.

Examples of vinyl aromatic monomers include:
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Examples thereof include styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

Examples of the (meth) acrylic acid ester-based monomer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate. , Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, γ-aminoacrylate propyl, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.

Examples of vinyl ester-based monomers include vinyl acetate, vinyl propionate, vinyl benzoate, and the like, and examples of vinyl ether-based monomers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether. Etc.

As the mono-olefin type monomer, ethylene, propylene, isobutylene, 1-butene, 1-
Examples thereof include pentene and 4-methyl-1-pentene, and examples of the diolefin-based monomer include butadiene, isoprene and chloroprene.

(2) Crosslinkable Monomer A crosslinkable monomer may be added to improve the properties of the resin particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and diallyl phthalate.

(3) Monomer having acidic polar group As the monomer having an acidic polar group, (a) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH), and (b) ) Examples thereof include α, β-ethylenically unsaturated compounds having a sulfone group (—SO ₃ H).

Α, β-having a carboxyl group of (a)
Examples of ethylenically unsaturated compounds include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid,
Examples thereof include cinnamic acid, maleic acid monobutyl ester, maleic acid monooctyl ester, and metal salts thereof such as Na and Zn.

Examples of the α, β-ethylenically unsaturated compound having a sulfone group (b) include sulfonated styrene and its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and their Na salts. Can be mentioned.

(4) Monomer Having Basic Polar Group As the monomer having a basic polar group, (i) an amine group or a quaternary ammonium group having 1 to 1 carbon atoms
2, preferably 2 to 8, particularly preferably 2 (meth) acrylic acid ester of an aliphatic alcohol, (ii) (meth)
Acrylic amide or optionally 1 to 1 carbon atoms on N
(Meth) acrylic acid amide mono- or di-substituted with 18 alkyl groups, (iii) vinyl compound substituted with a heterocyclic group having N as a ring member, and (iv) N, N-diallyl-alkylamine or A quaternary ammonium salt can be illustrated. Among them, (i) an (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group is preferable as the monomer having a basic polar group.

Examples of the (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the above. Quaternary ammonium salt of 4 compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-
3-methacryloxypropyl trimethyl ammonium salt etc. can be mentioned.

Examples of the (meth) acrylic acid amide of (ii) or the (meth) acrylic acid amide optionally substituted with mono- or dialkyl on N include acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, Methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide,
N-octadecyl acrylamide etc. can be mentioned.

Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) include vinyl pyridine and
Examples thereof include vinylpyrrolidone, vinyl-N-methylpyridinium chloride and vinyl-N-ethylpyridinium chloride.

Examples of N, N-diallyl-alkylamine of (iv) include N, N-diallylmethylammonium chloride, N, N-diallylethylammonium chloride and the like.

(Polymerization Initiator) The radical polymerization initiator used in the present invention can be appropriately used if it is water-soluble. For example, persulfates (eg, potassium persulfate, ammonium persulfate, etc.), azo compounds (eg, 4,4 ′)
-Azobis-4-cyanovaleric acid and its salts, 2,2'-azobis (2-amidinopropane) salt, etc.), peroxide compounds and the like. Further, the above radical polymerization initiator can be combined with a reducing agent as required to form a redox initiator. By using the redox type initiator, the polymerization activity can be increased, the polymerization temperature can be lowered, and further the polymerization time can be shortened, which is a preferable aspect.

The polymerization temperature is not particularly limited as long as it is at least the minimum radical generation temperature of the polymerization initiator, but is in the range of 50 ° C. to 90 ° C., for example. However, it is also possible to carry out the polymerization at room temperature or higher by using a room temperature-initiated polymerization initiator in which a hydrogen peroxide-reducing agent (ascorbic acid or the like) is combined.

(Chain transfer agent) A known chain transfer agent can be used for the purpose of adjusting the molecular weight. The chain transfer agent is not particularly limited, for example, octyl mercaptan, dodecyl mercaptan,
A compound having a mercapto group such as tert-dodecyl mercaptan is used. In particular, the following compounds are preferably used because they suppress odor during heat fixing, obtain a toner having a sharp molecular weight distribution, and are excellent in storage stability, fixing strength, and offset resistance. For example, ethyl thioglycolate, propyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate. , A compound having a mercapto group of ethylene glycol, a compound having a mercapto group of neopentyl glycol, and a compound having a mercapto group of pentaerythritol. Of these, from the viewpoint of suppressing odor at the time of toner heating and fixing, n
-Octyl-3-mercaptopropionic acid ester
Particularly preferred.

(Surfactant) In order to carry out the polymerization using the above-mentioned polymerizable monomer, it is preferable to use a surfactant to disperse oil droplets in an aqueous medium. The surfactant that can be used in this case is not particularly limited, but the following ionic surfactants can be mentioned as examples of suitable compounds.

Examples of the ionic surfactant include sulfonates (sodium dodecylbenzene sulfonate,
Aryl alkyl polyether sodium sulfonate,
3,3-disulfone diphenylurea-4,4-diazo-
Sodium bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol -6-
Sodium sulfonate, etc.), sulfate ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Examples thereof include fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.).

In the present invention, the surfactants represented by the following general formulas (1) and (2) are particularly preferably used. General formula (1) R ¹ (OR ² ) _n OSO ₄ M General formula (2) R ¹ (OR ² ) _n SO ₃ M In general formulas (1) and (2), R ¹ has 6 to 22 carbon atoms.
Is preferably an alkyl group or an arylalkyl group having 8 to 20 carbon atoms, and more preferably an alkyl group or an arylalkyl group having 9 to 16 carbon atoms.

Examples of the alkyl group having 6 to 22 carbon atoms represented by R ¹ include n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-undecyl group and n-hexadecyl group. Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc., and the arylalkyl group represented by R ¹ includes benzyl group, diphenylmethyl group, cinnamyl group, styryl group, trityl group, phenethyl group and the like. .

In the general formulas (1) and (2), R ² represents an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. ² carbon atoms represented by R 2
Examples of the alkylene group of to 6 include ethylene group, trimethylene group, tetramethylene group, propylene group and ethylethylene group.

In the general formulas (1) and (2), n is 1 to
Although it is an integer of 11, it is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 2 to 3.

In the general formulas (1) and (2), the monovalent metal element represented by M includes sodium, potassium and lithium. Among them, sodium is preferably used.

Specific examples of the surfactants represented by the general formulas (1) and (2) are shown below, but the invention is not limited thereto.

Compound (101): C ₁₀ H ₂₁ (OCH ₂ C
H _{2) 2} OSO ₃ Na Compound _{(102): C 10 H 21} (OCH 2 CH 2) 3 OSO 3
Na compound _{(103): C 10 H 21} (OCH 2 CH 2) 2 SO 3 N
a Compound (104): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₃ SO ₃ N
a Compound (105): C ₈ H ₁₇ (OCH ₂ CH (CH ₃ )) ₂
OSO ₃ Na compound (106): C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₂ OSO ₃
In the present invention, from the viewpoint of keeping the charge retention function of the toner in a good state, suppressing fog generation under high temperature and high humidity, and improving transferability, and suppressing increase in charge amount under low temperature and low humidity, From the viewpoint of stabilizing the development amount, the content of the surfactant represented by the general formulas (1) and (2) in the toner for developing an electrostatic latent image is preferably 1 to 1000 ppm, and more preferably Is 5 to 500 ppm, particularly preferably 7 to 100 ppm.

In the present invention, by setting the amount of the surfactant contained in the toner within the above described range, the electrostatic property of the electrostatic latent image developing toner of the present invention is not affected by the environment, It can always be applied and maintained in a uniform and stable state.

The content of the surfactants represented by the above general formulas (1) and (2) contained in the electrostatic latent image developing toner of the present invention is calculated by the following method. It

1 g of the toner is dissolved in 50 ml of chloroform, and the surfactant is extracted from the chloroform layer with 100 ml of ion-exchanged water. The extracted chloroform layer was extracted again with 100 ml of ion-exchanged water to obtain a total of 200 ml of extract liquid (water layer).
Dilute to 00 ml.

Using this diluted solution as a test solution, JIS 33
According to the method defined in Item 636, the color is developed with methylene blue, the absorbance is measured, and the content of the surfactant in the toner is measured from a separately prepared calibration curve.

The structures of the surfactants represented by the general formulas (1) and (2) were determined by analyzing the above extract using 1H-NMR.

In the present invention, a nonionic surfactant may be used. Specifically, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, an ester of polyethylene glycol and higher fatty acid, an alkylphenol. Examples thereof include polyethylene oxide, higher fatty acid and polyethylene glycol ester, higher fatty acid and polypropylene oxide ester, and sorbitan ester.

In the present invention, these surfactants are mainly used as an emulsifier during emulsion polymerization, but may be used for other steps or for other purposes.

(Molecular Weight Distribution of Resin Particles and Toner) The toner of the present invention has a peak or shoulder of 10 in the molecular weight distribution.
20,000 to 1,000,000, and 1,000 to 5
It is preferable that the peak or shoulder of the molecular weight distribution is 100,000 to 1,000,000.
0, 25,000-150,000 and 1,000-5
It is preferably present at 10,000.

The molecular weight of the resin particles is 100,000 to
A resin containing at least a high molecular weight component having a peak or shoulder in the region of 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000 is preferable, and more preferably Is
It is preferable to use an intermediate molecular weight resin having a peak or shoulder in the portion of 15,000 to 100,000.

The method for measuring the molecular weight of the above-mentioned toner or resin is carried out by using GP (THF) as a solvent.
Measurement by C (gel permeation chromatography) is preferable. That is, 1.0 ml of THF is added to 0.5 to 5 mg of the measurement sample, more specifically 1 mg, and stirred at room temperature using a magnetic stirrer or the like to sufficiently dissolve the sample. Next, pore size 0.45
After treatment with a 0.50 μm membrane filter,
Inject into GPC. The GPC measurement conditions are as follows: the column is stabilized at 40 ° C., THF is allowed to flow at a flow rate of 1.0 ml / min, and a sample having a concentration of 1 mg / ml is injected in an amount of about 100 μl. The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC KF-801, 80 manufactured by Showa Denko KK
2, 803, 804, 805, 806, 807 combinations and Tosoh TSKgel G1000H, G20
00H, G3000H, G4000H, G5000H,
G6000H, G7000H, TSK guard c
A combination of columns can be used. A refractive index detector (IR detector) or a UV detector may be used as the detector. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve prepared using monodisperse polystyrene standard particles. About 10 points may be used as polystyrene for preparing the calibration curve.

(Aggregating agent) In the present invention, a metal salt can be preferably used as an aggregating agent in the steps of salting out, aggregating and fusing resin particles from a dispersion liquid of resin particles prepared in an aqueous medium. It is further preferable to use a divalent or trivalent metal salt as the aggregating agent. The reason is that a divalent or trivalent metal salt is preferable to a monovalent metal salt because the critical aggregation concentration (coagulation value or coagulation point) is smaller.

The coagulant used in the present invention is, for example, a monovalent metal salt which is a salt of an alkali metal such as sodium, potassium and lithium, for example, a salt of an alkaline earth metal such as calcium and magnesium and manganese and copper. Examples thereof include divalent metal salts and trivalent metal salts such as iron and aluminum.

Specific examples of these metal salts are shown below.
Examples of the monovalent metal salt include sodium chloride, potassium chloride, lithium chloride, and examples of the divalent metal salt include calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, and the like. Examples include aluminum chloride and iron chloride. These are appropriately selected according to the purpose, but divalent or trivalent metal salts having a small critical aggregation concentration are preferable.

The critical coagulation concentration referred to in the present invention is an index relating to the stability of the dispersion in the aqueous dispersion, and shows the addition concentration of the coagulant when the coagulant is added and the coagulation occurs. This critical coagulation concentration greatly changes depending on the latex itself and the dispersant. For example, it is described in Seizo Okamura et al., Polymer Chemistry 17,601 (1960),
The value can be known by following these descriptions.
Further, as another method, a desired salt is added to the target particle dispersion liquid while changing the concentration, and the ζ potential of the dispersion liquid is measured,
It is also possible to set the salt concentration at the point where the ζ potential changes as the critical aggregation concentration.

In the present invention, the polymer fine particle dispersion is treated with a metal salt so as to have a concentration higher than the critical aggregation concentration. At this time, of course, directly add the metal salt,
Whether to add as an aqueous solution is arbitrarily selected according to the purpose. When it is added as an aqueous solution, the added metal salt needs to have a critical coagulation concentration of the polymer particles or more with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

In the present invention, the concentration of the metal salt may be equal to or higher than the critical aggregation concentration, but is preferably 1.
The amount is 2 times or more, more preferably 1.5 times or more.

(Colorant) The toner of the present invention is obtained by aggregating / fusing the above-mentioned composite resin particles and colorant particles. Examples of the colorant (colorant particles used for aggregation / fusion with the composite resin particles) that constitutes the toner of the present invention include various inorganic pigments, organic pigments, and dyes.
As the inorganic pigment, conventionally known ones can be used. Specific inorganic pigments are exemplified below.

Examples of black pigments include furnace black, channel black, acetylene black,
Carbon black such as thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.

These inorganic pigments can be used alone or in combination of two or more as desired. Further, the amount of the pigment added is 2 to 20% by mass, preferably 3 to 15% by mass, based on the polymer.

When used as a magnetic toner, the above magnetite can be added. In this case, from the viewpoint of imparting a predetermined magnetic characteristic, 20 to 6 is contained in the toner.
It is preferable to add 0% by mass.

Conventionally known organic pigments and dyes can be used, and specific organic pigments and dyes are shown below.

As the magenta or red pigment,
For example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I.
Pigment Red 6, C.I. I. Pigment Red 7,
C. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I.
I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 1
66, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222
Etc.

Examples of pigments for orange or yellow include C.I. I. Pigment Orange 31, C.I.
I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I.
Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 9
4, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 1
85, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 156 and the like.

As the pigment for green or cyan,
For example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

Examples of dyes include C.I. I. Solvent Red 1, 49, 52, 58, 63,
111, 122, C.I. I. Solvent yellow 1
9, the same 44, the same 77, the same 79, the same 81, the same 82, the same 9
3, ibid 98, ibid 103, ibid 104, ibid 112, ibid 16
2, C.I. I. Solvent Blue 25, 36, 60,
No. 70, No. 93, No. 95 and the like can be used, and a mixture thereof can also be used.

These organic pigments and dyes can be used alone or in combination of two or more as desired.
The amount of pigment added is 2 to 20% by mass based on the polymer.
And preferably 3 to 15% by mass.

The colorant (colorant particles) constituting the toner of the present invention may be surface-modified. As the surface modifier, conventionally known ones can be used, and specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent and the like can be preferably used. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane and vinyltrisilane. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane and the like can be mentioned. As the titanium coupling agent, for example, TTS, 9S, 38S, 41B, 46B, 55, 138, which is commercially available under the trade name "Planeact" manufactured by Ajinomoto Co., Inc.
Commercial products A-1, B- manufactured by Nippon Soda Co., Ltd. such as S, 238S.
1, TOT, TST, TAA, TAT, TLA, TO
G, TBSTA, A-10, TBT, B-2, B-4,
B-7, B-10, TBSTA-400, TTS, TO
A-30, TSDMA, TTAB, TTOP and the like can be mentioned. As the aluminum coupling agent, for example,
Examples include "Planeact AL-M" manufactured by Ajinomoto Co., Inc.

The amount of these surface modifiers added is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, based on the colorant. In addition, as a method for modifying the surface of the colorant particles, a method of adding a surface modifier to the dispersion liquid of the colorant particles and heating the system to react them can be mentioned. Colorant particles surface-modified in this way,
It is obtained by collecting by filtration, repeating washing treatment with the same solvent and filtration treatment, and then drying treatment.

(Crystalline Compound) The toner of the present invention has a DS
A crystalline compound having a peak top temperature of the maximum endothermic peak in the endothermic curve measured by C of 70 to 120 ° C. is contained. By containing the crystalline compound, a large plasticizing effect is obtained, and thus the fixability is significantly improved.
Since such a crystalline compound has a low melt viscosity and tends to exist near the surface of the toner particles due to the action of phase separation with the binder resin component, the plasticizing effect on the surface of the toner particles is large, and It has effects on storability, toner fluidity, toner fusion, development durability, and cleaning stability. If the temperature is lower than 70 ° C., the blocking resistance and the preservability are deteriorated, and if the temperature exceeds 120 ° C., a large fixing effect cannot be expected.

Further, i (iso) having a branched structure structurally
-The presence of a paraffin structure or a naphthene structure (cycloparaffin structure) hydrocarbon or an aromatic hydrocarbon further increases the plasticizing action, and therefore the crystalline compound according to the present invention has a linear structure n (normal). -The content of hydrocarbons having a paraffin structure is 92% by mass or more, and the fixability is improved without affecting storage stability, fluidity, fusion resistance, durable development, and cleaning stability. Can be achieved. The n-paraffin content is preferably 93% by mass or more, more preferably 94.
It is at least mass%, particularly preferably at least 95 mass%, and a more excellent fixing property improving effect can be obtained without causing any adverse effect. If it is less than 92% by mass, fluidity, storability,
Either the anti-fusing property or the durable developing property is affected, and the effect of improving the fixability cannot be fully enjoyed.

The crystalline compound according to the present invention is characterized in that the half-value width of the maximum endothermic peak of the endothermic curve measured by DSC is 12 ° C. or less, and the storage stability and the fixability of the toner are balanced. it can. Preferably, this half width is 1
It is 0 ° C or lower, and more preferably 8 ° C or lower. Since the plasticizing effect is efficiently exhibited by the crystalline compound having this half-value width, it is possible to obtain an excellent fixing property improving effect even with a small amount of addition. Further, a decrease in developability by increasing the addition amount of the crystalline compound, a decrease in blocking resistance,
Since the occurrence of cleaning troubles, drum fusion and the like caused by deterioration of fluidity is suppressed, further improvement in fixing property can be expected by increasing the amount of the crystalline compound component. Half-width is 1
When the temperature exceeds 2 ° C., either the storage stability or the fixability is affected, and it becomes difficult to obtain a toner having both the storage stability and the fixability.

It is preferable that the end point onset temperature is 50 ° C. or higher and the end point onset temperature is 100 ° C. or lower in the endothermic peak measured by DSC in order to enhance these effects. When the starting point onset temperature is lower than 50 ° C., the preservability becomes poor, and when the ending point onset temperature exceeds 100 ° C., the fixing property improving effect becomes small.

In order to exert the above effects more strongly, it is preferable that the starting point onset temperature is 55 ° C. or higher and the ending point onset temperature is 95 ° C. or lower, and more preferably
The starting point onset temperature is 60 ° C. or higher and the ending point onset temperature is 90 ° C. or lower.

The plasticizing effect in the present invention not only lowers the melt viscosity of the toner and improves the fixing property of the toner,
In the present invention, since the plasticizing effect in the vicinity of the toner surface is larger, the melt viscosity of the toner in the vicinity of the surface is further lowered, and the anchoring effect to the recording medium is exerted, which greatly contributes to the improvement of fixing property. On the other hand, since an excessive plasticizing action does not occur, it is possible to obtain a toner which has excellent blocking resistance, storage stability, and is easy to use.

Further, in the case of the conventional toner excellent in low-temperature fixing property, when the toner is rubbed by the cleaning blade in the cleaning device or the doctor blade on the sleeve, a part of the toner may be melted to cause toner fusion. . Even in such a case, since the toner of the present invention can save the plasticizing effect to some extent, the occurrence of fusion can be suppressed.

Further, since the toner of the present invention has good fluidity, the movement of the toner in the cleaning device is stable, the toner is clogged in the cleaning device, the cleaning device is damaged, and the amount of toner staying in a specific portion is large. The toner can have excellent fixability without increasing the number of defects and causing cleaning failure. Further, the movement of the toner in the developing device and the toner hopper is stable, and the replenishment of the toner and the mixing of the toner before and after the replenishment are good, so that the developing property is stabilized. Thus, since the stability in the cleaning device and the developing device is increased, the durability stability is improved in the high speed machine and the like in combination with the improvement in the fixing property.

The following compounds can be used as the crystalline compound used in the present invention. The crystalline compound preferably used is a polyolefin obtained by purifying a low molecular weight by-product obtained during the polymerization of a high molecular weight polyolefin; a polyolefin polymerized by using a catalyst such as a Ziegler catalyst or a metallocene catalyst; paraffin wax, Fischer-Tropsch wax; coal, Synthetic hydrocarbon wax synthesized from natural gas or the like by the gintol method, hydrocoal method, Arge method, etc .; synthetic wax having a compound having 1 carbon atom as a monomer; hydrocarbon having functional groups such as hydroxyl group and carboxyl group System wax: There is a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group.

Further, these crystalline compounds have a sharp molecular weight distribution obtained by a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a fused liquid crystal deposition method, or have a low molecular weight. Solid fatty acids, low-molecular weight solid alcohols, low-molecular weight solid compounds, and those from which other impurities have been removed are preferably used.

More preferably used are paraffin wax, Fischer-Tropsch wax, polyethylene synthesized using a metallocene catalyst, and a distillative purified product of a low molecular weight by-product obtained during polyethylene polymerization.

From the viewpoint of dispersibility, paraffin wax and Fischer-Tropsch wax are particularly preferably used, and a remarkable effect of improving the fixing property is obtained and the developing property becomes excellent.

The average carbon number of n-paraffin is 30.
Is preferably 55 to 55, more preferably 32 to
When the number is 50, and particularly the number is 34 to 45, it is possible to balance the improvement in fixing property and the storability and fluidity. When it is less than 30, the storage stability and fluidity are poor, and when it is more than 55, the effect of improving the fixability is reduced.

In the present invention, n-paraffin is refined by using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, a fused liquid crystal precipitation method and the like to perform purification and fractionation with high accuracy. It can be a highly crystalline compound. Among them, a method applying a solvent method in which purification is performed using a poor solvent for the crystalline compound is preferable. For example, solvents such as benzene or toluene and ketones (acetone or methyl ethyl ketone); methyl isobutyl ketone; liquefied propane; trichloroethylene and benzene; dichloroethane and dichloromethane are used.

For example, the following method can be applied. A solvent is added to the starting crystalline compound and heated to completely dissolve the crystalline compound component, and then cooled by a cooler to crystallize the crystalline compound. The crystalline compound of interest is cooled to a predetermined temperature and filtered according to the peak top temperature of the DSC maximum heat peak of the crystalline compound. At this time, strict temperature control is performed and the cooling rate is increased over time to separate isoparaffins, naphthenes, aromatics, and the like, thereby increasing the n-paraffin ratio. Furthermore, the cake of the crystalline compound is washed with a solvent to separate oil, isoparaffin, naphthene, aromatic and the like. By repeating this process, the n-paraffin ratio can be increased. Finally, the solvent is separated by a solvent recovery device to obtain a crystalline compound. Further, after that, if necessary, hydrogen purification, activated clay treatment, and deodorization treatment are performed.
In addition, it is preferable that the raw material crystalline compound has a narrow molecular weight distribution previously obtained by vacuum distillation, gas extraction, or melted liquid crystal deposition in order to increase the n-paraffin ratio.

Conventionally, a crystalline compound having a low melting point such that the peak top temperature of the DSC maximum-class peak is less than 65 ° C. was able to increase the n-paraffin ratio even in the conventional solvent method, but it was 70 ° C. or higher. Those having a high melting point of 75 ° C. or higher were difficult. Although it is possible to fractionally fractionate the molecular weight only by a conventional method such as distillation, it was difficult to sufficiently reduce the amount of isoparaffin and naphthene.

The starting crystalline compound preferably used in this solvent method is slack wax or paraffin wax obtained from petroleum wax, a polymerization by-product obtained at the time of ethylene polymerization, a low molecular weight polyethylene polymerized by using metallocene as a catalyst, There is Fischer-Tropsch wax obtained from coal and natural gas.

Further, the crystalline compound of the present invention can be produced according to JIS K
The kinematic viscosity at 100 ° C. measured by 2283-3.8 is preferably 20 mm ² / s or less,
More preferably, a preferable plasticizing effect is obtained at 1 to 10 mm ² / s or less.

Further, the crystalline compound of the present invention can be produced according to JIS K
When the penetration at 25 ° C. measured by 2235-5.4 is 4 or less, more preferably 3 or less, an excessive plasticizing effect can be prevented.

In the toner of the present invention, the content of these crystalline compounds is 100 parts by mass of the binder resin.
It is used in an amount of 0.2 to 20 parts by mass, and it is effective to use 0.5 to 10 parts by mass.

In the DSC measurement of the present invention, for example,
Perkin Elmer DSC-7 can be used.

The measuring method is ASTM D3418-82.
Carry out according to. As the DSC curve used in the present invention, the DSC curve measured when the temperature is raised once and the previous history is taken, and then the temperature is lowered and the temperature is raised at a temperature rate of 10 ° C./min is used.
The definition of each temperature is defined as follows. -Peak top temperature of the maximum endothermic peak The peak top temperature of the peak with the highest height from the baseline.・ Half width of maximum endothermic peak Temperature width of peak of maximum endothermic peak at half height from baseline to peak top ・ Starting point of endothermic peak Differential value of onset temperature rising curve Temperature at the intersection of the tangent of the curve at the maximum point and the baseline, end point of the endothermic peak Onset temperature When temperature rises The temperature at the intersection of the tangent of the curve and the baseline at the point where the differential value of the curve is the minimum n- The paraffin content can be determined by quantitative analysis by gas chromatography. For example, GC made by Shimadzu
-17A can be used, the column is liquid phase: dimethyl siloxane, film thickness: 0.25 μm, inner diameter × length = 0.25 mm ×
15 m, the detector uses FID.

As measurement conditions, helium is used as a carrier gas. The temperature conditions are as follows: the column constant temperature bath is initially 60 ° C. and the temperature is raised at 40 ° C./min to 160 ° C., then at 15 ° C./min to 350 ° C., and then 7 ° C.
/ Min to raise the temperature to 445 ° C and hold for 4 minutes. The vaporization chamber is heated to 250 ° C / min at the initial 70 ° C,
Hold at 445 ° C. for 0.1 minute. The detector is 445
Hold at ℃. The sample uses heptane as a solvent, and 0.1
Adjust to a mass% concentration.

As a standard substance, carbon numbers 20, 24, 28,
Using n-paraffins of 30, 32, 36, 40, and 44, the peak area for each carbon number of the n-paraffin component is determined by the retention time interpolation and extrapolation. This can be expressed in mass% by determining the content rate for each sample in terms of the content of each carbon number. The other peaks between the normal component peaks are treated as non-normal component (eg, isoparaffin). The n-paraffin content is represented by mass% as the n-paraffin content in all components of the sample, and corresponds to the area ratio of the n-paraffin components in the total peak area.

The average carbon number is calculated from the following formula by mass average in the distribution of n-paraffin. Average carbon number C = (1/100) × ΣCi · Fi (Ci represents the carbon number, Fi represents the percentage of the content of the carbon number Ci). Further, the standard deviation S of the carbon number distribution of n-paraffin is 0. 5
It is preferably from 10 to 10, and more preferably from 1.0 to 8.0.
Is more preferable, and more preferably 1.5 to 6.0.
A well-balanced plastic effect is obtained. N-paraffins having a standard deviation of less than 0.5, especially those having a component close to a single pure paraffin, have high crystallinity and are difficult to be finely dispersed in the toner. On the other hand, when the standard deviation exceeds 10, the plasticizing effect becomes large and the blocking resistance is affected.

Further, in the present invention, the content changes continuously as the carbon number increases or decreases (the content does not change at every other carbon number, and the content smoothly changes with the continuous increase or decrease in the carbon number). Hydrocarbon wax is preferable,
The hardness at room temperature and the low viscosity at the time of melting can be highly achieved at the same time, and excellent storage stability, powder characteristics and fixability can be achieved at the same time.

In the present invention, other crystalline compounds may be used in combination in order to supplement the releasing action. The crystalline compound used in combination preferably has a peak top temperature of the maximum endothermic peak of 90 to 150 ° C. For example, the following crystalline compounds may be mentioned. Waxes such as montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, which are oxides and blocks with vinyl monomers. Includes copolymers and graft modified products. In addition, alcohol wax, fatty acid wax, acid amide wax, ester wax, ketone wax, hydrogenated castor oil and its derivatives, vegetable wax, animal wax, mineral wax, petrolactam.

Among them, the crystalline compound used in combination is preferably a low molecular weight polyolefin obtained by radical polymerization of an olefin under high pressure or by using a Ziegler catalyst / metallocene catalyst, a by-product at this time, and a high molecular weight polyolefin. A low molecular weight polyolefin obtained by decomposition, a hydrocarbon distillation residue obtained by using a catalyst from a synthesis gas consisting of carbon monoxide and hydrogen, or a crystal obtained from a synthetic hydrocarbon obtained by hydrogenating these The compound is used and an antioxidant may be added. Alternatively, it is a linear alcohol wax, a fatty acid wax, an acid amide wax, an ester wax, or a montan derivative. Further, it is also preferable that impurities such as fatty acids have been removed in advance.

From these waxes, the wax was fractionated according to its molecular weight by using a press sweating method, a solvent method, a vacuum distillation, a supercritical gas extraction method, a fractional crystallization (for example, melted liquid crystal precipitation and a crystal filtration). The crystalline compound used in combination is also preferably used in the present invention. In addition, oxidation, block copolymerization, or graft modification may be performed after the fractionation.

The content of these crystalline compounds to be used in combination can be 0.5 to 20 parts by mass in total with the above-mentioned crystalline compound per 100 parts by mass of the binder resin, preferably 1 part by mass. It is effective to use it in an amount of 0.0 to 15 parts by mass.

(Developer) The toner of the present invention may be used as a one-component developer or a two-component developer. When used as a one-component developer, a non-magnetic one-component developer or a toner of 0. A magnetic one-component developer containing magnetic particles of about 1 to 0.5 μm can be used, and any of them can be used.

It is also possible to use it as a two-component developer by mixing it with a carrier. In this case, as the magnetic particles of the carrier, metals such as iron, ferrite and magnetite, and those metals and metals such as aluminum and lead are used. Conventionally known materials such as alloys of can be used. Ferrite particles are particularly preferable. The volume average particle diameter of the magnetic particles is 15 to 100 μm, and more preferably 25 to 80 μm.
μm is preferable.

The volume average particle diameter of the carrier is typically measured by a laser diffraction type particle size distribution measuring apparatus "HELOS" equipped with a wet disperser (SYMPATIC (SYMP).
(Made by ATEC)).

The carrier is preferably one in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, but, for example, an olefin resin, a styrene resin, a styrene-acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for forming the resin-dispersed carrier is not particularly limited, and known ones can be used. For example, styrene-acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. be able to.

Among these resins, a fluorine-containing polymer type resin is particularly preferable, and a fluorinated arylate resin is particularly preferable. For example, 1,1-dihydroperfluoroalcohol or trihydroperfluoroalcohol, tetrahydroperfluoroalcohol, other fluoroalcohol, fluoroacetyl alcohol, N-fluoroalkylsulfonyl-N-alkylaminoalcohol, etc. and acrylic acid or methacrylic acid. A resin obtained by polymerizing an esterification reaction product with (for example, 1,1,1-trifluoroethyl methacrylate), or an aliphatic olefin, a halogenated aliphatic olefin, a conjugated diene-based aliphatic diolefin, an aromatic vinyl-based resin with these Examples thereof include compounds, nitrogen-containing vinyl compounds, and copolymer resins with (meth) acrylic acid alkyl ester.

(Image Forming Method and Image Forming Apparatus) Next, an image forming apparatus used in the image forming method using the toner of the present invention will be described.

FIG. 2 is a sectional view showing an example of the image forming apparatus of the present invention. Reference numeral 4 denotes a photosensitive drum which is a member to be charged, which is formed by forming an organic photoconductor (OPC) which is a photosensitive layer on an outer peripheral surface of a drum base made of aluminum, and rotates at a predetermined speed in an arrow direction. .

In FIG. 2, exposure light is emitted from the semiconductor laser light source 1 based on information read by a document reading device (not shown). This is distributed by the polygon mirror 2 in the direction perpendicular to the paper surface of FIG. 2, and is irradiated on the surface of the photoconductor through the fθ lens 3 that corrects image distortion to form an electrostatic latent image. The photoconductor drum 4 is uniformly charged in advance by the charger 5, and starts rotating clockwise in accordance with the timing of image exposure.

The electrostatic latent image on the surface of the photosensitive drum is the developing device 6
The developed image formed by is transferred by the action of the transfer device 7 to the transfer paper 8 which has been conveyed at a timing. Further, the photosensitive drum 4 and the transfer paper 8 are separated by a separator (separation pole) 9, and the developed image is transferred and carried on the transfer paper 8 and guided to a fixing device 10 to be fixed.

The untransferred toner and the like remaining on the surface of the photoconductor are
It is cleaned by a cleaning device 11 of a cleaning blade type, the residual charge is removed by pre-charge exposure (PCL) 12, and it is uniformly charged again by the charging device 5 for the next image formation.

The method for carrying out toner recycling is not particularly limited, but, for example, the toner collected in the cleaning section is transferred between the toner supply hopper, the developing device or the toner replenishment by a conveyor or a conveyor screw. Examples of the method include mixing in a chamber and supplying the mixture to the developing device. A method of returning directly to the developing device or a method of mixing and supplying the replenishment toner and the recycled toner in the intermediate chamber can be preferably used.

Next, referring to FIG. 3, an example of a perspective view of a toner recycling member is shown. This method is a method in which recycled toner is directly returned to the developing device.

The untransferred toner collected by the cleaning blade 13 is collected in the toner recycling pipe 14 by the carrying screw in the toner cleaning device 11,
Further, it is returned to the developing device 6 from the receiving port 15 of the recycle pipe and used again as a developer.

FIG. 3 is also a perspective view of a process cartridge detachably mountable to the image forming apparatus of the present invention. This Figure 3
In the drawing, the photoconductor unit and the developer unit are shown separately for the sake of easy understanding of the perspective structure, but they can be detachably mounted in the image forming apparatus as a unit in which they are all integrated. In this case, the photoconductor, the developing device, the cleaning device, and the recycling member are integrated to form a process cartridge.

Further, the image forming apparatus may be configured such that a photosensitive drum and a process cartridge including at least one of a charging device, a developing device, a cleaning device, a recycling member and the like are mounted.

Next, the transfer paper is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and of course, a PET base for OHP and the like are also included.

Also, the cleaning blade 13 has a thickness of 1
A rubber-like elastic body of about 30 mm is used, and urethane rubber is most often used as the material. Since this is used in pressure contact with the photoconductor, it is easy to transfer heat. In the present invention, it is desirable to provide a releasing mechanism and keep it away from the photoconductor when the image forming operation is not performed.

The present invention can also be used in an image forming apparatus by electrophotography, particularly an apparatus for forming an electrostatic latent image on a photosensitive member by a modulated beam modulated with digital image data from a computer or the like.

In recent years, in the field of electrophotography in which an electrostatic latent image is formed on a photosensitive member and the latent image is developed to obtain a visible image, it is easy to improve the image quality, convert it, edit it, etc. Research and development of an image forming method using a digital method capable of forming an image are actively performed.

As a scanning optical system optically modulated by a digital image signal from a computer or a copy original employed in this image forming method and apparatus, an acousto-optic modulator is interposed in a laser optical system, and the acousto-optic modulator is used to emit light. There is a device for modulating and a device for directly modulating the laser intensity by using a semiconductor laser. These scanning optical systems perform spot exposure on a uniformly charged photoconductor to form a dot-shaped image.

The beam emitted from the above-mentioned scanning optical system has a circular or elliptical luminance distribution which has a skirt that spreads to the left and right and approximates a normal distribution. For example, in the case of a laser beam, it is usually the main beam on the photoconductor. One or both of the scanning direction and the sub-scanning direction is an extremely narrow round or elliptical shape of 20 to 100 μm.

The toner of the present invention is suitable for an image forming method including a step of passing an image forming support on which a toner image is formed between a heating roller and a pressure roller constituting a fixing device to fix the image. used.

FIG. 4 is a sectional view showing an example of the fixing device used in the image forming method using the toner of the present invention. The fixing device 10 shown in FIG. And a pressure roller 72. In FIG. 4, T is a toner image formed on the transfer paper (image support).

The heating roller 71 has a coating layer 82 made of fluororesin or an elastic material formed on the surface of a core metal 81, and contains a heating member 75 made of a linear heater.

The core metal 81 is made of metal and has an inner diameter of 10 to 70 mm. The metal forming the core metal 81 is not particularly limited, but examples thereof include metals such as iron, aluminum and copper, and alloys thereof.

The core metal 81 has a wall thickness of 0.1 to 15 mm, and is determined in consideration of a balance between a request for energy saving (thinning) and strength (depending on constituent materials). For example,
In order for the core metal made of aluminum to maintain the same strength as the core metal made of iron of 0.57 mm, it is necessary to make the wall thickness 0.8 mm.

As the fluororesin constituting the coating layer 82, PTFE (polytetrafluoroethylene) and P
FA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) etc. can be illustrated.

The coating layer 82 made of fluororesin has a thickness of 1
The thickness is 0 to 500 μm, and preferably 20 to 400 μm.

The coating layer 82 made of fluororesin has a thickness of 1
When the thickness is less than 0 μm, the function as the coating layer cannot be sufficiently exhibited, and the durability as the fixing device cannot be ensured. On the other hand, there is a problem in that the surface of the coating layer having a thickness of more than 500 μm is easily scratched by paper dust, and toner or the like adheres to the scratched portion, resulting in image stain.

As the elastic material forming the coating layer 82, it is preferable to use silicone rubber or silicone sponge rubber having good heat resistance such as LTV, RTV and HTV.

Asker C, which is an elastic material constituting the coating layer 82
The hardness is less than 80 °, preferably less than 60 °.

The thickness of the coating layer 82 made of an elastic material is 0.1 to 30 mm, preferably 0.1 to 20 mm.
It is said that

Asker C, which is an elastic material forming the coating layer 82
When the hardness exceeds 80 ° and the thickness of the coating layer 82 is less than 0.1 mm, the fixing nip cannot be increased, and the effect of soft fixing (for example, smoothed interface Effect of improving color reproducibility by toner layer)
Can't exert.

As the heating member 75, a halogen heater can be preferably used. The pressure roller 72 has a coating layer 84 made of an elastic material formed on the surface of the cored bar 83. The elastic body forming the coating layer 84 is not particularly limited, and various soft rubbers such as urethane rubber and silicone rubber and sponge rubber can be exemplified. The silicone rubbers exemplified as the material forming the coating layer 84 and It is preferable to use silicone sponge rubber.

Asker C, which is an elastic body forming the coating layer 84
The hardness is less than 80 °, preferably less than 70 °, and more preferably less than 60 °.

The coating layer 84 has a thickness of 0.1 to 30 m.
m, preferably 0.1 to 20 mm.

Asker C, which is an elastic body forming the coating layer 84
If the hardness exceeds 80 ° and the thickness of the coating layer 84 is less than 0.1 mm, the fixing nip cannot be increased and the soft fixing effect cannot be exhibited.

The material constituting the core metal 83 is not particularly limited, but metals such as aluminum, iron and copper or alloys thereof can be mentioned.

The contact load (total load) between the heating roller 71 and the pressure roller 72 is usually 40 to 350 N,
Preferably 50-300 N, more preferably 50-2
It is set to 50N. This abutting load is defined in consideration of the strength of the heating roller 71 (thickness of the cored bar 81), for example, 0.
For a heating roller having a cored bar made of iron of 3 mm, it is preferably 250 N or less.

From the viewpoint of offset resistance and fixing property, the nip width is preferably 4 to 10 mm, and the surface pressure of the nip is 0.6 × 10 ⁵ Pa to 1.5.
It is preferably × 10 ⁵ Pa.

As an example of the fixing conditions by the fixing device shown in FIG. 4, the fixing temperature (surface temperature of the heating roller 10) is 150 to 210 ° C., and the fixing linear velocity is 80 to 640 mm.
/ Sec.

[0246]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.
In addition, "part" in a sentence represents a "mass part."

[1] Preparation of Crystalline Compound Crystalline Compounds 1 to 4 Commercially available Fischer-Tropsch wax obtained by using natural gas as a raw material was subjected to vacuum distillation, and distillation conditions were changed to use different fractions in a dissolved state. After repeatedly washing with methyl butyl ketone, the mixture was gradually cooled to obtain crystalline compounds 1 to 4.

Crystalline Compounds 5 to 6 Crystalline compounds 5 to 6 were obtained by washing with polyethylene obtained by using metallocene as a catalyst in the same manner as in the case of crystalline compounds 1 to 4.

Crystalline Compound 7 A mixed solvent of toluene and methyl ethyl ketone was used as a solvent, and the raw material wax was dissolved at 80 ° C. to obtain 0.2 ° C./mi.
The mixture was cooled to 68 ° C. by n, held for 1 hour, and then filtered. The filtered wax was washed twice with a new mixed solvent, the wax was taken out, the solvent was separated by a solvent recovery device, and hydrorefining was performed to obtain a crystalline compound 7.

Crystalline Compound 8 Xylene was used as a solvent, the raw material wax was dissolved at 134 ° C., cooled to 98 ° C. at 0.2 ° C./min, and held for 1 hour, and then filtered. The filtered wax was washed twice with a new solvent, the wax was taken out, the solvent was separated by a solvent recovery device, and hydrorefining was performed to obtain a crystalline compound 8.

The characteristics of the crystalline compounds 1 to 8 are shown in Table 1 below.

[0252]

[Table 1]

[2] Preparation of Crystalline Compound Dispersion Liquid Crystalline Compound Dispersion 1 Crystalline Compound 1 50 parts by mass Anionic surfactant (Neogen SC, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass Ion-exchanged water 200 parts by mass Parts The components were heated to 96 ° C. and dispersed with a homogenizer (Ultra Turrax T50, manufactured by IKA), and then dispersed with a pressure discharge type homogenizer to obtain a crystalline compound dispersion liquid 1.

Crystalline Compound Dispersion Liquids 2-8 Crystalline Compound Dispersion Liquid 2 was prepared in the same manner as Crystalline Compound Dispersion Liquid 1 except that Crystalline Compound 1 was changed to Crystalline Compounds 2-8.
~ 8 was obtained.

[3] Preparation of Resin for Toner [Latex 1HML] (1) Preparation of Core Particles (First Stage Polymerization) Anion was placed in a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device. Surfactant (101) C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ OSO ₃ Na 7.08 g was dissolved in ion-exchanged water 3010 g to prepare a surfactant solution (aqueous medium), and the mixture was stirred under a nitrogen stream at 230 rpm. The temperature in the flask was raised to 80 ° C. while stirring at a speed.

To this surfactant solution, 9.2 g of a polymerization initiator (potassium persulfate: KPS) was added 200 g of ion-exchanged water.
Was added to the solution of the initiator, and the temperature was adjusted to 75 ° C. Then, 70.1 g of styrene and 1 of n-butyl acrylate were added.
A monomer mixture liquid consisting of 9.9 g and methacrylic acid 10.9 g was added dropwise over 1 hour, and this system was heated and stirred at 75 ° C. for 2 hours to perform polymerization (first-stage polymerization), A latex (dispersion of resin particles composed of a high molecular weight resin) was prepared. This is designated as "latex (1H)".

(2) Formation of Intermediate Layer (Second Stage Polymerization) In a flask equipped with a stirrer, styrene 1
A monomer mixture liquid consisting of 05.6 g, 30.0 g of n-butyl acrylate, 6.2 g of methacrylic acid and 5.6 g of n-octyl-3-mercaptopropionic acid ester was added to 90
A monomer solution was prepared by heating at 0 ° C. and dissolving.

On the other hand, the anionic surfactant (the above formula (1
01)) 1.6 g of ion-exchanged water dissolved in 2700 ml of a surfactant solution was heated to 98 ° C., and the latex solution (1H) as a dispersion of core particles was added to the surfactant solution.
After adding 28 g of solid content, a mechanical dispersion machine with a circulation path "CLEARMIX"
A dispersion liquid (emulsion liquid) containing emulsified particles (oil droplets) was prepared by (M-Technique Co., Ltd.).

Then, to this dispersion (emulsion), an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion-exchanged water and 750 ml of ion-exchanged water were added, and this system was added to 98 Polymerization (second-stage polymerization) is performed by heating and stirring at ℃ for 12 hours to obtain latex (dispersion liquid of composite resin particles having a structure in which the surface of resin particles made of high molecular weight resin is coated with intermediate molecular weight resin). Obtained. This is designated as "latex (1HM)".

(3) Formation of Outer Layer (Third Stage Polymerization) Into the latex (1HM) obtained as described above, an initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water Was added, and under the temperature condition of 80 ° C., 300 g of styrene and 95% of n-butyl acrylate were added.
g, 15.3 g of methacrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester were added dropwise over 1 hour. After completion of the dropping, polymerization (third stage polymerization) was carried out by heating and stirring for 2 hours, followed by cooling to 28 ° C. and latex (a central part made of a high molecular weight resin, an intermediate layer made of an intermediate molecular weight resin, and a low layer). A dispersion liquid of composite resin particles having an outer layer made of a molecular weight resin was obtained.

This latex is referred to as "latex (1HM
L) ”. The composite resin particles constituting this latex (1HML) had peak molecular weights of 138,000, 80,000 and 13,000, and the weight average particle diameter of the composite resin particles was 122 nm.

[Latex 2HML] Surfactant (10
In the same manner as latex (1HML), except that anionic surfactant (sodium dodecylbenzene sulfonate: SDS) 7.08 g was used instead of 1), a latex (a central part made of a high molecular weight resin, A dispersion liquid of composite resin particles having an intermediate layer made of an intermediate molecular weight resin and an outer layer made of a low molecular weight resin was obtained. This latex is referred to as "latex (2HML)".

The composite resin particles constituting this latex (2HML) are 138,000, 80,000 and 1
It has a peak molecular weight of 2,000, and
The weight average particle diameter of the composite resin particles was 110 nm.

[Colored Particles 1 to 6 and Comparative Colored Particles 1 to 1
Production of 4] 59.0 g of anionic surfactant (101)
Is dissolved in 1600 ml of ion-exchanged water with stirring, and while stirring this solution, carbon black "Regal 330"
A dispersion of colorant particles (hereinafter referred to as "Colorant dispersion 1") was gradually added with 420.0 g (manufactured by Cabot) and then subjected to a dispersion treatment using "CLEARMIX" (manufactured by M-Technique). Was prepared). The particle size of the colorant particles in this colorant dispersion was measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), and the weight average particle size was 89 nm.

Latex 1HML 420.7 g (as solid content), ion-exchanged water 900 g, colorant dispersion liquid 166 g and crystalline compound dispersion liquids 1 to 8 in combination of Table 2, 210 g each, temperature sensor, cooling tube , Reaction vessel equipped with nitrogen introducing device and stirring device (four-necked flask)
And stirred. After adjusting the temperature in the container to 30 ℃,
A 5 mol / L sodium hydroxide aqueous solution was added to this solution to adjust the pH to 8 to 10.0.

Then, magnesium chloride hexahydrate 1
An aqueous solution prepared by dissolving 2.1 g in 1000 ml of ion-exchanged water was added with stirring at 30 ° C. for 10 minutes. The temperature was started after standing for 3 minutes, and the system was heated to 90 ° C. over 6 to 60 minutes to generate associated particles. In that state, the particle size of the associated particles was measured with a “Coulter counter TA-II”, and when the number average particle size reached 4 to 7 μm, 80.4 g of sodium chloride was added to ion-exchanged water 1
Aqueous solution dissolved in 000 ml was added to stop grain growth, and as aging treatment, at a liquid temperature of 85 to 98 ° C., 2 to
By heating and stirring for 12 hours, fusion of particles and phase separation of crystalline compound were continued (aging step).

Thereafter, the mixture was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped. The formed associated particles are filtered, repeatedly washed with ion-exchanged water at 45 ° C., and then dried with warm air at 40 ° C.,
Colored particles were obtained.

By controlling the pH of the aggregating step, the temperature of the aging treatment step, the aging time, and the stirring strength, the crystalline compound, the colorant dispersion state, the shape and the coefficient of variation of the shape coefficient are controlled, and further, in the liquid. By adjusting the coefficient of variation of the toner particle size and the particle size distribution by classification, the colored particles 1 to 6 and the comparative colored particles 1 to 4 having the dispersion state, the shape characteristics, and the sea-island structure characteristics shown in Table 2 are obtained. (These are shown as Examples 1 to 6 and Comparative Examples 1 to 4, respectively).

[0269]

[Table 2]

Each of the colored particles 1 to 6 and the comparative colored particles 1 to 4 obtained as described above has an average primary particle diameter of 35.
nm hydrophobic silica 0.8 parts by mass, average primary particle size 25
1.0 parts by mass of hydrophobic titanium oxide of 10 nm is added,
The rotating blade peripheral speed of the Henschel mixer was set to 30 m / s and mixed for 25 minutes. Incidentally, for these colored particles,
The shape and particle size do not change with the addition of external additives.

Manufacture of Carrier Manufacture of Ferrite Core Material 18 mol% of MnO, 4 mol% of MgO, Fe ₂ O ₃
78 mol% was pulverized with a wet ball mill for 2 hours, mixed and dried, and then temporarily calcined by holding at 900 ° C. for 2 hours, and this was pulverized with a ball mill for 3 hours to form a slurry. A dispersant and a binder were added, the mixture was granulated with a spray dryer, dried, and then main-calcined at 1200 ° C. for 3 hours to obtain ferrite core material particles having a resistance value of 4.3 × 10 ⁸ Ω · cm.

Production of coating resin First, 1,1,1 was prepared by an emulsion polymerization method using sodium benzenesulfonate having an alkyl group having 12 carbon atoms as a surfactant and the concentration in an aqueous medium was 0.3% by mass.
A copolymer of 1-trifluoroethyl methacrylate / methyl methacrylate (copolymerization ratio 2/8) was synthesized, and the volume average primary particle size was 0.1 μm and the weight average molecular weight (Mw) was 20.
50,000, number average molecular weight (Mn) 91,000, Mw
Resin fine particles having /Mn=2.2, a softening point temperature (Tsp) of 230 ° C. and a glass transition temperature (Tg) of 110 ° C. were obtained.
The resin fine particles were azeotroped with water in the emulsified state, and the residual monomer amount was 510 ppm.

Next, 100 parts by mass of the ferrite core material particles and 2 parts by mass of the resin fine particles are put into a high-speed stirring mixer having a stirring blade and stirred and mixed at 120 ° C. for 30 minutes to utilize the action of mechanical impact force. Thus, a resin-coated carrier having a volume average particle diameter of 61 μm was obtained.

Manufacture of Developer Each of the colored particles added with the external additive and the carrier were mixed to prepare a developer having a toner concentration of 6% by mass.

Production of Photosensitive Member P1 A cylindrical conductive support having a length of 380 mm and a diameter of 60 mm was coated with the following coating solution to prepare a photosensitive member P1.

<Undercoat Layer> Titanium chelate compound (TC-750, manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml Cylindrical conductive support using the above coating liquid A film thickness of 0.
It was applied so as to have a thickness of 5 μm.

<Charge Generation Layer> Y-type titanyl phthalocyanine (titanyl phthalocyanine having a maximum peak at 27.2 ° of Bragg angle 2θ (± 0.2 °) in Cu-Kα characteristic X-ray diffraction spectrum measurement) 60 g Silicone modified Butyral resin (X-40-1211M: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml was mixed and dispersed for 10 hours using a sand mill to prepare a charge generation layer coating solution. This coating solution was applied onto the undercoat layer by a dip coating method to form a charge generation layer having a thickness of 0.2 μm.

<Charge Transport Layer> Charge Transport Material N- (4-Methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g Antioxidant Agent (Exemplified compound 1-3) 6 g Dichloromethane 2000 ml was mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied onto the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

<Protective Layer> Methyltrimethoxysilane 150 g Dimethyldimethoxysilane 30 g Reactive charge transporting compound (Exemplary compound B-1) 15 g Polyvinylidene fluoride particles (volume average particle size 0.2 μm) 10 g Antioxidant (Exemplary compound 2-1) 0.75 g 2-propanol 75 g 3% acetic acid 5 g were mixed to prepare a coating liquid for the protective layer. A resin layer having a thickness of 2 μm was formed on the charge transport layer by using a circular amount regulating type coating device, and the coating solution was heated and cured at 120 ° C. for 1 hour to form a siloxane resin protective layer.

[0280]

[Chemical 1]

As an evaluation machine, a photoconductor P1 and each developing device are installed in a digital copying machine (corona charging, laser exposure, reversal development, electrostatic transfer, nail separation, cleaning blade) having the image forming process shown in FIG. The agent was mounted and evaluated. The above digital copying machine was evaluated under the following conditions.

Charging conditions Charging device: Scorotron charger, initial charging potential of -750
V exposure condition Set exposure amount to make exposed part potential −50 V Development condition DC bias; −550 V transfer pole; corona charging method Further, as fixing device, iron is used as core metal, and surface is 25 μm thick PFA. Using a heating roller having a surface roughness Ra of 0.8 μm coated with (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer),
An iron cored bar was used as the pressure roller, and a pressure roller having a surface roughness Ra of 0.8 μm was used in which a 120 μm thick PFA tube was coated on the HTV silicone rubber. The nip width is 3.8 mm and the linear velocity is 420 mm /
sec.

The cleaning mechanism of the fixing device and the silicone oil supply mechanism are not mounted. The fixing temperature was controlled by the surface temperature of the heating roller and set to 165 ° C.

The copying conditions are low temperature and low humidity environment (10 ° C., 20 ° C.).
% RH), 500,000 continuous copies were made, and the following evaluation criteria were used to evaluate the offset resistance of copy images, stains during bookbinding, standard glossiness, cleaning properties, and occurrence of filming on the photoconductor.

The evaluation was performed by copying an original image in which a character image having a pixel ratio of 7%, a human face photograph image, a solid white image, and a solid black image are equally divided into quarters on A4 neutral paper.
The halftone, solid white image, solid black image, and fine line image were evaluated for every 10,000 sheets.

Offset resistance A 1000 sheets of continuous transfer paper of A4 size were continuously printed, and then a white paper was printed, and the occurrence of stains on the white paper due to offset and the toner stain on the surface of the heating roller were visually evaluated. As the transfer paper used for evaluation, fine paper 200 g / m
A line image having a width of 0.3 mm and a length of 150 mm parallel to the paper traveling direction (heat roller circumferential direction) was formed using the thick paper of No. ² .

⊚: No image offset on the white paper and toner stain on the heating roller are observed at all ◯: No image offset on the white paper is confirmed, but toner stain is observed on the heating roller ×: Image on the white paper The evaluation rank in which the offset is confirmed is ⊚, ◯ is pass, and x is fail.

Dirt during bookbinding Double-sided printing on plain paper with 64 g / m ²
After making a booklet, stains on the white background were observed after turning 20 times.

Rank A: No stain is generated on the image Rank B: Very slight stain is generated on the image (no practical problem) Rank C: Slight stain is generated on the image (No problem in practical use) Level) Rank D: A, B, and C were evaluated as acceptable and D was unacceptable as evaluation ranks that were not suitable for practical use due to stains on the image.

Standard glossiness The standard glossiness is the gloss meter VGS-1D at an incident angle of 75 ° in an image portion in which 90% or more of a recording material is covered with an image forming material (toner for developing an electrostatic latent image).
(Manufactured by Nippon Denshoku Industries Co., Ltd.).

If the standard glossiness is 17 to 37 degrees, the photographic image has a three-dimensional effect due to the appropriate glossiness and the characters are easy to read.

⊚: Standard glossiness of 22 to 32 degrees ◯: Standard glossiness of 17 to less than 22 degrees or standard glossiness of 3
2 or more but 37 degrees or less x: Standard glossiness of less than 17 degrees, or higher than 37 degrees The evaluation ranks were ⊚ and ◯, and x was disqualified.

Toner Filming of Photoreceptor The presence or absence of filming was determined by visually observing the surface of the photoreceptor after the above-mentioned continuous 500,000 copies.

Uniformity of Halftone The uniformity of the halftone image due to the toner filming on the photoreceptor, the cleaning property, and the transfer property variation after the continuous 500,000 copies were evaluated. The rank was evaluated as follows.

Rank A: Uniform image without unevenness Rank B: Presence of extremely thin stripe-like unevenness Rank C: Level with some thin stripe-like unevenness but practically no problem Rank D: Clear stripes In the presence evaluation rank of several unevennesses, A to C were passed and D was not passed.

A 10% halftone dot image was formed on the entire surface of the fine dot dust image, and dust around the dots was observed with a magnifying glass. "◎" indicates that dust is hardly detected, "○" indicates that there is a slight dust, but is not noticeable without attention, and "X" indicates that dust can be easily detected.

[0297] "⊚" and "∘" were accepted and "x" was rejected. Developer life The fog density in the non-image area (relative density to the transfer paper measured with a Macbeth densitometer) is 0.006 continuously for 500 or more
It evaluated by the number of sheets which became above.

The evaluation results are shown in Table 3.

[0299]

[Table 3]

As is clear from the above examples, Examples 1 to 6 using the toner of the present invention have good offset resistance,
It was also confirmed that an image having an appropriate gloss could be obtained. Further, in the toner of the present invention, the crystalline compound having a releasing property oozes out onto the surface of the fixed image, so that it is resistant to rubbing and contaminates other transfer paper even when printed materials are stacked and stored during bookbinding. It was confirmed that there was nothing. Further, since the amount of the crystalline compound released from the toner is reduced, the life of the developer is extended, the toner filming of the photoreceptor does not occur, and the fluidity is improved, so that the toner has excellent image characteristics such as excellent cleaning property. It was confirmed that there is.

[0301]

EFFECTS OF THE INVENTION Firstly, according to the present invention, it is possible to form a high-quality image which is excellent in offset resistance corresponding to oilless fixing, has an appropriate gloss on the image surface, and is free from image stains for a long period of time. It is possible to provide a toner for developing an electrostatic latent image and a method for producing the same.

Secondly, it is possible to provide a toner for developing an electrostatic latent image which prevents occurrence of toner filming on the photosensitive member and has good cleaning property, and a method for producing the same.

Thirdly, an electrostatic latent image which has strength against rubbing and contact between papers and which has a strong fixing property without contaminating papers even when printed materials are stored in piles such as during bookbinding. An image developing toner and a method for producing the same can be provided.

Further, fourthly, an electrostatic latent image developing toner which is excellent in developability and fine dot reproducibility and is excellent in fine line reproducibility, and which is capable of stably forming a high quality image for a long period of time. A manufacturing method can be provided.

Fifthly, it is possible to provide a developer, an image forming method and an image forming apparatus using the above excellent toner.

[Brief description of drawings]

FIG. 1 is a schematic diagram illustrating toner particles having a sea-island structure.

FIG. 2 is a cross-sectional configuration diagram showing an example of an image forming apparatus applied to the present invention.

FIG. 3 is a perspective view of a toner recycling member.

FIG. 4 is a sectional view of a fixing device applied to the present invention.

[Explanation of symbols]

1 Semiconductor laser light source 2 polygon mirror 3 fθ lens 4 photoconductor drum 5 charger 6 developer 7 Transfer device 8 Transfer paper 9 separator 10 Fixing device 11 Cleaning device 12 Exposure before charging 13 Cleaning blade 14 Toner recycling pipe 15 Recycle pipe socket 71 heating roller 72 Pressure roller 75 Heating member 81, 83 core metal 82, 84 coating layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshimori Nishimori             2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica stock             In the company F-term (reference) 2H005 AA06 AB03 AB06 CA13 CA14                       EA03 EA05 EA10

Claims (13)

[Claims] 1. A toner for developing an electrostatic latent image containing at least a resin, a colorant and a crystalline compound, comprising:
A toner for developing an electrostatic latent image, which satisfies the condition of. The toner particles have a sea-island structure, and the average horizontal ferret diameter of the islands of the crystalline compound is 200.
~ 900 nm, and the ferret horizontal diameter variation coefficient is 4
It is 0% or less. The crystalline compound is n (normal) -paraffin 9
It contains 2% by mass or more and a plurality of n-paraffin components having different carbon numbers, and the peak end temperature of the maximum endothermic peak in the endothermic curve measured by DSC is 70 to 1
20 ° C., the peak half width of the maximum endothermic peak is 12
℃ or less, and the penetration is 4 or less. 2. A toner for developing an electrostatic latent image containing at least a resin, a colorant and a crystalline compound, comprising:
A toner for developing an electrostatic latent image, which satisfies the condition of. The toner particles have a sea-island structure, and the toner having 5 to 40 crystalline compound islands per toner particle accounts for 99% or more of the total. The crystalline compound is molecularly distilled Fischer-Tropsch wax or polyethylene using a metallocene catalyst. 3. A toner for developing an electrostatic latent image containing at least a resin, a colorant and a crystalline compound, comprising:
A toner for developing an electrostatic latent image, which satisfies the condition of. The toner particles have a sea-island structure, an average value of the island shape factor of the crystalline compound is 110 to 200, the variation coefficient is 35% or less, and the island shape factor is 100.
The proportion of islands in the range of from 110 to 30 is 30% by number or less of all the islands present in the toner particles, and the shape factor is 200.
The ratio of the above islands is 10% by number or less of all the islands present in the toner particles. The crystalline compound is n (normal) -paraffin 9
It contains 2% by mass or more and a plurality of n-paraffin components having different carbon numbers, and the peak end temperature of the maximum endothermic peak in the endothermic curve measured by DSC is 70 to 1
20 ° C., the peak half width of the maximum endothermic peak is 12
℃ or less, and the penetration is 4 or less. 4. A toner for electrostatic latent image development containing at least a resin, a colorant and a crystalline compound, wherein the toner particles have a sea-island structure, and the resin constitutes a sea part, The toner for developing an electrostatic latent image according to claim 1, wherein the toner comprises a compound island and a colorant island. 5. The electrostatic latent image developing toner according to claim 1, wherein the toner has a number average particle diameter of 3 to 9 μm. Toner for image development. 6. The electrostatic latent image developing toner manufacturing method according to claim 1, wherein at least the polymerizable monomer is polymerized in an aqueous medium. Method for producing latent image developing toner. 7. The electrostatic latent image developing toner manufacturing method according to claim 1, wherein at least the resin particles are aggregated / fused in an aqueous medium. Method for producing latent image developing toner. 8. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the composite resin fine particles obtained by the multistage polymerization method and the colorant particles are aggregated / fused. A method for producing a toner for developing an electrostatic latent image, which is obtained by 9. An electrostatic latent image developing toner produced by the method for producing an electrostatic latent image developing toner according to claim 6. 10. A developer containing the toner for developing an electrostatic latent image according to claim 1. Description: 11. A developer containing an electrostatic latent image developing toner produced by the method for producing an electrostatic latent image developing toner according to claim 6. 12. An image forming method comprising a step of converting an electrostatic latent image formed on a photoconductor into a visible image, transferring the visible image onto a recording paper, and heating and fixing the visible image. 10. An image forming method, which is performed using the toner for developing an electrostatic latent image according to any one of 5 and 9. 13. An image forming apparatus using the image forming method according to claim 12, wherein the image exposure irradiation onto the photoconductor is performed by digital exposure.