JP2014089434A - Developing device and developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing device which is capable of maintaining the charge stability of a developer and capable of preventing crushed loose flocculation as well by sufficiently mixing toner in a developing device even when a specific gravity is low because of containing a large amount of crystalline resin, while maintaining the fixability of the toner containing the large amount of crystalline resin contributing to low-temperature fixation.SOLUTION: The developing device includes a developer storage part storing a two-component developer containing a carrier and a toner, a toner storage part storing the toner supplied to the developer storage part, and a conveyance mechanism conveying the toner while stirring the toner. The toner contains a crystalline resin having an urethane bond and/or an urea bond in a main chain as a binder resin and has a true specific gravity of 1.00 to 1.20.

Description

  The present invention relates to a developing device provided in an image forming apparatus such as a copying machine or a printer using an electrophotographic system, and a developing method thereof, and more particularly, to a developing provided with a toner transport path for transporting toner supplied in the developing device with a screw. Relates to the device.

  Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, or the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.

  In a heat fixing type image forming apparatus, since a large amount of electric power is required in the process of heat melting and fixing a toner on a recording medium such as paper, the toner has low temperature fixability from the viewpoint of energy saving. It is one of the important characteristics.

  In order to improve the low-temperature fixability of the toner, it is necessary to control the thermal characteristics of the binder resin that occupies most of the toner. For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-077419), low-temperature fixability and heat resistance are determined by defining the composition and thermal characteristics of a crystalline resin in a toner having a crystalline resin as a main component of a binder resin. Technologies that can achieve both storability have been proposed. Further, in Patent Document 2 (Japanese Patent Laid-Open No. 2009-014926), a toner containing two types of crystalline resins having different molecular weights as a binder resin (especially that a crystalline polyester resin is preferred) is used under specific fixing conditions. There has been proposed a technique that can improve the low-temperature fixability and suppress cracking of a fixed image. In Patent Document 3 (Japanese Patent Laid-Open No. 2010-151996), two types of crystalline polyester resins having different storage elastic moduli at 160 ° C. are contained as a binder resin, so that both low-temperature fixability and pressure storage stability are achieved. A possible technology has been proposed.

As the inventors of the present invention are studying low-temperature fixing of a toner, in a toner containing a crystalline resin as a binder resin, the higher the content of the crystalline resin, the more particularly the crystalline resin is added to the binder resin. When the main component is used, the low-temperature fixability is excellent, but the hardness of the toner is low due to the low resin hardness. It has been found that there is a problem in that agglomerates that are difficult to disintegrate are formed, resulting in a white image.
Further, if the content of the amorphous resin is increased in order to increase the toner hardness, the effect of the crystalline resin is reduced and the low-temperature fixability is deteriorated. On the other hand, if the crystalline resin is modified with urethane or the like and the toner hardness is increased, the image that has fallen white in the developing device can be eliminated, but the toner can be crushed and loosely aggregated and transferred as it is. It became clear that image unevenness occurred. Further, as a side effect, a problem that positively charged toner is easily generated when mixing is insufficient is revealed.
Furthermore, since the specific gravity of the toner decreases as the content of the crystalline resin increases, the developer and the replenishment toner are not sufficiently mixed in the developing device, and the toner charge amount varies, which may cause toner scattering. It became clear that there was a problem of becoming.

  In a system in which toner having a relatively low specific gravity is dropped from the two-component developer transport path and replenished, the replenished toner slides up on the surface of the developer contained in the developing device. The replenished toner that has slipped on the surface of the developer cannot be sufficiently stirred in the developer stirring portion, and moves on the surface of the developer without being charged, resulting in image defects such as background smearing. .

  In order to solve the above-described problems caused by insufficient stirring of the replenished toner, various proposals have been made as a toner replenishing method for the developing device. For example, Patent Document 4 (Japanese Patent Application Laid-Open No. 2011-164530) does not use a method of dropping toner from the two-component developer transport path and replenishing toner, but toner that transports only toner different from the developer transport path. A developing device that replenishes toner on a conveyance path (toner storage unit) is disclosed. In this developing device, the toner replenished on the toner conveyance path is conveyed by a screw disposed on the same axis as the screw provided in the developer conveyance path, and merged with the developer conveyance path. Yes.

  In the developing device having such a configuration, the replenishment toner is conveyed so as to be pushed in by the rotation of the conveying screw toward the boundary with the developer. Therefore, since the toner is submerged and mixed in the developer, the toner is less likely to slip, and there is an advantage that the replenishment toner has good dispersibility and chargeability as compared with the method of replenishing from the developer. Further, since the agent is relatively strongly stirred so as to be immersed in the developer, the toner and the carrier are sufficiently in contact with each other, so that the charging stability is excellent. In addition, the toner in the toner conveyance path (toner accommodating portion) is more likely to be in a compacted state than the developer mixed with the carrier, and toner aggregates are likely to be generated. Only the toner is driven and the toner on the toner conveyance path is sent to the developer accommodating portion, thereby suppressing the generation of toner aggregates.

However, in the method of driving the screw on the toner conveyance path and sending the toner on the toner conveyance path to the developer container, an external force is applied by the screw, which is suitable for suppressing aggregation in a high temperature and high humidity environment. On the other hand, a sufficient effect cannot be obtained against agglomeration accompanying an increase in contact area due to deformation of the toner. In particular, the tendency is remarkable in the toner containing a large amount of crystalline resin. Further, since the toner is conveyed and pushed into the developer by being pushed in by the conveying screw, the pressure on the toner and the developer is increased, and the toner is easily deformed.
As described above, due to insufficient suppression of toner aggregation and large pressure applied to the toner, if a large amount of crystalline resin having a low hardness is used compared to the conventional toner, a large amount of toner aggregate is generated, causing image defects. A new issue was revealed.

  The present invention has been made in view of the problems in the prior art described above, and is caused by containing a large amount of crystalline resin while maintaining the fixability of a toner containing a large amount of crystalline resin that contributes to low-temperature fixing. Thus, it is possible to provide a developing device that can sufficiently mix the toner in the developing device even at a low specific gravity, maintain the charging stability of the developer, and prevent loose aggregation that can be crushed. The purpose is to do.

  In order to solve the above problems, a developing device according to the present invention includes a developer accommodating portion that accommodates a two-component developer including a carrier and toner, and a toner accommodating portion that accommodates toner supplied to the developer accommodating portion. And a transport mechanism that transports the toner while stirring, the toner containing a crystalline resin having a urethane bond and / or a urea bond in the main chain as a binder resin, and The true specific gravity is 1.00 to 1.20.

  According to the present invention, while maintaining the fixability of a toner containing a large amount of crystalline resin that contributes to low-temperature fixing, the toner in the developing device can be used even in a low specific gravity due to the high content of crystalline resin. Can be sufficiently mixed, the charging stability of the developer can be maintained, and loose agglomeration that can be crushed can also be prevented.

It is a graph which shows the example which has a main peak (P1, P2) in 2 (theta) = 21.3 degrees and 24.2 degrees in the diffraction spectrum obtained by a X-ray-diffraction measurement. 2 is a graph showing a fitting function superimposed on the diffraction spectrum shown in FIG. 1. It is a graph which shows the 13C-NMR spectrum near carbonyl carbon of polyurea which is a reaction product of 4,4'-diphenylmethane diisocyanate (MDI) and water. 1 is an overall view showing a schematic configuration of a printer which is an embodiment of an image forming apparatus equipped with a developing device according to the present invention. It is the enlarged view which showed the outline of the image creation part in FIG. FIG. 6 is an enlarged view showing an outline of a developer container and a toner container in FIG. 5. FIG. 4 is a schematic diagram of a transport screw that transports toner from a toner storage unit to a developer storage unit in an embodiment of the developing device according to the present invention. FIG. 3 is a schematic configuration diagram of a toner conveyance path including a toner storage portion and a conveyance screw in the first embodiment of the developing device according to the present invention. FIG. 6 is a schematic configuration diagram of a toner conveyance path including a toner storage portion and a conveyance screw in a second embodiment of a developing device according to the present invention. FIG. 10 is a schematic cross-sectional view of a toner transport path including a toner storage portion and a transport screw in a third embodiment of a developing device according to the present invention. It is a schematic block diagram of the toner conveyance path | route which consists of a toner accommodating part and the conveyance screw in 6th Embodiment (comparative example) of a developing device.

The developing device according to the present invention includes a developer accommodating portion that accommodates a two-component developer including a carrier and toner, a toner accommodating portion that accommodates toner to be supplied to the developer accommodating portion, and the toner. The toner contains a crystalline resin having a urethane bond and / or a urea bond in the main chain as a binder resin, and a true specific gravity of 1.00 to 1.0. It is characterized by being 1.20.
The present inventors have found that toner containing a large amount of a crystalline resin and modified with a urethane bond or the like forms loose aggregates that can be crushed in the developing unit while maintaining low-temperature fixability. It has been found that loose agglomerates can be suppressed and toner density unevenness can be prevented by loosening the toner in advance with a conveying mechanism such as a screw. Furthermore, with this configuration, the toner is pushed in by a conveying mechanism such as a screw and merged with the developer, so even a toner with a low specific gravity such as a toner containing a large amount of crystalline resin can be easily mixed, and the toner charge amount Has been found to be relatively uniform, and the generation of positively charged toner due to the introduction of urethane can also be suppressed, and the present invention has been completed.

Next, the developing device and the developing method according to the present invention will be described in more detail.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

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

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

  The maximum peak temperature of the heat of fusion of the resin can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). As a pretreatment, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then from 70 ° C. to 10 ° C. The temperature is lowered at a rate of 0.5 ° C./min. Here, by DSC, the temperature is increased at a rate of temperature increase of 10 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 100 ° C. is defined as “Ta *”. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is Ta *. Thereafter, the sample is stored at (Ta * −10) ° C. for 6 hours, and further stored at (Ta * −15) ° C. for 6 hours. Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 10 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of heat quantity was defined as the maximum peak temperature of heat of fusion.

  The content of the crystalline resin relative to the binder resin is preferably 50% by mass or more from the viewpoint of maximizing the compatibility of excellent low-temperature fixability and heat-resistant storage stability due to the crystalline resin, 65 mass% or more is more preferable, 80 mass% or more is still more preferable, and 95 mass% or more is especially preferable. When the content is less than 50% by mass, the heat steepness of the binder resin cannot be expressed on the viscoelastic properties of the toner, and it is difficult to achieve both low-temperature fixability and heat-resistant storage stability.

Further, in the diffraction spectrum obtained by the X-ray diffractometer of the binder resin, the integrated intensity of the spectrum derived from the crystal structure is (C), and the integrated intensity of the spectrum derived from the amorphous structure is (A). The ratio (C) / ((C) + (A)) is preferably 0.15 or more from the viewpoint of achieving both fixing properties and heat-resistant storage stability, more preferably 0.20 or more, and 0.30 or more. Is more preferable, and 0.45 or more is particularly preferable.
In the present invention, when the toner contains a wax, a diffraction peak specific to the 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 will be replaced with “integrated intensity (C) of the derived spectrum”.

  In the present invention, the ratio (C) / ((C) + (A)) can be obtained by X-ray diffraction measurement. Specifically, the X-ray diffractometer with a two-dimensional detector (D8 DISCOVER with GADDS / (Manufactured by 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 (C) / ((C) + (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 / (2cp1 ² )} (Formula A (1))
fp2 (2θ) = ap2exp {− (2θ−bp2) ² / (2cp2 ² )} (Formula A (2))
fh (2θ) = ahexp {− (2θ−bh) ² / (2ch ² )} (Formula A (3))
However, (fp1 (2θ), fp2 (2θ), 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 (C) and (Sh) is (A), the ratio (C) / ((C) + (A)), which is an index indicating the amount of crystallization sites, is calculated. be able to.

  The maximum peak temperature of the heat of fusion of the crystalline resin is preferably 50 ° C. to 70 ° C., more preferably 55 ° C. to 68 ° C., and 60 ° C. to 65 ° C. from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. Particularly preferred. When the maximum peak temperature is lower than 50 ° C., the low temperature fixability is improved but the heat resistant storage stability is deteriorated. When the maximum peak temperature is higher than 70 ° C., the heat resistant storage stability is improved, but the low temperature fixability is deteriorated.

  The ratio of the softening temperature of the crystalline resin to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is 0.8 to 1.6, preferably 0.8 to 1.5. 0.8 to 1.4 is more preferable, and 0.8 to 1.3 is particularly preferable. The smaller the ratio, the more rapidly the resin softens, which is superior from the viewpoint of both low-temperature fixability and heat-resistant storage stability.

  For toners whose main component is a crystalline resin as a binder resin, the property of sharply decreasing viscoelasticity above the melting point that was previously considered effective for low-temperature fixability (sharp melt properties) can be fixed depending on the paper type. It is considered that the temperature range is greatly different. Therefore, a conventional toner having excellent low-temperature fixability has a higher molecular weight, specifically, a component having a polystyrene equivalent molecular weight of 100,000 or more in gel permeation chromatography (GPC), and a weight average. It is preferable that the molecular weight is within a certain range, so that fixing can be performed at a constant temperature and at a constant speed regardless of the type of paper. In the molecular weight measurement of gel permeation chromatography in the present invention, a binder resin or toner is dissolved in tetrahydrofuran (THF) as a solvent, and the molecular weight is obtained by measuring the soluble content (details will be described later). .

  Having 5% or more of a component having a molecular weight of 100,000 or more reduces the temperature dependency of the fluidity and viscoelasticity of the toner after melting, so that heat is transferred to the toner even if it is a thin paper that easily transfers heat during fixing. Even with thick paper that is difficult to transmit, there is no significant difference in toner fluidity and elastic modulus, and the fixing device can be fixed at a constant temperature and at a constant speed. Furthermore, it is preferable to have 1% or more of a component having a molecular weight of 250,000 or more because both low-temperature fixability and heat-resistant storage stability can be achieved, and the difference in glossiness between thin paper and cardboard can be reduced. If the component having a molecular weight of 100,000 or more is less than 5%, the fluidity and viscoelasticity after melting the toner vary greatly depending on the temperature. For example, in fixing on thin paper, the deformability of the toner becomes too large, and the fixing member is not fixed. The adhesion area increases, and as a result, release from the fixing member may not be successful and paper wrapping may occur.

The reason why the effect of the present invention can be obtained is considered as follows. That is, the crystalline resin has a sharp melt property as described above, but the internal cohesive force and viscoelasticity of the toner in a molten state vary greatly depending on the molecular weight and structure of the resin. For example, when it has a urethane bond or urea bond, which is a linking group having a large cohesive energy, it behaves like an elastic body such as rubber at a relatively low temperature even when melted, while the polymer chain becomes As thermal kinetic energy increases, the agglomeration between bonds gradually dissolves and approaches a viscous body.
When such a resin is used as a binder resin for toner, even if the fixing can be performed without any problem when the fixing temperature is low, the internal cohesive force when the toner is melted is small when the fixing temperature is high. A so-called hot offset phenomenon in which the upper side (fixing member side) of the toner adheres to the fixing member may occur, and the image quality is significantly impaired. Increasing the number of urethane bonds and urea bonds to avoid hot offset can be performed without any problem in fixing at high temperatures, but the image gloss is low when fixing at low temperatures, and melt impregnation into paper is difficult. Inadequate and the image tends to detach from the paper, especially when fixing to paper with a large thickness and uneven surface, the heat transfer efficiency to the toner at the time of fixing is low, so the fixing state is further Since the toner is deteriorated or the pressure is not sufficiently applied to the toner by the fixing member in the concave portion, the fixing state of the toner which is in an especially elastic state is remarkably deteriorated.

  When the molecular weight is considered as a means for controlling the viscoelasticity after melting, as a matter of course, the larger the molecular weight, the more obstacles to the movement of the molecular chain, so the viscoelasticity increases. Further, when the molecular weight is large, entanglement occurs, and the elastic behavior is exhibited. Considering the fixability to paper, a smaller molecular weight is preferable because the viscosity at the time of melting is lower. On the other hand, if there is no elasticity, hot offset occurs. However, if the molecular weight is increased as a whole, the fixability is impaired, and particularly in the case of thick paper, the heat transfer efficiency to the toner at the time of fixing is low, and the fixing state is further deteriorated. Therefore, the viscoelasticity after melting can be suitably controlled by including a high molecular weight crystalline component while preventing the molecular weight of the binder resin from being too large as a whole. Regardless of this, a toner that can be fixed at a constant temperature and at a constant speed can be obtained.

  The range of the weight average molecular weight (Mw) is preferably 20,000 or more and 70,000 or less, more preferably 30,000 or more and 60,000 or less, and particularly preferably 35,000 or more and 50,000 or less. is there. When the weight average molecular weight exceeds 70,000, the entire toner is too high in molecular weight, so that the fixability is deteriorated, the gloss is too low, and the image after fixing is easily lost due to external stress. . On the other hand, if the amount is less than 20,000, no matter how much high molecular weight components are present, the internal cohesion force at the time of melting the toner becomes too low, causing hot offset and wrapping of paper around the fixing member. .

As a method of obtaining a toner having a binder resin having a molecular weight distribution as described above, there is a method of using a resin having a controlled molecular weight distribution during polymerization, using two or more resins having different molecular weight distributions in combination. .
When two or more kinds of resins having different molecular weight distributions are used in combination, at least two kinds of the first crystalline resin (A) having a relatively low molecular weight and the second crystalline resin (B) having a high molecular weight are used. As the high molecular weight resin, a resin having a large molecular weight may be used in advance, or a modified resin having an isocyanate group at the terminal may be elongated in the production process of the toner to form a high molecular weight body. In the latter method, the high molecular weight body can be uniformly present in the toner, and in the production method in which the binder resin is dissolved in the organic solvent, the high molecular weight resin is first dissolved than the high molecular weight resin. Is preferable because it is easy.

  As the ratio when the binder resin is composed of two types of high molecular weight second resin (including modified resin having an isocyanate group) (B) and low molecular weight first resin (A), The resin (B) / first resin (A) ratio is 5/95 to 60/40, preferably 8/92 to 50/50, more preferably 12/88 to 35/65, and still more preferably 15 / 85-25 / 75. When the number of high molecular weight substances is less than 5/95, or when the number of high molecular weight substances is larger than 60/40, it becomes difficult to obtain a toner having a binder resin having the molecular weight distribution described above.

  When using a resin whose molecular weight distribution is controlled at the time of polymerization, as a method for obtaining such a resin, for example, in the case of a polymerization form such as polycondensation, polyaddition or addition condensation, in addition to a bifunctional monomer The molecular weight distribution can be broadened by adding a small amount of monomers having different numbers of functional groups. Monomers with different numbers of functional groups include tri- or higher-functional monomers and mono-functional monomers. However, when tri- or higher-functional monomers are used, a branched structure is generated. May be difficult to form. If a monofunctional monomer is used, the polymerization reaction is stopped by the monofunctional monomer, so that the low molecular weight resin in the case of using two or more types of resins is purified, and a part of the polymerization reaction proceeds to increase the high molecular weight component. It becomes.

  In the present invention, the tetrahydrofuran-soluble content of the toner and the molecular weight distribution and weight average molecular weight (Mw) of the resin are measured using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)). It can be measured. As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.

The molecular weight was calculated using a calibration curve prepared with a monodisperse polystyrene standard sample. As the standard polystyrene sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three kinds of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
An RI (refractive index) detector was used as the detector.

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

  The ratio of the component having a molecular weight of 100,000 or more and the ratio of the component having a molecular weight of 250,000 or more can be examined from the intersection of the molecular weight of 100,000 and the molecular weight of 250,000 in the integral molecular weight distribution curve.

When the high molecular weight component has a resin structure close to that of the entire binder resin, it may interact with other resins (such as compatibility) to improve the viscoelasticity and cohesion of the entire toner. is there. From this point of view, if the binder resin has crystallinity, the high molecular weight component preferably has crystallinity as well. When the high molecular weight component is significantly different in structure from the other resin components, the polymer easily phase-separates into a sea-island state, and the desired degree of contribution to improving the viscoelasticity and cohesion of the toner cannot be obtained. There is.
However, it is not always necessary that the resin structure of the high molecular weight component be close to the entire binder resin.

  As a comparison of the degree of crystalline structure content between the high molecular weight component and the whole binder resin, for example, differential scanning of insolubles in a mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by weight). The ratio of the endothermic amount (ΔH (H)) (J / g) in the calorimeter (DSC) to the endothermic amount (ΔH (T)) (J / g) in the DSC of the toner (ΔH (H) / ΔH (T) ) Is preferably in the range of 0.2 to 1.25, more preferably in the range of 0.3 to 1.0, and particularly preferably in the range of 0.4 to 0.8.

  As a specific test method for obtaining an insoluble content in a mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by weight), the toner was mixed with 40 g of the above mixed solvent at room temperature (20 ° C.). After adding 4 g and shaking and mixing for 20 minutes, a solution obtained by precipitating the insoluble component and removing the supernatant by a centrifugal separator can be obtained by vacuum drying.

  In the present invention, the insoluble content of the toner in a THF / ethyl acetate mixed solvent (50/50 by weight) is preferably 10% by weight or more from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability.

  The crystalline resin used in the present invention is preferably composed mainly of a resin having a crystalline polyester unit because it is easy to design a melting point suitable as a toner and has excellent binding properties to paper. Specifically, the resin having a crystalline polyester unit is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass, and still more preferably 90% by mass or more of the entire binder resin. This is because the more the resin having a crystalline polyester unit, the better the low-temperature fixability of the toner.

  The resin having a crystalline polyester unit includes a resin composed only of a crystalline polyester unit (also simply referred to as a crystalline polyester resin), a resin in which a crystalline polyester unit is linked, and a crystalline polyester unit and another polymer bonded together. Resin (so-called block polymer, graft polymer). A resin composed only of a crystalline polyester unit has a portion having a crystal structure, but may be easily deformed by an external force. The reason for this is that it is difficult to crystallize all the parts of the crystalline polyester, and it is easily deformed due to the high degree of freedom of the molecular chain of the non-crystallized part (non-crystalline part), or the crystalline polyester. Regarding the part that has the structure, the higher order structure is usually a so-called lamellar structure in which the molecular chains are folded and overlapped so that the surface is overlapped. However, since a large bonding force does not work between the lamellar layers, it is easy. Possible causes such as the lamellar layer being easily displaced. As a binder resin for toner, if it is easily deformed by an external force, it is deformed and aggregated in the image forming apparatus, adheres to or adheres to a member, and an image that is finally output is easily damaged. Therefore, the binder resin must be able to withstand deformation to some extent against external force and toughness.

  From the viewpoint of imparting toughness of the resin, a resin in which a crystalline polyester unit having a urethane cohesive site having a large cohesive energy, a urea bonding site, or a phenylene site, or a crystalline polyester unit and another polymer are bonded. Resins (so-called block polymers and graft polymers) are preferred. Among these, in particular, urethane bonding sites and urea bonding sites are considered to be able to form pseudo-crosslinking points due to large intermolecular forces between non-crystalline sites and lamellar layers by being present in the molecular chain. Even after fixing, it is easy to get wet with the paper and the fixing strength can be increased.

<Crystalline polyester unit>
Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

-Polyol-
Examples of the polyol include diols, trivalent to octavalent or higher polyols.
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably, For example, aliphatic diols, such as a linear aliphatic diol and a branched aliphatic diol; 36 alkylene ether glycol; alicyclic diol having 4 to 36 carbon atoms; alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; carboxyl group Diols having sulfonic acid groups or sulfamic acid groups, and diols having other functional groups such as salts thereof. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. 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 diol 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-pentanediol 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, Examples include 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. 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.

  The branched aliphatic diol having 2 to 36 chain carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2-propylene glycol, butanediol, hexanediol, octanediol, Examples include decanediol, dodecanediol, tetradecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.

  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 And glycols.

  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.

  There is no restriction | limiting in particular as alkylene oxide (henceforth AO) of the said alicyclic diol, According to the objective, it can select suitably, For example, ethylene oxide (henceforth EO), propylene oxide ( Hereinafter, adducts (number of added moles of 1 to 30) such as butylene oxide (hereinafter abbreviated as BO) and the like can be mentioned.

  There is no restriction | limiting in particular as said bisphenol, It can select suitably according to the objective, For example, AO (EO, PO, BO, etc.) addition products (addition mole number 2-such as bisphenol A, bisphenol F, bisphenol S). 30).

  There is no restriction | limiting in particular as said polylactone diol, According to the objective, it can select suitably, For example, poly-epsilon-caprolactone diol etc. are mentioned.

  There is no restriction | limiting in particular as said diol which has a carboxyl group, According to the objective, it can select suitably, For example, 2, 2- dimethylol propionic acid (DMPA), 2, 2- dimethylol butanoic acid, 2, 2 -Dialkylol alkanoic acids having 6 to 24 carbon atoms such as dimethylol heptanoic acid and 2,2-dimethylol octanoic acid.

  The diol having the sulfonic acid group or the sulfamic acid group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N- Sulfamic acid diols such as bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) and AO adduct (AO) As EO or PO, AO addition mole number 1 to 6); bis (2-hydroxyethyl) phosphate and the like can be mentioned.

  There is no restriction | limiting in particular as a neutralization base of the diol which has these neutralization bases, According to the objective, it can select suitably, For example, the said C3-C30 tertiary amine (triethylamine etc.), an alkali metal ( Sodium salt).

  Among these, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof are preferable.

  Moreover, there is no restriction | limiting in particular as said trivalent-8 valence or more polyol used as needed, According to the objective, it can select suitably, For example, alkane polyol and its intramolecular or intermolecular dehydration thing (E.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), saccharides and derivatives thereof (e.g., sucrose, methylglucoside, etc.), etc. Octahydric or higher polyhydric aliphatic alcohols; AO adducts of trisphenols (trisphenol PA, etc.) (addition moles 2-30); AO adducts of novolac resins (phenol novolac, cresol novolac, etc.) (addition) Mole number 2-30); hydroxyethyl (meth) acrylate and other vinyl And acrylic polyols such as a copolymer of monomers. Among these, trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts are preferred, and novolak resin AO adducts are more preferred.

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

The dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids such as linear aliphatic dicarboxylic acids and branched aliphatic dicarboxylic acids; aromatic dicarboxylic acids and the like. Are preferable. Among these, linear aliphatic dicarboxylic acid is more preferable.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose.For example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc. Alkane dicarboxylic acids having 4 to 36 carbon atoms; alkenedicarboxylic acids having 4 to 36 carbon atoms such as alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid Preferable examples include acids; alicyclic dicarboxylic acids having 6 to 40 carbon atoms such as dimer acid (dimerized linoleic acid).

  The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4 Preferred examples include aromatic dicarboxylic acids having 8 to 36 carbon atoms such as 4,4'-biphenyldicarboxylic acid.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid used as necessary include C9-20 aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid.

  As the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) are used. It may be used.

  Among the dicarboxylic acids, it is particularly preferable to use the aliphatic dicarboxylic acid (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone, but the aromatic dicarboxylic acid and the aromatic Those obtained by copolymerizing an aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

-Lactone ring-opening polymer-
The lactone ring-opening polymer is not particularly limited and may be appropriately selected depending on the purpose. For example, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc. A lactone ring-opening polymer obtained by ring-opening polymerization of lactones such as 12 monolactones (one ester group in the ring) using a metal oxide, an organometallic compound or the like; glycol ( Examples thereof include a lactone ring-opening polymer having a hydroxyl group at the terminal, obtained by ring-opening polymerization of the monolactone having 3 to 12 carbon atoms using ethylene glycol, diethylene glycol, or the like.
There is no restriction | limiting in particular as said C3-C12 monolactone, Although it can select suitably according to the objective, (epsilon) -caprolactone is preferable from a crystalline viewpoint.
In addition, as the lactone ring-opening polymer, a commercially available product may be used. Examples of the commercially available product include highly crystalline polycaprolactones such as H1P, H4, H5, and H7 of the PLACEL series manufactured by Daicel Corporation. Can be mentioned.

-Polyhydroxycarboxylic acid-
The method for preparing the polyhydroxycarboxylic acid is not particularly limited and may be appropriately selected depending on the purpose. Dehydration condensation method: cyclic ester having 4 to 12 carbon atoms corresponding to dehydration condensate between two or three molecules of hydroxycarboxylic acid such as glycolide, lactide (L-form, D-form, racemate, etc.) Examples of the method include ring-opening polymerization of 2 to 3 ester groups using a catalyst such as a metal oxide or an organometallic compound. The method of ring-opening polymerization is preferable from the viewpoint of adjusting the molecular weight.
Among the cyclic esters, L-lactide and D-lactide are preferable from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

<Resin connected with crystalline polyester unit>
Examples of a method for obtaining a resin in which a crystalline polyester unit is linked include a method in which a crystalline polyester unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and linked with polyisocyanate. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.
Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.

  There is no restriction | limiting in particular as said diisocyanate, According to the objective, it can select suitably, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate etc. are mentioned. Among these, the carbon number excluding carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these Preferred is a modified product of diisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and a mixture of two or more of these. . If necessary, trivalent or higher isocyanates may be used in combination.

  The aromatic diisocyanates are not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6- Tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) or a mixture thereof] Condensation product: phosgenation product of polyaminopolyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4, a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanate Anatophenyl sulfonyl isocyanate etc. are mentioned.

  There is no restriction | limiting in particular as said aliphatic diisocyanate, According to the objective, it can select suitably, For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane Triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2- And isocyanatoethyl-2,6-diisocyanatohexanoate.

  There is no restriction | limiting in particular as said alicyclic diisocyanate, According to the objective, it can select suitably, For example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate. , Methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and 2,6-norbornane diisocyanate.

  There is no restriction | limiting in particular as said araliphatic diisocyanate, According to the objective, it can select suitably, For example, m- and p-xylylene diisocyanate (XDI), (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl And xylylene diisocyanate (TMXDI).

  The modified diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanate Examples thereof include modified products containing a nurate group and an oxazolidone group. Specifically, modified MDI such as urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, and modified diisocyanates such as urethane-modified TDI such as isocyanate-containing prepolymers; a mixture of two or more of these modified diisocyanates (For example, combined use of modified MDI and urethane-modified TDI).

  Among these diisocyanates, aromatic diisocyanates having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanates, and 4 to 15 alicyclic diisocyanates are preferable, and TDI, MDI, HDI, Hydrogenated MDI and IPDI are particularly preferred.

<Resin combining crystalline polyester unit and other polymer>
As a method of obtaining a resin in which a crystalline polyester unit and another polymer are bonded, a method in which a crystalline polyester unit and another polymer unit are separately prepared and bonded together, a crystalline polyester unit and another polymer in advance are combined. A method in which one of the units is prepared and then combined by polymerizing the other polymer in the presence of the prepared unit, or a crystalline polyester unit and another polymer unit are simultaneously or sequentially polymerized in the same reaction field However, the first or second method is preferable in that the reaction can be easily controlled as designed.

  As the first method, a method in which a unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and connected with polyisocyanate, as in the method for obtaining the resin in which the crystalline polyester unit is connected, is mentioned. It is done. As the polyisocyanate, those described above can be used, and it can also be obtained by introducing an isocyanate group at the terminal of one unit and reacting with the active hydrogen of the other unit. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.

  As a second method, when the crystalline polyester unit is prepared first, if the next polymer unit to be prepared is an amorphous polyester unit, a polyurethane unit, a polyurea unit or the like, the hydroxyl group at the terminal of the crystalline polyester unit is used. By reacting a group or a carboxyl group with a monomer for obtaining another polymer unit, a resin in which the crystalline polyester unit and another polymer are bonded can be obtained.

<Amorphous polyester unit>
As an amorphous polyester unit, the polycondensation polyester unit synthesize | combined from a polyol and polycarboxylic acid is mentioned, for example. For the polyol and polycarboxylic acid, those exemplified in the above-mentioned crystalline polyester unit can be used. However, in order to design the polymer so as not to have crystallinity, the polymer skeleton should be provided with many bending points and branch points. In order to give an inflection point, for example, bisphenol such as AO (EO, PO, BO, etc.) adduct (addition mole number 2 to 30) such as bisphenol A, bisphenol F, bisphenol S, etc. As the derivative or polycarboxylic acid, phthalic acid, isophthalic acid, or t-butylisophthalic acid may be used. In addition, a trivalent or higher polyol or polycarboxylic acid may be used to introduce the branch point.

<Polyurethane unit>
Examples of the polyurethane unit include a polyurethane unit synthesized from a polyol such as a diol, a trivalent to octavalent or higher polyol, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. Among these, a polyurethane unit synthesized from the diol and the diisocyanate is preferable.
Examples of the diol and the trivalent to octavalent or higher polyol include those similar to the diol and the trivalent to octavalent or higher polyol cited in the polyester resin.
Examples of the diisocyanate and the trivalent or higher polyisocyanate include the same diisocyanates and trivalent or higher polyisocyanates.

<Polyurea unit>
Examples of the polyurea unit include a polyurea unit synthesized from a polyamine such as a diamine or a trivalent or higher polyamine, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate.

  There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aliphatic diamines and aromatic diamines are mentioned. Among these, C2-C18 aliphatic diamines and C6-C20 aromatic diamines are preferable. Further, if necessary, the above trivalent or higher amines may be used.

  There is no restriction | limiting in particular as said C2-C18 aliphatic diamine, According to the objective, it can select suitably, For example, carbon, such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. Alkylene diamine having 2 to 6 carbon atoms; polyalkylene diamine having 4 to 18 carbon atoms such as diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; dialkylaminopropylamine , Alkylene diamines such as trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, and the polyal C1-C4 alkyl or C2-C4 hydroxyalkyl substituted range amine; 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedi C 4-15 alicyclic diamine such as aniline); piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3, C4-C15 heterocyclic diamine such as 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane; xylylenediamine, tetrachloro-p-xylylenediamine And aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms such as amines.

  There is no restriction | limiting in particular as said C6-C20 aromatic diamine, According to the objective, it can select suitably, For example, 1, 2-, 1, 3- and 1, 4- phenylene diamine, 2, 4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m -Unsubstituted aromatic diamines such as aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine; 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltri Range amine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4, 4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2 , 5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1 , 5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'- Methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphe Lumethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5 An aromatic diamine having a C1-C4 nucleus-substituted alkyl group such as' -tetraisopropyl-4,4'-diaminodiphenylsulfone; the unsubstituted aromatic diamine to the C1-C4 nucleus-substituted alkyl group; Mixtures of various proportions of isomers of aromatic diamines having; methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromodiphenylmethane, 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4 -Amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4- Aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4 , 4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline) ), Aromatic diamines having a nucleus-substituted electron withdrawing group such as 4-aminophenyl-2-chloroaniline (halogens such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups and the like); Aromatic diamines having secondary amino groups such as 4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene [the unsubstituted aromatic diamine, the nucleus having 1 to 4 carbon atoms] Aromatic diamines having a substituted alkyl group, and mixtures of various ratios of these isomers, and part or all of the primary amino groups of the aromatic diamine having a nucleus-substituted electron withdrawing group are lower alkyl groups such as methyl and ethyl In which the secondary amino group is replaced with a secondary amino group].

In addition to these, as the diamine, a low molecular weight polyamide obtained by condensation of a dicarboxylic acid (such as a dimer acid) and an excess (more than 2 moles per mole of the acid) the polyamine (the alkylene diamine, the polyalkylene polyamine, etc.). Polyamide polyamines such as polyamines; polyether polyamines such as hydrides of cyanoethylated polyether polyols (polyalkylene glycol and the like).
Moreover, you may use what capped the amino group of the amine compound with the ketone compound etc.
Among these, a polyurea unit synthesized from the diamine and the diisocyanate is preferable.

  Examples of the diisocyanate and the trivalent or higher polyisocyanate include those similar to the diisocyanate and the trivalent or higher polyisocyanate.

<Vinyl polymer unit>
The vinyl polymer unit is a polymer unit obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbons:
Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene and the like.
Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and salts thereof:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-24) ester, for example, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino- 2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3 -(Meth) acrylamide-2-hi Roxypropane sulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene, butylene: single, random or block) mono (meth) acrylate sulfate [Poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, etc.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids, such as 2-acryloyloxyethylphosphonic acid; and salts thereof.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
Amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, Morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
Amide group-containing vinyl monomers; (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, cinnamon Acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like.
Quaternary ammonium cationic group-containing vinyl monomers: tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine Monomer quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, Vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) ) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (2 Each alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraaryl. Roxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) ac Lilate, lauryl alcohol ethylene oxide 30-mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxy Ethyl ether, 3,4-dibutyro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene and the like.
Vinyl ketones, such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, etc.
Vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(9) Other vinyl monomers:
Isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

(10) Fluorine atom element-containing vinyl monomer:
4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 2, 2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyl ( Acrylate), trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate and the corresponding compounds derived from α-fluoroacrylic acid, bis-hexafluoroisopropyl itaconate, bis-hexafluoroisopropyl maleate, bis-perfluoro Octyl itaconate, bis-perfluorooctyl maleate, bis-trifluoroethyl itaconate and bis-trifluoroethyl maleate, vinyl heptafluorobutyrate, Vinyl perfluoroheptanoate, vinyl perfluorononanoate, vinyl perfluorooctanoate and the like.

<Crystalline resin having urea bond in main chain>
The binder resin preferably includes a crystalline resin having a urea bond in the main chain. According to ^{Solubility Parameter Values (Polymer handbook 4 th} Ed), the cohesive energy of the urea bond is 50,230 [J / mol], 2 times the urethane bond cohesive energy (26,370 [J / mol]) ) Therefore, even if the amount is small, it can be expected to improve the toughness of the toner and the offset resistance at the time of fixing.

  In order to obtain a resin having a urea bond in the main chain, a polyisocyanate compound and a polyamine compound are reacted, or a polyisocyanate compound and water are reacted to react an amino group generated by hydrolysis of the isocyanate with the remaining isocyanate group. There is a way. In addition, in obtaining a resin having a urea bond in the main chain, in addition to the above-mentioned compounds, a polyol compound can be reacted at the same time to increase the degree of freedom in resin design.

<<< Polyisocyanate >>>
As polyisocyanates, in addition to diisocyanates as described above, trivalent or higher polyisocyanates (hereinafter also referred to as low molecular weight polyisocyanates), polymers having isocyanate groups at the terminals and side chains (hereinafter also referred to as prepolymers). May be used.
As a preparation method of the prepolymer, a method of obtaining a polyurea prepolymer having an isocyanate group at the terminal by reacting a low molecular weight polyisocyanate with a polyamine compound described below in an excess amount of isocyanate, a low molecular weight polyisocyanate and a polyol compound, The method of making it react with excess and obtaining the prepolymer which has an isocyanate group at the terminal is mentioned. The prepolymers obtained by these methods may be used alone, or two or more kinds of prepolymers obtained by the same method, or two or more kinds of prepolymers obtained by the above two methods may be used in combination. Alternatively, the prepolymer and the low molecular weight polyisocyanate may be used alone or in combination.

The use ratio of polyisocyanate is equivalent ratio [NCO] / [NH ₂ ] of isocyanate group [NCO] and amino group [NH ₂ ] of polyamine, or equivalent ratio [NCO] / [ OH] is usually 5/1 to 1.01 / 1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1.
If the molar ratio of [NCO] exceeds 5, urethane bonds and urea bonds increase too much, and if the finally obtained resin is used as a binder resin for toner, the elastic modulus in the molten state is too high and the fixability deteriorates. If the molar ratio of [NCO] is less than 1.01, the degree of polymerization increases and the molecular weight of the prepolymer produced increases, making it difficult to mix with other materials in the production of toner. Or, the elastic modulus in the molten state is too high, and the fixability may be deteriorated.

<<< polyamine >>>
Examples of the polyamine include diamines as described above, trivalent or higher polyamines, and the like.

<<< Polyol >>>
Examples of the polyol include diols as described above, trivalent to octavalent or higher polyols (hereinafter also referred to as low molecular weight polyols), and polymers having hydroxyl groups at the terminals and side chains (hereinafter referred to as high molecular weight polyols). May be used.
As a method for producing a high molecular weight polyol, a low molecular weight polyisocyanate and a low molecular weight polyol are reacted with an excessive amount of hydroxyl group to obtain a polyurethane having a hydroxyl group at the terminal, and a polycarboxylic acid and a low molecular weight polyol compound are combined with an excess amount of hydroxyl group. And a method of obtaining a polyester having a hydroxyl group at the terminal by reacting with.

In order to adjust the polyurethane or polyester having a hydroxyl group at the terminal, the ratio [OH] / [NCO] of the low molecular weight polyol and the low molecular weight polyisocyanate, or the ratio [OH] / [COOH] of the low molecular weight polyol and the polycarboxylic acid. Is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.
When the molar ratio of the hydroxyl groups exceeds 2, the polymerization reaction does not proceed, so that a desired high molecular weight polyol cannot be obtained. When the molar ratio is less than 1.02, the degree of polymerization becomes high and the molecular weight of the resulting high molecular weight polyol becomes too large. In manufacturing, mixing with other materials becomes difficult, or the elastic modulus in the molten state is too high, and the fixability may be deteriorated.

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

<<< Crystalline resin with urea bond in the main chain >>>
In order for the obtained resin to have crystallinity, a polymer unit having crystallinity may be introduced into the main chain. Examples of the crystalline polymer unit having a melting point suitable as a binder resin for toner include a crystalline polyester unit and a long-chain alkyl ester unit of polyacrylic acid or polymethacrylic acid. A terminal alcohol can be easily prepared, and is preferable because it can be easily introduced into a resin having a urea bond as the polyol compound.

  Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

As the diol, the diols mentioned in the aforementioned polyols can be used. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together. 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.
The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. 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.

As dicarboxylic acid, the dicarboxylic acid mentioned in the above-mentioned polycarboxylic acid can be used, Among these, linear aliphatic dicarboxylic acid is more preferable.
Among the dicarboxylic acids, it is particularly preferable to use the aliphatic dicarboxylic acid (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone, but the aromatic dicarboxylic acid and the aromatic Those obtained by copolymerizing an aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

<<< Introduction of crystalline resin with urea bond in the main chain into toner >>>
A resin in which a urea bond is formed in advance as a binder resin is used, and a toner can be obtained by mixing with a toner constituent material other than the binder resin such as a colorant, a release agent, and a charge control agent to form particles. However, a urea bond is formed by mixing a polyisocyanate compound, a polyamine compound and / or water with a toner constituent material other than a binder resin such as a colorant, a release agent, and a charge control agent as necessary. May be. In particular, by using a prepolymer as the polyisocyanate compound, a crystalline resin having a high molecular weight urea bond can be uniformly introduced into the toner, so that the toner has uniform heat characteristics and chargeability and is fixable. It is preferable because it can easily balance the stress resistance of the toner with the toner. Furthermore, as the prepolymer, a prepolymer obtained by reacting a low molecular weight polyisocyanate and a polyol compound in an excess amount of isocyanate is preferable because the viscoelasticity is suppressed. As the polyol compound, a polycarboxylic acid and a low molecular weight polyol compound are preferred. Is preferred because polyesters having a hydroxyl group at the terminal by reacting with an excess amount of hydroxyl groups are easy to obtain thermal characteristics suitable for the toner. Further, when the polyester comprises a crystalline polyester unit, the high molecular weight component in the toner becomes a sharp melt. This is preferable because a toner having excellent low-temperature fixability can be obtained.
Further, when the toner of the present invention is obtained by granulating in an aqueous medium, the urea bond can be formed under mild conditions by the water of the dispersion medium reacting with the polyisocyanate compound.

<True specific gravity>
The true specific gravity was measured using an air comparison hydrometer (MODEL-930 manufactured by Beckman).

<CHN analysis (amount of N element)>
The amount of the N element derived from the urethane bond and / or urea bond of the THF soluble part in the toner is preferably in the range of 0.3 to 2.0% by weight, preferably 0.5 to 1.8% by weight. Is more preferably in the range of 0.7 to 1.6% by weight. If it exceeds 2.0% by weight, the viscoelasticity in the molten state of the toner may become too high, which may cause deterioration of fixing property, reduction of gloss, deterioration of chargeability, etc. If it is less than that, there is a possibility that problems such as agglomeration in the image forming apparatus due to a decrease in toughness of the toner, contamination of members, and a high temperature offset due to a decrease in viscoelasticity when the toner is melted.

The amount of N element in the present invention is measured simultaneously with CHN under the conditions of a combustion furnace at 950 ° C., a reduction furnace at 550 ° C., a helium flow rate of 200 ml / min, and an oxygen flow rate of 25 to 30 ml / min using a vario MICRO cube (manufactured by Elementar). It was set as the average of the values measured twice. When the amount of N element was less than 0.5% by weight in this measurement method, the measurement was further performed with a trace nitrogen analyzer ND-100 (manufactured by Mitsubishi Chemical Corporation). Electric furnace temperature (horizontal reactor) pyrolysis part 800 ° C, catalyst part 900 ° C, measurement conditions are main O ₂ flow rate 300 ml / min, O ₂ flow rate 300 ml / min, Ar flow rate 400 ml / min, sensitivity Low, pyridine Both calibration curves prepared with the standard solution were quantified.
The THF-soluble matter in the toner can be obtained by placing 5 g of toner in a Soxhlet extractor in advance and extracting it with 70 mL of THF (tetrahydrofuran) for 20 hours. .

[Urea bond]
The presence of a urea bond in the THF soluble component in the toner is important because even if the urea bond is small, an effect of improving the toughness of the toner and the offset resistance during fixing can be expected.
The presence of a urea-soluble urea bond in the toner can be performed by 13C-NMR. Specifically, the analysis was performed as follows.
2 g of the sample to be analyzed is immersed in 200 ml of a potassium hydroxide methanol solution having a concentration of 0.1 mol / L and placed at 50 ° C. for 24 hours. The solution is removed, and the residue is further neutralized with ion-exchanged water. The remaining solid was dried. The sample after drying was added to a mixed solvent (volume ratio 9: 1) of dimethylacetamide (DMAc) and deuterated dimethylsulfoxide (DMSO-d6) at a concentration of 100 mg / 0.5 ml, and the mixture was stirred at 70 ° C. for 12-24. After dissolving for a period of time, the temperature was set to 50 ° C., and 13C-NMR measurement was performed. The measurement frequency this time was 125.77 MHz, the 1H — 60 ° pulse was 5.5 μs, and the reference substance was tetramethylsilane (TMS) 0.0 ppm.

  Presence of urea binding in the sample is confirmed by checking whether a signal is seen in the chemical shift of the signal derived from the carbonyl carbon of the urea binding site of the polyurea used as a sample. The chemical shift of carbonyl carbon is generally seen at 150-160 ppm. As an example of polyurea, FIG. 3 shows a 13C-NMR spectrum near the carbonyl carbon of polyurea, which is a reaction product of 4,4′-diphenylmethane diisocyanate (MDI) and water. A signal derived from carbonyl carbon is seen at 153.27 ppm.

<Two-component developer>
In the present invention, the toner described above is used as a two-component developer together with a carrier.
A well-known and commonly used carrier can be used.

<Developing device, image forming device>
Hereinafter, an embodiment in which a developer containing toner used in the present invention is applied to an image forming apparatus will be described with reference to FIGS. In addition, in each figure, the same code | symbol is attached | subjected to the part which is the same or it corresponds, The duplication description is simplified or abbreviate | omitted suitably.

First, the configuration and operation of the entire image forming apparatus will be described.
FIG. 4 is an overall view showing a schematic configuration of a printer which is an image forming apparatus according to the present embodiment. As shown in FIG. 4, four toner containers 32Y, 32M, 32C, and 32K corresponding to the respective colors (yellow, magenta, cyan, and black) are attached to and detached from the toner container housing 31 above the image forming apparatus main body 100. It is installed freely (changeable).

  An intermediate transfer unit 15 is disposed below the toner container housing 31. Image forming portions 6Y, 6M, 6C, and 6K corresponding to the respective colors (yellow, magenta, cyan, and black) are arranged in parallel so as to face the intermediate transfer belt 8 of the intermediate transfer unit 15. Below the toner containers 32Y, 32M, 32C, and 32K, toner replenishing devices 60Y, 60M, 60C, and 60K are disposed, respectively. The toner or premix toner (replenishment developer including unused toner and unused carrier) stored in the toner containers 32Y, 32M, 32C, and 32K is respectively supplied by toner replenishing devices 60Y, 60M, 60C, and 60K. The image forming units 6Y, 6M, 6C, and 6K are supplied (supplied).

  As shown in FIG. 5, the image forming unit 6Y corresponding to yellow includes a photosensitive drum 1Y, a charging unit 4Y disposed around the photosensitive drum 1Y, a developing device 5Y (developing unit), a cleaning unit 2Y, It consists of a static elimination unit (not shown). Then, an image forming process (charging process, exposure process, developing process, transfer process, cleaning process) is performed on the photosensitive drum 1Y, and a yellow image is formed on the photosensitive drum 1Y.

  The other three image forming units 6M, 6C, and 6K have substantially the same configuration as that of the image forming unit 6Y corresponding to yellow except that the color of the toner used is different. A corresponding image is formed. Hereinafter, description of the other three image forming units 6M, 6C, and 6K will be omitted as appropriate, and only the image forming unit 6Y corresponding to yellow will be described.

  The photosensitive drum 1Y is rotationally driven in a clockwise direction in FIG. 5 by a drive motor (not shown). First, the surface of the photosensitive drum 1Y is uniformly charged at the position of the charging unit 4Y (charging process). Next, the surface of the photosensitive drum 1Y reaches the irradiation position of the laser beam L emitted from the exposure device 7 (described in FIG. 4), and an electrostatic latent image corresponding to yellow is formed by exposure scanning at this position. Formed (exposure process). The surface of the drum 1Y reaches a position facing the developing device 5Y, and the electrostatic latent image is developed at this position to form a yellow toner image (developing process). Thereafter, the surface of the photosensitive drum 1Y reaches a position facing the intermediate transfer belt 8 and the first transfer bias roller 9Y, and the toner image on the photosensitive drum 1Y is transferred onto the intermediate transfer belt 8 at this position. (Primary transfer process). At this time, a small amount of untransferred toner remains on the photosensitive drum 1Y.

  The surface of the photosensitive drum 1Y after the toner image is transferred onto the intermediate transfer belt 8 reaches a position facing the cleaning unit 2Y, and untransferred toner remaining on the photosensitive drum 1Y is removed from the cleaning blade at this position. It is mechanically recovered by 2a (cleaning step). Finally, the surface of the photosensitive drum 1Y reaches a position facing a neutralization unit (not shown), and the residual potential on the photosensitive drum 1Y is removed at this position. In this way, a series of image forming processes performed on the photosensitive drum 1Y is completed.

  The image forming process described above is performed in the other image forming units 6M, 6C, and 6K in the same manner as the yellow image forming unit 6Y.

  In the exposure process, a laser beam L based on image information is irradiated from the exposure unit 7 disposed below the image forming unit onto the photosensitive drums 1 of the image forming units 6M, 6C, and 6K. Is done. Specifically, the exposure unit 7 emits laser light L from a light source, and irradiates each photoconductive drum 1 via a plurality of optical elements while scanning the laser light L with a polygon mirror that is rotationally driven. Thereafter, the toner images of the respective colors formed on the respective photosensitive drums 1 through the development process are superimposed on the intermediate transfer belt 8 and primarily transferred. In this way, a color image is formed on the intermediate transfer belt 8.

  As shown in FIG. 4, the intermediate transfer unit 15 includes an intermediate transfer belt 8, four primary transfer bias rollers 9Y, 9M, 9C, 9K, a secondary transfer backup roller 12, a plurality of tension rollers, intermediate transfer cleaning, and the like. Parts. The intermediate transfer belt 8 is stretched and supported by a plurality of roller members, and is endlessly moved in the direction of the arrow in FIG.

  The four primary transfer bias rollers 9Y, 9M, 9C, and 9K respectively sandwich the intermediate transfer belt 8 with the photosensitive drums 1Y, 1M, 1C, and 1K to form a primary transfer nip. Then, a transfer bias reverse to the polarity of the toner is applied to the primary transfer bias rollers 9Y, 9M, 9C, and 9K.

  The intermediate transfer belt 8 travels in the direction of the arrow and sequentially passes through the primary transfer nips of the primary transfer bias rollers 9Y, 9M, 9C, and 9K. In this way, the toner images of the respective colors on the photosensitive drums 1Y, 1M, 1C, and 1K are primarily transferred while being superimposed on the intermediate transfer belt 8.

  Thereafter, the intermediate transfer belt 8 on which the toner images of the respective colors are transferred in a superimposed manner reaches a position facing the secondary transfer roller 19. At this position, the secondary transfer backup roller 12 sandwiches the intermediate transfer belt 8 with the secondary transfer roller 19 to form a secondary transfer nip. The four color toner images formed on the intermediate transfer belt 8 are secondarily transferred onto a transfer material P such as transfer paper conveyed to the position of the secondary transfer nip. At this time, the untransferred toner that has not been transferred to the transfer material P remains on the intermediate transfer belt 8.

  The intermediate transfer belt 8 that has passed the position of the secondary transfer nip reaches the position of an intermediate transfer cleaning unit (not shown). At this position, the untransferred toner on the intermediate transfer belt 8 is collected. In this way, the transfer is performed on the intermediate transfer belt 8, and a series of transfer processes is completed.

  Here, the transfer material P transported to the position of the secondary transfer nip is transported from a paper feed unit 26 disposed below the apparatus main body 100 via a paper feed roller 27, a registration roller pair 28, and the like. It has been done.

  Specifically, a plurality of transfer materials P such as transfer paper are stacked and stored in the paper supply unit 26. When the paper feeding roller 27 is driven to rotate counterclockwise in FIG. 4, the uppermost transfer material P is fed toward the rollers of the registration roller pair 28. The transfer material P conveyed to the registration roller pair 28 is temporarily stopped at the position of the roller nip of the registration roller pair 28 that has stopped rotating. Then, the registration roller pair 28 is rotationally driven in synchronization with the color image on the intermediate transfer belt 8, and the transfer material P is conveyed toward the secondary transfer nip. In this way, a desired color image is transferred onto the transfer material P.

  The material P to which the color image is transferred at the secondary transfer nip position is conveyed to the position of the fixing unit 20. At this position, the color image transferred to the surface is fixed on the transfer material P by heat and pressure generated by the fixing belt and the pressure roller. Thereafter, the transfer material P is discharged out of the apparatus through the rollers of the discharge roller pair 29. The transfer material P discharged from the apparatus by the discharge roller pair 29 is sequentially stacked on the stack unit 30 as an output image. In this way, a series of image forming processes in the image forming apparatus is completed.

  Next, the configuration and operation of the developing device 5Y in the image forming unit 6Y will be described in more detail with reference to FIGS.

  The developing device 5Y includes a developing roller 51Y facing the photosensitive drum 1Y, a doctor blade 52Y facing the developing roller 51Y, and two transporting screws 55Y as a developer transporting mechanism disposed in the developer containing portions 53Y and 54Y. , 56Y, a density detection sensor 58Y for detecting the toner density in the developer, and the like. The developing roller 51Y includes a magnet fixed inside, a sleeve rotating around the magnet, and the like. In the developer accommodating portions 53Y and 54Y, a two-component developer G composed of a carrier and a toner is accommodated. As shown in FIG. 6, the developer accommodating portion 53Y and the developer accommodating portion 54Y are partitioned by a partition member, and openings for allowing the developer G to circulate through the developer accommodating portions 53Y and 54Y are provided at both ends thereof. In the department. The toner accommodating portion 57Y formed in the upstream portion in the transport direction of the developer accommodating portion 54Y is formed above the opening where the developer G flows back from the developer accommodating portion 53Y to the developer accommodating portion 54Y. It communicates with a toner dropping path 64Y (shown by a broken line in FIG. 5) through an opening (not shown).

The developing device 5Y configured as described above operates as follows. The sleeve of the developing roller 51Y rotates in the direction of the arrow in FIG. The developer G carried on the developing roller 51Y by the magnetic field formed by the magnet moves on the developing roller 51Y as the sleeve rotates.
Here, the developer G in the developing device 5Y is adjusted so that the ratio of toner in the developer (toner concentration) is within a predetermined range. Specifically, according to the consumption of toner in the developing device 5Y, the toner stored in the toner container 32Y is supplied into the toner storage portion 57Y via the toner supply device 60Y.

  The replenishment toner conveyed into the developer accommodating portion 54Y by the rotation of the conveying screw 56Y circulates through the two developer accommodating portions 53Y and 54Y while being mixed and stirred together with the developer G (in the direction of the arrow in FIG. 6). The toner in the developer G is attracted to the carrier by frictional charging with the carrier, and is carried on the developing roller 51Y together with the carrier by the magnetic force formed on the developing roller 51Y.

  The developer G carried on the developing roller 51Y is conveyed in the direction of the arrow in FIG. 5 and reaches the position of the doctor blade 52Y. The developer G on the developing roller 51Y is conveyed to a position facing the photosensitive drum 1Y (development region) after the developer amount is made appropriate at this position. The toner is attracted to the latent image formed on the photosensitive drum 1Y by the electric field formed in the development area. Thereafter, the developer G remaining on the developing roller 51Y reaches above the developer containing portion 53Y as the sleeve rotates, and is detached from the developing roller 51Y at this position.

  Here, the developing device according to the present invention stirs the replenishment toner from the developer storage portions 53Y and 54Y, the toner storage portion 57Y that stores the replenishment toner, and the toner storage portion 57Y to the developer storage portions 53Y and 54Y. And a transporting mechanism 56Y that transports the developing device. The transport mechanism may include a developer transport mechanism 56aY in the developer storage portions 53Y and 54Y and a toner transport mechanism 56bY in the toner storage portion, and the developer transport mechanism 56aY and the toner transport mechanism 56bY are respectively independent. It is preferable that it can be driven. Here, a developer conveying screw is exemplified as the developer conveying mechanism, and a toner conveying screw is exemplified as the toner conveying mechanism. The toner supplied to the toner storage unit is transported to the developer storage unit 54Y by the transport mechanism 56Y and merges with the developer.

In the present invention, even when a toner having a relatively low specific gravity is used, in order to sufficiently mix the replenishment toner with the developer in the developing device, the replenishment toner is merged so as to be submerged into the developer. ing. In FIG. 5, the transport screw 56bY as the replenishing toner transport mechanism is disposed at the same or lower position as the transport screw 56aY as the developer transport mechanism. When the axis of the transport screw 56bY is inclined with respect to the horizontal direction, the replenishment toner is removed from the developer if the height of the transport screw 56bY at the front end in the replenishment toner traveling direction is the same as or lower than that of the transport screw 56aY. Can be merged to be submerged. When the axis of the transport screw 56aY is inclined with respect to the horizontal direction, the transport screw 56bY is at a position equal to or lower than the height at the position closest to the replenishment toner and developer joining portion of the transport screw 56aY. The replenishment toner can be merged into the developer.
Here, the height of the screw means the highest position of the stirring blade of the screw during the stirring (the highest position of the locus of the stirring blade during the stirring). The joining portion of the replenishment toner and the developer means a position where the replenishment toner comes into contact with the developer for the first time.

  In the present invention, even when a toner having a relatively low specific gravity is used, in order to sufficiently mix the replenishment toner with the developer in the developing device, the replenishment toner is merged so as to be submerged into the developer. ing. In order to achieve sufficient mixing, it is preferable that the height of the front end of the toner transport mechanism in the direction of travel from the toner storage portion floor is lower than the height of the developer transport mechanism from the developer storage floor. Further, as shown in FIG. 8, it is more preferable that the transport screw 56bY as the replenishing toner transport mechanism is disposed at the same or lower position as the transport screw 56aY as the developer transport mechanism. When the axis of the transport screw 56bY is inclined with respect to the horizontal direction, the replenishment toner is removed from the developer if the height of the transport screw 56bY at the front end in the replenishment toner traveling direction is the same as or lower than the transport screw 56aY. Can be merged to be submerged. When the axis of the transport screw 56aY is inclined with respect to the horizontal direction, the transport screw 56bY is at a position equal to or lower than the height at the position closest to the replenishment toner and developer joining portion of the transport screw 56aY. The replenishment toner can be merged into the developer.

  Here, the height of the tip of the conveying screw is the highest position among the outermost portions of the stirring blade closest to the tip.

  Next, the toner and the configuration of the toner storage unit 57 as the toner conveyance path in the developing device 5 and the behavior of the toner supplied to the toner storage unit 57, which are characteristic parts of the present embodiment, will be described in more detail. To do. The other developing devices 5M, 5C, and 5K can also have the same configuration, and even if a part or all of them are process cartridges, the same functions and effects as those of the embodiments described later can be obtained. .

(Example of developing device (1): see FIG. 8)
First, the developing device 5Y of the developing device example (1) will be described below. FIG. 8 shows a transport screw 56Y disposed in the developer container 54Y and the toner container 57Y. The outer diameter of the conveying screw in the toner accommodating portion 57Y and the diameter of the inner wall of the accommodating portion are smaller than those in the developer accommodating portion 54Y. Further, the conveying screw 56Y is composed of two fins 56aY and 56bY having different outer diameters as shown in FIG. Since the outer diameter of 57aY is smaller than the outer diameter of 56bY and the replenishment toner surface is lower than the developer surface, the replenishment toner is replenished so as to be pushed into the developer. As a result, even the replenishment toner having a specific gravity smaller than that of the conventional toner can be sufficiently mixed with the carrier.

(Developing device example (2): see FIG. 9)
Next, the developing device 5Y of the developing device example (2) will be described. The developing device 5Y of the developing device example (2) defines the configurations of the toner storage portion 57Y and the transport mechanism. Specifically, the toner container 57Y is inclined so that the side closer to the developer container is lower, and the replenishment toner is joined to the developer by ultrasonic vibration by the piezo element 101. Since the replenishment toner merges from a position lower than the developer surface, even the replenishment toner having a specific gravity smaller than that of the conventional surface can be sufficiently mixed with the carrier. Note that the replenishment toner accommodated in the toner accommodating portion 57Y is accommodated in the developer accommodating portion 54Y at a connection location with the developer accommodating portion 54Y (a location that serves as an interface between the replenishment toner and the developer). The supply amount of the supply toner and the position of the toner container 57Y are controlled such that the height of the supply toner is lower than the height of the developer.

(Developing device example (3): see FIG. 10)
The developing device 5Y of the developing device example (3) defines the toner container 57Y and the screw 56Y. Specifically, in addition to the configuration of the developing device example 1, the gap between the inner wall of the toner accommodating portion 57Y and the screw outer diameter of the screw 56Y disposed in the toner accommodating portion 57Y is eliminated. That is, there is no gap between the toner conveying range of the replenishing toner conveying mechanism 56bY and the inner wall of the toner accommodating portion 57Y in a portion lower than the height of the toner surface of the replenishing toner replenished to the toner accommodating portion 57Y.
In the following description, the same reference numerals are used for the same components as those in the developing device example (1), and the description thereof is omitted.

  If there is a gap between the outer diameter of the conveying screw 56Y disposed in the toner accommodating portion 57Y and the inner wall of the toner accommodating portion 57Y, the toner in that portion is conveyed as shown in FIG. Even if the screw rotates, it is not conveyed to the developer accommodating portion 54Y, and forms a non-moving layer. The toner in which the non-moving layer is formed (hereinafter referred to as non-moving layer toner) tends to be compacted and easily aggregated when left in a high temperature and high humidity environment for a long time. Then, the immobile layer toner adhering to the inner wall collapses due to the vibration applied to the developing device 5Y. Then, the aggregates therein are transported to the developer accommodating portions 54Y and 53Y as the transport screws 56Y and 55Y rotate, and finally clog the doctor blade 52Y and become a white image or a white streak image. There is sex. The thicker the non-moving layer (that is, the size of the gap between the inner wall and the outer diameter of the conveying screw), the greater the risk that large aggregates are generated. In the present embodiment, the gap (doctor gap) between the doctor blade and the developing roller is 0.4 mm.

From the background as described above, it is preferable that the gap between the inner wall of the toner containing portion 57Y and the outer diameter of the conveying screw 56bY is smaller. Furthermore, it can be expected that mixing of the developer and the replenishment toner in the developer accommodating portion is promoted. Therefore, in the present embodiment, as shown in FIG. 10B, at least the inner wall of the toner containing portion 57Y is at a portion lower than the height of the toner surface of the toner replenished to the toner containing portion 57 that is the toner transport path. And the conveyance screw outer diameter of the conveyance screw 56Y are set to be almost zero. Specifically, the toner accommodating portion is designed to have a step so as to be smaller by 0 to 0.1 mm than the outer diameter of the conveying screw 56Y and the inner wall diameter of the toner accommodating portion 57Y. With such a configuration, the toner replenished to the toner storage portion 57Y is transported to the developer storage portion 54Y without forming a non-moving layer, and is then dispersed and charged with the carrier.
Note that a gap preventing member may be interposed between the outer surface of the replenishing toner transport mechanism 56bY and the inner wall of the toner containing portion 57Y so that the gap is almost zero.

(Developing device example (4))
The developing device 5Y of the developing device example (4) defines the screw 56Y. Specifically, in addition to the configuration of the developing device example 1, the screw 56Y disposed in the toner storage portion 57Y is configured by screws 56aY and 56bY divided on the same axis as shown in FIG. The end of each has a concave shape, and the end of 56bY has a convex shape (the concavity and convexity may be the reverse combination), and is configured to fit. Then, screw driving gears 59aY and 59bY are attached to the opposite end portions of the respective screws, and each can be driven independently by engaging with a driving gear (not shown).

  After completion of the developing operation, the driving of the developing device 5Y is also stopped in synchronization with the stop of the photoreceptor 1Y. However, due to the configuration of the developing device example 5, only the transport screw 56bY is stopped after being rotationally driven (several seconds depending on the linear speed, etc.) until the toner stored in the toner storage portion 57Y is fed to the developer storage portion 54Y side. Is controlled to do.

  In the developing device 5Y of the developing device example 4, with the configuration described above, the conveying screw 56bY can be rotated only by the toner accommodating portion 57 while the conveying screws 55Y and 56aY of the developer accommodating portions 53Y and 54Y are stopped. it can. Then, by rotating the conveying screw only in the toner accommodating portion 57Y, the toner accumulated in the toner accommodating portion 57Y (toner conveying path) can be eliminated, and the developer in the developer accommodating portions 53Y and 54Y is unnecessary. Agitation can be eliminated. Therefore, toner aggregation in the toner storage portion 57Y can be prevented and the life of the developer can be extended.

  In the developing device example 4, since the transport screw 56 is divided on the same axis, the transport screws 56aY and 56bY can be supported at their divided ends with a simple configuration. Further, it is not necessary to separately provide a support member that supports one end of the transport screws 56aY and 56bY at the divided positions. Therefore, a support member provided separately, a shaft end portion of the conveyance screw 55Ya provided in the developer accommodating portion 54Y, or the like is obstructed on the toner conveyance path in the communication portion between the toner accommodating portion 57 and the developer accommodating portion 54Y. It doesn't become a thing. In addition, it is possible to eliminate the replenishment toner accumulated in the toner storage portion 57Y (toner transport path) due to the presence of an obstacle at the communication portion between the toner storage portion 57 and the developer storage portion 54Y.

(Developing device example (5))
The developing device 5Y of the developing device example (5) defines the toner container 57Y and the screw 56Y. Specifically, the features of developing device example 3 and developing device example 4 are added to the configuration of developing device example 1. That is, in addition to the configuration of the developing device example 1, the gap between the inner wall of the toner accommodating portion 57Y and the screw outer diameter of the screw 56Y disposed in the toner accommodating portion 57Y is eliminated, and the screw 56Y is configured. However, it is composed of screws 56aY and 56bY divided on the same axis as shown in FIG. 7, and the end of 56aY has a concave shape and the end of 56bY has a convex shape (the concavity and convexity may be the reverse combination). The screw driving gears 59aY and 59bY are attached to the opposite ends of the respective screws, and meshed with the driving gears (not shown), respectively. It can be driven independently.

(Example of developing device (6): see FIG. 11)
The developing device 5Y of the developing device example (6) defines the toner storage portion 57Y and the toner dropping path 64Y. Specifically, in contrast to the configuration of the developing apparatus example 1, the toner storage portion 57Y is not provided, and the connection portion of the toner storage portion 57Y of the developer storage portion 54Y is an outer wall. 64Y is disposed in the vicinity of the partition plate opening (upstream side of the developer container 54Y) of the developer container 54Y. Since the replenishment toner is dropped onto the developer from vertically above, it is mixed with the carrier from the state on the developer surface. Accordingly, in the case of the replenishment toner having a small specific gravity, the toner is conveyed without being uniformly mixed due to the specific gravity difference with the carrier.

(Production Example 1)
<Production of crystalline polyurethane resin A-1>
In a reaction vessel equipped with a stirrer and a thermometer, 45 parts by weight (0.50 mol) of 1,4-butanediol, 59 parts by weight of 1,6-hexanediol (0.50 mol), and methyl ethyl ketone (hereinafter referred to as MEK) 200 parts by weight were added. To this solution, 250 parts by weight (1.00 mol) of 4,4′-diphenylmethane diisocyanate (MDI) was added, reacted at 80 ° C. for 5 hours, and then the solvent was removed to obtain [Crystalline Polyurethane Resin A-1]. . The obtained [Crystalline Polyurethane Resin A-1] had Mw 20000 and a melting point of 60 ° C.

(Production Example 2)
<Production of urethane-modified crystalline polyester resin A-2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 15 parts by weight (0.10 mol) of adipic acid, 177 parts by weight of 1,6-hexanediol (1 .50 mol) and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off generated water. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was approximately 12 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the value reached 1,000, and [crystalline polyester resin A′-2] was obtained. The obtained [Crystalline Polyester Resin A′-2] was Mw 12,000.
Subsequently, the obtained [crystalline polyester resin A′-2] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 350 parts by weight of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 30 parts by weight (0.12 mol) was added, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin A-2]. The obtained [urethane-modified crystalline polyester resin A-2] had an Mw of 22,000 and a melting point of 62 ° C.

(Production Example 3)
<Production of crystalline polyester resin A-3>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 185 parts by weight (0.91 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, 125 parts by weight of 1,4-butanediol (1 .39 mol) and 0.5 part by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted for 8 hours at 180 ° C. while distilling off the generated water under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream, and the Mw was about 10 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [Crystalline Polyester Resin A-3] was obtained. The obtained [Crystalline Polyester Resin A-3] had an Mw of 9,500 and a melting point of 57 ° C.

(Production Example 4)
<Production of urethane-modified crystalline polyester resin B-1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 204 parts by weight (1.01 mol) of sebacic acid, 13 parts by weight (0.09 mol) of adipic acid, 136 parts by weight of 1,6-hexanediol (1 .15 mol), and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were added and reacted at 180 ° C. for 8 hours while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 20 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin B′-1] was obtained. The obtained [Crystalline Polyester Resin B′-1] was Mw 20,000.
Subsequently, the obtained [crystalline polyester resin B′-1] was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 200 parts by weight of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 15 parts by weight (0.06 mol) was added, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin B-1]. The obtained [urethane-modified crystalline polyester resin B-1] had an Mw of 39,000 and a melting point of 63 ° C.

(Production Example 5)
<Production of crystalline resin precursor B-2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by weight (1.00 mol) of sebacic acid, 122 parts by weight (1.03 mol) of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst. (Triethanolaminate) 0.5 parts by weight was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 25 under reduced pressure of 5 to 20 mmHg. The reaction was carried out until reaching 1,000.
The obtained [crystalline resin] was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 300 parts by weight of ethyl acetate and 27 parts by weight (0.16 mol) of hexamethylene diisocyanate (HDI) were added. The mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream to obtain a 50 wt% ethyl acetate solution of [crystalline resin precursor B-2] having an isocyanate group at the terminal. 10 parts by weight of the obtained [crystalline resin precursor B-2] in ethyl acetate was mixed with 10 parts by weight of tetrahydrofuran (THF), and 1 part by weight of dibutylamine was added thereto, followed by stirring for 2 hours. As a result of GPC measurement using the obtained solution as a sample, Mw of [crystalline resin precursor B-2] was 54,000. Moreover, as a result of performing DSC measurement about the sample obtained by removing a solvent from the said solution, melting | fusing point of [crystalline resin precursor B-2] was 57 degreeC.

(Production Example 6)
<Production of crystalline polyester resin B-3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 230 parts by weight (1.00 mol) of dodecanedioic acid, 118 parts by weight (1.00 mol) of 1,6-hexanediol, and tetrabutoxy as a condensation catalyst. 0.5 parts by weight of titanate was added, and the reaction was carried out for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 50 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [Crystalline Polyester Resin B-3] was obtained. The obtained [Crystalline Polyester Resin B-3] had Mw of 52,000 and a melting point of 66 ° C.

(Production Example 7)
<Production of Amorphous Resin C-1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube, 222 parts by weight of bisphenol A EO 2 mol adduct, 129 parts by weight of bisphenol A PO 2 mol adduct, 166 parts by weight of isophthalic acid, and 0.5 parts by weight of tetrabutoxy titanate The reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value reached 2, the mixture was cooled to 180 ° C., added with 35 parts by weight of trimellitic anhydride, and reacted at normal pressure for 3 hours. Resin C-1] was obtained. The obtained [Amorphous resin C-1] was Mw 8,000 and Tg 62 ° C.

(Production Example 8)
<Production of urethane-modified amorphous resin C-2>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 302 parts by weight of bisphenol A EO 2 mol adduct, 129 parts by weight of bisphenol A PO 2 mol adduct, 166 parts by weight of isophthalic acid, and tetrabutoxy titanate as a condensation catalyst were added in an amount of 0.1%. 5 parts by weight was added, and the reaction was carried out for 8 hours at 180 ° C. while distilling off the generated water under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 6 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the value reached 1,000, and [amorphous polyester resin C′-2] was obtained. The obtained [Non-crystalline polyester resin C′-2] was Mw 6,000.
Subsequently, the obtained [amorphous polyester resin C′-2] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, and 350 parts by weight of ethyl acetate, hexamethylene diisocyanate (HDI) 27 A part by weight was added, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified amorphous polyester resin C-2]. The obtained [urethane-modified amorphous polyester resin C-2] had Mw of 7,000 and a melting point of 66 ° C.

  Table 1 below shows the formulations and characteristics of the resins obtained in the above Production Examples 1-8.

<Manufacture of toner>
-Production of graft polymer-
In a reaction vessel equipped with a stir bar and a thermometer, 480 parts by mass of xylene and 100 parts by mass of low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128 ° C.) are sufficiently dissolved and purged with nitrogen. After that, a mixed solution of 740 parts by mass of styrene, 100 parts by mass of acrylonitrile, 60 parts by mass of butyl acrylate, 36 parts by mass of di-t-butylperoxyhexahydroterephthalate, and 100 parts by mass of xylene was dropped at 170 ° C. for 3 hours. The polymer was polymerized and held at this temperature for 30 minutes. Next, the solvent was removed to synthesize [graft polymer]. The obtained [graft polymer] had Mw of 24,000 and Tg of 67 ° C.

-Preparation of release agent dispersion (1)-
50 parts by weight of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8), 30 parts by weight of graft polymer, Charge 420 parts of ethyl acetate, raise the temperature to 80 ° C. with stirring, hold it at 80 ° C. for 5 hours, cool to 30 ° C. at 1 hour, and use a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), Dispersion was carried out under the conditions of a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, filling with 80% by volume of 0.5 mm zirconia beads, and 3 passes to obtain [Partitioner Dispersion Liquid (1)].

-Preparation of master batches (1)-(4)-
-Urethane modified crystalline polyester resin A-1 100 parts by weight-Carbon black (Printtex 35, manufactured by Degussa) 100 parts by weight (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
・ Ion exchange water 50 parts by weight

Said raw material was mixed using the Henschel mixer (made by Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. The kneading temperature started kneading from 90 ° C., and then gradually cooled to 50 ° C. The obtained kneaded product was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch (1)].
In the production of [Masterbatch (1)], [Crystalline Polyester Resin A-2], [Crystalline Polyester Resin A-3], and Urethane Modified Amorphous instead of [Urethane Modified Crystalline Polyester Resin A-1] [Masterbatch (2)], [Masterbatch (3)], and [Masterbatch (4)] were produced in the same manner as the production of masterbatch (1) except that polyester resin C-2] was added. .

-Preparation of oil phase (1)-(3), (5), (6)-
In a container equipped with a thermometer and a stirrer, 74 parts by weight of [Polyurethane resin A-1] may be added, and ethyl acetate in an amount so that the solid content may be 50% by weight may be added and heated to the melting point of the resin or higher. Dissolved. To this, 40 parts by weight of 50% by weight ethyl acetate solution of [non-crystalline resin C-1], 60 parts by weight of [release agent dispersion (1)], 12 parts by weight of [masterbatch (1)] were added, The mixture was stirred at 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 5,000 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, and was used within 5 hours from preparation so as not to crystallize.
For the oil phases (2), (3), (5), and (6), the type / addition amount of the crystalline resin A, the type / addition amount of the crystalline resin B, and the type / addition amount of the amorphous resin C , And the type of masterbatch were changed according to Table 2, and were similarly produced. The crystalline resin B in Table 2 was used by dissolving and dispersing together with other toner materials in the oil phase preparation stage.

―Manufacture of aqueous dispersion of resin fine particles―
In a reaction vessel equipped with a stirring bar and a thermometer, 600 parts by weight of water, 120 parts by weight of styrene, 100 parts by weight of methacrylic acid, 45 parts by weight of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) (Product) 10 parts by weight and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 20 minutes to obtain a white emulsion. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by weight of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain [Aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion] was 80 nm, the weight average molecular weight of the resin was 160,000, and Tg was 74 ° C.

-Preparation of aqueous phase (1)-
990 parts by weight of water, 83 parts by weight of an aqueous dispersion of resin fine particles, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate Part by weight was mixed and stirred to obtain [Aqueous phase (1)].

-Preparation of toner bases (1) to (3), (5), (6)-
In a separate container in which a stirrer and a thermometer are set, 520 parts by weight of [Aqueous Phase (1)] is put and held at 40 to 50 ° C., and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used. While stirring at 13,000 rpm, 260 parts by weight of [oil phase (1)] was added and emulsified for 1 minute to obtain [emulsified slurry 1].
Next, [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 60 ° C. for 6 hours to obtain [Slurry 1]. The obtained [Slurry 1] was filtered under reduced pressure, and then the following washing treatment was performed.

(1) 100 parts by weight 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 by weight of a 10 wt% 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 by weight of 10% by weight hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(4) Add 300 parts by weight 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 to filter cake (1) Got.
The obtained filter cake (1) was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the toner base (1) was prepared by sieving with a mesh of 75 μm.

  Similarly, toner bases (2), (3), (5), and (6) were prepared using oil phases (2), (3), (5), and (6), respectively.

-Preparation of oil phase (4)-
In a container equipped with a thermometer and a stirrer, 54 parts by weight of [urethane-modified crystalline polyester resin A-2] is added, and ethyl acetate is added in an amount such that the solid content concentration is 50% by weight. Heat well to dissolve. To this, 40 parts by weight of 50% by weight ethyl acetate solution of [non-crystalline resin C-1], 60 parts by weight of [release agent dispersion (1)], 12 parts by weight of [masterbatch (2)] were added, The mixture was stirred at 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [oil phase (4)]. The temperature of [oil phase (1)] was kept at 50 ° C. in the container, and was used within 5 hours from preparation so as not to crystallize.

―Manufacture of aqueous dispersion of resin fine particles―
In a reaction vessel equipped with a stirring bar and a thermometer, 600 parts by weight of water, 120 parts by weight of styrene, 100 parts by weight of methacrylic acid, 45 parts by weight of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) (Product) 10 parts by weight and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 20 minutes to obtain a white emulsion. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by weight of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain [Aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion] was 80 nm, the weight average molecular weight of the resin was 160,000, and Tg was 74 ° C.

-Preparation of aqueous phase (1)-
990 parts by weight of water, 83 parts by weight of an aqueous dispersion of resin fine particles, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate Part by weight was mixed and stirred to obtain [Aqueous phase (1)].

-Preparation of toner base (4)-
In a separate container equipped with a stirrer and a thermometer, 520 parts by weight of [Aqueous Phase (1)] was placed and heated to 40 ° C. 40 parts by weight of an ethyl acetate solution of [crystalline resin precursor B-2] is added to 220 parts by weight of [oil phase (1)] maintained at 50 ° C., and a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). ) At a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to prepare [oil phase (4 ′)]. While stirring the above [water phase (1)] kept at 40 to 50 ° C. at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [oil phase (4 ′)] The resultant was added and emulsified for 1 minute to obtain [Emulsified slurry 4].
Next, [Emulsion slurry 4] was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 6 hours to obtain [Slurry 4]. The obtained [Slurry 4] was filtered under reduced pressure, and then the following washing treatment was performed.

(1) 100 parts by weight 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 by weight of a 10 wt% 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 by weight of 10% by weight hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(4) Add 300 parts by weight 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 to filter cake (1) Got.

  The obtained filter cake (1) was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the toner base (4) was prepared by sieving with a mesh of 75 μm.

-Preparation of toners (1)-(6)-
100 parts by weight of the obtained toner bases (1) to (6) and 1.0 part by weight of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) as an external additive were added to a Henschel mixer (Mitsui Mining Co., Ltd.). The product is mixed for 30 seconds at a peripheral speed of 30 m / sec using a product made by the company, and after 5 cycles of treatment for 1 minute, sieved with a mesh having a mesh opening of 35 μm to produce toner (1) to toner (6) did.

  For the obtained toners (1) to (6), particle size distribution (Dv, Dn, Dv / Dn), specific gravity, measurement of N element amount in CHN analysis of THF soluble matter, molecular weight measurement, thermal characteristic measurement, and solvent insolubility Minute measurements were taken. About these measurements, it measured according to the above-mentioned measuring method. The results are shown in Table 3.

<Creation of carrier>
-Silicone resin (organostraight silicone) 100 parts by weight-γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by weight-Carbon black 10 parts by weight-Toluene 100 parts by weight

  The above raw materials were dispersed with a homomixer for 20 minutes to prepare a resin layer coating solution. Thereafter, using a fluidized bed type coating apparatus, a resin layer coating solution was applied to the surface of 1,000 parts by weight of spherical ferrite having a volume average particle size of 35 μm to prepare a carrier.

<Production of developer>
Developers (1) to (6) were prepared by mixing 5 parts by weight of toner (1) to toner (6) and 95 parts by weight of the carrier.

Example 1
Toner (1) was evaluated for toner aggregate, toner spent, mixing with carrier, and positive charge rate as follows. Similarly, Examples 2 to 8 and Comparative Examples 1 to 3 were carried out according to the combinations of toner and developing device shown in Table 4.

<Toner aggregate>
Using the developer (1), the developing device example (1) and the toner (1), and outputting 50,000 sheets of an image area ratio of 0.5%, the developer (1) is taken out from the developing device, The sieve was sieved with a mesh having an opening of 106 μm, the amount of toner remaining on the mesh after sieving was measured, and the change in the weight of the developer (1) was calculated and evaluated.

〔Evaluation criteria〕
◎: Less than 1% ○: 1% or more and less than 3% △: 3% or more and less than 5% ×: 5% or more

  Since the toner forms aggregates, the amount of toner that can pass through the mesh decreases. Therefore, it is determined that the smaller the amount of toner remaining on the mesh, the fewer toner aggregates formed in the developing device.

<Toner spent>
Using the developer (1), the developing device example (1), and the toner (1), a 20% image area chart is obtained while controlling the toner density so that the image density becomes 1.4 ± 0.2. Change amount of charge (μc / g) of developer (1) after output of 10,000 sheets (charge reduction after 200,000 sheets run / charge amount at start of run) compared with initial value before output The following criteria were evaluated. The charge amount was measured by a blow-off method.

〔Evaluation criteria〕
◎: Less than 15% ○: 15% or more and less than 30% △: 30% or more and less than 50% ×: 50% or more

  When the toner is filmed on the electrophotographic carrier, the composition of the outermost surface of the electrophotographic carrier is changed and the charge amount is reduced. It is determined that the smaller the change in the charge amount before and after the run, the less the degree of filming of the toner onto the electrophotographic carrier.

<Mixing with carrier>
Using developer (1), developing device example (1) and toner (1), after outputting 50,000 sheets of a chart with an image area ratio of 0.5%, developer (1) is taken out from the developing device, and the developer The standard deviation of the charge amount distribution (charge amount conversion per toner surface area) of (1) was measured, and compared with the standard deviation of the developer charge amount distribution sufficiently stirred by a turbula mixer, and evaluated according to the following criteria. The charge amount distribution was measured using an E-spart analyzer manufactured by Hosokawa Micron.

〔Evaluation criteria〕
◎: Less than 10% ○: 10% or more and less than 20% △: 20% or more and less than 30% ×: 30% or more

  If the toner is not sufficiently mixed with the carrier, the contact frequency between the toner and the carrier tends to be uneven, and the charge amount distribution becomes broad. Therefore, the closer the charge amount distribution is to the sufficiently mixed developer, the better the toner mixed state with the carrier.

<Positive charge rate>
In the above <mixing with carrier>, the ratio of positively charged toner having a charge of 0 C or more was measured instead of the charge amount distribution, and the following criteria were similarly evaluated.

〔Evaluation criteria〕
◎: Less than 10% ○: 10% or more and less than 20% △: 20% or more and less than 30% ×: 30% or more

  The above evaluation results are shown in Table 4 below.

  Comparative Example 3 is easy to mix because of its specific gravity of 1.24, but positively charged because it contains urethane.

  As described above, according to the present invention, the developing device can maintain the fixability of a toner containing a large amount of crystalline resin that contributes to low-temperature fixing, and has a low specific gravity due to containing a large amount of crystalline resin. It was found that the toner can be sufficiently mixed in the toner, the charging stability of the developer can be maintained, and loose aggregation that can be crushed can be prevented.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Photoconductor cleaning part 4 Charging part 5 Developing device 6 Image forming part 7 Exposure apparatus 8 Intermediate transfer belt 9 First transfer bias roller 31 Toner container accommodating part 32 Toner container 53, 54 Developer accommodating part 55 Developer Conveying mechanism 56 disposed on the storage portion 53 side Conveying mechanism 56a disposed on the developer storage portion 54 side Conveyance mechanism portion 56b disposed on the developer storage portion 54 Conveyance disposed on the toner storage portion Mechanism portion 57 Toner storage portion 58 Concentration detection sensor 64 for detecting the toner concentration disposed in the developer storage portion Toner drop path 100 Image forming apparatus

JP 2010-0777419 A JP 2009-014926 A JP 2010-151996 JP 2011-164530 A

Claims (15)

A developer containing portion for containing a two-component developer containing a carrier and toner;
A toner container that contains toner to be replenished in the developer container;
A developing device comprising: a conveying mechanism that conveys the toner while stirring;
The developing device according to claim 1, wherein the toner contains a crystalline resin having a urethane bond and / or a urea bond in the main chain as a binder resin, and has a true specific gravity of 1.00 to 1.20. The transport mechanism includes a toner transport mechanism that transports the toner from the toner container to the developer container, and a developer transport mechanism that transports the two-component developer in the developer container.
2. The development according to claim 1, wherein a height from a floor surface of the toner storage unit at a front end in a traveling direction of the toner transport mechanism is lower than a height from the floor surface of the developer storage unit of the developer transport mechanism. apparatus. The toner transport mechanism includes a toner transport screw,
The developer transport mechanism includes a developer transport screw,
The highest position of the outermost part of the stirring blade closest to the toner supply part of the toner transport screw is the highest position of the outermost part of the stirring blade closest to the toner supply part of the developer transport screw, and the highest position. The developing device according to claim 1, wherein the developing devices are arranged at the same or lower positions.   4. The developing device according to claim 1, wherein the amount of N element when the CHN analysis of the THF soluble matter of the toner is performed is 0.3 to 2.0% by weight. 5. .   In the gel permeation chromatography measurement of the tetrahydrofuran soluble part of the toner, the ratio of the molecular weight of 100,000 or more is 5% or more, and the weight average molecular weight (Mw) is 20,000 or more and 70,000 or less. The developing device according to claim 1.   6. The developing device according to claim 1, wherein a ratio of a molecular weight of 250,000 or more is 1% or more in gel permeation chromatography measurement of a tetrahydrofuran soluble part of the toner.   A differential scanning calorimeter (DSC) of the toner has an endothermic amount of ΔH (T) (J / g), and a differential scanning of insoluble content of the toner with respect to a THF / ethyl acetate mixed solvent (50/50 by weight). 7. Any one of claims 1 to 6, wherein ΔH (H) / ΔH (T) is 0.2 to 1.25 when the heat absorption amount in the calorimeter is ΔH (H) (J / g). The developing device according to any one of the above.   8. The developing device according to claim 1, wherein an insoluble content of the toner in a THF / ethyl acetate mixed solvent (50/50 by weight) is 10% by weight or more.   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 (C) and the integrated intensity of the spectrum derived from the amorphous structure is (A) 9. The developing device according to claim 1, wherein the ratio (C) / ((C) + (A)) is 0.15 or more.   The developing device according to claim 1, wherein the crystalline resin is a resin having a crystalline polyester unit.   11. The developing device according to claim 1, wherein the crystalline resin is a copolymer having a crystalline polyester unit and a polyurethane unit.   The developing device according to claim 1, wherein the developer transport mechanism and the toner transport mechanism can be independently driven.   2. The gap between the toner conveying range of the toner conveying mechanism and the inner wall of the toner accommodating portion is not present in a portion lower than the height of the toner surface of the toner replenished in the toner accommodating portion. The developing device according to any one of Items 12 to 12.   The developing device according to claim 1, wherein a gap preventing member is interposed between an outer surface of the toner conveying mechanism and an inner wall of the toner containing portion. A developer containing portion for containing a two-component developer containing a carrier and toner;
A developer transport mechanism for transporting the two-component developer in the developer container;
A toner container that contains toner to be replenished in the developer container;
A developing method using a developing device including a toner transport mechanism for transporting the toner in the toner container,
The toner container is connected to a toner replenisher provided in the developer container,
The toner transport mechanism is arranged such that the toner transported by the toner transport mechanism and the developer transported by the developer transport mechanism merge at the toner replenishing unit,
The developing method according to claim 1, wherein the toner contains a crystalline resin having a urethane bond and / or a urea bond in the main chain as a binder resin, and has a true specific gravity of 1.00 to 1.20.