JP2015072442A - Toner, and developer using the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can achieve both low-temperature fixability and heat-resistant storage property at high level and has excellent abrasion resistance, and provides a good charging property and image density.SOLUTION: There is provided a toner containing at least a binder resin, where the binder resin contains a block copolymer resin having an amorphous polyester part (A) and a crystalline polyester part (C) and a crystalline resin, and the toner has a spin-spin relaxation time (t'70), which is measured at 70°C by pulse NMR after the temperature is reduced from 130°C to 70°C, of 0.3 ms or more and 2.0 ms or less.

Description

  The present invention relates to a toner and a developer using the 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 step for fixing the toner image onto 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, there are problems that the toner is fused and contaminated inside the developing device and the carrier in the developing device, and that the toner is likely to film on the surface of the photoreceptor.

In order to solve these problems, many toners using both a crystalline resin and an amorphous resin have been proposed (see, for example, Patent Documents 1 and 2). These improve the compatibility between low-temperature fixability and heat-resistant storage as compared with conventional toners composed only of amorphous resins.
However, when the amount of the crystalline resin added is increased, there is a problem that the abrasion resistance of the image deteriorates. That is, when the toner melts on the fixing medium at the time of heat fixing, the crystalline resin and the amorphous resin phase separate, and in the molten state, the soft crystalline resin floats on the image surface, and the crystalline resin in the toner is Since it takes time to crystallize again, the toner image surface is sent to the paper discharge process in a soft state.
For this reason, there are problems that a scar is generated on the surface of the image or a change in glossiness occurs due to contact with the paper discharge roller and the conveying member in the paper discharge process and rubbing.

Further, a technique for improving toner strength by blending crystalline resins having different molecular weights and improving the crystal growth rate after fixing has been proposed (for example, Patent Document 3).
However, the time from the fixing process to passing through the paper discharge roller in the paper discharge process is generally several seconds to several tens of seconds, which does not solve the abrasion resistance of the image, and the addition of crystalline resin Since the amount is also limited, it is not a technique that sufficiently satisfies rubbing resistance and low-temperature fixability.

In addition, many toners using a resin in which a crystalline segment and an amorphous segment are chemically bonded are proposed.
For example, a toner has been proposed in which a resin in which crystalline polyester and polyurethane are bonded is used as a binder resin (see, for example, Patent Documents 4 and 5). In addition, a toner has been proposed in which a resin in which crystalline polyester and amorphous polyester are bonded is used as a binder resin (see, for example, Patent Documents 6 and 7).

These proposed technologies can finely disperse the crystalline segments in the non-crystalline segments, and further suppress the exposure of the crystalline segments on the toner particle surface and the image surface. The amount of segments having can be relatively large.
However, the resin in which the crystalline polyester and the amorphous polyester are bonded does not phase-separate the crystalline polyester and the amorphous polyester after fixing even if the amount of the crystalline segment is adjusted. Amorphous segments are compatible with each other, resulting in a decrease in crystallinity, and the trade-off relationship between improved low-temperature fixability and improved image abrasion resistance cannot be resolved. It was.

Further, in order to phase-separate the crystalline polyester and the amorphous polyester after fixing, the crystalline resin may be used in combination with a resin obtained by chemically bonding a crystalline segment and an amorphous segment. If the crystalline resin is not used properly, the degree of phase separation before fixing is large, as in the case where a crystalline resin and an amorphous resin are used together. When heat is applied outside the region, charging characteristics deteriorate due to carrier contamination and filming, and a suitable image density cannot be obtained.
However, development of means for controlling the domain diameter derived from the crystalline resin before fixing to be suitable is desired.

Accordingly, 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, and further has excellent rubbing resistance, and can obtain good charging characteristics and image density. And

  The present inventors chemically bond the crystalline segment and the amorphous segment to form a block copolymer resin, and further add a crystalline resin to improve the crystallinity, and a desired spin-spin relaxation time. By satisfying the requirements, not only the low-temperature fixability but also the molecular motion of the crystalline segment is constrained, and the heat-resistant storage stability is improved, and the crystallinity of the crystalline segment is increased and the abrasion resistance can be improved. It has been found that good charging characteristics and image density can be obtained, and the present invention has been completed.

The said subject is solved by following (1)-(11) of this invention.
(1) A toner containing at least a binder resin, wherein the binder resin includes a block copolymer resin having an amorphous polyester portion (A) and a crystalline polyester portion (C), a crystalline resin, The spin-spin relaxation time (t′70) at 70 ° C. when the temperature is lowered from 130 ° C. to 70 ° C. measured by pulse NMR of the toner is 0.3 ms to 2.0 ms. A toner characterized by being.
(2) The toner according to item (1), wherein the toner has a hydrophobicity of 40% to 80%.
(3) When the toner is measured by differential scanning calorimetry (DSC), the peak temperature of the heat of fusion at the second temperature rise is 60 ° C. when the insoluble matter that is insoluble in 40 ° C. ethyl acetate is dried. The toner according to (1) or (2), wherein the toner is present at 100 ° C. or lower.
(4) The block copolymer resin has a mass ratio ((A) / (C)) between the amorphous polyester portion (A) and the crystalline polyester portion (C) of 90/10 to 60/40. The toner according to any one of (1) to (3), wherein the toner is present.
(5) The toner according to any one of (1) to (4) above, which contains 5% by mass to 30% by mass of a crystalline polyester resin with respect to the block copolymer resin.
(6) The toner according to any one of (1) to (5), wherein the block copolymer resin has a urethane bond and / or a urea bond.
(7) The binder resin includes a portion having a large phase difference obtained by binarizing a phase image observed by the tapping mode AFM with an intermediate value between the maximum value and the minimum value of the phase difference. Items (1) to (6), wherein one phase difference image is dispersed in a second phase difference image composed of a portion having a small phase difference, and a dispersion diameter of the first phase difference image is 100 nm or less. The toner according to any one of Items.
(8) In the diffraction spectrum obtained by the X-ray diffractometer of the toner,
When the integrated intensity of the spectrum derived from the crystal structure of the binder resin is I (C) and the integrated intensity of the spectrum derived from the amorphous structure is I (A), the ratio I (C) / (I (C) The toner according to any one of (1) to (7), wherein + I (A)) is 0.10 or more and 0.30 or less.
(9) The toner according to item (8), wherein I (C) / (I (C) + I (A)) is 0.15 or more.
(10) A developer containing the toner according to any one of (1) to (9).
(11) 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 the item (10).

  As will be understood from the following detailed and specific description, according to the present invention, a toner having not only low-temperature fixability but also excellent heat-resistant storage stability, abrasion resistance, charging characteristics, and image density is provided. Can do.

It is an example of the diffraction spectrum obtained by X-ray diffraction measurement. It is an example of the diffraction spectrum obtained by X-ray diffraction measurement. It is an example of the AFM phase image of block copolymer resin. It is an example of the binarized image binarized by the intermediate value between the maximum value of the phase difference and the minimum value of the phase difference. It is an example of the micro diameter image excluded from calculation of an average diameter. 1 is a schematic diagram illustrating an example of an image forming apparatus. It is the schematic which shows another example of an image forming apparatus. It is the schematic which shows another example of an image forming apparatus. It is the schematic which shows an example of an image formation means.

The toner of the present invention will be described in detail.
The property of the resin having a crystalline segment that is easily plastically deformed is considered to be caused by the folded structure of the polymer chain in the crystalline segment. Not all of the crystalline segments exhibit crystallinity, and the crystalline segment is composed of a crystal part in which molecular chains are folded and arranged, and an amorphous part composed of molecular chain folding parts and molecular chains existing between the crystal parts. Composed.
For example, even a straight-chain polyethylene single crystal with a high degree of crystallinity has about 3% non-crystalline sites.

It is thought that the non-crystalline part of the crystalline segment with high molecular mobility contributes greatly to the plastic deformation of the crystalline segment, and how the molecular mobility of the non-crystalline part can be constrained. It becomes important when utilizing the resin which has.

In the present invention, a microphase separation structure of a refined sea-island structure in which the amorphous segment is the sea inside the toner particles and the crystalline segment is an island is formed, and the molecular mobility of the crystalline segment is controlled by the amorphous segment. It is preferable to use a block copolymer resin restrained by. Thereby, below the melting point of the crystalline segment, the molecular mobility of the non-crystalline part of the crystalline segment is restricted, and excellent mechanical durability is obtained. On the other hand, the crystalline segment melts in the fixing temperature region, and the entire toner particles are quickly elastically relaxed and deformed. Then, after image fixing, at the time of paper discharge, the amorphous segment immediately suppresses excessive molecular motion of the crystalline segment.
In addition, the fine sea-island structure prevents excessive exposure of the crystalline segments to the image surface, enabling rapid image hardness recovery.

Furthermore, in order to satisfy the melting characteristics of the toner, it is desirable that the crystalline segment and the amorphous segment are polyester.
However, if the crystalline segment and the amorphous segment are polyester, the composition approaches and the compatibility of the crystalline segment and the amorphous segment increases, so the crystalline segment and the amorphous segment are mixed. The region widens and the crystallinity decreases.

In the present invention, by adding a crystalline resin having a composition close to that of the crystalline segment of the block copolymer resin to the block copolymer resin, the crystallinity of the crystalline segment after being once melted and solidified is large. It is possible to improve both low-temperature fixability and heat-resistant storage stability, and further improve the scratch resistance.

The details of this phenomenon have not been clarified, but when there is no crystalline resin, the crystalline segment and amorphous segment, which are close in composition, are almost uniformly mixed by melting, and the state is maintained even when solidified. Is done. In contrast, when there is a crystalline resin, the crystalline segment and the crystalline resin are compatible in the molten state. However, when solidifying, the amorphous segment of the block copolymer resin is excluded from the crystalline resin. In addition, since the crystalline segment is attracted to and separated from the crystalline resin, it is considered that the crystalline segment and the amorphous segment are difficult to mix and the crystallinity is improved.

  In addition, by incorporating a crystalline segment and an amorphous segment in the same molecular chain, the crystalline segment greatly reduces the viscosity at low temperatures, thereby exhibiting low-temperature fixability, and amorphous at high temperatures. It is possible to exhibit suppression of hot offset due to the entangled viscoelastic behavior of the segments having entanglement and satisfy two conflicting characteristics at the same time.

However, preservability and fluidity under high temperature and high humidity conditions may decrease.
Polyesters have weak hydrophilic ester bond sites and hydrophilic OH groups and COOH groups at the ends, and the polyester as a whole has many hydrophilic sites. In particular, in the case of crystalline polyester, since many of the monomers used are aliphatic short-chain skeletons, the number of hydrophilic sites per weight of the resin is larger than that of other resins, and it has a property of easily absorbing moisture.

Therefore, those containing a crystalline resin are more likely to have a significant problem under the “high temperature and high humidity condition” than those using a conventional resin for electrophotographic toner.

For example, preservability and fluidity deteriorate due to easy aggregation under high-temperature and high-humidity conditions, and aggregation causes problems in the system such as a decrease in charge amount due to poor agitation and insufficient image density resulting therefrom. The occurrence of such defects is fatal to the electrophotographic process.

In order to prevent the occurrence of the above-described problems under high temperature and high humidity conditions, the moisture resistance performance is improved by using, as a toner, an external additive obtained by hydrophobizing the surface of the inorganic fine particles.
However, when a crystalline segment and a resin obtained by block copolymerization of a crystalline segment and an amorphous segment are included, the main resin is hydrophilic, resulting in high temperature and high humidity conditions. Therefore, it is necessary to cover the entire surface of the toner particles with the hydrophobic inorganic fine particles in order to ensure the moisture resistance by only one means of externally adding the hydrophobic inorganic fine particles to the surface of the toner particles. The fixability to paper is greatly impaired. This is contrary to the good low-temperature fixability, which is the purpose of introducing crystalline segments into the main resin.

In the case of a toner using a binder resin containing a block copolymer obtained by block copolymerization of a crystalline segment and an amorphous segment and a crystalline resin as in the present invention, the toner is hydrophobicized. Even if inorganic fine particles are used, it is necessary to suppress moisture absorption by the portion where the binder resin is exposed on the surface.

Therefore, it is necessary to suppress the hygroscopicity of the binder resin itself as the main component, and after reducing the hydrophilicity of the binder resin, such as removal of low molecular weight components in the binder resin, It is necessary to compensate for the influence of hygroscopicity that inevitably exists as a property by coating with hydrophobic inorganic fine particles or organic fine particles, and to adjust the degree of hydrophobicity of the entire toner.

In the case of a toner using a binder resin containing a crystalline resin and a resin obtained by block copolymerization of a crystalline segment and an amorphous segment, low-temperature fixability, hot offset resistance, and In order to simultaneously satisfy the storage stability and fluidity under high temperature and high humidity conditions, the hydrophobicity of the whole toner is preferably 40% or more and 80% or less.

The material constituting the toner of the present invention will be described.
The toner of the present invention contains at least a binder resin, and further contains other components as necessary.

<Binder resin>
The binder resin contains a block copolymer resin having an amorphous polyester portion (A) and a crystalline polyester portion (C), and a crystalline resin.

(Block copolymer resin)
The block copolymer resin (hereinafter sometimes simply referred to as copolymer resin) is a copolymer resin having a structural unit derived from a crystalline resin and a structural unit derived from an amorphous resin. By using the copolymer resin, a specific higher order structure represented by a microphase separation structure can be formed.

The copolymer resin is obtained by covalently bonding different polymer chains. In general, many different types of polymer chains are incompatible with each other and do not mix as they are like water and oil.
In a simple mixed system of different polymer materials, the polymer chains can move independently, so the same kind of polymer chains gather together, for example, macrophase separation into two phases, but in the case of copolymer resins, polymers with different structures Since the chains are connected to each other, the same kind of polymer chains cannot be collected and phase-separated. However, in the copolymer resin, although the different polymer chains are linked to each other, even if the same kind of polymer chains are aggregated and the different polymer chains are separated as much as possible, the respective polymer chains It can only be divided into a size about a structural unit, for example, a portion with many A structural units and a portion with many B structural units.
For this reason, if the degree of phase mixing (compatibility), composition, and length (molecular weight and distribution) of component A and component B, and the blending ratio of both are changed, the form (structure) of phase separation changes, for example A. K. Khandpur, S .; Forster, and F.M. S. Bates, Macromolecules, 28 (1995) 8996-8806. As illustrated in the above, periodic ordered mesostructures such as a Sphere structure, a Cylinder structure, a Gyroid structure, and a Lamella structure can be controlled.

The copolymer resin of the present invention comprises a crystalline component and an amorphous component. When the copolymer resin is crystallized from the state of the microphase separation structure, by controlling the periodic ordered mesostructure, the microphase separation structure of the melt is used as a template, so that the crystalline phase is several dozen. Regular arrangement can be achieved on a scale of nm to several hundred nm.
Therefore, by utilizing these higher-order structures, in the case where fluidity such as fixing is required, sufficient fluidity and deformability based on the solid-liquid phase transition phenomenon of the crystal part is given, while the inside of the machine after storage and fixing In situations where fluidity and deformability are not required, such as in the transport process, the mobility can be constrained by enclosing the crystal part in the structure.

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

For example, whether or not the toner contains a block copolymer resin having an amorphous polyester portion (A) and a crystalline polyester portion (C) 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.

Further, the purified membrane is subjected to FT-IR measurement, NMR measurement (1H, 13C), GC / MS measurement, and in some cases, NMR measurement (2D) capable of analyzing the molecular structure in more detail, thereby obtaining its composition and structure. In addition, various properties can be grasped, and for example, the presence of a polyester skeleton or urethane bond, their composition, and composition ratio can be confirmed.
By comprehensively judging the above measurement and analysis results, it can be judged whether or not the first resin (copolymer) 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 2.5 mg, S-678 2.5 mg, S-46.5 2.5 mg, S-2.90 2.5 mg, THF 50 ml
Solution B: S-3730 2.5 mg, S-257 2.5 mg, S-19.8 2.5 mg, S-0.580 2.5 mg, THF 50 ml
Solution C: S-1470 2.5 mg, S-112 2.5 mg, S-6.93 2.5 mg, Toluene 2.5 mg, THF 50 ml
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>
5 mg of a sample was sealed in a T-Zero simple sealed pan manufactured by TA Instruments, and measured using a differential scanning calorimeter (DSC) (Q2000 manufactured by TA Instruments). The measurement was performed under a nitrogen stream, 1st. As heating, the temperature was raised from 40 ° C. to 150 ° C. at 5 ° C./min, held for 5 minutes, and then to −70 ° C. at 5 ° C./min. And cooled for 5 minutes.
Then 2nd. As heating, the temperature change is measured at a heating rate of 5 ° C./minute, and the change in heat is measured. Asked. 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.

<Example of TEM observation>
-Procedure-
(I) The sample was exposed to an atmosphere of RuO ₄ aqueous solution and dyed for 2 hours.
(II) 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
Sections were fixed on a mesh using diamond knife (Ultra Sonic 35 °) (III), and stained for 5 minutes by exposure to an atmosphere of aqueous RuO ₄ solution.
-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 an 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. for all, and 1H-NMR measurement was performed with 256 integrations and a repetition time of 5.0 s. In the 13C measurement, the number of integrations was 10,000, and the repetition time was 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 1H-1H shift correlation two-dimensional NMR measurement (DQF-COSY) measurement and the like. It can be carried out at 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 1H and 13C 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 reaction 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 ° C
Column: Ultra ALLOY-5 L = 30 m ID = 0.25 mm Film = 0.25 μm
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 (70 eV)
Mass range: m / z 29-700
Injection mode: Split (1: 100)

<About characteristics required by pulse NMR>
In the block copolymer resin of the present invention, the crystalline segment and the amorphous segment are chemically bonded, and the molecular motion of the crystalline segment is restricted by controlling the structure of each segment.

Pulsed NMR (hereinafter sometimes referred to as “pulsed NMR”) is effective for scaling molecular mobility.
Unlike the high-resolution NMR, the pulsed NMR does not give chemical shift information (such as local chemical structure). Instead, the pulsed NMR method can quickly measure relaxation times (spin-lattice relaxation time (T1) and spin-spin relaxation time (T2)) of 1H nuclei that are closely related to molecular mobility. In recent years, its use has spread rapidly.

Examples of the measurement method in the pulse method NMR include the Hahn echo method, the solid echo method, the CPMG method (Car Purcell, Mayboom, Gill method), the 90 ° pulse method, and the like, and any of them can be suitably used.
In general, the solid echo method and the 90 ° pulse method are suitable for short T2 measurement, the Hahn echo method is suitable for medium T2 measurement, and the CPMG method is suitable for long T2 measurement.

Since the toner and toner resin in the present invention have a medium spin-spin relaxation time (T2), the measurement by the Hahn echo method is most suitable.

In the present invention, the spin-spin relaxation time (t50) at 50 ° C. represents a measure of molecular mobility related to storage stability, and the spin-spin relaxation time (t130) at 130 ° C. represents a measure of molecular mobility related to fixing. Represent.
Further, the spin-spin relaxation time (t′70) at 70 ° C. when the temperature is lowered from 130 ° C. to 70 ° C. represents a measure of molecular mobility related to the abrasion resistance during image conveyance.

  In these regulations, satisfying a specific range has sufficient mobility when fluidity such as fixing is required, and sufficient mobility when fluidity is not required, such as storage and transport in the machine. Indicates that it is restrained.

The t50, t130, and t′70 of the toner will be described.
The t50, which is a measure of molecular mobility related to storage stability, is preferably 2.0 ms or less. If the t50 exceeds 2.0 ms, the toner motility at 50 ° C. becomes high, and deformation and aggregation due to external force are likely to occur, which may cause difficulties in overseas transportation and storage in summer and sea mail.
The t50 is more preferably 1.0 ms or less.

  The t130, which is a measure of molecular mobility relating to fixing characteristics, is preferably 15 ms or more and 17 ms or less. If the t130 is less than 15 ms, the molecular mobility during heating becomes insufficient, and the flow and deformation of the toner decrease. As a result, a decrease in image spreadability and a decrease in bonding with a print target occur, which may result in a decrease in image quality such as a decrease in gloss and image peeling.

  Further, the t′70, which is a measure of molecular mobility related to abrasion resistance during image conveyance, is 0.3 ms to 2.0 ms. When the t′70 is less than 0.3 ms, the heat resistant storage stability may be deteriorated. When the t′70 is more than 2.0 ms, the roller and the transport in the paper discharge process after fixing are sufficiently performed before the molecular mobility is sufficiently restricted. Contact with a member or rubbing may occur, and a scar or a change in glossiness may occur on the image surface.

<Measurement method using pulsed NMR>
The spin-spin relaxation time can be measured using, for example, “Minispec-MQ20” manufactured by Bruker Optics. In the examples to be described later which are embodiments of the present invention, the measurement was performed by the following method using the apparatus.

Specifically, an attenuation curve is measured with a pulse sequence of the Hahn-echo method (90 ° x−Pi−180 ° x) under the conditions that the observation nucleus is 1H, the resonance frequency is 19.65 MHz, and the measurement interval is 5 s.
Pi is 0.01 ms to 100 ms, the number of data points is 100, the number of integration is 32 times, and the measurement temperature is changed in the order of 50 ° C. → 130 ° C. → 70 ° C.
The sample is measured by putting 0.2 g of toner powder or 0.2 g of toner resin powder in a dedicated sample tube and inserting the sample into the sample tube up to an appropriate range of the magnetic field. By this measurement, for each sample, the spin-spin relaxation time at 50 ° C. (t50), the spin-spin relaxation time at 130 ° C. (t130), and the spin-spin relaxation at 70 ° C. when the temperature is lowered from 130 ° C. to 70 ° C. Each time (t′70) is obtained.

In the toner of the present invention, in a diffraction spectrum at 25 ° C. obtained by an X-ray diffractometer, the integrated intensity of the spectrum derived from the crystal structure is I (C), and the integrated intensity of the spectrum derived from the non-crystalline structure is I In the case of (A), the ratio I (C) / (I (C) + I (A)) is preferably 0.10 or more and 0.25 or less from the viewpoint of compatibility between fixability and heat-resistant storage stability. 0.15 to 0.2 is more preferable.

In the present invention, when the toner contains wax, a diffraction peak specific to wax often appears at a position of 2θ = 23.5 to 24 °. However, when the wax content with respect to the total weight of the toner is 15% by weight or less, the contribution of the diffraction peak inherent to the wax is negligible.
When the amount exceeds 15% by weight, the value obtained by subtracting the integral intensity of the spectrum derived from the crystal structure of the wax from the integral intensity of the spectrum derived from the crystal structure of the binder resin is the above-mentioned “crystal structure of the binder resin”. It is to be replaced with “integrated intensity I (C) of the derived spectrum”.

In the present invention, the ratio I (C) / (I (C) + I (A)) can be obtained by X-ray diffraction measurement, and specifically, a two-dimensional detector-mounted X-ray diffractometer (D8 DISCOVER with). GADDS / Bruker).
In addition, a conventionally known toner containing a crystalline resin or wax to the extent of an additive has a ratio of less than about 0.15.

The capillary used for the measurement was a mark tube (Lindenman glass) having a diameter of 0.70 mm. The sample was packed up to the top of the capillary tube and measured.
Further, tapping was performed when filling the sample, and the number of tapping was 100 times.
For the incident optical system, a collimator having a pinhole of φ1 mm was used. The obtained two-dimensional data was integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted into one-dimensional data of diffraction intensity and 2θ.

Detailed measurement conditions are shown below.

Tube current: 40 mA
Tube voltage: 40 kV
Goniometer 2θ axis: 20.0000 °
Goniometer Ω axis: 0.0000 °
Goniometer φ axis: 0.0000 °
Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
Measurement time: 600 sec

A method for calculating the ratio I (C) / (I (C) + I (A)) based on the obtained X-ray diffraction measurement result will be described below.
Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. The horizontal axis is 2θ, the vertical axis is the X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum in FIG. 1, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and halo (h) is observed in a wide range including these two peaks.
Here, the main peak is derived from the crystal structure, and the halo is derived from the amorphous structure.
These two main peaks and halos are represented by Gaussian functions represented by the following formulas A (1) to (3).

fp1 (2θ) = ap1exp {− (2θ−bp1) 2 / (2cp12)} (formula A (1))
fp2 (2θ) = ap2exp {− (2θ−bp2) 2 / (2cp22)} (formula A (2)
)
fh (2θ) = ahexp {− (2θ−bh) 2 / (2ch2)} (Formula A (3))
However, (fp1 (2θ), fp2 (2θ), and fh (2θ) are functions corresponding to the main peaks P1, P2, and halo, respectively)

The sum of these three functions is expressed by the following formula A (4).

f (2θ) = fp1 (2θ) + fp2 (2θ) + fh (2θ) (formula A (4))

The above equation A (4) was used as a fitting function (shown in FIG. 2) of the entire X-ray diffraction spectrum, and fitting by the least square method was performed.
There are nine fitting variables, ap1, bp1, cp1, ap2, bp2, cp2, ah, bh, and ch. As initial values of the fitting of each variable, the peak positions of X-ray diffraction (bp1 = 21.3, bp2 = 24.2, bh = 22.5 in the example of FIG. 1) are other than bp1, bp2, and bh. The value obtained by matching the two main peaks and the halo with the X-ray diffraction spectrum as much as possible was set by appropriately inputting the variable.
Fitting can be performed using, for example, Microsoft 2003 Excel 2003 solver.
The integrated areas (SP1, Sp2, Sp2, Sp2) of the Gaussian functions fp1 (2θ), fp2 (2θ) corresponding to the two main peaks (P1, P2) after the fitting, and the Gaussian function fh (2θ) corresponding to the halo. From (Sh), when (Sp1 + Sp2) is I (C) and (Sh) is I (A), the ratio I (C) / (I (C) + I (A) is an index indicating the amount of crystallization sites. ) Can be calculated.

<Characteristics required by AFM>
The structure of the toner of the present invention is confirmed by a phase image in a tapping mode by an atomic force microscope (AFM).
The copolymer in the present invention is characterized in that it has a soft part, that is, a part observed as an image having a large phase difference and a part that is hard and observed as an image having a small phase difference.
At this time, the second phase difference image consisting of a hard low phase difference portion is an outer phase, and the first phase difference image consisting of a soft high phase difference portion is an inner phase and has a finely dispersed structure. Is important in the present invention.

The toner binarizes the phase image observed by the tapping mode AFM with an intermediate value between the maximum value and the minimum value of the phase difference, and the first phase difference image including a portion having a large phase difference and the phase difference The binarized image divided into the second phase difference image composed of a small portion of the first phase difference image has a structure in which the first phase difference image is dispersed in the second phase difference image.
Further, the average (dispersion diameter) of the maximum ferret diameter in the dispersed phase of the first phase difference image composed of a portion having a large phase difference is preferably 100 nm or less, more preferably 10 nm to 100 nm, and further preferably 60 nm to 100 nm. preferable.

In the present invention, the fact that the first phase difference image has a structure dispersed in the second phase difference image means that a boundary between domains can be defined in the binarized image. This means that the ferret diameter in the dispersed phase of the phase difference image can be defined.
If the first phase difference image in the binarized image has a minute particle size that is difficult to distinguish between image noise and phase difference image, or if a clear ferret diameter cannot be defined, “the structure is not dispersed. " When the first phase difference image is buried in image noise and the boundary between domains cannot be defined, the ferret diameter cannot be defined.
Only when the domain shape is striped and the maximum ferret diameter is 300 nm or more, the minimum ferret diameter is used as the domain diameter instead of the maximum ferret diameter.

In order to improve the toughness of the binder resin, it is necessary to introduce a structure that relieves external deformation and pressure inside the resin. One means for this is to introduce a softer structure.
In this case, however, the toner particles are likely to be blocked during storage, or damage and adhesion of the image due to its softness. In order to achieve both toughness and relaxability, it is necessary to solve the trade-off relationship between the two.

  For the binder resin, the second phase image composed of a part having a small phase difference is obtained from the first phase difference image composed of a part having a large phase difference, which can effectively act on stress relaxation and improve toughness. It was found that the trade-off relationship between improved resin toughness and relaxability can be eliminated by adopting a structure having a fine structure dispersed in the phase difference image.

(AFM measurement method)
The tapping mode in the atomic force microscope is a method described in Surface Science Letter, 290, 668 (1993). In this method, for example, as described in Polymer, 35, 5778 (1994), Macromolecules, 28, 6773 (1995), the shape of the sample surface is measured while vibrating the cantilever. At this time, due to the viscoelastic nature of the sample surface, a phase difference occurs between the drive that is the vibration source of the cantilever and the actual vibration. A phase image is obtained by mapping the phase difference. A soft part is observed with a large phase delay, and a hard part is observed with a small phase delay.

As a sample for obtaining the phase image, for example, observation can be performed by using a Leica ultramicrotome ULTRACUT UCT and cutting a toner particle under the following conditions to obtain a section.
・ Cutting thickness: 60 nm
・ Cutting speed: 0.4mm / sec
・ Use of 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. can be used and observed using the OMCL-AC240TS-C3 as a cantilever under the following measurement conditions.
・ Target amplitide: 0.5V
-Target percent: -5%
・ Amplitude setpoint: 315 mV
・ Scan rate: 1Hz
・ Scan points: 256 × 256
・ Scan angle: 0 °

  As the AFM phase image of the block copolymer resin, for example, an image as shown in FIG. 3 is obtained. As a specific measurement method of the average of the maximum ferret diameter of the first phase difference image (that is, the soft unit) composed of a portion where the phase difference of the phase image by the AFM is large, a phase image obtained by the tapping mode AFM is used. A binarized image that is binarized with an intermediate value between the maximum value of the phase difference and the minimum value of the phase difference is created (see FIG. 4). As described above, the binarized image is obtained by photographing a phase image so that a portion having a small phase difference has a dark color and a portion having a large phase difference has a light color contrast, and then the maximum value of the phase difference in the phase image is obtained. And binarization processing with the intermediate value of the minimum value of the phase difference as a boundary. In the binarized image, 30 points are selected in order from the ten largest images of the first phase contrast image among the ten images in the 300 nm square range, and the average is set as the average of the maximum ferret diameter.

However, a minute diameter image (see FIG. 5) that is clearly judged as image noise or that is difficult to distinguish between image noise and phase difference image is excluded from the calculation of the average diameter.
Specifically, in the observed phase image, the first phase difference image having an area ratio of 1/100 or less existing on the same image with respect to the first phase difference image having the maximum maximum ferret diameter. Is not used to calculate the average diameter. The maximum ferret diameter is the maximum distance between parallel lines when a phase difference image is sandwiched between two parallel lines.

  The average value (dispersion diameter) of the maximum ferret diameter of the resin for toner is preferably 100 nm or less, and more preferably 10 nm to 100 nm. When the average value (dispersion diameter) of the maximum ferret diameter exceeds 100 nm, a unit having strong adhesion is likely to be exposed due to stress, and toner filming property may be deteriorated. When the average value (dispersion diameter) of the maximum ferret diameter is less than 10 nm, the degree of stress relaxation is remarkably weakened, and the improvement effect on toughness may be insufficient. The average value of the maximum ferret diameter is particularly preferably 10 nm to 45 nm.

  The average value (dispersion diameter) of the maximum ferret diameter of the toner is preferably 100 nm or less, and more preferably 10 nm to 100 nm. When the average value (dispersion diameter) of the maximum ferret diameter exceeds 100 nm, a unit having strong adhesion is likely to be exposed due to stress, and toner filming property may be deteriorated. When the average value (dispersion diameter) of the maximum ferret diameter is less than 10 nm, the degree of stress relaxation is remarkably weakened, and the improvement effect on toughness may be insufficient. The average value of the maximum ferret diameter is particularly preferably 10 nm to 45 nm.

(Crystalline component)
There is no restriction | limiting in particular as crystalline resin which comprises the crystalline component of the said block copolymer resin, Although it can select suitably according to the objective, A crystalline polyester resin is preferable.

-Crystalline polyester resin-
There is no restriction | limiting in particular as crystalline polyester resin which comprises the crystalline component of the said block copolymer resin, According to the objective, it can select suitably, For example, the polycondensation polyester synthesize | combined from a polyol and polycarboxylic acid Examples thereof include a resin, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid, and a crystalline polyester resin having a divalent aliphatic alcohol component and a divalent aliphatic carboxylic acid component as constituent components is preferable.

  Examples of the polyol constituting the crystalline component of the block copolymer resin 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.

  Examples of the polycarboxylic acid constituting the crystalline component of the block copolymer resin include dicarboxylic acid, trivalent to hexavalent or higher polycarboxylic acid.

  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.

  There is no restriction | limiting in particular as melting | fusing point of the crystalline resin which comprises the crystalline component of the said block copolymer 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.

The weight average molecular weight (Mw) of the crystalline resin is preferably 3,000 to 100,000, and more preferably 6,000 to 80,000, from the viewpoint of the domain diameter of the microphase separation of the sea-island structure.
When the weight average molecular weight is less than 3,000, the domain diameter becomes small, stress relaxation due to the sea-island structure may be weakened, and the improvement effect on toughness may be insufficient. When the weight average molecular weight is greater than 100,000, the domain diameter becomes large. Stress tends to expose units with strong adhesion, and toner filming tends to deteriorate.

  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.

(Non-crystalline component)
There is no restriction | limiting in particular as an amorphous resin which comprises the amorphous component of the said block copolymer resin, Although it can select suitably according to the objective, Amorphous polyester resin is preferable.

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.

  Examples of the polyol constituting the amorphous polyester resin 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 branched 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.

  Examples of the polycarboxylic acid constituting the amorphous polyester resin include dicarboxylic acid, trivalent to hexavalent or higher polycarboxylic acid. 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. Of these, branched aliphatic dicarboxylic acids are preferred.

  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.

  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.

  As a weight average molecular weight (Mw) of the said amorphous resin, 4,000-80,000 are preferable and 6,000-60,000 are more preferable. When the weight average molecular weight is less than 4,000, the hot offset resistance may be deteriorated, and when it is more than 80,000, the low temperature fixability tends to be deteriorated.

  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.

In the block copolymer resin of the present invention, the mass ratio (A / C) between the amorphous polyester portion (A) and the crystalline polyester portion (C) is preferably 90/10 to 60/40.

Moreover, it is preferable that content of the block copolymer resin in binder resin is 65 mass% or more and 95 mass% or less.

(Manufacture of block copolymer resin)
There is no restriction | limiting in particular as a manufacturing method of the said block copolymer resin, According to the objective, it can select suitably, For example, although the method in any one of the following (1)-(3) etc. are mentioned, From the viewpoint of the degree of design freedom, (1) and (3) are preferable, and (1) 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.
(2) 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.
(3) A method in which a hydroxyl group of a crystalline resin prepared in advance by a polymerization reaction is used as a polymerization initiation component, and an amorphous resin is subjected to ring-opening polymerization and copolymerization from a polymer chain end of the crystalline resin.

As the extender, polyisocyanate is preferable, and 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 molar ratio (crystalline resin / amorphous resin) between the crystalline resin and the amorphous resin in the copolymer resin is not particularly limited and may be appropriately selected depending on the intended purpose. / 90-40 / 60 is preferable.
The number of moles of the crystalline resin and the number of moles of the amorphous resin can be obtained by the following equations.
Number of moles = (weight of resin (g) × OHV / 56.11) / 1,000
Here, OHV is a hydroxyl value, and the unit is mgKOH / g.

  The copolymer resin preferably has a weight average molecular weight (Mw) of 20,000 to 150,000 from the viewpoints of satisfying the above properties and compatibility between low-temperature fixability and heat-resistant storage stability. When the Mw is less than 20,000, the heat resistant storage stability of the toner may be lowered, and the hot offset resistance may be further lowered. On the other hand, when the Mw exceeds 150,000, the toner is not sufficiently melted particularly at the time of fixing at a low temperature, and the image is liable to be peeled off, so that the low-temperature fixability of the toner may be lowered.

  The Mw can be measured using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)). In Examples described later, which are embodiments of the present invention, the Mw was measured by the following method using the apparatus.

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

(Crystalline resin)
The binder resin of the present invention contains a crystalline resin together with the block copolymer resin. The crystalline resin in the present invention prevents compatibility even when the block copolymer resin has a high compatibility between the crystalline segment and the amorphous segment and the crystallinity tends to decrease. The crystallinity is sufficiently maintained.
By including the crystalline resin, the amorphous segment of the block copolymer resin is excluded from the crystalline resin, and the crystalline segment is attracted to the crystalline resin, so the crystalline segment and the amorphous segment are difficult to mix. The crystallinity is considered to be improved.

The content of the crystalline resin with respect to the block copolymer resin is preferably 5% by mass or more and 30% by mass or less. If it is less than 5% by mass, the crystallinity of the binder resin may not be sufficiently improved, and if it exceeds 30% by mass, there are many free crystal components, and the heat resistant storage stability and paper discharge rub resistance may be reduced.

There is no restriction | limiting in particular as said crystalline resin, Although it can select suitably according to the objective, It is preferable that it is close to the composition of the crystalline segment of the said block copolymer resin.

Examples of the structure of the crystalline resin include the crystalline resin described in the structural unit of the copolymer resin.

The melting temperature Tm of the crystalline resin is preferably 60 ° C. or higher and 100 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. When the melting temperature of the binder resin is as high as 60 ° C. or higher, it is difficult to melt in the toner manufacturing process and exists as a solid component or a high viscosity component, so the crystalline segment and the amorphous segment that are the main components are blocked. It is difficult to phase separate from the formed resin and can be suitably present in the toner as a fine domain diameter.
When the temperature is lower than 60 ° C., the domain diameter of the crystalline resin in the toner may become coarse, so that charging characteristics are deteriorated due to carrier contamination and image density is deteriorated as a result, and the temperature exceeds 100 ° C. In some cases, sufficient low-temperature fixability may not be obtained.

The melting temperature Tm of the crystalline resin can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation).
Specifically, 5.0 mg of crystalline resin is put into 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.

  Further, since the resin obtained by blocking the crystalline segment and the amorphous segment contained in the toner of the present invention has many amorphous parts, the block resin is used when the toner is dissolved in ethyl acetate heated to 40 ° C. Is dissolved, but mainly the crystalline resin and the release agent are not dissolved but become a dissolved residue. By collecting and dissolving the dissolution residue, it is possible to measure the melting temperature of the crystalline resin and the release agent in the toner.

The melting temperature Tm of the dried product obtained by drying the dissolution residue can be measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation).
Specifically, 5.0 mg of the dried product is placed 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, the peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point using an analysis program in the DSC-60 system.

When the peak of the release agent and the crystalline resin can be distinguished, the maximum peak temperature of each peak is defined as the Tm of the crystalline resin and the release agent. Let the maximum peak temperature be the Tm of both.

<Other ingredients>
Examples of other components that can be used together with the binder resin 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 pigment include a Cu-phthalocyanine pigment, a Zn-phthalocyanine pigment, and an Al-phthalocyanine pigment.

  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, It is preferable to use the said block copolymer resin.

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. Among these, a carbonyl group-containing wax is preferable.

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).
Specifically, 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-
There is no restriction | limiting in particular as said charge control agent, According to the objective, it can select suitably. 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 substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like.

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% by mass, the charge rising 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. .

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.

Specifically, 0.1 mL to 5 mL of a surfactant (preferably alkylbenzene 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.

<Hydrophobicity indicated by methanol wettability>
The toner of the present invention preferably has a degree of hydrophobicity of 40% or more and 80% or less. If it is less than 40%, sufficient storage stability under high-temperature and high-humidity conditions cannot be obtained, and if it exceeds 80%, fixing of toner onto paper may be inhibited.

The degree of hydrophobicity of the toner of the present invention is indicated by the degree of hydrophobicity measured by wettability with methanol. The degree of hydrophobicity indicated by wettability with methanol can be calculated using a powder wettability tester WET-100P (manufactured by Reska).

Specifically, 60 ml of ion-exchanged water was put into a 300 ml beaker, 0.025 g of toner was added thereto, and methanol was added dropwise at 1.6 ml / min while stirring under the condition that the stirrer rotation speed was 200 rpm. The methanol concentration at the time when the permeability reaches 50% is calculated as the degree of hydrophobicity. The liquid temperature for the measurement is 20 ° C.
When the toner settles and the liquid transmittance reaches 50%, the methanol concentration calculated from the initial amount of ion-exchanged water and the amount of methanol dropped is calculated as the degree of hydrophobicity.

Any method can be used to control the hydrophobicity of the toner as long as it does not cause problems in the electrophotographic process. However, the problem of storage stability under high temperature and high humidity conditions depends on the properties of the resin itself. In this case, it is necessary to use a plurality of means in combination in order to prevent excessive use of external additives rather than controlling the degree of hydrophobicity only by external addition of hydrophobic inorganic fine particles.
For example, a method of removing a low molecular weight component by washing the resin itself or a method of performing a resin coating process on the surface of the base particle can be used in combination.

The removal of the low molecular weight component may be performed on the block copolymer resin which is the main component of the binder resin, but may be performed on the entire binder resin in order to adjust the desired degree of hydrophobicity.
In addition, the block copolymer resin in the toner of the present invention not only forms a microphase separation structure in which the amorphous segment is the sea and the crystalline segment is the island, but the amorphous segment and the crystalline segment are connected. Therefore, it contributes to the reduction of the hydrophilic part at the molecular chain end.

The removal of the low molecular weight component needs to be performed in a state where the resin is dissolved, and the low molecular weight component cannot be removed by washing after granulation of the toner base particles.

<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 manufacturing 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.

-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, resin fine particles described later, and the like are appropriately added to the aqueous medium is to improve the dispersion of the toner material.
The amount of the anionic surfactant and resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. % To 10% by 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.

(Resin fine particle adhesion process)
In the toner of the present invention, a step of separately attaching resin fine particles to the surface of the toner base particles after emulsification may be included as a separate step after emulsification.
The dispersion liquid of the emulsified particles to be the toner base particles obtained by the emulsification step can stably have the droplets of the emulsified particles present while stirring. In this state, a resin fine particle dispersion such as the above-mentioned vinyl resin fine particles is added and adhered onto the emulsified particles.
The vinyl resin fine particle dispersion is preferably charged over 30 seconds. If the charging is performed in less than 30 seconds, it is not preferable because the dispersion system changes abruptly to generate aggregated particles or uneven adhesion of vinyl resin fine particles. On the other hand, it is not preferable to add to the dark cloud for a long time, for example, more than 60 minutes from the viewpoint of production efficiency.

The vinyl resin fine particle dispersion may be diluted or concentrated to adjust the concentration as appropriate before being added to the emulsified particle dispersion. The concentration of the vinyl resin fine particle dispersion is preferably 5 to 30% by weight, and more preferably 8 to 20% by weight.
If it is less than 5%, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and the adhesion of the resin fine particles becomes insufficient. If it exceeds 30% by weight, the resin fine particles are likely to be unevenly distributed in the emulsified particle dispersion, and as a result, the adhesion of the resin fine particles becomes nonuniform.

The vinyl resin fine particles adhere to the emulsified particles that become the toner base particles with sufficient strength by the method of the present invention when the vinyl resin fine particles adhere to the droplets of the emulsified particles. To form a sufficient interface between the vinyl resin fine particles and the contact surface, and the vinyl resin fine particles are swollen or dissolved by the organic solvent, and the vinyl resin fine particles and the resin in the emulsified particles are likely to adhere to each other. It seems to be due to the situation.
Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, in the state of the emulsified particle dispersion, it is 50 wt% to 150 wt%, preferably 70 wt% with respect to the solid content (resin, colorant, and if necessary, release agent, charge control agent, etc.). It should be in the range of% to 125% by weight.
If it exceeds 150% by weight, the amount of colored resin particles obtained in a single production process is reduced and the production efficiency is low, and if there is a large amount of organic solvent, the dispersion stability is lowered and stable production becomes difficult. .

The temperature at which the vinyl resin fine particles adhere to the emulsified particles is 10 to 60 ° C, preferably 20 to 45 ° C. If the temperature exceeds 60 ° C, the energy required for production increases and the environmental burden on the production increases. In addition, low acid value vinyl resin fine particles may be present on the droplet surface, making dispersion unstable. Since coarse particles may be generated, it is not preferable.
On the other hand, when the temperature is less than 10 ° C., the viscosity of the dispersion is increased, and adhesion of resin fine particles becomes insufficient, which is not preferable.

-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. Examples thereof include a method in which the organic solvent in the oil droplets of the emulsion or dispersion is completely removed by spraying in a dry atmosphere. 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.

-Washing 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.

(Crushing method)
The pulverization method pulverization method is, for example, a method of producing the toner base particles 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 of the present invention contains the toner of 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>
The image forming apparatus of the present invention has at least an electrostatic latent image carrier (hereinafter sometimes referred to as a “photosensitive member”), an electrostatic latent image forming unit, and a developing unit, and if necessary. And have other means.
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 that charges the surface of the electrostatic latent image carrier and an exposure member that exposes 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.

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

<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, but is preferably 10 N / cm ² to 80 N / cm ² .

<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. 6 includes an electrostatic latent image carrier 10, a charging roller 20 as the charging unit, the exposure unit L, a developing device 40 as the developing unit, and an intermediate transfer member 50. And 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. 6, for example, the charging roller 20 charges the electrostatic latent image carrier 10 uniformly. The exposure device L 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. 7 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.

The image forming apparatus shown in FIG. 8 includes a copying apparatus main body 100C, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying machine main body 100C 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. 8. 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 charging device 160 as the charging member for uniformly charging the electrostatic latent image carrier 10 and exposure of the electrostatic latent image carrier in an image corresponding to each color image based on each color image information (FIG. 9). 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.

  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.

[Production Example 1-1 (Production of Amorphous Segment 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 adipate as dicarboxylic acids, dimethyl terephthalate and dimethyl adipate The molar ratio (dimethyl terephthalate / dimethyl adipate) is 80/20 and the ratio of OH groups to COOH groups (OH / COOH) is 1.2. 300 ppm of titanium tetraisopropoxide was charged with respect to the mass, and the reaction was carried out with methanol 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 segment A1] which is a linear amorphous polyester resin was obtained.

[Production Example 1-2 (Production of Amorphous Segment A2)]
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 90/10, and the ratio of OH groups to COOH groups (OH / COOH) is 1.15. 300 ppm of titanium tetraisopropoxide was added to the reaction, and the reaction was carried out with methanol 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 segment A2] which is a linear amorphous polyester resin was obtained.

[Production Example 2-1 (Production of Crystalline Segment C1 (Crystalline Polyester Resin C1))]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,4-butanediol as a diol, sebacic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups ( (OH / COOH) was set to 1.1, and further, 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was carried out with water 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 the reduced pressure of 10 mmHg or less for 5 hours, and [Crystalline segment resin C1] [Crystalline segment C1] was obtained.

[Production Example 2-2 (Production of Crystalline Segment C2 (Crystalline Polyester Resin C2))]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,6-hexanediol as a diol, sebacic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups ( (OH / COOH) was adjusted to 1.15, and 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was performed 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 reduced pressure of 10 mmHg or less for 4 hours, and [Crystalline segment resin C2] [Crystalline segment C2] was obtained.

[Production Example 3-1 (Production of Crystalline Resin C′1 (Crystalline Polyester Resin C′1))]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,6-hexanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups ( (OH / COOH) was set to 1.1, and further, 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was carried out with water 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 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′1].

[Production Example 3-2 (Production of Crystalline Resin C′2 (Crystalline Polyester Resin C′2))]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,8-octanediol as a diol, adipic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups ( (OH / COOH) was set to 1.1, and further, 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was carried out with water 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 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′2].

[Production Example 3-3 (Production of Crystalline Resin C′3 (Crystalline Polyester Resin C′3))]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,6-hexanediol as a diol, sebacic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups ( (OH / COOH) was set to 1.1, and further, 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was carried out with water 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 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′3].

[Production Example 3-4 (Production of Crystalline Resin C′4 (Crystalline Polyester Resin C′4))]
In a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, ethylene glycol as diol, sebacic acid as dicarboxylic acid, and ratio of OH group to COOH group (OH / COOH) Was made to be 1.1, and further 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was allowed 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 reduced pressure of 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′4].

[Production Example 3-5 (Production of Crystalline Resin C′5 (Crystalline Polyester Resin C′5))]
A 5-L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, was mixed with 1,10-decanediol as a diol, dodecanedioic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups. (OH / COOH) was charged to 1.1, and further, 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was carried out with water 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 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′5].

[Production Example 3-6 (Production of Crystalline Resin C′6 (Crystalline Polyester Resin C′6))]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,4-butanediol as a diol, sebacic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups ( (OH / COOH) was set to 1.1, and further, 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was carried out with water 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 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′6].

[Production Example 3-7 (Production of Crystalline Resin C′7 (Crystalline Polyester Resin C′7))]
In a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, ethylene glycol as diol, malonic acid as dicarboxylic acid, and ratio of OH group to COOH group (OH / COOH) Was made to be 1.1, and further 300 ppm of titanium tetraisopropoxide was charged with respect to the mass of the charged raw material, and the reaction was allowed 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 reduced pressure of 10 mmHg or less for 6 hours to obtain [Crystalline Polyester Resin C′7].

Table 1 shows the monomer components, Tg or Tm, of the resins obtained in Production Examples 1-1 to 3-7.
Shown in
<Measurement of glass transition point of resin, melting point, and maximum melting point peak temperature of toner>
The glass transition point of the resin, the melting point, and the maximum melting point peak temperature of the toner 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, in the case of resin, the maximum endothermic peak temperature is the melting point of the resin, and in the case of toner, the maximum endothermic peak temperature corresponding to the melting point of the resin is Determined by

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: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature decrease rate: 10 ° C / min
End temperature: -20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

Table 1 shows the composition of Production Example 1-1 to Production Example 3-7. In Table 1, the numerical values described in the column of the alcohol component and the carboxylic acid component are molar ratios (mol%) in the alcohol component and the carboxylic acid component, respectively.

[Production Example 4-1 (Production of Block Copolymer Resin B1)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1600 g of [Amorphous Segment A1] and 400 g of [Crystalline Segment C1], and at 60 ° C. for 2 hours. Vacuum drying was performed at 10 mmHg. After nitrogen depressurization, 2000 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 (MDI) 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 [Block Copolymer Resin B1].

[Production Example 4-2 (Production of Block Copolymer Resin B2)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1300 g of [Amorphous Segment A1] and 700 g of [Crystalline Segment C1], and at 60 ° C. for 2 hours. Vacuum drying was performed 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, 133 g of 4,4′-diphenylmethane diisocyanate (MDI) 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 [Block Copolymer Resin B2].

[Production Example 4-3 (Production of block copolymer resin B3)]
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1600 g of [Amorphous segment A2] and 400 g of [Crystalline segment C1] were charged at 60 ° C. for 2 hours. Vacuum drying was performed at 10 mmHg. After nitrogen depressurization, 2000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform.
Next, 145 g of 4,4′-diphenylmethane diisocyanate (MDI) 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 [Block Copolymer Resin B3].

[Production Example 4-4 (Production of block copolymer resin B4)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1600 g of [Amorphous Segment A1] and 400 g of [Crystalline Segment C2] at 60 ° C. for 2 hours. Vacuum drying was performed at 10 mmHg. After nitrogen depressurization, 2000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform.
Next, 140 g of 4,4′-diphenylmethane diisocyanate (MDI) 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 [Block Copolymer Resin B4].

[Production Example 4-5 (Production of block copolymer resin B5)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1600 g of [Amorphous Segment A1] and 400 g of [Crystalline Segment C2] at 60 ° C. for 2 hours. Vacuum drying was performed at 10 mmHg. After nitrogen depressurization, 2000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform.
Next, 130 g of 1,6-hexane diisocyanate (HDI) was added to the system and stirred under visual observation until it became 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 [Block Copolymer Resin B5].

[Production Example 4-6 (Production of block copolymer resin B6)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1300 g of [Amorphous Segment A2] and 700 g of [Crystalline Segment C1] at 60 ° C. for 2 hours. Vacuum drying was performed at 10 mmHg. After nitrogen depressurization, 2000 g of ethyl acetate dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform.
Next, 132 g of 4,4′-diphenylmethane diisocyanate (MDI) was added to the system and stirred under visual observation until it became 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 [Block Copolymer Resin B6].

[Production Example 4-7 (Production of block copolymer resin B7)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1100 g of [Amorphous Segment A1] and 900 g of [Crystalline Segment C1], and at 60 ° C. for 2 hours. Vacuum drying was performed 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, 142 g of 4,4′-diphenylmethane diisocyanate (MDI) was added to the system and stirred under visual observation until it became 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. Next, ethyl acetate was distilled off under reduced pressure to obtain [Block Copolymer Resin B7].

[Production Example 4-8 (Production of block copolymer resin B8)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1600 g of [Amorphous Segment A1] and 400 g of [Crystalline Segment C1], and at 60 ° C. for 2 hours. Vacuum drying was performed 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, 142 g of 4,4′-diphenylmethane diisocyanate (MDI) was added to the system and stirred under visual observation until it became 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.
Ethyl acetate was added at a rate of 400 g to 100 g of the obtained resin to sufficiently stir to obtain a resin solution, and then the resin solution was slowly dropped into 1 L of methanol to perform reprecipitation to remove methanol-dissolved components. The operation of obtaining the resin as a precipitate was repeated 5 times to obtain [Block Copolymer Resin B8].

[Production Example 4-9 (Production of block copolymer resin B9)]
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1600 g of [Amorphous segment A1] and 500 g of [Crystalline segment C2] were charged at 60 ° C. for 2 hours. Vacuum drying was performed 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, 142 g of 4,4′-diphenylmethane diisocyanate (MDI) was added to the system and stirred under visual observation until it became 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.
Ethyl acetate was added at a rate of 400 g to 100 g of the obtained resin to sufficiently stir to obtain a resin solution, and then the resin solution was slowly dropped into 1 L of methanol to perform reprecipitation to remove methanol-dissolved components. The operation of obtaining the resin as a precipitate was repeated 5 times to obtain [Block Copolymer Resin B9].

[Production Example 4-10 (Production of block copolymer resin B10)]
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1600 g of [Amorphous Segment A1] and 400 g of [Crystalline Segment C2] at 60 ° C. for 2 hours. Vacuum drying was performed 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, 130 g of 1,6-hexane diisocyanate (HDI) was added to the system and stirred under visual observation until it became 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.
Ethyl acetate was added at a rate of 400 g to 100 g of the obtained resin to sufficiently stir to obtain a resin solution, and then the resin solution was slowly dropped into 1 L of methanol to perform reprecipitation to remove methanol-dissolved components. The operation of obtaining the resin as a precipitate was repeated 5 times to obtain [Block Copolymer Resin B10].

（ＭＤＩ）４，４’−ジフェニルメタンジイソシアネート
（ＨＤＩ）１，６−ヘキサンジイソシアネート

(MDI) 4,4′-diphenylmethane diisocyanate (HDI) 1,6-hexane diisocyanate

[Production Example 5 (Production of Colorant Masterbatch)]
[Block copolymer resin B1] 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 masterbatch P1] in which the ratio (mass ratio) of the resin to the pigment was 1: 1.

  [Colorant masterbatch P2] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B2].

  [Colorant masterbatch P3] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B3].

  [Colorant masterbatch P4] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B4].

  [Colorant masterbatch P5] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B5].

  [Colorant masterbatch P6] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B6].

  [Colorant masterbatch P7] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B7].

  [Colorant masterbatch P8] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B8].

  [Colorant masterbatch P9] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B9].

  [Colorant masterbatch P10] was produced in the same manner except that [Block copolymer resin B1] was changed to [Block copolymer resin B10].

  [Colorant master batch PA1] was produced in the same manner except that [Block copolymer resin B1] was changed to [Amorphous resin A1] (amorphous polyester resin produced in Production Example 1-1). did.

  [Colorant master batch PA2] was produced in the same manner except that [Block copolymer resin B1] was changed to [Amorphous resin A2] (amorphous polyester resin produced in Production Example 1-2). did.

[Colorant masterbatch PC1] was produced in the same manner except that [Block copolymer resin B1] was changed to [Crystalline resin C1] (crystalline polyester resin produced in Production Example 2-1).

[Production Example 6 (Production of Wax (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 under conditions of 0.5mm zirconia bead filling 80 volume% and 6 passes, adjust the solid content by adding ethyl acetate, and produce [Wax (WAX) dispersion] with 20% solid content did.

[Production Example 7 (Production of vinyl resin fine particle dispersion 1)]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution prepared by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 250 parts of styrene monomer and 5.4 parts of n-octanethiol was dropped over 90 minutes, Thereafter, the polymerization reaction was carried out at 80 ° C. for another 60 minutes.
Thereafter, the mixture was cooled to obtain white [vinyl resin fine particle dispersion 1]. The obtained dispersion was placed in a 2 ml petri dish, and the dried solid obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 8,700, the weight average molecular weight was 18400, and Tg was 85 ° C.

Example 1 (Production of Toner 1)
<Production of oil phase>
In a container equipped with a thermometer and a stirrer, the amount of [block copolymer resin B1] is 74% by mass of the solid content of the entire oil phase, and [crystalline resin C′1] is 15 of the solid content of the entire oil phase. The amount to be mass% is charged, ethyl acetate is added in an amount so that the solid content of the entire oil phase is 50%, and heated to the melting point of the resin or more to dissolve well, and [Wax (WAX) dispersion] is the amount of wax. TK type homomixer at 50 ° C. by adding an amount of 5% by mass of the solid content of the entire oil phase and an amount of 6% by mass of the pigment of the solid content of the entire oil phase. (Primics Co., Ltd.) was stirred at a rotational speed of 10,000 rpm, and uniformly dissolved and dispersed to obtain [Oil Phase 1].
The temperature of [Oil Phase 1] was kept at 50 ° C. in the container.

<Preparation of aqueous phase>
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]).

<Preparation of slurry>
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] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 50 ° C. for 2 hours to obtain [Slurry 1].

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].

<Addition of external additives>
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].

Example 2 (Production of Toner 2)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 2] was prepared in the same manner as described above.

Example 3 (Production of Toner 3)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 3] was produced in the same manner as described above.

Example 4 (Production of Toner 4)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 4] was produced in the same manner as described above.

Example 5 (Production of Toner 5)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 5] was produced in the same manner as described above.

Example 6 (Production of Toner 6)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 6] was produced in the same manner as described above.

Example 7 (Production of Toner 7)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 7] was produced in the same manner as described above.

Example 8 (Production of Toner 8)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 8] was produced in the same manner as described above.

Example 9 (Production of Toner 9)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are each replaced as shown in the formulation of Table 3 below, and further the solvent is removed. [Toner 9] was prepared in the same manner as in Example 1 except that the subsequent [Slurry] was allowed to stand for 24 hours or more in a temperature environment lower than the melting point of the toner for 24 hours or more, and then transferred to the filtration step. .

[Comparative Example 1 (Production of Toner 10)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], [Amorphous Polyester Resin], and [Colorant Masterbatch] are shown in the formulation of Table 3 below. Instead, [Toner 10] was produced in the same manner as in Example 1.

[Comparative Example 2 (Production of Toner 11)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], [Amorphous Polyester Resin], and [Colorant Masterbatch] are shown in the formulation of Table 3 below. Instead, [Toner 11] was produced in the same manner as in Example 1.

[Comparative Example 3 (Production of Toner 12)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 12] was produced in the same manner as described above.

[Comparative Example 4 (Production of Toner 13)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 13] was produced in the same manner as described above.

[Comparative Example 5 (Production of Toner 14)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], [Amorphous Polyester Resin], and [Colorant Masterbatch] are shown in the formulation of Table 3 below. Instead, [Toner 14] was produced in the same manner as in Example 1.

[Comparative Example 6 (Production of Toner 15)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] are respectively replaced as shown in the prescription in Table 3 below. [Toner 15] was produced in the same manner as described above.

Example 10 (Production of Toner 16)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 16] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner and then annealed and then transferred to the filtration step.

Example 11 (Production of Toner 17)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 17] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

Example 12 (Production of Toner 18)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 18] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

Example 13 (Production of Toner 19)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 19] was produced in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

Example 14 (Production of Toner 20)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 20] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment lower than the melting point of the toner for 24 hours or more and then the process was shifted to the filtration step.

Example 15 (Production of Toner 21)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 21] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, followed by annealing.

Example 16 (Production of Toner 22)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 22] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, followed by annealing.

Example 17 (Production of Toner 23)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 23] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment lower than the melting point of the toner for 24 hours or more and then transferred to the filtration step.

Example 18 (Production of Toner 24)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 24] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

Example 19 (Production of Toner 25)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 25] was prepared in the same manner as in Example 1 except that the [Slurry] was left to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

Example 20 (Production of Toner 26)
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 26] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, followed by annealing.

[Example 21 (production of toner 27)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 27] was prepared in the same manner as in Example 1 except that the [Slurry] was left to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

[Example 22 (production of toner 28)]
In <Preparation of Oil Phase> in Example 1, [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were respectively replaced as shown in the formulation of Table 3 below, and after solvent removal [Toner 28] was prepared in the same manner as in Example 1 except that the [Slurry] was allowed to stand for 24 hours or more in a temperature environment 5 ° C. lower than the melting point of the toner, and then the process was shifted to the filtration step.

Example 23 (Production of Toner 29)
Except that [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were changed as shown in Table 3 below in <Preparation of Oil Phase> in Example 1. Similarly, [Toner 29] was produced.

Example 24 (Production of Toner 30)
Except that [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were changed as shown in Table 3 below in <Preparation of Oil Phase> in Example 1. Similarly, [Toner 30] was produced.

[Example 25 (Production of Toner 31)]
Except that [Block Copolymer Resin], [Crystalline Polyester Resin], and [Colorant Masterbatch] were changed as shown in Table 3 below in <Preparation of Oil Phase> in Example 1. Similarly, [Toner 31] was produced.

Example 26 (Production of Toner 32)
In <Preparation of Slurry> in Example 23, immediately after obtaining [Emulsion Slurry], the liquid temperature was adjusted while stirring [Emulsion Slurry] while adjusting the number of revolutions between 130 and 350 rpm with a three-one motor equipped with anchor blades. Is a mixture of 100 parts of [Vinyl resin fine particle dispersion 1] and 75 parts of ion-exchanged water (solid content concentration 15%) is dropped over 3 minutes, and after the dropwise addition, the rotational speed is 200. [Toner 32] was produced in the same manner except that the step of adjusting to ˜450 rpm and continuing stirring for 30 minutes to add [Composite Particle Emulsion Slurry] was added.

Example 27 (Production of Toner 33)
In <Preparation of slurry> in Example 24, immediately after obtaining [Emulsion slurry], the liquid temperature was adjusted while stirring [Emulsion slurry] with a three-one motor with an anchor blade attached and adjusted at a rotational speed of 130 to 350 rpm. Is a mixture of 100 parts of [Vinyl resin fine particle dispersion 1] and 75 parts of ion-exchanged water (solid content concentration 15%) is dropped over 3 minutes, and after the dropwise addition, the rotational speed is 200. [Toner 33] was prepared in the same manner except that the step of adjusting to ˜450 rpm and continuing stirring for 30 minutes to add [Composite Particle Emulsion Slurry] was added.

Example 28 (Production of Toner 34)
In <Production of Slurry> in Example 25, immediately after obtaining [Emulsion slurry], the liquid temperature was adjusted while the [Emulsion slurry] was agitated by adjusting the rotation speed between 130 to 350 rpm with a three-one motor equipped with anchor blades. Is a mixture of 100 parts of [Vinyl resin fine particle dispersion 1] and 75 parts of ion-exchanged water (solid content concentration 15%) is dropped over 3 minutes, and after the dropwise addition, the rotational speed is 200. [Toner 34] was prepared in the same manner except that the step of adjusting to ˜450 rpm and continuing stirring for 30 minutes to add [Composite Particle Emulsion Slurry] was added.

Example 29 (Production of Toner 35)
In <Addition of external additive> in Example 1, 100 parts of [toner base particle 1], 2 parts of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie), and titanium oxide (MT-150AI, Takeca Co., Ltd.) [Toner 35] was prepared in the same manner except that 1 part was mixed using a Henschel mixer.

The toner composition is shown in Table 3. The obtained toner was measured for particle size distribution, integrated intensity of X-ray diffraction spectrum, pulse NMR relaxation time, and phase difference image dispersion diameter. The evaluation results are shown in Table 4.

なお、ブロック共重合樹脂、非晶性ポリエステル（Ａ）、及び結晶性ポリエステル（Ｃ）の含有量には、マスターバッチ由来の樹脂量を含む。
表３中、「結晶性セグメント」の欄の数値は、ブロック共重合樹脂中の結晶性セグメントの割合（質量％）を示す。

The content of the block copolymer resin, the amorphous polyester (A), and the crystalline polyester (C) includes the amount of resin derived from the master batch.
In Table 3, the numerical value in the column of “Crystalline segment” indicates the ratio (% by mass) of the crystalline segment in the block copolymer resin.

<Manufacture of carrier 1>
As a core material, 5000 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>
[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.

[Developer 2] to [Developer 28] were obtained in the same manner except that [Toner 1] was replaced with [Toner 2] to [Toner 28], respectively.

  As for the produced two-component developer, the image of the tandem type image forming apparatus shown in FIG. 8 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 roller fixing method of external heating. The development unit was loaded to form an image, and the following performance evaluation was performed. The evaluation results are shown in Table 5.

<Fixability (fixing lower limit temperature)>
Using the image forming apparatus shown in FIG. 8, on the transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>), the amount of toner adhered after transfer is 0.85 ± 0.10 mg / cm 2. A solid image (image size: 3 cm × 8 cm) is formed, fixing is performed by changing the temperature of the fixing belt, and the surface of the obtained fixed image is drawn using a drawing tester AD-401 (manufactured by Ueshima Seisakusho Co., Ltd.). , A ruby needle (tip radius 260 μmR to 320 μmR, tip angle 60 degrees), drawing with a load of 50 g, rubbing the drawing surface strongly with fiber (Hanicot # 440, manufactured by Honeylon) 5 times, fixing belt temperature at which there is almost no image scraping Was taken 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〕
◎: 105 ° C. or less ◎: 105 ° C. or more and 110 ° C. or less ○: 110 ° C. or more and 115 ° C. or less △: 115 ° C. or more and 130 ° C. or less

<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 20 mm or more and less than 25 mm ○: Needle penetration 10 mm or more but less than 20 mm △: Needle penetration 5 mm or more but less than 10 mm ×: Needle penetration less than 5 mm

<Evaluation of paper discharge rubbing resistance>
The image obtained using the image forming apparatus shown in FIG. 8 was visually observed for the presence or absence of a low-gloss or high-gloss area on the fixed image due to contact with the conveying member, and the presence or absence of scratches or peeling of the image. The evaluation was based on the following criteria.
〔Evaluation criteria〕
A: Contact marks with the member after fixing are not observed.
A: There is a slight difference in gloss between the member contact portion and the surrounding non-contact portion, and depending on how light is applied, the contact trace is barely visible.
○: There is a slight difference in gloss between the member contact portion and the surrounding non-contact portion, and the contact trace can be visually recognized depending on how the light is applied.
Δ: There is a clear difference in gloss between the member contact portion and the surrounding non-contact portion, and the contact trace can be visually confirmed. Or there are streak-like scratches.
X: There is a clear difference in gloss between the member contact portion and the surrounding non-contact portion, and the contact trace can be seen visually. Or there is a place where there is a streak-like deep scratch and the toner is peeled off and the paper surface can be seen.

<Image density>
Using the tandem type color image forming apparatus used for the evaluation of the fixing property, the surface temperature of the fixing roller is set to 160 ± 2 ° C., and the image area ratio is applied to transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>) After printing 7 sheets of 7%, a solid image having a toner adhesion amount of 1.00 ± 0.05 mg / cm 2 was formed. The image density of arbitrary six places of the obtained solid image was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Rite), and the image density (average value) was obtained and evaluated according to the following criteria. . More than Δ is practical.
〔Evaluation criteria〕
◎: Image density is 2.0 or more ○: Image density is 1.8 or more and less than 2.0 △: Image density is 1.6 or more and less than 1.8 ×: Image density is less than 1.6

<Charge amount distribution>
For the charge distribution, after measuring the image density, measure the Q / d distribution (fC / μm) for the developer collected from the sleeve of the development unit using a charge distribution analyzer (Espert Analyzer, manufactured by Hosokawa Micron Corporation). Then, the half width was obtained from this measured value. In addition, as a measurement condition of the Espert Analyzer (E-SPART ANALYZER), the nitrogen gas flow rate was 0.3 NL / min and the gas pressure was 0.3 atm. As an index indicating the distribution of the charge amount, it is represented by the mode (peak value) [q / d] and the width of the distribution (half-value width) at the half height position of the most frequent. It was evaluated with. More than Δ is practical.
〔Evaluation criteria〕
A: Mode value 0.25 fC / μm or more and less than half value width 0.2 ○: Mode value 0.20 or more and less than 0.25 fC / μm or half value width 0.2 or more and less than 0.3 Δ: Mode value 0 .15 or more and less than 0.20 fC / μm or half width 0.3 to less than 0.4 ×: Mode value less than 0.15 fC / μm and half width 0.4 or more

<Evaluation of fluidity under high temperature and high humidity>
Measurement was performed using a powder tester (PT-N type, manufactured by Hosokawa Micron Corporation) installed in a high temperature and high humidity environment (35 ° C., 70%).
When 2.0 g of toner was passed through a sieve having a mesh size of 150 μm, 75 μm, and 45 μm (plain woven wire mesh, standard JIS Z 8801-1), the amount of residual toner on each sieve was measured. Used to calculate.

Fluidity (%) = [(A + 0.6 × B + 0.2 × C) /2.0] × 100
A: Remaining toner amount (g) on a sieve having an opening of 150 μm, B: Remaining toner amount (g) on a sieve having an opening of 75 μm, C: Remaining toner amount (g) on a sieve having an opening of 45 μm
A smaller fluidity value was better and was evaluated according to the following criteria.
〔Evaluation criteria〕
◎: 10 or less ○: Over 10 and 20 or less △: Over 20 and 30 or less ×: Over 30

(Fig. 6, Fig. 7)
100A Image forming apparatus 100B Image forming apparatus L Exposure means

DESCRIPTION OF SYMBOLS 10 Electrostatic latent image carrier 20 Charging roller 40 Developing device 41 Developing belt 42 Developer accommodating portion 43 Developer supplying roller 44 Developing roller 45 Developing unit 50 Intermediate transfer member 51 Roller 60 Cleaning device 70 Electric discharge lamp 90 Cleaning device 95 Transfer paper

(Fig. 8, Fig. 9)
100C Copying apparatus 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
DESCRIPTION OF SYMBOLS 10 Electrostatic latent image carrier 14, 15, 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 21 Exposure device 22 Secondary transfer device 24 Secondary transfer belt 23 Roller 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 49 Registration roller 50 Intermediate transfer body 52 Separating roller 53 Manual feed path 54 Manual tray 55 Switching claw 56 Discharge roller 57 Discharge Tray 61 Developing device 62 Transfer charging device 63 Cleaning device 64 Static eliminator 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device Body 160 Charging device

Japanese Patent No. 3949553 Japanese Patent No. 4155108 JP 2010-151996 A Japanese Patent Publication No. 4-024702 JP-B-4-024703 JP-A 63-027855 Japanese Patent No. 4563546

Claims (10)

  A toner containing at least a binder resin, wherein the binder resin contains a block copolymer resin having an amorphous polyester portion (A) and a crystalline polyester portion (C), and a crystalline resin. The spin-spin relaxation time (t′70) at 70 ° C. when the temperature is lowered from 130 ° C. to 70 ° C. measured by pulse NMR of the toner is from 0.3 ms to 2.0 ms. Features toner. The toner according to claim 1, wherein the toner has a hydrophobicity of 40% or more and 80% or less. When the toner is measured by differential scanning calorimetry (DSC) on a dried product obtained by drying an insoluble matter not dissolved in ethyl acetate at 40 ° C., the peak temperature of the heat of fusion at the second temperature rise is 60 ° C. or more and 100 ° C. The toner according to claim 1, wherein the toner is present below. The block copolymer resin has a mass ratio ((A) / (C)) between the amorphous polyester portion (A) and the crystalline polyester portion (C) of 90/10 to 60/40. The toner according to claim 1, wherein the toner is a toner. The toner according to claim 1, wherein the toner contains a crystalline polyester resin in an amount of 5% by mass to 30% by mass with respect to the block copolymer resin.   The toner according to claim 1, wherein the block copolymer resin has a urethane bond and / or a urea bond.   The binder resin is obtained by binarizing a phase image observed by the tapping mode AFM with an intermediate value between the maximum value and the minimum value of the phase difference, and the first unit consisting of a portion having a large phase difference. 7. The toner according to claim 1, wherein the phase difference image is dispersed in a second phase difference image including a portion having a small phase difference, and the dispersion diameter of the first phase difference image is 100 nm or less. . In the diffraction spectrum obtained by the X-ray diffractometer of the toner,
When the integrated intensity of the spectrum derived from the crystal structure of the binder resin is I (C) and the integrated intensity of the spectrum derived from the amorphous structure is I (A), the ratio I (C) / (I (C) The toner according to claim 1, wherein + I (A)) is 0.10 or more and 0.30 or less. The toner according to claim 8, wherein I (C) / (I (C) + I (A)) is 0.15 or more.   A developer comprising the toner according to claim 1.

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