JP2015084076A - Toner for electrophotography - Google Patents

Abstract

An object of the present invention is to provide a toner capable of achieving both low-temperature fixability and heat-resistant storage stability at a high level. An electrophotographic toner containing at least a binder resin, wherein a maximum peak temperature of heat of fusion at a temperature rise measured by a differential scanning calorimeter (DSC) is in a range from 50 ° C. to 70 ° C. The free induction decay curve obtained by the pulse NMR method having a heat of fusion of 10 J / g to 30 J / g is separated into two curves derived from the hard component and the soft component constituting the toner. In this case, the electron is characterized in that the soft component spin-spin relaxation time T2tl (100) at 100 ° C. is 20 ms or more and the proton ratio Htl (100) of the soft component is 0.2 or more. Toner for photography. [Selection figure] None

Description

  The present invention relates to an electrophotographic toner.

  Conventionally, in an electrophotographic image forming apparatus or the like, a latent image formed electrically or magnetically has been visualized with an electrophotographic toner (hereinafter also simply referred to as “toner”). . For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper, and then fixed onto the transfer material such as paper. In the fixing process for fixing the toner image on the transfer paper, a heat fixing method such as a heating roller fixing method or a heating belt fixing method is widely used because of its energy efficiency.

  In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and can provide high-quality images. In order to achieve low-temperature fixability of the toner, there is a method of lowering the softening temperature of the toner binder resin. However, if the softening temperature of the binder resin is low, a part of the toner image adheres to the surface of the fixing member at the time of fixing, and so-called offset (hereinafter also referred to as hot offset) occurs on the copy paper. It becomes easy. Further, the heat-resistant storage stability of the toner is lowered, and so-called blocking occurs in which toner particles are fused with each other particularly in a high temperature environment. In addition, in the developing device, there are problems that the toner is fused and contaminated inside the developing device and the carrier, and that the toner is liable to film on the surface of the photoreceptor.

  As a technique that can solve these problems, many toners using a crystalline resin and an amorphous resin in combination have been proposed (see, for example, Patent Documents 1 and 2). These were excellent in compatibility between low-temperature fixability and heat-resistant storage stability as compared with conventional toners composed only of amorphous resins. Furthermore, proposals have been made to further improve the compatibility between the low-temperature fixability and the heat-resistant storage stability by improving the dispersibility of the crystalline resin in the toner (see, for example, Patent Documents 3 to 4).

However, further fine dispersion of the crystalline resin is required in order to achieve both low-temperature fixability and heat-resistant storage stability at a high level.
As in Patent Document 3, a combination of resin skeletons in which the amorphous resin is styrene acrylic and the crystalline resin is polyester has low compatibility, and it is difficult to further improve the dispersibility of the crystalline resin. In Patent Document 4, fine dispersion is achieved by adjusting the compatibility between the amorphous polyester and the crystalline polyester so that the crystalline polyester is not exposed to a large amount on the surface. When the compatibility of the polyester is improved, there is a problem that the interfacial area between the amorphous polyester and the crystalline polyester becomes large, in addition to the large amount of the crystalline polyester exposed on the surface. At the interface, amorphous polyester and crystalline polyester exist in a mixed state, but crystalline polyester exists in a non-crystallized state, so the thermal properties are significantly lower than amorphous polyester. Softens at low temperatures. For this reason, the more the interfacial components, the worse the heat-resistant storage stability, which hinders compatibility between the low-temperature fixability and the heat-resistant storage stability. In particular, in a state where the crystalline polyester is finely dispersed, a large amount of the crystalline polyester is present near the surface, and this tendency becomes remarkable.
Therefore, the present situation is that there is a need to provide a toner that can solve the above-described problems and can achieve both low-temperature fixability and heat-resistant storage stability at a high level.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner that can achieve both low-temperature fixability and heat-resistant storage stability at a high level.

Means for solving the problems are as follows. That is,
An electrophotographic toner containing at least a binder resin,
The maximum peak temperature of the heat of fusion measured by differential scanning calorimeter (DSC) is in the range of 50 ° C. to 70 ° C. and the heat of fusion is 10 J / g to 30 J / g,
When the free induction decay curve obtained by the pulse NMR method is separated into two curves derived from the hard component and the soft component constituting the toner, the spin-spin relaxation time T of the soft component at 100 ° C. _{An electrophotographic toner} , wherein _2tl (100) is 20 ms or more and a proton ratio H _tl (100) of the soft component is 0.2 or more.

  According to the present invention, the above-described problems can be solved, and a toner capable of achieving both low-temperature fixability and heat-resistant storage stability at a high level can be provided.

1 is a schematic explanatory diagram illustrating an example of an image forming apparatus according to the present invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus which concerns on this invention. 1 is a schematic explanatory diagram illustrating an example of an image forming apparatus (tandem color image forming apparatus) according to the present invention. FIG. 4 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. 3. It is a figure which shows the example of the free induction decay curve of the electrophotographic toner of this invention measured by a pulse NMR method, and a hard component and a soft component separation. It is a figure which shows the example of the free induction decay curve measured by the pulse NMR method of the non-crosslinking component of binder resin, and a hard component, a soft component, and interface component separation.

By controlling the skeleton and molecular weight of the crystalline resin and the amorphous resin contained in the binder resin and the toner production conditions, the present inventors can control the dispersion diameter of the crystalline resin, the amorphous resin, and the crystalline property. We have found technical means to control the interfacial area of the resin and achieve a substantially clearer functional separation between the amorphous resin and the crystalline resin. By using this technique, the toner can be designed. The toner can solve the problem.
The embodiment of the present invention will be described in detail. Here, the toner, the manufacturing method and material of the developer, and the overall system relating to the electrophotographic process that are used in the present invention can be used as long as the conditions are satisfied.

The toner for electrophotography of the present invention is
An electrophotographic toner containing at least a binder resin,
The maximum peak temperature of the heat of fusion measured by differential scanning calorimeter (DSC) is in the range of 50 ° C. to 70 ° C. and the heat of fusion is 10 J / g to 30 J / g,
When the free induction decay curve obtained by the pulse NMR method is separated into two curves derived from the hard component and the soft component constituting the toner, the spin-spin relaxation time T of the soft component at 100 ° C. _2tl (100) is 20 ms or more, and the proton ratio H _tl (100) of the soft component is 0.2 or more.

-Amount of crystalline resin component in toner-
Since the crystalline resin component introduced for the purpose of low-temperature fixability and heat-resistant storage stability is designed to have a melting point lower than the fixing temperature, the glass transition temperature is below room temperature. Therefore, if the content is too small, the target effect cannot be obtained. On the other hand, if the content is too large, plastic deformation due to the softness of the crystalline resin is likely to occur, so that a toner agglomeration occurs in the developing device. For this reason, an appropriate range exists for the content of the crystalline resin component. The maximum peak temperature of the heat of fusion at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the toner depends on the maximum peak temperature of the heat of fusion of the crystalline resin component. The amount of heat of fusion at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the toner indicates the content of the crystalline resin component, and the content of the crystalline resin component can be confirmed by the amount of heat of fusion at the time of temperature rise.

A differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)) measures the temperature of the reference material and the sample while giving a constant heat, and determines the thermal properties of the sample as a temperature difference. It is a device that measures endothermic reactions and exothermic reactions due to changes in the state of the sample, making it possible to grasp the phase transition and crystallization of the structure, and evaluate physical properties of polymer materials, organic materials, metals, ceramics, etc. Widely applied to. When the crystalline resin component is dispersed in the amorphous resin component, the heat of crystal fusion at the crystallized portion of the crystalline resin component is measured as an exothermic peak as the temperature rises.
In the present invention, the maximum peak temperature of the heat of fusion at the time of temperature rise of the toner needs to be in the range of 50 ° C. to 70 ° C., and more preferably in the range of 50 ° C. to 65 ° C. The heat of fusion needs to be 10 J / g or more and 30 J / g or less, and more preferably 15 J / g or more and 30 J / g or less.
For example, using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation), measurement is performed under the following measurement conditions.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C
A graph of “endothermic heat generation” and “temperature” is drawn from the obtained measurement data, and the heat of fusion is obtained from the area value surrounded by the baseline and the endothermic peak. In addition, it is also possible to isolate | separate an enthalpy relaxation component by applying a modulation of +/- 0.3 degreeC at the time of temperature rising.

--Softening component at 100 ° C. in toner--
In a situation where the amorphous resin component and the crystalline resin component are in contact with each other, if the crystalline region of the crystalline resin component melts, the adjacent region of the amorphous resin component is softened. In the toner, these components are considered to contribute to the low-temperature fixability. The degree of softening is determined by various characteristics including the thermal characteristics of the amorphous resin component, but it must be sufficiently softened at the time of fixing. With respect to the width of the softened region, since the region where the crystalline resin component is dispersed in the amorphous resin component is more finely dispersed and the region in contact with each other is wider, the effect is higher.
The degree of softening at 100 ° C. in the toner and its width are measured by pulsed NMR. Details will be described below.

The pulse NMR method is used when analyzing the molecular mobility of a polymer material, and is an effective means for evaluating the molecular mobility and heterogeneity of a heterogeneous composite polymer material such as a toner. When a polymer material is irradiated with a pulsed electromagnetic wave in a magnetic field, the spin energy of hydrogen nuclei in the polymer material transitions to a high energy state, and then follows a relaxation process in which the hydrogen nuclei return to the original energy state again. Pulsed NMR observes this relaxation process, and a relaxation curve in which magnetization decays with respect to time is obtained. Here, this relaxation curve is called a free induction decay curve (FID: Free Induction Decay), and the relaxation time obtained from this is the spin-spin relaxation time (T ₂ ). The free induction decay curve is a superposition of relaxation curves derived from multiple components with different molecular motility. By fitting the free induction decay curve using the nonlinear least squares method, it is separated into relaxation curves derived from each component. can do. Thereby, the hydrogen element ratio (proton ratio) and the spin-spin relaxation time of each component can be calculated. The standard deviation by the fitting is desirably smaller, and the fitting is performed so that the proton intensity and the spin-spin relaxation time obtained are within a range.
The hard component having low molecular mobility is generally a component derived from a hard material having high crosslinkability and crystallinity, and conversely, the soft component having high molecular mobility is derived from a soft material. In the case of the crystalline resin in the present invention, it is considered that the crystallized region is a hard component and the non-crystallized region is a soft component. On the other hand, it is known that the spin-spin relaxation time is shorter as the molecular mobility is lower and longer as the molecular mobility is higher.

Therefore, when the free induction decay curve is separated into two, the relaxation curve having a short spin-spin relaxation time (T _2ts ) is a hard component, and the relaxation curve having a long spin-spin relaxation time (T _2tl ) is soft. It is an ingredient.

The proton ratio of each component is obtained from each relaxation curve, and the proton ratios of the hard component and the soft component are represented by H _ts and H _tl (H _ts + H _tl = 1), respectively.

In the present invention, the spin-spin relaxation time (T _2tl ) and proton ratio H _tl (100) of the soft component at 100 ° C. are defined. T _2tl needs to be 20 ms or more, preferably 30 ms or more and 100 ms or less. If it is shorter than 20 ms, the low-temperature fixability deteriorates because the adhesion to paper is lowered. H _tl (100) needs to be 0.2 or more, and more preferably 0.4 or more and 0.5 or less. If it is lower than 0.2, the entire toner is not sufficiently plasticized, and the low-temperature fixability deteriorates. If it is higher than 0.5, the amorphous resin and the crystalline resin are mixed and present at the molecular level, so that the low-temperature fixability is excellent, but the heat-resistant storage stability may be deteriorated.
For example, measurement is carried out under the following measurement conditions using a Bruker pulse NMR; Minispec mq series.
〔Measurement condition〕
1) Sample 40 mg of toner was weighed into an NMR tube having a diameter of 10 mm and used for measurement.
2) Measurement conditions
First90 ° Pulse Separation; 0.01 msec
Final Pulse Separation ； 70 msec
Number of Data Poin for Fitting ； 20 points
Cumulated number ； 64 times
Temperature ； 100 ℃
By using the fitting of the exponential function of ORIGIN 8.5 (OriginLab) by the least square method to the obtained free induction curve, the obtained echo signal is separated into two relaxation curves, Calculate proton intensity and spin-spin relaxation time.

--- Interface between amorphous resin and crystalline resin in toner-
In general, when different resins are in contact with each other, the interface area increases as the structures are similar to each other, and conversely, the interface area decreases as the structure is different. For example, the interface tends to increase in the combination of the polyester resin and the polyester resin than in the combination of the styrene acrylic resin and the polyester resin. On the other hand, it is known that the resin characteristic at the interface takes a value between the characteristics of the resin in contact. Therefore, when the amorphous resin and the crystalline resin form a contact interface in the toner, since the crystalline resin is intertwined with the amorphous resin, it does not form a folding structure and is not crystallized. The resin characteristic at the interface is a value between the characteristic of the amorphous resin and the characteristic of the amorphous state of the crystalline resin, and the thermal characteristic is lower than that of the amorphous resin. This causes deterioration of heat resistant storage stability. For this reason, a smaller interface is preferable. On the other hand, if the interface is too small, when the amorphous resin is softened, the crystalline resin is easily exposed on the toner surface, causing deterioration in heat resistant storage stability and fixing hot offset. Therefore, a certain amount of interface is required.
The ratio of the amorphous resin component, the crystalline resin component, and the interface component can be measured by pulsed NMR in the same manner as the softening component at 100 ° C. in the toner. However, the binder resin in the toner often contains three components: a cross-linking component of an amorphous resin component, a non-cross-linking component, and a crystalline resin component (non-cross-linking component). It is difficult to measure only the interface component between the non-crosslinked component of the amorphous resin component and the crystalline resin component, which affects the above. Therefore, the measurement is carried out by separating and purifying the non-crosslinked component of the binder resin, that is, the non-crosslinked component of the amorphous resin component and the crystalline resin component. Details will be described below.

For example, by the following operation, the non-crosslinked component of the binder resin (the non-crosslinked component of the amorphous resin component and the crystalline resin component) can be separated and purified from the toner.
First, the toner is dissolved using a solvent such as ethyl acetate or THF (soxhlet extraction is also possible). At that time, the temperature is maintained in the range of the melting point of the crystalline resin component from -5 ° C to the melting point + 5 ° C. Next, using a high-speed centrifuge with a cooling function, for example, 10,000 rpm × 10 min. To separate the soluble and insoluble components. Similarly, the temperature is maintained in the range of the melting point of the crystalline resin component from -5 ° C to the melting point + 5 ° C. The soluble matter is purified by reprecipitation multiple times. By this treatment, highly crosslinked resin components, pigments, waxes and the like can be separated, and the non-crosslinked component and the crystalline resin component of the amorphous resin can be separated and purified. In addition, the presence or absence of the crystalline resin component in the obtained separation and purification component can be determined by confirming the crystallization peak or the crystal melting peak of DSC measurement.

For the components separated and purified as described above, the free induction decay curve obtained by the pulse NMR method is separated into three relaxation curves by the same method. At this time, the relaxation curve having the shortest spin-spin relaxation time (T _2rs ) has the non-crosslinked component of the amorphous resin component and the crystalline region of the crystalline resin component, and the longest spin-spin relaxation time (T _2rl ). The relaxation curve corresponds to the amorphous region of the crystalline resin component. The remaining component is an interface component between the non-crosslinked component of the amorphous resin component and the amorphous region of the crystalline resin component, and the spin-spin relaxation time of this component is represented by T _2rm . The proton ratio of each component is obtained from each relaxation curve. The non-crosslinked component of the amorphous resin component and the crystalline region of the crystalline resin component (hard component), the amorphous region of the crystalline resin component (soft component), non- The proton ratio of the interface component between the non-crosslinked component of the crystalline resin component and the amorphous region of the crystalline resin component is represented by H _rs , H _rl , and H _rm (H _rs + H _rl + H _rm = 1), respectively.

In the present invention, the ratio H _rm (50) / H _rl (50) of the proton ratio H _rm of the interface component of the toner at 50 ° C. and the proton ratio H _rl of the soft component is defined. H _rm (50) / H _rl (50) is preferably 1.0 or less, and more preferably 0.7 or less. When the ratio is higher than 1.0, the interface component having lower thermal characteristics than the soft component increases, so that the toner aggregation property may be deteriorated.

FIG. 5 shows an example of a free induction decay curve obtained by measuring the electrophotographic toner of the present invention by the pulse NMR method, and two hard and soft relaxation curves obtained by decomposing it.
FIG. 6 shows an example of a free induction decay curve obtained by measuring a non-crosslinked component of a binder resin by a pulse NMR method, and a hard component, a soft component, and an interface between the hard component and the soft component obtained by decomposing it Three relaxation curves of the components are shown.

<Binder resin>
The binder resin in the present invention preferably contains an amorphous resin component and a crystalline resin component.
The mass ratio of the amorphous resin component (a) to the crystalline resin component (c) ((a) / (c)) is not particularly limited and may be appropriately selected depending on the purpose. 80 / 20-70 / 30 is preferable. When the crystalline resin component (c) is less than 80/20, the plastic effect is reduced. When the amount of the crystalline resin is more than 70/30, the interface area between the amorphous resin component and the crystalline resin component tends to increase, and the exposure of the crystalline resin on the toner surface increases, and the heat resistant storage stability deteriorates. In addition, since the dispersion diameter of the crystalline resin component tends to increase, the low-temperature fixability may be deteriorated. H _rl (50) increases as the crystalline resin component increases.
The amorphous resin component and the crystalline resin component amorphous resin and the crystalline resin may be chemically bonded, for example, a block copolymer resin containing the amorphous resin and the crystalline resin. . The block copolymer resin is preferable from the viewpoint of dispersibility of the crystalline resin.

-Dispersibility of crystalline resin-
In the toner of the present invention, the crystalline resin is preferably present in a dispersed state in the amorphous resin. In the present invention, the average value of the maximum ferret diameters of the crystalline resin dispersed in the amorphous resin is referred to as “dispersion diameter”.
The dispersion state of the crystalline resin can be confirmed by observing a cross section of the ruthenium tetroxide dyed toner. In the present invention, the dispersion diameter of the crystalline resin in the cross section of the toner is preferably 200 nm or less, and more preferably 10 nm to 100 nm. When the dispersion diameter exceeds 200 nm, the area that can be contacted with the amorphous resin becomes narrow, and the plastic effect may be insufficient.

In the present invention, examples of the method for confirming that the crystalline resin is dispersed in the amorphous resin include a method of observing a cross section of the toner particles with a transmission electron microscope. As the transmission electron microscope, for example, LEM-2000 type (manufactured by Topcon Corporation), JEM-2000FX (manufactured by JEOL Ltd.) or the like is used.
More specifically, the following procedure is used for confirmation. First, the toner particles are sufficiently dispersed in a room-temperature curable epoxy resin and then embedded to fully cure the epoxy resin. A cross section of the toner is prepared with an ultramicrotome (ultrasonic), and dyeing is performed using ruthenium tetroxide or osmium tetroxide as necessary. This is observed with a scanning transmission electron microscope (STEM), and an amorphous crystalline resin and a crystalline resin are identified and observed from the difference in contrast.

--- Crystalline resin--
The crystalline resin in the present invention is a resin having a portion having a crystal structure, and has a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The property of the crystalline resin is the ratio between the softening temperature measured by an elevated flow tester and the maximum peak temperature of heat of fusion measured by a differential scanning calorimeter (DSC) (softening temperature / maximum peak temperature of heat of fusion). ) Is 0.8 to 1.6, and shows a property of being softened sharply by heat.
The amorphous resin in the present invention is a resin having no crystal structure, and does not have a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffraction apparatus. The property of the amorphous resin is such that the ratio of the softening temperature to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is greater than 1.6 and softens softly with heat.

  The softening temperature of the resin can be measured using an elevated flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). While heating 1 g of resin as a sample at a heating rate of 3 ° C./min, a load of 2.94 MPa was applied by a plunger, extruded from a nozzle with a diameter of 0.5 mm and a length of 1 mm, and the plunger drop of the flow tester against the temperature The amount was plotted, and the temperature at which half the sample flowed out was defined as the softening temperature.

The maximum peak temperature of the heat of fusion of the resin can be measured, for example, under the following measurement conditions using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). From the obtained DSC curve, the DSC curve at the second temperature rise is selected using the analysis program “endothermic peak temperature” in the DSC-60 system, and the above-mentioned maximum peak temperature at the second temperature rise of the target sample is obtained. . In addition, it is also possible to isolate | separate an enthalpy relaxation component by applying a modulation of +/- 0.3 degreeC at the time of temperature rising.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 5 ° C / min
End temperature: -20 ° C
Holding time: 5 min
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C

  As the crystalline resin, the closer the main skeleton to the amorphous resin, the better the dispersibility of the crystalline resin in the amorphous resin, and the boundary between the amorphous resin and the crystalline resin. The area tends to increase. The crystalline resin can be appropriately selected depending on the purpose, but a crystalline polyester resin is preferable.

--- Crystalline polyester resin ---
The crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polycondensed polyester resin synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, a polyhydroxycarboxylic acid An acid etc. are mentioned.
There is no restriction | limiting in particular as said crystalline polyester resin, Although it can select suitably according to the objective, The crystalline polyester which has a bivalent aliphatic alcohol component and a bivalent aliphatic carboxylic acid component as a structural component Resins are preferred.

---- Polyol ----
Examples of the polyol include divalent diols, trivalent to octavalent or higher polyols.

  The divalent diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic alcohols such as linear aliphatic alcohols and branched aliphatic alcohols (divalent aliphatic alcohols). ), An alkylene ether glycol having 4 to 36 carbon atoms, an alicyclic diol having 4 to 36 carbon atoms, an alkylene oxide of the alicyclic diol (hereinafter, “alkylene oxide” may be abbreviated as “AO”), Examples thereof include AO adducts of bisphenols, polylactone diols, polybutadiene diols, diols having carboxyl groups, diols having sulfonic acid groups or sulfamic acid groups, and diols having other functional groups such as salts thereof. Among these, an aliphatic alcohol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic alcohol having 2 to 36 chain carbon atoms is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content with respect to the whole diol of the said linear aliphatic alcohol, Although it can select suitably according to the objective, 80 mol% or more is preferable and 90 mol% or more is more preferable. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between the low temperature fixability and the heat resistant storage stability is good, and the resin hardness tends to be improved.

  The linear aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability. Among these, a linear aliphatic alcohol having 2 to 36 chain carbon atoms is preferable.

  The branched aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a branched aliphatic alcohol having 2 to 36 chain carbon atoms. Examples of the branched aliphatic alcohol include 1,2-propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, and the like.

  The alkylene ether glycol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Ether glycol etc. are mentioned.

  The alicyclic diol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

The trivalent to octavalent or higher polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the trivalent to octavalent or higher polyvalent fat having 3 to 36 carbon atoms. Alcohol; AO adduct of trisphenol (addition mole number 2-30); AO adduct of novolak resin (addition mole number 2-30); Copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers Examples include acrylic polyols such as products.
Examples of the trivalent to octavalent or higher polyhydric aliphatic alcohol having 3 to 36 carbon atoms include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin.
Among these, trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts are preferred, and novolak resin AO adducts are more preferred.

---- Polycarboxylic acid ----
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids.

  There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid (divalent aliphatic carboxylic acid), aromatic dicarboxylic acid, etc. are mentioned. Examples of the aliphatic dicarboxylic acid include linear aliphatic dicarboxylic acid and branched aliphatic dicarboxylic acid. Among these, linear aliphatic dicarboxylic acid is preferable.

There is no restriction | limiting in particular as said aliphatic dicarboxylic acid, According to the objective, it can select suitably, For example, alkane dicarboxylic acid, alkenyl succinic acid, alkene dicarboxylic acid, alicyclic dicarboxylic acid etc. are mentioned.
Examples of the alkanedicarboxylic acid include alkanedicarboxylic acid having 4 to 36 carbon atoms. Examples of the alkanedicarboxylic acid having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid.
Examples of the alkenyl succinic acid include dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid.
Examples of the alkene dicarboxylic acid include alkene dicarboxylic acids having 4 to 36 carbon atoms. Examples of the alkene dicarboxylic acid having 4 to 36 carbon atoms include maleic acid, fumaric acid, and citraconic acid.
As said alicyclic dicarboxylic acid, a C6-C40 alicyclic dicarboxylic acid etc. are mentioned, for example. Examples of the alicyclic dicarboxylic acid having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid).

  There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, C8-36 aromatic dicarboxylic acid etc. are mentioned. Examples of the aromatic dicarboxylic acid having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. It is done.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms. Examples of the aromatic polycarboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

  In addition, as the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or alkyl esters having 1 to 4 carbon atoms may be used. Examples of the alkyl ester having 1 to 4 carbon atoms include methyl ester, ethyl ester, and isopropyl ester.

  Among the dicarboxylic acids, the aliphatic dicarboxylic acid is preferably used alone, and adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, or isophthalic acid is more preferably used alone. Also preferred are those obtained by copolymerizing the aromatic dicarboxylic acid together with the aliphatic dicarboxylic acid. As the aromatic dicarboxylic acid to be copolymerized, terephthalic acid, isophthalic acid, t-butylisophthalic acid, and alkyl esters of these aromatic dicarboxylic acids are preferable. Examples of the alkyl ester include methyl ester, ethyl ester, isopropyl ester, and the like. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

  The molecular weight of the crystalline resin is not particularly limited and may be appropriately selected depending on the intended purpose. The range of the weight average molecular weight (Mwc) is preferably 10,000 or more and 50,000 or less, and 15,000. More preferably, it is 30,000 or less. When the weight average molecular weight exceeds 50,000, the dispersion diameter of the crystalline resin in the amorphous resin tends to increase, and since the entire toner is too high in molecular weight, the fixability is deteriorated and the gloss is deteriorated. Since it is too low, it is not preferable. In the case of less than 10,000, the interfacial area between the amorphous resin and the crystalline resin tends to increase, and the internal cohesive force at the time of melting the toner becomes too low. This is not preferable because it causes wrapping.

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline resin, Although it can select suitably according to the objective, 50 to 80 degreeC is preferable. When the melting point is less than 50 ° C., the crystalline resin is likely to melt at a low temperature and the heat-resistant storage stability of the toner may be reduced. When the melting point exceeds 80 ° C., the crystalline resin is heated by fixing. Insufficient melting may lower the low-temperature fixability of the toner.

  There is no restriction | limiting in particular as a hydroxyl value of the said crystalline resin, Although it can select suitably according to the objective, 5 mgKOH / g-40 mgKOH / g are preferable.

  About crystallinity, molecular structure, etc. of the crystalline resin, for example, NMR measurement, differential scanning calorimeter (DSC) measurement, X-ray diffraction measurement, GC / MS measurement, LC / MS measurement, infrared absorption (IR) spectrum measurement Etc. can be confirmed.

--- Amorphous resin--
The amorphous resin preferably has a main skeleton close to the crystalline resin in order to improve the dispersibility of the crystalline resin in the amorphous resin. The amorphous resin can be appropriately selected according to the purpose, but an amorphous polyester resin is preferable.

--- Amorphous polyester resin ---
There is no restriction | limiting in particular as said amorphous polyester resin, According to the objective, it can select suitably, For example, the polycondensation polyester resin etc. which are synthesize | combined from a polyol and polycarboxylic acid are mentioned.
The amorphous polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. The amorphous polyester resin includes a divalent aliphatic alcohol component and a polyvalent aromatic carboxylic acid component as constituent components. A preferred polyester resin is preferred.

---- Polyol ----
Examples of the polyol include divalent diols, trivalent to octavalent or higher polyols.

  The divalent diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic alcohols such as linear aliphatic alcohols and branched aliphatic alcohols (divalent aliphatic alcohols). ) And the like. Among these, an aliphatic alcohol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic alcohol having 2 to 36 chain carbon atoms is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  The linear aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like. Among these, considering availability, ethylene glycol, 1,3-propanediol (propylene glycol), 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane Diols are preferred. Among these, a linear aliphatic alcohol having 2 to 36 chain carbon atoms is preferable.

---- Polycarboxylic acid ----
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids. Of these, polyvalent aromatic carboxylic acids are preferred.

  There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, etc. are mentioned. Examples of the aliphatic dicarboxylic acid include linear aliphatic dicarboxylic acid and branched aliphatic dicarboxylic acid. Among these, linear aliphatic dicarboxylic acid is preferable.

There is no restriction | limiting in particular as said aliphatic dicarboxylic acid, According to the objective, it can select suitably, For example, alkane dicarboxylic acid, alkenyl succinic acid, alkene dicarboxylic acid, alicyclic dicarboxylic acid etc. are mentioned.
Examples of the alkanedicarboxylic acid include alkanedicarboxylic acid having 4 to 36 carbon atoms. Examples of the alkanedicarboxylic acid having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid.
Examples of the alkenyl succinic acid include dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid.
Examples of the alkene dicarboxylic acid include alkene dicarboxylic acids having 4 to 36 carbon atoms. Examples of the alkene dicarboxylic acid having 4 to 36 carbon atoms include maleic acid, fumaric acid, and citraconic acid.
As said alicyclic dicarboxylic acid, a C6-C40 alicyclic dicarboxylic acid etc. are mentioned, for example. Examples of the alicyclic dicarboxylic acid having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid).

  There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, C8-36 aromatic dicarboxylic acid etc. are mentioned. Examples of the aromatic dicarboxylic acid having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. It is done.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms. Examples of the aromatic polycarboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

  In addition, as the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or alkyl esters having 1 to 4 carbon atoms may be used. Examples of the alkyl ester having 1 to 4 carbon atoms include methyl ester, ethyl ester, and isopropyl ester.

  The molecular weight of the amorphous resin is not particularly limited and may be appropriately selected according to the purpose. The range of the weight average molecular weight (Mwc) is preferably 5,000 or more and 60,000 or less, 000 or more and 40,000 or less are more preferable. When the weight average molecular weight exceeds 60,000, the whole toner is too high in molecular weight, so that the fixability is deteriorated and the gloss is too low. If the ratio is less than 5,000, the interfacial area between the amorphous resin and the crystalline resin tends to increase, and the internal cohesive force when the toner melts becomes too low. This is not preferable because it causes wrapping.

  There is no restriction | limiting in particular as a glass transition temperature of the said amorphous resin, Although it can select suitably according to the objective, 40 to 75 degreeC is preferable. If the glass transition temperature is less than 40 ° C., the heat-resistant storage stability may be lowered, and the durability against stress such as stirring in the developing device may be reduced. When the glass transition temperature exceeds 75 ° C., the low-temperature fixability may be deteriorated. The glass transition temperature of the amorphous resin can be measured, for example, by differential scanning calorimetry (DSC method).

  There is no restriction | limiting in particular as a hydroxyl value of the said amorphous resin, Although it can select suitably according to the objective, 5 mgKOH / g-40 mgKOH / g are preferable.

  The molecular structure of the amorphous resin can be confirmed by GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

--Copolymerization--
As described above, the block copolymer resin is preferable from the viewpoint of dispersibility of the crystalline resin. There is no restriction | limiting in particular as a manufacturing method of the said copolymer resin, According to the objective, it can select suitably, For example, although any one of the following methods (1)-(4) etc. are mentioned, molecular design (1), (2) and (4) are preferable from the viewpoint of the degree of freedom, and the interface area between the amorphous resin component and the crystalline resin component can be reduced by making the molecular weight of the block uniform, (2) is more preferable.
(1) An amorphous resin prepared in advance by a polymerization reaction and a crystalline resin prepared in advance by a polymerization reaction are dissolved or dispersed in a suitable solvent, and a hydroxyl group at the end of a polymer chain such as an isocyanate group, an epoxy group, or a carbodiimide group. Or a method of copolymerization by reacting with an extender having two or more functional groups that react with carboxylic acid (block copolymerization).
(2) Crystal obtained by reacting a crystalline resin prepared in advance by a polymerization reaction with an extender having two or more functional groups that react with a hydroxyl group of a polymer chain such as an isocyanate group, an epoxy group or a carbodiimide group, or a carboxylic acid. A method of copolymerizing by dissolving or dispersing an adhesive resin prepolymer and an amorphous resin prepared in advance by a polymerization reaction in an appropriate solvent, followed by an extension reaction (block copolymerization prepolymer method).
(3) A method in which an amorphous resin prepared in advance by a polymerization reaction and a crystalline resin prepared in advance by a polymerization reaction are melt-kneaded and prepared by transesterification under reduced pressure (block copolymer transesterification method).
(4) A method in which a hydroxyl group of a crystalline resin prepared in advance by a polymerization reaction is used as a polymerization initiating component, and an amorphous resin is subjected to ring-opening polymerization and copolymerization from the polymer chain end of the crystalline resin (graft copolymerization).

As the extender in the block copolymerization in the above (1) and (2), polyisocyanate is preferable. By using polyisocyanate as an extender, a block copolymer resin having a urethane bond can be obtained.
Examples of the polyisocyanate include diisocyanate.
Examples of the diisocyanate include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and araliphatic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), crude TDI, 2, 4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m-isocyanatophenyl Examples include sulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. Can be mentioned.

  Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanate). Natoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.

  Examples of the araliphatic diisocyanate include m-xylylene diisocyanate (XDI), p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like. .

  The amount of the polyisocyanate used in the production of the copolymer resin is not particularly limited and can be appropriately selected according to the purpose. The total moles of hydroxyl groups of the crystalline resin and the amorphous resin can be selected. The number / total mole number of isocyanate groups of the polyisocyanate (OH / NCO) is preferably in the range of 0.35 to 0.7. When the OH / NCO is less than 0.35, the bonding between the amorphous resin and the crystalline resin is insufficient, the number of components present independently increases, and quality stability can be ensured. It may disappear. If the OH / NCO exceeds 0.7, the influence of the molecular weight of the copolymer resin and the interaction between urethane groups becomes too strong, and sufficient fluidity and deformability are ensured in situations where fluidity is required. It may not be possible.

  The mass ratio of the crystalline resin to the amorphous resin in the copolymer resin (amorphous resin / crystalline resin) is not particularly limited and may be appropriately selected depending on the intended purpose. / 20 to 70/30 is preferable.

<Other ingredients>
Examples of the other components include a colorant, a release agent, a charge control agent, and an external additive.

-Colorant-
There is no restriction | limiting in particular as said colorant, According to the objective, it can select suitably, For example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment etc. are mentioned. Among these, it is preferable to contain any of a yellow pigment, a magenta pigment, and a cyan pigment.
The black pigment is used for black toner, for example. Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetite, nigrosine dye, and iron black.
The yellow pigment is used for yellow toner, for example. Examples of the yellow pigment include CI Pigment Yellow (CI Pigment Yellow) 74, 93, 97, 109, 128, 151, 154, 155, 166, 168, 180, 185, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow and the like can be mentioned.
The magenta pigment is used for magenta toner, for example. Examples of the magenta pigment include quinacridone pigments, CI Pigment Red 48: 2, 57: 1, 58: 2, 5, 31, 146, 147, 150, 176, And monoazo pigments such as 184 and 269. Further, the quinacridone pigment may be used in combination with the monoazo pigment.
The cyan pigment is used for cyan toner, for example. Examples of the cyan pigments include Cu-phthalocyanine pigments such as CI Pigment Blue 15: 3, Zn-phthalocyanine pigments, and Al-phthalocyanine pigments.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded with the production of the master batch or the master batch include, for example, polymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, or substitutes thereof; styrene-p-chlorostyrene copolymers, styrene- Propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene- Octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl Styrene copolymers such as methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Combined; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin Aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The master batch can be obtained, for example, by mixing and kneading the master batch resin and the colorant under high shear. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed is called a colorant. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably, For example, carbonyl group containing wax, polyolefin wax, long chain hydrocarbon etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones.
Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane. Examples thereof include diol distearate.
Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate.
Examples of the polyalkanoic acid amide include dibehenyl amide.
Examples of the polyalkylamide include trimellitic acid tristearylamide.
Examples of the dialkyl ketone include distearyl ketone.
Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable and 60 to 90 degreeC is more preferable. If the melting point is less than 50 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 100 ° C., a cold offset may easily occur during fixing at a low temperature.
The melting point of the release agent can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). First, 5.0 mg of the mold release agent is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the maximum peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point.

  The melt viscosity of the release agent is preferably 5 mPa · sec to 100 mPa · sec, more preferably 5 mPa · sec to 50 mPa · sec, and particularly preferably 5 mPa · sec to 20 mPa · sec as a measured value at 100 ° C. If the melt viscosity is less than 5 mPa · sec, the releasability may be lowered, and if it exceeds 100 mPa · sec, the hot offset resistance and the releasability at low temperatures may be lowered.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 10 parts by mass is more preferable. When the content is less than 1 part by mass, the hot offset resistance may be reduced, and when it exceeds 20 parts by mass, the heat resistant storage stability, charging property, transferability, and stress resistance may be reduced. .

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Can be mentioned. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industries, Ltd.), LRA -901, LR-147 (manufactured by Nippon Carlit Co., Ltd.) which is a boron complex.

  There is no restriction | limiting in particular as content of the said charge control agent, Although it can select suitably according to the objective, 0.01 mass part-5 mass parts are preferable with respect to 100 mass parts of said toner. 02 parts by mass to 2 parts by mass is more preferable. When the content is less than 0.01 parts by mass, the charge rise property and the charge amount are not sufficient, and the toner image may be easily affected. When the content exceeds 5 parts by mass, the chargeability of the toner is too high, and the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density. .

-External additive-
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica, fatty acid metal salts, metal oxides, hydrophobized titanium oxide, and fluoropolymers.
Examples of the fatty acid metal salt include zinc stearate and aluminum stearate.
Examples of the metal oxide include titanium oxide, aluminum oxide, tin oxide, and antimony oxide.
Examples of the commercially available silica include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of commercially available titanium oxide include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (Fuji Titanium Industry Co., Ltd.). Company-made), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
Commercially available products of the hydrophobized titanium oxide include, for example, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T. , TAF-1500T (all manufactured by Fuji Titanium Industrial Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  Examples of the hydrophobic treatment method include a method of treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane.

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of the said toner. 3 mass parts-3 mass parts are more preferable.

  There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said external additive, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm-70 nm are more preferable. If the average particle size is less than 3 nm, the external additive may be buried in the toner and its function may not be exhibited effectively, and if it exceeds 100 nm, the surface of the photoreceptor may be damaged unevenly. .

<Toner>
--Average particle size--
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 μm to 16 μm. The upper limit is more preferably 11 μm and particularly preferably 9 μm. The lower limit is more preferably 0.5 μm and particularly preferably 1 μm.
The ratio of the volume average particle diameter to the number average particle diameter of the toner [volume average particle diameter / number average particle diameter] is not particularly limited and may be appropriately selected depending on the intended purpose. In view of the above, 1.0 to 1.4 is preferable, and 1.0 to 1.3 is more preferable.

The volume average particle diameter (Dv) and the number average particle diameter (Dn) are measured by a Coulter counter method. Examples of the measuring device include Coulter Counter TA-II, Coulter Multisizer II, and Coulter Multisizer III (all manufactured by Coulter). The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% by mass NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured using the 100 μm aperture as the aperture by the measuring device. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

Higher order structures such as the molecular structure, crystallinity, and microphase separation structure of the toner resin in the toner can be easily analyzed by a conventionally known method. Specifically, high-resolution NMR measurement ( ¹ H, ¹³ C, etc.), differential scanning calorimeter (DSC) measurement, wide-angle X-ray diffraction measurement, (thermal decomposition) GC / MS measurement, LC / MS measurement, infrared absorption ( It can be confirmed by IR measurement, atomic force microscope observation, TEM observation, and the like.

For example, whether or not the copolymer specified in the present invention is contained in the toner can be determined as follows.
First, the toner is dissolved using a solvent such as ethyl acetate or THF (soxhlet extraction is also possible). Next, using a high-speed centrifuge with a cooling function, for example, 20 ° C., 10,000 rpm × 10 min. To separate the soluble and insoluble components. The soluble matter is purified by reprecipitation multiple times. By this treatment, highly crosslinked resin components, pigments, waxes and the like can be separated.
Next, GPC measurement is performed on the obtained resin component to obtain molecular weight, distribution, and chromatogram. At this time, when the obtained chromatogram is multimodal, fractionation / sorting is performed using a fraction collector or the like, and each of the obtained fractions is formed in the same manner as described above. By this operation, various resin components are separated and purified, and each is subjected to various analysis operations.

About the obtained refinement | purification film | membrane, first, DSC measurement is performed and Tg, melting | fusing point, crystallization behavior, etc. are grasped | ascertained. If a crystallization peak is observed during cooling and cooling, the crystal component is grown by annealing for 24 h or more in that temperature range. Crystallization is not observed, but when a melting peak is observed, annealing is performed at a temperature of about melting point −10 ° C. Thereby, the existence of various transition points and a crystalline skeleton can be grasped.
Next, SPM (AFM) observation and, in some cases, TEM observation are also used to confirm the presence or absence of a phase separation structure. When a so-called micro phase separation structure is confirmed, a copolymer or high intramolecular / interval This means that the system has an interaction.
Furthermore, the purification membrane, FT-IR measurement, NMR measurement ^{(1 H, 13 C),} GC / MS measurements, in some cases, by performing NMR measurements to analyze the molecular structure in more detail (2D), its composition The structure and various characteristics can be grasped, and for example, the presence of a polyester skeleton and a urethane bond, their composition, and composition ratio can be confirmed.
By comprehensively judging the above measurement and analysis results, it is possible to judge whether or not the copolymer defined in the present invention is contained in the toner.

Hereinafter, an example of procedures and conditions of the various measurement methods introduced above will be shown (only SPM (AFM) observation will be described later).
<Example of GPC measurement>
It can measure using a gel permeation chromatography (GPC) measuring apparatus (for example, HLC-8220GPC (made by Tosoh Corporation)), and a thing with a fraction collector is preferable.
As the column, TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation) can be suitably used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.
The molecular weight was calculated using a calibration curve prepared with a monodisperse polystyrene standard sample. As the standard polystyrene sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three kinds of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
Solution A: S-7450 2.5mg, S-678 2.5mg, S-46.5 2.5mg, S-2.90 2.5mg, THF 50ml
Solution B: S-3730 2.5mg, S-257 2.5mg, S-19.8 2.5mg, S-0.580 2.5mg, THF 50ml
Solution C: S-1470 2.5mg, S-112 2.5mg, S-6.93 2.5mg, Toluene 2.5mg, THF 50ml
An RI (refractive index) detector can be used as the detector, but a UV detector with higher sensitivity can be used when fraction fractionation is performed.

<Example of DSC measurement>
It measured on the following measurement conditions using the differential scanning calorimeter (DSC) (For example, TA-60WS and DSC-60 (made by Shimadzu Corporation)). From the obtained DSC curve, a graph of “endothermic value” and “temperature” was drawn, and Tg, cold crystallization, melting point, crystallization temperature and the like were determined according to a conventional method. Tg is 1st. The value obtained by the midpoint method from the DSC curve of heating was used. In addition, it is also possible to isolate | separate an enthalpy relaxation component by applying a modulation of +/- 0.3 degreeC at the time of temperature rising.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 5 ° C / min
End temperature: -20 ° C
Holding time: None Temperature increase rate: 5 ° C / min
End temperature: 150 ° C

<Example of SPM observation>
The phase separation structure of the resin in the toner is confirmed by a phase image in a tapping mode by an atomic force microscope (AFM). The copolymer according to the present invention is low in softness, that is, a portion observed as an image having a large phase difference (crystalline resin component (including both a crystalline region and an amorphous region)), an image that is hard and has a small phase difference. It is preferable that the portion (amorphous resin component (including both cross-linked and non-cross-linked)) observed as is finely dispersed. At this time, the second phase difference image consisting of a hard low phase difference portion is the outer phase, and the first phase difference image consisting of a soft high phase difference portion is finely dispersed in the inner phase.
As a sample for obtaining the phase image, for example, observation can be made by using a Leica ultramicrotome ULTRACUT UCT which is obtained by cutting a resin block under the following conditions and taking out a section.
・ Cutting thickness: 60nm
・ Cutting speed: 0.4mm / sec
-Use of a diamond knife (Ultra Sonic 35 °) As a typical apparatus for obtaining the AFM phase image, for example, MFP-3D manufactured by Asylum Technology Co., Ltd., and the following measurement using OMCL-AC240TS-C3 as a cantilever It can be observed under conditions.
・ Target amplitude: 0.5V
-Target percent: -5%
・ Amplitude setpoint: 315mV
・ Scan rate: 1Hz
・ Scan points: 256 × 256
・ Scan angle ： 0 °

<Example of TEM observation>
(procedure)
(1) The sample was exposed to an atmosphere of RuO ₄ aqueous solution and dyed for 2 hours.
(2) After trimming the sample with a glass knife, a section was prepared using an ultramicrotome under the following conditions.
―Cutting conditions―
Cutting thickness: 75nm
Cutting speed: 0.05 to 0.2 mm / sec
Using a diamond knife (Ultra Sonic 35 °) (3) A section was fixed on a mesh, and exposed to an atmosphere of an aqueous RuO ₄ solution, and stained for 5 minutes.
(Observation conditions)
Equipment used: JEOL transmission electron microscope JEM-2100F
Accelerating voltage: 200kV
Morphological observation: Bright field method Setting condition: spot size: 3, CLAP: 1, OLAP: 3, Alpha: 3

<Example of FT-IR measurement>
FT-IR spectrum measurement was performed using a FT-IR spectrometer (Perkin Elmer, trade name “Spectrum One”) (16 scans, resolution: 2 cm ⁻¹ ), mid-infrared region (400-4000 cm ⁻¹ ). I went there.

<Example of NMR measurement>
The sample was dissolved in deuterated chloroform at the highest possible concentration, then placed in a 5 mmφ NMR sample tube and subjected to various NMR measurements. The measuring device used was JNM-ECX-300 manufactured by JEOL Resonance.
The measurement temperature was 30 ° C., and the ¹ H-NMR measurement was performed with 256 integrations and a repetition time of 5.0 s. ^{The 13} C measurement was performed with an integration count of 10,000 times and a repetition time of 1.5 s. It is possible to assign a component from the obtained chemical shift and calculate the blending ratio from a numerical value obtained by dividing the integrated value of the corresponding peak by the proton or the number of carbons.
For further detailed structural analysis, it is also possible to perform two-quantum filter ¹ H- ¹ H shift correlation two-dimensional NMR measurement (DQF-COSY) measurement, etc. In this case, the number of integration is 1,000 times, It can be performed at a repetition time of 2.45 s or 2.80 s, and the coupling state, that is, the reaction site can be identified from the obtained spectrum, but can be sufficiently discriminated by ordinary ¹ H and ¹³ C measurements.

<Example of GC / MS measurement>
In this analysis, a reaction pyrolysis gas chromatography mass spectrometry (GC / MS) method using a reaction reagent was performed. The reaction reagent used in the reactive pyrolysis GC / MS method was a 10% methanol solution of tetramethylammonium hydroxide (TMAH) (Tokyo Chemical Industry). The GC-MS apparatus used was QP2010 manufactured by Shimadzu Corporation, the data analysis software used was GCMSsolution manufactured by Shimadzu Corporation, and the heating apparatus used was Py2020D manufactured by Frontier Laboratories.
(Analysis conditions)
Reaction pyrolysis temperature: 300 ℃
Column: Ultra ALLOY-5 L = 30m ID = 0.25mm Film = 0.25μm
Column heating: 50 ° C (holding 1 minute) to 10 ° C / min to 330 ° C (holding 11 minutes)
Carrier gas pressure: 53.6 kPa constant Column flow rate: 1.0 ml / min
Ionization method: EI method (70eV)
Mass range: m / z 29-700
Injection mode: Split (1: 100)

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably, For example, a wet granulation method, a grinding method, etc. are mentioned. Examples of the wet granulation method include a dissolution suspension method and an emulsion aggregation method. From the difficulty of molecular kneading by kneading and uniform kneading of a high molecular weight resin and a low molecular weight resin, the dissolution suspension method and the emulsion aggregation method, which are production methods not involving the kneading of the binder resin, are preferable. The dissolution suspension method is more preferable from the viewpoint of resin uniformity.

  Further, the toner is produced by a particle production method as disclosed in Japanese Patent No. 4531076, that is, after the material constituting the toner is dissolved in carbon dioxide in a liquid or supercritical state, the liquid or supercritical state of carbon dioxide is dissolved. It can also be produced by a particle production method for obtaining toner particles by removing carbon.

-Dissolution suspension method-
The dissolution suspension method includes, for example, a toner material phase preparation step, an aqueous medium phase preparation step, an emulsification or dispersion preparation step, and an organic solvent removal step, and further includes other steps as necessary. The method of including is mentioned.
The toner of the present invention comprises a step of emulsifying or dispersing an oil phase in which at least a binder resin is dissolved or dispersed in an aqueous medium to produce an emulsified dispersion containing emulsified particles, and converging the emulsified particles. It is preferably obtained by a production method having a step of granulating toner base particles and a step of removing the organic solvent.

--- Toner material phase (oil phase) preparation process-
The toner material phase preparation step includes at least the binder resin and, if necessary, further dissolves or disperses the toner material containing the colorant, the release agent, and the like in an organic solvent. There is no particular limitation as long as it is a step for preparing a dissolved or dispersed liquid (sometimes referred to as a toner material phase or an oil phase), and it can be appropriately selected according to the purpose.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The volatile thing whose boiling point is less than 150 degreeC is preferable at the point of the ease of removal.
Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable, and ethyl acetate is more preferable.
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, Although it can select suitably according to the objective, 0 mass part-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 0 mass part-100 parts. Mass parts are more preferable, and 25 mass parts to 70 mass parts is particularly preferable.

--- Aqueous medium phase (aqueous phase) preparation process--
The aqueous medium phase preparation step is not particularly limited as long as it is a step of preparing an aqueous medium phase, and can be appropriately selected according to the purpose. In this step, it is preferable to prepare an aqueous medium phase containing resin fine particles in the aqueous medium.

There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. Among these, water is particularly preferable.
The solvent miscible with water is not particularly limited as long as it is miscible with water and can be appropriately selected according to the purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Is mentioned.
Examples of the alcohol include methanol, isopropanol, and ethylene glycol.
Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

The aqueous medium phase is prepared, for example, by dispersing the resin fine particles in the aqueous medium in the presence of a surfactant. The reason why the surfactant, the resin fine particles, and the like are appropriately added to the aqueous medium is to improve the dispersion of the toner material.
The amount of the surfactant and the resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.5% by mass with respect to the aqueous medium, respectively. -10 mass% is preferable.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, a cationic surfactant, an amphoteric surfactant etc. are mentioned.
Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl diaryl ether disulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonic acid formalin condensates, Examples thereof include oxyethylene alkyl phosphate ester salts and glyceryl borate fatty acid esters.

The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. Examples of the resin fine particles include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a combination thereof are preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
Examples of the vinyl resin include polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, and (meth) acrylic acid-acrylic. Examples include acid ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.
There is no restriction | limiting in particular as an average particle diameter of the said resin fine particle, Although it can select suitably according to the objective, 5 nm-200 nm are preferable and 20 nm-300 nm are more preferable.

  In the preparation of the aqueous medium phase, cellulose may be used as a dispersant. Examples of the cellulose include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and sodium carboxymethyl cellulose.

--Emulsification or dispersion preparation process--
The emulsification or dispersion preparation step is a step for preparing an emulsification or dispersion by mixing and dissolving and dispersing and dissolving the toner material (toner material phase) and the aqueous medium phase. There is no restriction | limiting in particular, According to the objective, it can select suitably.
There is no restriction | limiting in particular as the method of emulsification thru | or dispersion | distribution, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser.

  There is no restriction | limiting in particular as the usage-amount of the said aqueous medium phase with respect to 100 mass parts of said toner material phases, Although it can select suitably according to the objective, 50 mass parts-2,000 mass parts are preferable, 100 mass parts is preferable. -1,000 mass parts is more preferable. If the amount used is less than 50 parts by mass, the toner material phase may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. If the amount used exceeds 2,000 parts by mass, it is not economical.

-Convergence process-
The converging step is not particularly limited as long as it is a step of converging emulsified particles in the emulsified or dispersed liquid to granulate toner base particles having a narrow particle size distribution, and may be appropriately selected according to the purpose. it can.
The method of convergence is not particularly limited and can be appropriately selected according to the purpose.For example, it can be achieved by a method of gradually making the particle size uniform under a low shear force, and a known stirring blade or the like Can be used.

-Organic solvent removal process-
The organic solvent removing step is not particularly limited as long as it is a step of removing the organic solvent from the emulsified or dispersed liquid to obtain a desolvent slurry, and can be appropriately selected according to the purpose.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets of the emulsified or dispersed liquid, and (2) the emulsified or dispersed liquid is removed. A method of completely removing the organic solvent in the oil droplets of the emulsified or dispersed liquid by spraying in a dry atmosphere, and (3) reducing the pressure of the emulsified or dispersed liquid to completely remove the organic solvent in the oil droplets. And the like. In the organic solvent removal step, by rapidly cooling the crystalline resin component from the molten state, the ratio of crystal nucleation to crystal growth is relatively increased, and as a result, the dispersion diameter of the crystalline resin component can be reduced. ,preferable. Specifically, the emulsification or dispersion temperature is preferably rapidly cooled from Tm-20 ° C. to Tm-40 ° C. with respect to the melting point Tm of the crystalline resin component. Furthermore, by removing the organic solvent from the oil droplets at a high speed in the organic solvent removal step, the viscosity of the oil droplets increases rapidly, and the movement of the crystalline resin component in the oil droplets is restricted to disperse. This is preferable because the diameter can be reduced. As a method of increasing the speed of removing the organic solvent from the oil droplets, the method of increasing the speed of the organic solvent that volatilizes from the aqueous medium phase by reducing the pressure, the amount of the organic solvent that can be dissolved in the aqueous medium phase by adding an additional aqueous medium phase, etc. And a method for increasing the value. When the organic solvent is removed, toner particles are formed.

-Annealing process-
An annealing step is preferably performed after the organic solvent removing step in terms of improving the crystallinity of the toner. In the annealing process, it is necessary to leave the solvent removal slurry in a temperature environment lower than the melting point of the crystalline resin contained in the binder resin of the toner, and the temperature is between 5 ° C. lower than the melting point and the melting point. It is preferable to leave the solvent removal slurry.

-Other processes-
As said other process, a washing | cleaning process, a drying process, etc. are mentioned, for example.

--- Cleaning process ---
The washing step is not particularly limited as long as it is a step of washing the solvent-removed slurry with water after the organic solvent removing step, and can be appropriately selected depending on the purpose. Examples of the water include ion-exchanged water.

--- Drying process ---
The drying step is not particularly limited as long as it is a step of drying the toner particles obtained in the washing step, and can be appropriately selected according to the purpose.

-Grinding method-
The pulverization method is, for example, a method for producing mother particles of the toner by pulverizing and classifying a toner material containing at least a binder resin that has been melt-kneaded.
The melt kneading is performed by charging a mixture obtained by mixing the toner materials into a melt kneader. Examples of the melt kneader include a uniaxial or biaxial continuous kneader, a batch kneader using a roll mill, and the like. Specifically, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works, manufactured by Bus Connieder and so on. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  The pulverization is a step of pulverizing the kneaded product obtained by the melt-kneading. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

  The classification is a step of adjusting the pulverized product obtained by the pulverization to particles having a predetermined particle size. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.

(Developer)
The developer according to the present invention contains the toner according to the present invention. The developer may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer. Among these, the two-component developer is preferable from the viewpoint of improving the service life when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed.

In the case of the one-component developer using the toner, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to the layer thickness regulating member such as the like, and good and stable developability and image can be obtained even when the developing means is used (stirred) for a long time.
Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

<< Core material >>
The core material is not particularly limited as long as it has magnetic properties, and can be appropriately selected according to the purpose. Ferrite, magnetite, iron, and nickel are preferable. In addition, considering the adaptability to environmental aspects that are remarkably advanced in recent years, the ferrite is not a conventional copper-zinc ferrite, but manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese-magnesium-strontium ferrite Lithium ferrite is preferable.

<< Resin layer >>
The material of the resin layer is not particularly limited and may be appropriately selected depending on the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin , Polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and vinyl fluoride For example, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, and silicone resins. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said silicone resin, According to the objective, it can select suitably, For example, straight silicone resin which consists only of organosilosan bonds; alkyd resin, polyester resin, epoxy resin, acrylic resin, urethane resin, etc. Modified silicone resins modified with

A commercial item can be used as said silicone resin.
Examples of the straight silicone resin include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd.
Examples of the modified silicone resin include KR206 (alkyd modified silicone resin), KR5208 (acryl modified silicone resin), ES1001N (epoxy modified silicone resin), KR305 (urethane modified silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified silicone resin), SR2110 (alkyd-modified silicone resin) manufactured by Dow Corning Silicone Co., Ltd. and the like can be mentioned.

  The silicone resin can be used alone, but a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like can also be used at the same time.

  As content in the said carrier of the component which forms the said resin layer, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, it may not be possible to form the uniform resin layer on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer becomes thick. It becomes too much and granulation of carriers occurs, and uniform carrier particles may not be obtained.

  The content of the toner when the developer is a two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 2.0 mass relative to 100 mass parts of the carrier. Parts to 12.0 parts by mass are preferable, and 2.5 parts to 10.0 parts by mass are more preferable.

(Image forming apparatus and image forming method)
An image forming apparatus according to the present invention includes an electrostatic latent image carrier (hereinafter sometimes referred to as a “photosensitive member”), a charging unit that charges the surface of the electrostatic latent image carrier, and a charged static image. An exposure unit that exposes the electrostatic latent image carrier to form an electrostatic latent image, a developing unit that develops the electrostatic latent image using a developer to form a visible image, and the visible image recorded An image forming apparatus having at least a transfer means for transferring to a medium and a fixing means for fixing the transferred image transferred to the recording medium, wherein the developer is the developer of the present invention. The charging unit and the exposure unit are also collectively referred to as an electrostatic latent image forming unit. The image forming apparatus of the present invention further includes other means as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) is formed on the support. ), A photo-CVD method, a plasma CVD method, or other film forming methods can be used to provide a photoconductor having a photoconductive layer made of a-Si. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  There is no restriction | limiting in particular as a shape of the said electrostatic latent image carrier, Although it can select suitably according to the objective, A cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and more preferably 10 mm to 30 mm. Particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member (charging means) for charging the surface of the electrostatic latent image carrier and an exposure member (exposure means) for exposing the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
When the magnetic brush is used as the charging member, as the magnetic brush, for example, various ferrite particles such as Zn-Cu ferrite are used as the charging member, and a non-magnetic conductive sleeve for supporting the ferrite member is included in the charging member. It consists of a magnet roll.
When the fur brush is used as the charging member, as the material of the fur brush, for example, a fur conductively treated with carbon, copper sulfide, metal, or metal oxide is used. A charging member can be obtained by winding or sticking to a cored bar.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and developing process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.

The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed every time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state where the toners of the respective colors are stacked.
The fixing step can be performed by the fixing unit.
The heating in the heating and pressing member is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing unit depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

<Other means and other processes>
Examples of the other means include a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a cleaning process, a charge removal process, a recycling process, and a control process.

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

<< Recycling means and recycling process >>
The recycling unit is not particularly limited as long as it is a unit that causes the developing device to recycle the toner removed in the cleaning step, and can be appropriately selected depending on the purpose. Can be mentioned.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. For example, the recycling unit performs the recycling process. Can do.

<< Control means and control process >>
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
The control process is not particularly limited as long as it can control the movement of each process, and can be appropriately selected according to the purpose. For example, the control process can be performed by the control means.

  Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100A shown in FIG. 1 includes an electrostatic latent image carrier 10, a charging roller 20 as the charging unit, an exposure device (not shown) as the exposure unit, and a developing device 40 as the developing unit. And an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Also, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a recording medium. The intermediate transfer member 50 is disposed opposite to the intermediate transfer member 50. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 and the intermediate transfer member in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion with the body 50 and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the image forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 charges the electrostatic latent image carrier 10 uniformly. An exposure device (not shown) performs imagewise exposure on the electrostatic latent image carrier 10 to form an electrostatic latent image. The electrostatic latent image formed on the electrostatic latent image carrier 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the electrostatic latent image carrier 10 is removed by the cleaning device 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination lamp 70.

  FIG. 2 shows another example of the image forming apparatus of the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are directly opposed to each other around the electrostatic latent image carrier 10 without providing the developing belt 41. Except for this, the configuration is the same as that of the image forming apparatus 100A shown in FIG.

An image forming apparatus 100 </ b> C illustrated in FIG. 3 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Forming means). In each image forming unit, black, yellow, magenta, and cyan toner images are formed. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed in an image corresponding to each color image based on each color image information (FIG. 4). L), and an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And cyan tona ), A developing device 61 as the developing means for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, The static eliminator 64 is provided. Each image forming unit 18 can form each monochrome image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145, sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying apparatus main body 150, and abutted against the registration roller 49 to stop. It is done. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. Then, the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. By doing so, a color image is transferred and formed on the sheet (recording paper). The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 and is stacked on a discharge tray 57. Alternatively, the sheet is switched by the switching claw 55 and reversed by the sheet reversing device 28 and guided to the transfer position again. After the image is recorded on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57. Is done.

The present invention relates to the following electrophotographic toner (1), and includes the following (2) to (9) as embodiments.
(1) An electrophotographic toner containing at least a binder resin,
The maximum peak temperature of the heat of fusion measured by differential scanning calorimeter (DSC) is in the range of 50 ° C. to 70 ° C. and the heat of fusion is 10 J / g to 30 J / g,
When the free induction decay curve obtained by the pulse NMR method is separated into two curves derived from the hard component and the soft component constituting the toner, the spin-spin relaxation time T of the soft component at 100 ° C. _{An electrophotographic toner} , wherein _2tl (100) is 20 ms or more and a proton ratio H _tl (100) of the soft component is 0.2 or more.
(2) The toner for electrophotography as described in (1) above, wherein the soft component has a proton ratio H _tl (100) of 0.4 or more and 0.5 or less.
(3) The toner for electrophotography according to (1) or (2), wherein the binder resin contains an amorphous resin component (a) and a crystalline resin component (c).
(4) The binder resin has a non-crosslinking component,
The free induction decay curve obtained by the pulse NMR method for the non-crosslinked component is divided into three curves derived from the hard component, the soft component, and the interface component between the hard component and the soft component constituting the non-crosslinked component. When separated, H _rm (50) / H _rl (50), which is the ratio of the proton ratio H _rm (50) of the interface component to the proton ratio H _rl (50) of the soft component at 50 ° C., is 1.0. The toner for electrophotography according to any one of (1) to () 3), wherein:
(5) The toner for electrophotography according to (4), wherein the H _rm (50) / H _rl (50) is 0.7 or less.
(6) The binder resin includes a block copolymer obtained by block polymerization of an amorphous resin (A) and a crystalline resin (C), and the amorphous resin (A) is the amorphous resin. The toner for electrophotography according to any one of (3) to (5), wherein the toner constitutes component (a), and the crystalline resin (C) constitutes the crystalline resin component (c) .
(7) An oil phase obtained by dissolving or dispersing at least a binder resin,
Emulsifying or dispersing in an aqueous medium to produce an emulsified dispersion containing emulsified particles;
A step of converging the emulsified particles to granulate toner base particles;
Removing the organic solvent;
The toner for electrophotography according to any one of the above (1) to (6), wherein the toner is obtained by a production method comprising:
(8) A developer comprising the electrophotographic toner according to any one of (1) to (7).
(9) an electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, exposure means for exposing the charged electrostatic latent image carrier to form an electrostatic latent image, Developing means for developing the electrostatic latent image using a developer to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit, wherein the developer is the developer described in (8).

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

<Measurement of weight average molecular weight Mw>
The weight average molecular weight of the resin was measured as follows using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)).
As the column, TSKgel SuperHZM-H 15 cm triplet (manufactured by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.
The molecular weight was calculated using a calibration curve prepared with a monodisperse polystyrene standard sample. As the standard polystyrene sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three kinds of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
Solution A: S-7450 2.5mg, S-678 2.5mg, S-46.5 2.5mg, S-2.90 2.5mg, THF 50ml
Solution B: S-3730 2.5mg, S-257 2.5mg, S-19.8 2.5mg, S-0.580 2.5mg, THF 50ml
Solution C: S-1470 2.5mg, S-112 2.5mg, S-6.93 2.5mg, Toluene 2.5mg, THF 50ml
An RI (refractive index) detector was used as the detector.

<Measurement of glass transition temperature of resin>
The glass transition temperature of the resin was measured using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). Specifically, the heat change was determined by the following procedure.
From the obtained DSC curve, using the analysis program in the DSC-60 system, the DSC curve at the second temperature increase was selected, and the glass transition temperature at the second temperature increase of the target sample was obtained by the midpoint method. The value was used.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 5 ° C / min
End temperature: -20 ° C
Holding time: None Temperature increase rate: 5 ° C / min
End temperature: 150 ° C

<Measurement of melting point of resin>
The melting point (maximum peak temperature of heat of fusion) of the resin was measured using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
Specifically, among the endothermic peak temperatures of the target sample, in the case of a resin, the maximum endothermic peak temperature was taken as the melting point of the resin, and the following procedure was used.
From the obtained DSC curve, using the analysis program “endothermic peak temperature” in the DSC-60 system, the DSC curve at the second temperature increase was selected, and the endothermic peak at the second temperature increase of the target sample was obtained. .
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 5 ° C / min
End temperature: -20 ° C
Holding time: None Temperature increase rate: 5 ° C / min
End temperature: 150 ° C

<Measurement of maximum peak temperature and heat of fusion of toner>
The maximum peak temperature of heat of fusion of the toner and the amount of heat of fusion were measured using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
Specifically, among the endothermic peak temperatures of the target sample, the temperature of the maximum endothermic peak corresponding to the melting point of the resin was taken as the maximum peak temperature of the heat of fusion and was determined by the following procedure.
From the obtained DSC curve, using the analysis program “endothermic peak temperature” in the DSC-60 system, the DSC curve at the first temperature increase is selected, and the maximum peak of the heat of fusion at the first temperature increase of the target sample is selected. The temperature and heat of fusion were determined. The maximum peak temperature from the apex of the endothermic curve, and the area value surrounded by the baseline and endothermic peak were defined as the heat of fusion.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 5 ° C / min
End temperature: 150 ° C

(Production Example 1-1)
<Manufacture of amorphous resin A1>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, propylene glycol as a diol, dimethyl terephthalate and dimethyl fumarate as dicarboxylic acids, dimethyl terephthalate and dimethyl fumarate, The molar ratio (dimethyl terephthalate / dimethyl fumarate) is 80/20, and the ratio of OH groups to COOH groups (OH / COOH) is set to 1.2. The reaction was conducted with 300 ppm of titanium tetraisopropoxide while methanol was flowing out. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under reduced pressure of 20 mmHg-30 mmHg for 4 hours, and [Amorphous resin A1] which is a linear amorphous polyester resin was obtained.
The glass transition temperature (Tg) of the obtained resin was 64 ° C.

(Production Example 1-2)
<Production of amorphous resin A2>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, propylene glycol as a diol, dimethyl terephthalate and dimethyl fumarate as dicarboxylic acids, dimethyl terephthalate and dimethyl fumarate, The molar ratio (dimethyl terephthalate / dimethyl fumarate) is 95/5, and the ratio of OH groups to COOH groups (OH / COOH) is 1.2. The reaction was conducted with 300 ppm of titanium tetraisopropoxide while methanol was flowing out. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under reduced pressure of 20 mmHg-30mmHg for 4 hours, and [Amorphous resin A2] which is a linear amorphous polyester resin was obtained.
The obtained resin had a glass transition temperature (Tg) of 74 ° C.

(Production Example 1-3)
<Manufacture of amorphous resin A3>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol as a diol, dimethyl terephthalate and dimethyl fumarate as dicarboxylic acids, dimethyl terephthalate and dimethyl fumarate The molar ratio (dimethyl terephthalate / dimethyl fumarate) is 50/50, and the ratio of OH groups to COOH groups (OH / COOH) is 1.2, with respect to the mass of the charged raw materials. The reaction was conducted with 300 ppm of titanium tetraisopropoxide while methanol was flowing out. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under reduced pressure of 20 mmHg-30 mmHg for 4 hours, and [Amorphous resin A3] which is a linear amorphous polyester resin was obtained.
The glass transition temperature (Tg) of the obtained resin was 40 ° C.

(Production Example 2-1)
<Manufacture of crystalline resin C1>
A 5-L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 1,8-octanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups. (OH / COOH) was charged to 1.3 and reacted with 300 ppm of titanium tetraisopropoxide with respect to the mass of the charged raw material while water was discharged. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under the reduced pressure of 10 mmHg or less for 5 hours, and [crystalline resin C1] which is crystalline polyester resin was obtained.
The melting point (Tm) of the obtained resin was 68 ° C.

(Production Example 2-2)
<Manufacture of crystalline resin C2>
A 5-L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 1,4-butanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups. (OH / COOH) was charged to 1.3 and reacted with 300 ppm of titanium tetraisopropoxide with respect to the mass of the charged raw material while water was discharged. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under the reduced pressure of 10 mmHg or less for 5 hours, and [crystalline resin C2] which is crystalline polyester resin was obtained.
The melting point (Tm) of the obtained resin was 55 ° C.

(Production Example 2-3)
<Production of crystalline resin C3>
A 5-L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 1,4-butanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups. (OH / COOH) was charged to 1.2 and reacted with 300 ppm of titanium tetraisopropoxide with respect to the mass of the charged raw material while water was discharged. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under the reduced pressure of 10 mmHg or less for 5 hours, and [crystalline resin C3] which is crystalline polyester resin was obtained.
The obtained resin had a melting point (Tm) of 61 ° C.

(Production Example 2-4)
<Production of crystalline resin C4>
A 5-L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 1,3-hexanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups (OH / COOH) was charged to 1.3, and reacted with 300 ppm of titanium tetraisopropoxide with respect to the mass of the charged raw material while allowing water to flow out. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under the reduced pressure of 10 mmHg or less for 5 hours, and [crystalline resin C4] which is crystalline polyester resin was obtained.
The melting point (Tm) of the obtained resin was 46 ° C.

(Production Example 2-5)
<Production of crystalline resin C5>
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 1,10-decanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups. (OH / COOH) was charged to 1.3 and reacted with 300 ppm of titanium tetraisopropoxide with respect to the mass of the charged raw material while water was discharged. Finally, the temperature was raised to 230 ° C., and the reaction was continued until the resin acid value reached 5 mgKOH / g or less. Then, it was made to react under the reduced pressure of 10 mmHg or less for 5 hours, and [crystalline resin C5] which is crystalline polyester resin was obtained.
The melting point (Tm) of the obtained resin was 73 ° C.

Table 1 shows the molar ratios and physical properties of the alcohol components and carboxylic acid components of the amorphous resins A1 to A3 and the crystalline resins C1 to C5.

(Production Example 3-1)
<Manufacture of copolymer resin B1>
Into a 5 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer and a thermocouple, 1,800 g of [Amorphous Resin A1] and 200 g of [Crystalline Resin C2] were charged. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B1].

(Production Example 3-2)
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,400 g of [Amorphous resin A1] and 600 g of [Crystalline resin C2] were charged, and 2 at 60 ° C. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B2].

(Production Example 3-3)
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,400 g of [Amorphous resin A1] and 600 g of [Crystalline resin C3] were charged, and 2 at 60 ° C. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B3].

(Production Example 3-4)
<Manufacture of copolymer resin B4>
600 g of [Crystalline Resin C3] was charged into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and dried under reduced pressure at 10 mmHg at 60 ° C. for 2 hours. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Crystalline Resin Prepolymer C3 ′].
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, 1,400 g of [Amorphous Resin A1] and the obtained [Crystalline Resin Prepolymer C3 ′] were charged. Then, it was dried under reduced pressure at 10 mmHg for 2 hours at 60 ° C. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. The temperature was raised to 80 ° C. and reacted for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B4].

(Production Example 3-5)
<Manufacture of copolymer resin B5>
Into a 5 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple, 1,200 g of [Amorphous resin A1] and 800 g of [Crystalline resin C2] were charged, and 2 at 60 ° C. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B5].

(Production Example 3-6)
<Manufacture of copolymer resin B6>
Into a 5 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer and a thermocouple, 1,800 g of [Amorphous Resin A2] and 800 g of [Crystalline Resin C2] were charged, and 2 at 60 ° C. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B6].

(Production Example 3-7)
<Manufacture of copolymer resin B7>
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,400 g of [Amorphous resin A1] and 600 g of [Crystalline resin C4] were charged, and 2 at 60 ° C. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B7].

(Production Example 3-8)
<Manufacture of copolymer resin B8>
Into a 5 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple, 1,400 g of [Amorphous Resin A1] and 600 g of [Crystalline Resin C5] were charged. Vacuum drying was performed for 10 hours at 10 mmHg. After nitrogen depressurization, 2,000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 136 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate as a catalyst was added with respect to the mass of the resin solids, the temperature was raised to 80 ° C., and the reaction was performed for 5 hours under reflux. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [Copolymer Resin B8].

(Production Example 4)
<Manufacture of colorant master batch>
[Amorphous resin A1] 100 parts, 100 parts of cyan pigment (CI Pigment blue 15: 3) and 30 parts of ion-exchanged water were mixed well, and an open roll kneader (NIDEX, Nippon Coke Industries, Ltd.). Kneading was performed using The kneading temperature started kneading from 90 ° C. and then gradually cooled to 50 ° C. to prepare [Colorant master batch PA1] in which the ratio (mass ratio) of the resin to the pigment was 1: 1.
In addition, except that [Amorphous resin A1] is changed to [Amorphous resin A3] and [Copolymer resin B1] to [Copolymer resin B8], [Colorant masterbatch PA3], [Colorant master batch PB1] to [Colorant master batch PB8] were produced.

(Production Example 5)
<Manufacture of wax dispersion>
In a reaction vessel equipped with a condenser, a thermometer and a stirrer, 20 parts of paraffin wax (HNP-9 (melting point: 75 ° C.), manufactured by Nippon Seiwa Co., Ltd.) and 80 parts of ethyl acetate are placed and heated to 78 ° C. The solution was sufficiently dissolved and cooled to 30 ° C. with stirring for 1 hour, and further with an Ultra Visco Mill (manufactured by Imex), the liquid feeding speed was 1.0 kg / hour, the disk peripheral speed was 10 m / second, the diameter Wet pulverization was performed under the conditions of 80% by volume of 0.5 mm zirconia beads and 6 passes, and ethyl acetate was added to adjust the solid content concentration to produce a [wax dispersion] having a solid content concentration of 20%.

Example 1
<Manufacture of toner 1>
Into a container equipped with a thermometer and a stirrer, [Amorphous Resin A1] and [Crystalline Resin C1] are charged in the ratio shown in Table 3 (including the resin of the colorant masterbatch), and ethyl acetate is added. Add an amount so that the solid content of the entire oil phase is 50%, heat it to the melting point of the resin or higher and dissolve well, and add [Wax Dispersion] to an amount of 5% of the solid content of the entire oil phase, and [Colorant master batch PA1] was added in such an amount that the pigment became 6% of the solid content of the entire oil phase, and stirred at 50 ° C. with a TK homomixer (manufactured by Primics Co., Ltd.) at a rotation speed of 10,000 rpm. Was dissolved and dispersed in [Oil Phase 1]. The temperature of [Oil Phase 1] was kept at 50 ° C. in the container.
Next, in another container in which a stirrer and a thermometer are set, 75 parts of ion-exchanged water, organic resin fine particles for dispersion stabilization (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium, Salt copolymer) 3% dispersion (manufactured by Sanyo Chemical Industries, Ltd.), sodium carboxymethylcellulose (Serogen BS-H-3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), sodium dodecyl diphenyl ether disulfonate 16 parts of 48.5% aqueous solution (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 5 parts of ethyl acetate were mixed and stirred at 40 ° C. to prepare an aqueous phase solution ([aqueous phase 1]). 50 parts of [Oil Phase 1] maintained at 50 ° C. is added to the total amount of [Aqueous Phase 1], and mixed at 45 ° C. to 48 ° C. with a TK homomixer (manufactured by Primics Co., Ltd.) for 1 minute at 12,000 rpm. Thus, [Emulsified slurry 1] was obtained.
[Emulsion slurry 1] is charged into a container equipped with a stirrer and a thermometer, rapidly cooled from 50 ° C. to 10 ° C., 600 parts of ion-exchanged water is added, and the solvent is removed by decompression for 2 hours. 1] was obtained.
100 parts of [Slurry 1] of the obtained toner base particles was filtered under reduced pressure to obtain a filter cake. The following washing treatment was performed on the filter cake.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered.
(4) Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (5 minutes at 6,000 rpm) and then filter twice, and filter [filter cake 1]. Obtained.
The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to prepare [Toner Base Particles 1].
Next, 100 parts of the obtained [toner base particle 1] is added with 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) and 0.3% of titanium oxide (MT-150AI, manufactured by Teika Co., Ltd.). The parts were mixed using a Henschel mixer to prepare [Toner 1].
The obtained toner was measured for particle size distribution and component ratio by pulse NMR method.

<Manufacture of carrier 1>
As a core material, 5,000 parts of Mn ferrite particles (weight average diameter: 35 μm) were used.
As a coating material, 300 parts of toluene, 300 parts of butyl cellosolve, acrylic resin solution (composition ratio (molar ratio)) methacrylic acid: methyl methacrylate: 2-hydroxyethyl acrylate = 5: 9: 3, solid content 50% toluene solution, Tg 38 ° C. ) 60 parts, 15 parts of N-tetramethoxymethylbenzoguanamine resin solution (polymerization degree 1.5, solid content 77% toluene solution) and 15 parts of alumina particles (average primary particle size 0.30 μm) were dispersed with a stirrer for 10 minutes. The coating solution prepared in the above was used.
The core material and the coating liquid are charged into a coating apparatus that performs coating while forming a swirling flow provided with a rotary bottom plate disk and a stirring blade in a fluidized bed, and the coating liquid is placed on the core material. Applied. The obtained coated material was baked in an electric furnace at 220 ° C. for 2 hours to obtain [Carrier 1].

<Manufacture of developer 1>
[Carrier 1] 7 parts of [Toner 1] per 100 parts using a type of tumbler mixer (made by Willy et Bacofen (WAB)) in which the container rolls and stirs for 5 minutes at 48 rpm. Uniform mixing was performed to obtain [Developer 1] which is a two-component developer.

  As for the produced two-component developer, the image of the tandem type image forming apparatus shown in FIG. 3 of the indirect transfer method adopting the contact charging method, the two-component development method, the secondary transfer method, the blade cleaning method, and the externally heated roller fixing method. The development unit was loaded to form an image, and the following performance evaluation was performed.

<Evaluation>
<< Toner Aggregation >>
Using the produced two-component developer and the image forming apparatus shown in FIG. 3, after outputting 50,000 sheets of an image area ratio of 0.5%, the developer is taken out from the developing apparatus and sieved with a mesh having an aperture of 106 μm. The amount of toner remaining on the mesh after sieving was measured, and the amount of change in the developer weight was calculated and evaluated. Since the toner forms aggregates, the amount of toner that can pass through the mesh decreases. Therefore, it is determined that the smaller the amount of toner remaining on the mesh, the fewer toner aggregates formed in the developing device.
〔Evaluation criteria〕
◎: Less than 1% ○: 1% or more and less than 3% △: 3% or more and less than 5% ×: 5% or more

<< Heat-resistant storage stability (Penetration) >>
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.
In the present invention, the penetration is expressed by the penetration depth (mm).
〔Evaluation criteria〕
◎: Needle penetration 25 mm or more ○: Needle penetration 15 mm or more and less than 25 mm △: Needle penetration 10 mm or more but less than 15 mm ×: Needle penetration less than 10 mm

<< Low-temperature fixability (fixing minimum temperature) >>
Using the image forming apparatus shown in FIG. 3, the toner adhesion amount after transfer is 0.85 ± 0.10 mg / cm ² on transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>). A solid image (image size 3 cm × 8 cm) was formed on the entire paper surface, and fixing was performed by changing the temperature of the fixing belt. Using the drawing tester AD-401 (manufactured by Ueshima Seisakusho Co., Ltd.), the surface of the obtained fixed image is drawn with a ruby needle (tip radius 260 μmR to 320 μmR, tip angle 60 degrees), a load of 50 g, and a fiber (Hanicot # 440). (Manufactured by Hanilon Co., Ltd.), the drawing surface was rubbed strongly 5 times, and the fixing belt temperature at which the image was hardly scraped was determined as the minimum fixing temperature. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / second. The lower the fixing minimum temperature, the better the low-temperature fixability.
〔Evaluation criteria〕
A: 105 ° C. or lower ○: 105 ° C. or higher and 115 ° C. or lower Δ: 115 ° C. or higher and 130 ° C. or lower ×: 130 ° C. or higher

(Examples 2 to 7)
<Manufacture of toners 2-7 and developers 2-7>
In the production of the toner of Example 1, [Amorphous Resin A1] and [Crystalline Resin C1] are respectively changed as shown in Table 3 below, and [Colorant Master Batch PA1] is shown as shown in Table 3 below. Instead, [Toner 2] to [Toner 7] and [Developer 2] to [Developer 7] were produced in the same manner as in Example 1. However, in Table 3, with respect to the examples described as being present in the item of rapid cooling at the time of granulation, it was rapidly cooled from 50 ° C. to 10 ° C. during the solvent removal as in Example 1 and described as “None”. In some examples, the temperature was kept at 50 ° C. For the examples described as “Yes” in the item of water dilution, 600 parts of ion-exchanged water was added at the time of solvent removal in the same manner as in Example 1; Was not put in. Table 4 shows the results of quality evaluation of the toner and developer.

(Comparative Examples 1-6)
<Production of Toners 8 to 13 and Developers 8 to 13>
In the production of the toner of Example 1, [Amorphous Resin A1] and [Crystalline Resin C1] are respectively changed as shown in Table 3 below, and [Colorant Master Batch PA1] is shown as shown in Table 3 below. Instead, [Toner 8] to [Toner 13] and [Developer 8] to [Developer 13] were produced in the same manner as in Example 1. However, in Table 3, with respect to the examples described as being present in the item of rapid cooling at the time of granulation, it was rapidly cooled from 50 ° C. to 10 ° C. during the solvent removal as in Example 1 and described as “None”. In some examples, the temperature was kept at 50 ° C. For the examples described as “Yes” in the item of water dilution, 600 parts of ion-exchanged water was added at the time of solvent removal in the same manner as in Example 1; Was not put in. Table 4 shows the results of quality evaluation of the toner and developer.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer Supply roller 44K Developing roller 44Y Developing roller 44M Developing roller 4C developing roller 45K black developing unit 45Y yellow developing unit 45M magenta developing unit 45C cyan developing unit 49 registration roller 50 intermediate transfer member 51 roller 52 separation roller 53 manual feed path 54 manual feed tray 55 switching claw 56 discharge roller 57 discharge tray 58 corona Charger 60 Cleaning device 61 Development device 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 120 Tandem type developer 130 Document table 142 Feed Paper roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 160 Charging device 200 Paper feed table 300 CANA400 Automatic document feeder (ADF)

Japanese Patent No. 3949553 Japanese Patent No. 4155108 JP 2012-18391 A JP 2002-287426 A

Claims (9)

An electrophotographic toner containing at least a binder resin,
The maximum peak temperature of the heat of fusion measured by differential scanning calorimeter (DSC) is in the range of 50 ° C. to 70 ° C. and the heat of fusion is 10 J / g to 30 J / g,
When the free induction decay curve obtained by the pulse NMR method is separated into two curves derived from the hard component and the soft component constituting the toner, the spin-spin relaxation time T of the soft component at 100 ° C. _{An electrophotographic toner} , wherein _2tl (100) is 20 ms or more and a proton ratio H _tl (100) of the soft component is 0.2 or more. The electrophotographic toner according to claim 1, wherein a proton ratio H _tl (100) of the soft component is 0.4 or more and 0.5 or less.   The toner for electrophotography according to claim 1, wherein the binder resin contains an amorphous resin component (a) and a crystalline resin component (c). The binder resin has a non-crosslinked component;
The free induction decay curve obtained by the pulse NMR method for the non-crosslinked component is divided into three curves derived from the hard component, the soft component, and the interface component between the hard component and the soft component constituting the non-crosslinked component. When separated, H _rm (50) / H _rl (50), which is the ratio of the proton ratio H _rm (50) of the interface component to the proton ratio H _rl (50) of the soft component at 50 ° C., is 1.0. The toner for electrophotography according to any one of claims 1 to 3, wherein: The toner for electrophotography according to claim 4, wherein the H _rm (50) / H _rl (50) is 0.7 or less.   The binder resin includes a block copolymer obtained by block polymerization of an amorphous resin (A) and a crystalline resin (C), and the amorphous resin (A) is the amorphous resin component (a The electrophotographic toner according to claim 3, wherein the crystalline resin (C) constitutes the crystalline resin component (c). An oil phase in which at least a binder resin is dissolved or dispersed,
Emulsifying or dispersing in an aqueous medium to produce an emulsified dispersion containing emulsified particles;
A step of converging the emulsified particles to granulate toner base particles;
Removing the organic solvent;
The toner for electrophotography according to any one of claims 1 to 6, wherein the toner is obtained by a production method comprising:   A developer comprising the electrophotographic toner according to claim 1.   An electrostatic latent image carrier, a charging means for charging the surface of the electrostatic latent image carrier, an exposure means for exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and the electrostatic latent image carrier. Developing means for developing a latent image by using a developer to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus comprising: the image forming apparatus according to claim 8, wherein the developer is the developer according to claim 8.

Images