JP2014066999A - Image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming device configured to prevent toner aggregate from being generated even if toner containing crystalline resin having excellent low-temperature fixability is used.SOLUTION: An image forming device includes a replaceable toner container, conveyance means for conveying toner stored in the toner container, and a toner housing part for temporarily housing the toner conveyed by the conveyance means. The toner housing part has a conveyance screw for supplying the stored toner to a developing device. In a portion lower than a shaft of the conveyance screw in the toner housing part, a gap between an outer peripheral end of the conveyance screw and an inner wall of the toner housing part is 2.0 mm or less (1). The toner contains crystalline resin which includes a urethane bond and/or urea bond in a main chain (2).

Description

  The present invention relates to an electrophotographic image forming apparatus such as a copying machine, electrostatic printing, facsimile, printer, electrostatic recording or the like.

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 the heat-fixing type image forming apparatus, since a large amount of electric power is required in the process of heat-melting the toner and fixing it on a recording medium such as paper, the toner has a low-temperature fixability from the viewpoint of energy saving. 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. It has been proposed that both storability can be achieved. 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. It has been proposed that the use can improve low-temperature fixability and suppress cracks in 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. It has been proposed to be possible.

The toner is temporarily stored in a toner storage unit called a sub hopper between a replaceable toner container (toner cartridge or the like), a transport unit that transports the toner stored in the toner container, and the developing device. Thus, for example, the toner replenishment amount can be made to follow a rapid change in toner consumption accompanying a rapid change in the image area ratio.
As a new problem when a toner containing a crystalline resin is accommodated in the toner container, particularly when the crystalline resin is a main component of the binder resin, it is excellent in low-temperature fixability, but in the toner accommodating portion. It has been found that there is a problem that an image is caused due to an aggregate.
Since toner is replenished from the toner container so that a constant amount of toner is always stored in the toner storage unit, depending on the downtime and toner consumption of the printing machine, the toner is left in the toner storage unit for a long time. As a result, it was found that the above-mentioned problems are more likely to occur.
It is essential that the toner container is disposed in the vicinity of the developing device. Since there is a restriction on the place where the printer can be installed, a small printer or the like cannot keep a sufficient distance from the heat source in the printer, and the temperature of the toner container must be increased. On the other hand, toner containers such as toner cartridges that contain low-temperature fixing toner are susceptible to deterioration due to heat, so they are often installed away from heat sources in the printing press. These measures cannot be taken due to the limitations of where they can be.
An object of the present invention is to provide an image forming apparatus that has excellent low-temperature fixability and does not generate toner aggregates even when a toner containing a crystalline resin is used.

The present invention is based on the above findings by the present inventors, and specific means for solving the above problems are as follows.
A replaceable toner container; a transport unit that transports toner stored in the toner container; and a toner storage unit that temporarily stores the toner transported through the transport unit; Is an image forming apparatus having a conveying screw for replenishing the accommodated toner to the developing device,
(1) The gap between the outer peripheral end of the conveying screw and the inner wall of the toner accommodating portion is 2.0 mm or less at a portion lower than the axis of the conveying screw in the toner accommodating portion.
(2) The image forming apparatus, wherein the toner contains a crystalline resin, and the crystalline resin contains a crystalline resin having a urethane bond and / or a urea bond in the main chain.

  According to the present invention, it is possible to provide an image forming apparatus that does not generate aggregates even when a toner containing a crystalline resin having excellent low-temperature fixability is used.

FIG. 2 is a schematic configuration diagram illustrating an example of an image forming apparatus using a toner storage unit or a replenishment developer storage unit according to the present invention. FIG. 3 is an explanatory diagram illustrating a configuration of a toner replenishing device having a toner container according to the present invention. It is explanatory drawing which shows an example of a conveyance pump. FIG. 4 is a cross-sectional view of a toner container. 2 is an example of a diffraction spectrum obtained by X-ray diffraction measurement of a toner. It is a figure which shows the fitting function of the whole X-ray-diffraction spectrum shown in FIG. It is a ¹³ C-NMR spectrum near the carbonyl carbon of polyurea, which is a reaction product of 4,4′-diphenylmethane diisocyanate (MDI) and water.

The present inventor has studied a low-temperature fixing toner replenishing device using a crystalline resin in consideration of the above-described toner accommodating portion and toner problems.
(1) In a toner containing a crystalline resin, coarse particles are likely to be generated due to toner aggregation in a conveying screw that replenishes toner accommodated in the toner accommodating portion to a developing device. The reason is unknown, but since the conveying screw is installed in the lower part of the toner container and the compacted toner is conveyed by the screw, the toner is compressed and agglomerated and sparse due to the stress caused by the conveying in the high filling state. It is thought that liquefaction occurred. A crystalline resin is more easily plastically deformed than an amorphous resin having the same degree of hardness. Therefore, even when the amount of deformation during pressurization is small compared to an amorphous resin, it remains in a deformed state. Therefore, it is considered that such a problem due to pressure is likely to occur. This phenomenon is considered that the amount of plastic deformation increases as the temperature increases. The generated coarse particles are mainly soft coarse particles (coarse particles having hardness that can be broken when pinched with a finger).

(2) With regard to the conveying screw, it has been found that by generating no gap between the container wall and the screw blade, it is possible to suppress the generation of soft coarse particles by suppressing the toner staying in this gap. It was. However, instead of soft coarse particles, hard coarse particles (coarse particles having a hardness that can not be broken even if pinched with a finger) are generated instead, and thus the problem related to toner coarse particles has not been solved.

(3) Next, for the toner, the present inventors assume that the binder resin is obtained by finely dispersing the crystalline resin in the toner (for example, preventing uneven distribution on the surface directly connected to solidification of the toner). In addition, by introducing urethane bonds and / or urea bond sites that are elastically deformable and have high internal cohesion and high hardness into the crystalline resin, we attempted to solve the problems arising from plastic deformation of the crystalline resin. . In the toner container having a gap between the container wall and the screw blade (the gap is larger than 2 mm), hard coarse particles are generated, and soft coarse particles are not generated. The cause of the difference in the hardness distribution of the coarse particles due to the toner structure is not clear. On the other hand, no coarse particles were observed in the toner container in which no gap was formed between the container wall and the screw blade (the gap was 2 mm or less).

(4) The generation of aggregates is thought to be a phenomenon involving the adhesion and accumulation of toner on the container wall and the long-term residence in the container, but it is unclear what the hardness of the resulting aggregate is determined by. It is.
From the above results, there is a combination in which coarse particles are not generated specifically even under temperature conditions in the printing press in the combination of the presence or absence of a gap between the container wall and the screw blade and the finely dispersed state of the crystalline resin component. I found it.

  As a result of intensive studies in view of the above problems, the present inventors have introduced a urethane bond and / or a urea bond into the crystalline resin, thereby increasing the cohesive force derived from the bond, thereby increasing the hardness of the crystalline resin. It was found that it can be improved. In addition, since the crystalline resin having a urethane bond and / or a urea bond is a resin having a crystalline polyester unit, it is easy to design a melting point suitable as a toner and has excellent binding properties to paper. Further, by using a crystalline resin having two types of urethane bonds and / or urea bonds having different weight average molecular weights, it becomes possible to adjust the crystallinity of the toner as a whole more effectively. It has also been found that deterioration of the heat-resistant storage stability of the toner due to bond introduction can be suppressed, and that the dispersion state of the crystalline portion of the crystalline resin in the toner can be improved.

  Then, the toner containing the crystalline resin as a main component has a gap between the outer peripheral end of the conveying screw and the inner wall of the toner accommodating portion being 2.0 mm or less at a portion lower than the axis of the conveying screw in the toner accommodating portion. Thus, an image forming apparatus capable of being stably replenished without generating toner aggregates was obtained.

  The material constituting the toner of the present invention will be described. Note that it is easy for a person skilled in the art to change or modify the present invention within the scope of the claims to form other embodiments, and these changes and modifications are included in the scope of the claims, The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

(toner)
The toner of the present invention is a toner containing at least a binder resin, a colorant, and a release agent. The binder resin contains a crystalline resin, and the crystalline resin contains urethane bonds and It is characterized by containing a crystalline resin having a urea bond. The crystalline resin having a urethane bond and / or a urea bond is a resin having a crystalline polyester unit, and the first crystalline resin (low molecular weight body) and the second crystalline resin having different average molecular weights ( It is preferable to contain two types of crystalline resins of high molecular weight).
The introduction of a urethane bond and / or urea bond and the blending of a high molecular weight body are considered to be effective in suppressing the burying of the external additive by improving the toner hardness, suppressing the increase in the toner contact area due to deformation, and suppressing the adhesion.

(About toner powder characteristics and shape)
As a result of intensive studies, it has been found that it is preferable that the toner of the present invention has a preferable powder characteristic in which excessive self-weight compression does not occur and the compression progresses at an appropriate speed after replenishment. In particular,
It is preferable to satisfy the following relational expression for the toner volumes V1 and V2 (mL).
V2 / V1 ≧ 0.79
(Here, V1 and V2 indicate the toner capacity when left for 5 minutes and 20 minutes after stirring.)
Further, (1) the following relational expression for the toner volumes V1 and V3 (mL) is satisfied,
V3 / V1 ≧ 0.71
(Here, V1 and V3 indicate the toner capacity when left for 5 minutes and 24 hours after stirring.)
(2) The bulk density of the toner at the time of measuring V3 is preferably 0.44 to 0.51 (g / ml).

Here, V1, V2, and V3 indicate bulk volumes when left for 5 minutes, 20 minutes, and 24 hours after stirring.
Specifically, the toner capacities V1, V2, and V3 were measured as follows.
(1) Weigh 10 g of toner, put it into a closed graduated cylinder (made of Pyrex (registered trademark) glass, standard product with a capacity of 50 mL). Is included.
(2) Stand still at the end of swinging and measure the standing time.
(3) Read from the scale of the cylinder which calls the toner capacity at the time of standing for 5 minutes, 20 minutes and 24 hours, and set them as V1, V2 and V3 (mL), respectively.
In addition, the measurement of said V1, V2, V3 (mL) evaluated on the same environmental conditions using the sample left to stand at 22 degreeC and 50RH% for 30 minutes.

These powder characteristics are considered to indicate toner powder characteristics in which toner aggregation hardly occurs when the screw is operated for a long time or when the screw is restarted after long-term stoppage.
As a means for obtaining such powder characteristics, the shape, surface properties, particle size, adhesion amount of external additives, and the like of the toner base particles are considered to contribute. In order to make the body characteristics preferable, introduction of a urethane bond and / or urea bond and blending of a high molecular weight body are adjustment means excellent in control of the toner shape.

<Binder resin>
The binder resin in the present invention is 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 of the softening temperature measured by the Koka flow tester and the maximum peak heat of fusion measured by a differential scanning calorimeter (DSC) (softening temperature / maximum peak of melting heat). Temperature) 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.

(Softening temperature / Maximum peak temperature measurement conditions for heat of fusion)
The softening temperature of the resin can be measured using a Koka 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 having a diameter of 0.5 mm and a length of 1 mm, and the plunger of the flow tester was lowered with respect to 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)). A sample to be used for measurement of the maximum peak temperature of heat of fusion was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./minute, and then again the heating rate Measure the endothermic change by increasing the temperature at 10 ° C / min, draw a graph of "endothermic amount" and "temperature", and set the temperature corresponding to the maximum peak of the endothermic amount to the second heat of fusion The maximum peak temperature of In addition, the endothermic amount of the endothermic peak having the maximum peak temperature at this time was defined as the second endothermic endothermic amount.

  The content of the crystalline resin with respect to the binder resin is preferably 50% by mass or more from the viewpoint of maximizing the compatibility between excellent low-temperature fixability and heat-resistant storage stability due to the crystalline resin, and 65% by mass. The above is more preferable, 80% by mass or more is more preferable, and 95% by mass or more is particularly 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.

  In the diffraction spectrum obtained by the X-ray diffractometer of the toner of the present invention, 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.

When the toner in the present invention 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 mass of the toner is 15% by mass or less, the contribution of the diffraction peak inherent to the wax is negligible. In the case of 15% by mass or more, the value obtained by subtracting the integral intensity of the spectrum derived from the wax crystal structure 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”.
The ratio (C) / ((C) + (A)) is an index indicating the amount of crystallization sites in the toner (mainly the amount of crystallization sites in the binder resin which is the main component of the toner). The X-ray diffraction measurement in the present invention was performed using a two-dimensional detector-mounted X-ray diffraction apparatus (D8 DISCOVER with GADDS / Bruker). In addition, a conventionally known toner containing a crystalline resin or wax to the extent of an additive has a ratio of less than about 0.15.

The capillary used for the measurement was a mark tube (Lindenman glass) having a diameter of 0.70 mm. The sample was packed up to the top of the capillary tube and measured. Further, tapping was performed when filling the sample, and the number of tapping was 100 times.
Detailed measurement conditions are shown below.
Tube current: 40 mA
Tube voltage: 40 kV
Goniometer 2θ axis: 20.000 °
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
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. 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. 5, 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 Gaussian functions,
fp1 (2θ) = ap1exp {− (2θ−bp1) 2 / (2cp12)}
(Formula A (1))
fp2 (2θ) = ap2exp {− (2θ−bp2) 2 / (2cp22)}
(Formula A (2))
fh (2θ) = ahexp {− (2θ−bh) 2 / (2ch2)} (Formula A (3))
(Fp1 (2θ), fp2 (2θ), and fh (2θ) are functions corresponding to the main peaks P1, P2, and halo, respectively)
And the sum of these three functions: f (2θ) = fp1 (2θ) + fp2 (2θ) + fh (2θ) (formula A (4))
Was the fitting function of the entire X-ray diffraction spectrum (shown in FIG. 6), 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. 5) are others for 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,. 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, can be calculated. it can.

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.

In the case where the crystalline resin contains two crystalline resins, ie, a first crystalline resin (low molecular weight body) and a second crystalline resin (high molecular weight body) having different average molecular weights, The weight average molecular weight (Mw) of the crystalline resin (A) is preferably 10,000 to 40,000, more preferably 15,000 to 35,000, from the viewpoint of compatibility between low-temperature fixability and heat-resistant storage stability. 30,000 to 30,000 is particularly preferred. If it is less than 10,000, the heat resistant storage stability of the toner tends to deteriorate, and if it exceeds 40,000, the low temperature fixability of the toner tends to deteriorate, such being undesirable.
The weight average molecular weight (Mw) of the second crystalline resin (B) is preferably 40,000 to 300,000, particularly 50,000 to 150,000, from the viewpoints of low-temperature fixability and hot offset resistance. preferable. When it is less than 40,000, the hot offset resistance of the toner tends to deteriorate, and when it is more than 300,000, the toner is not sufficiently melted particularly at the time of fixing at a low temperature, and the image tends to peel off. This is not preferable because the low-temperature fixability of the toner tends to deteriorate.
The difference in Mw between the first crystalline resin (A) and the second crystalline resin (B) is preferably 5,000 or more, and more preferably 10,000 or more. If it is smaller than 5,000, the toner fixing width tends to be narrow, which is not preferable.
The content ratio of the crystalline resin (A) and the crystalline resin (B) is preferably in the range of (A) :( B) = 95: 5 to 70:30. When the ratio (A) is larger than this range, the hot offset resistance of the toner tends to deteriorate, and when the ratio (B) is larger than this range, the low-temperature fixability of the toner deteriorates. This is not preferable.

(Mw measurement conditions)
In the present invention, the weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GPC) measuring device (for example, GPC-8220 GPC (manufactured by Tosoh Corporation)). As the column, TSKgel SuperHZM-H 15 cm triplet (manufactured by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C. In measuring the molecular weight of the sample, it was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. Examples of the standard polystyrene sample include Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

  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 the final output image 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.

Therefore, in the present invention, as the crystalline resin having a urethane bond and / or a urea bond in the main chain, a crystalline polyurethane resin (a resin composed only of a polyurethane unit), a crystalline polyurea resin (a resin composed only of a polyurea unit), And a crystalline polyester resin having a urethane bond site or a urea bond site (a resin in which a crystalline polyester unit having a urethane bond site or a urea bond site is connected). A crystalline polyester resin is preferable.
In the present invention, the toner may contain, as a binder resin, a crystalline resin other than a crystalline resin having a urethane bond and / or a urea bond in the main chain, and an amorphous resin, and the main chain has a urethane bond. Examples of the crystalline resin other than the crystalline resin having a urea bond include a crystalline polyester resin (a resin composed only of a crystalline polyester unit), a resin obtained by bonding a crystalline polyester unit and another polymer, Examples of the non-crystalline resin include non-crystalline polyester resins (resins composed of non-crystalline polyester units).

<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; C4-C36 alkylene ether glycol; C4-C36 alicyclic diol; alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; diol having a carboxyl group, sulfonic acid And diols having other functional groups such as salts thereof, and the like. 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.

The AO adduct of the bisphenol is not particularly limited and may be appropriately selected depending on the intended purpose. Mole number 2-30) etc. are mentioned.
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 another functional group of diol which has other functional groups, such as these salts, It can select suitably according to the objective, For example, the said C3-C30 tertiary amine (triethylamine etc. ) And alkali metals (sodium salt, etc.).

  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 except 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.

<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 4th Ed), the cohesive energy of urea bonds is 50,230 [J / mol], which is about twice the cohesive energy of urethane bonds (26,370 [J / mol]]). Even so, 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 to make it. 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 in combination of two or more types of prepolymers obtained by the same method, or two or more types of prepolymers obtained by the above two methods. Alternatively, the prepolymer and the low molecular weight polyisocyanate may be used alone or in combination.

The ratio of polyisocyanate used 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 and 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.

  When the “crystalline resin having a urethane bond in the main chain” is used instead of the “crystalline resin having a urea bond in the main chain”, the above “crystalline resin having a urea bond in the main chain” is used. Instead of reacting the polycyanate compound with the polyamine compound in the description of "", it can be obtained by reacting the polyol compound with the polyamine compound.

  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.

  The said binder resin in this invention may be used individually by 1 type, and may use 2 or more types together. In addition, binder resins having different weight average molecular weights may be used in combination, and the crystalline resin having a urethane bond and / or a urea bond in the main chain includes at least the first crystalline resin and the first crystalline resin. It is preferable that the second crystalline resin having a weight average molecular weight Mw higher than that is included in that both excellent low-temperature fixability and hot offset resistance can be achieved.

  The second crystalline resin is obtained by extending the resin by reacting with a compound having an active hydrogen group using the binder resin precursor which is a modified crystalline resin having an isocyanate group. It is preferable that In this case, the reaction between the binder resin precursor and the compound having an active hydrogen group is more preferably performed in the toner production process, and a crystalline resin having a large weight average molecular weight can be uniformly dispersed in the toner. In addition, variation in characteristics among toner particles can be suppressed.

That is, the first crystalline resin is a crystalline resin having a urethane bond and / or a urea group bond in the main chain, and the second crystalline resin is a modification of the first crystalline resin. It is preferable that the binder resin precursor is reacted with a compound having an active hydrogen group and elongated. By bringing the composition structures of the first crystalline resin and the second crystalline resin close to each other, the two types of binder resins are more easily dispersed in the toner, and the variation in characteristics between toner particles is further increased. Can be suppressed.
As the binder resin, the crystalline resin and the amorphous resin may be used in combination, and the main component of the binder resin is preferably the crystalline resin.

[Toner characteristics]
In order for the toner of the present invention to have both low-temperature fixability and heat-resistant storage stability at a higher level and to be excellent in hot offset resistance, the toner has a temperature rise 2 measured by a differential scanning calorimeter (DSC). The second maximum endothermic peak T1 (maximum peak temperature of heat of fusion) is in the range of 50 ° C. or higher and 70 ° C. or lower, and the second endothermic amount ΔH (T) is 30 J / g or higher and 75 J / g or lower. It is preferable that

When the maximum endothermic peak temperature of the toner is less than 50 ° C., toner blocking is likely to occur in a high temperature environment, and when it exceeds 70 ° C., low temperature fixability is hardly exhibited. The maximum endothermic peak temperature is more preferably 55 ° C. or more and 68 ° C. or less, and particularly preferably 58 ° C. or more and 65 ° C. or less.
When the toner has an endothermic amount of less than 30 J / g, the number of sites having a crystal structure in the toner is reduced, sharp melt properties are lowered, and it is difficult to obtain a balance between heat-resistant storage stability and low-temperature fixability. If it exceeds g, the energy required for fusing and fixing the toner increases, and the fixing ability may deteriorate depending on the fixing device. The endothermic amount is more preferably 45 J / g or more and 70 J / g or less, and particularly preferably 50 J / g or more and 60 J / g or less.

In the differential scanning calorimeter (DSC) of the toner of the present invention, the maximum endothermic peak T1 for the second temperature increase in the range of 0 to 150 ° C. and the maximum exothermic peak T2 for the temperature decrease satisfy the following relational expression (1). preferable.
T1−T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)
(However, the rate of temperature increase from 0 ° C. to 150 ° C. at the time of temperature increase is 10 ° C./min, and the temperature decrease rate from 150 ° C. to 0 ° C. is 10 ° C./min.)

<Maximum endothermic / exothermic peak of toner, measuring method and condition of endothermic amount>
The maximum endothermic peak of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)) in the same manner as the resin. Specifically, first, about 5.0 mg of a sample used for measurement of the maximum peak temperature of heat of fusion was placed in an aluminum sample container, the sample container was placed on a holder unit, and set in an electric furnace. Next, after raising the temperature from 0 ° C. to 10 ° C./min to 150 ° C. in a nitrogen atmosphere, the temperature was lowered from 150 ° C. to 10 ° C./min to 0 ° C. Further, the temperature was raised from 0 ° C. to 150 ° C. at 10 ° C./min. Using the analysis program in the DSC system, the DSC curve at the second temperature rise was selected, and the maximum endothermic peak temperature T1 of the toner was measured. Similarly, the maximum heat generation peak temperature T2 of the toner when the temperature was lowered was measured. In addition, the endothermic amount of the endothermic peak having the maximum endothermic peak temperature at this time was defined as the second endothermic amount.

T1 of the toner is preferably 50 ° C to 70 ° C, more preferably 53 ° C to 65 ° C, and particularly preferably 58 ° C to 62 ° C. When the T1 is 50 ° C. to 70 ° C., the minimum heat-resistant storage stability required for the toner can be ensured, and a toner having excellent low-temperature fixability that is not conventionally obtained can be obtained. When T1 is lower than 50 ° C., the low-temperature fixability is improved, but the heat-resistant storage stability tends to deteriorate. When the T1 is higher than 70 ° C., the heat-resistant storage stability is improved, but the low-temperature fixability tends to deteriorate. It is in.
The T2 is preferably 30 ° C to 55 ° C, more preferably 35 ° C to 55 ° C, and particularly preferably 40 to 55 ° C. When the T2 is less than 30 ° C., the speed at which the fixed image is cooled to solidified is slow, and toner image (printed matter) may be blocked or transported. The T2 is desirably as high as possible. However, since T2 is a crystallization temperature, it is impossible to take a temperature higher than the melting point T1. That is, it is desirable that the difference between T1 and T2 (T1−T2) is within a certain range in order to suppress toner image blocking and conveyance flaws while maintaining excellent heat-resistant storage stability and low-temperature fixability. T1-T2 is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and particularly preferably 20 ° C. or lower. When T1-T2 is greater than 30 ° C., the difference between the fixing temperature and the temperature at which the toner image is solidified is large, and it is difficult to obtain the effect of suppressing toner image blocking and transport flaws.

  In addition, as a result of intensive studies by the present inventors, in a toner mainly composed of a crystalline resin as a binder resin, the viscoelasticity is drastically decreased at a temperature higher than the melting point that has been considered effective for low-temperature fixability. It has been found that the property (sharp melt property) is considered to cause the fixing temperature range to vary greatly depending on the paper type. Therefore, the molecular weight of the binder resin used in the conventional toner having excellent low-temperature fixability is a higher component, specifically, the molecular weight in terms of polystyrene in gel diffusion chromatography (GPC) soluble in tetrahydrofuran (THF) of the toner. Has been found to be capable of fixing at a constant temperature and at a constant speed regardless of the type of paper by containing a certain amount of 100,000 or more and a weight average molecular weight within a certain range. .

  The component having a molecular weight of 100,000 or more preferably has 5% or more, more preferably 7% or more, and more preferably 9% or more. When the component having a molecular weight of 100,000 or more has 5% or more, the temperature dependency of the fluidity and viscoelasticity of the toner after melting is reduced. 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. 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 the 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 a polymer chain increases as the temperature increases. As the thermal kinetic energy increases, the aggregation between the bonds gradually dissolves and approaches the 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 that the upper 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 particularly in an 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 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. When the weight average molecular weight exceeds 70,000, the whole binder resin is too high in molecular weight, so that the fixing property 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 relatively high molecular weight resins and low molecular weight resins 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.

  The ratio of the high molecular weight resin (including a modified resin having an isocyanate group) and the low molecular weight resin as the binder resin is such that the ratio of the high molecular weight resin / low molecular weight resin is 5 / It is 95-60 / 40, Preferably it is 8 / 92-50 / 50, More preferably, it is 12 / 88-35 / 65, More preferably, it is 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 the column, TSKgel SuperHZM-H 15 cm triplet (manufactured by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.

The molecular weight was calculated using a calibration curve prepared with a monodisperse polystyrene standard sample. As the standard polystyrene sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three kinds of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
Solution A: S-7450 2.5mg, S-678 2.5mg, S-46.5 2.5mg, S-2.90 2.5mg, THF 50ml
Solution B: S-3730 2.5mg, S-257 2.5mg, S-19.8 2.5mg, S-0.580 2.5mg, THF 50ml
Solution C: S-1470 2.5mg, S-112 2.5mg, S-6.93 2.5mg, Toluene 2.5mg, THF 50ml
An RI (refractive index) detector was used as the detector.
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.

The high molecular weight component needs to have a resin structure close to that of the entire binder resin. If the binder resin has crystallinity, the high molecular weight component also needs to have crystallinity. When the high molecular weight component is significantly different in structure from the other resin components, the polymer is easily phase-separated and becomes a sea-island state, so that it cannot be expected to contribute to improvement of viscoelasticity and cohesive force on the whole toner. As a comparison of the degree of crystalline structure content between the high molecular weight component and the entire binder resin, for example, differential scanning of insolubles with respect to a mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by mass ratio). The ratio (ΔH (H) / ΔH (T)) of the second endothermic amount (ΔH (H)) in the calorimeter (DSC) and the second endothermic amount (ΔH (T)) in the DSC of the toner. ) Is preferably in the range of 0.20 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 mass ratio), toner 0. 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. The endothermic amount (ΔH (H)) at the second temperature increase can be measured in the same manner as the endothermic amount (ΔH (T)) at the second temperature increase.

The storage elastic modulus G ′ (80) (Pa) of the toner at 80 ° C. is 1.0 × 10 ⁴ or more and 5.0 × 10 ⁵ or less, and the storage elastic modulus G ′ of the toner at 140 ° C. ( 140) (Pa) is preferably 1.0 × 10 ³ or more and 5.0 × 10 ⁴ or less.
When the storage elastic modulus G ′ (80) (Pa) is less than 1.0 × 10 ⁴ Pa, a blocking phenomenon in which the fixed images stick to each other after the continuous output of the fixed images easily occurs. If it exceeds 10 ⁵ Pa, the meltability of the toner in the low temperature region is lowered and the gloss of the fixed image tends to be low. Further, the storage elastic modulus G ′ (80) is more preferably 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁵ Pa or less, and 5.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁵ Pa or less. Particularly preferred.

When the storage elastic modulus G ′ (140) (Pa) is less than 1.0 × 10 ³ Pa, the hot offset resistance tends to deteriorate, and when it exceeds 5.0 × 10 ⁴ Pa, a fixed image is obtained. There is a tendency for the gloss of the to become low. The storage elastic modulus G ′ (140) is more preferably 1.0 × 10 ³ Pa to 1.0 × 10 ⁴ Pa, and more preferably 5.0 × 10 ³ Pa to 1.0 × 10 ⁴ Pa. Particularly preferred.

(G80, G140 temperature measurement conditions)
The dynamic viscoelastic characteristic values (storage elastic modulus G ′, loss elastic modulus G ″) of the toner can be measured using a dynamic viscoelasticity measuring device (for example, ARES (manufactured by TA Instruments)). Measured under the condition of 1 Hz The sample was molded into a pellet having a diameter of 8 mm and a thickness of 1 mm to 2 mm, fixed to a parallel plate having a diameter of 8 mm, stabilized at 40 ° C, and a frequency of 1 Hz (6.28 rad / s), The temperature was increased to 200 ° C. at a rate of temperature increase of 2.0 ° C./min at a strain amount of 0.1% (strain amount control mode).

[Amount of N element soluble in THF in toner]
The amount of N element soluble in THF in the toner is preferably in the range of 0.3 to 2.0 wt%, more preferably in the range of 0.5 to 1.8 wt%, and 0.7 More preferably, it is -1.6 wt%. If it exceeds 2.0 wt%, the viscoelasticity in the molten state of the toner may become too high, which may cause deterioration of fixability, decrease in gloss, deterioration of chargeability, etc. If there is, there is a risk that aggregation in the image forming apparatus or member contamination due to a decrease in toughness of the toner, or a high temperature offset due to a decrease in viscoelasticity in the molten toner state may occur.

(N element amount measurement conditions)
The amount of N element in the present invention is measured simultaneously with CHN using a vario MICRO cube (manufactured by Elementar) 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 25-30 ml / min. It was set as the average of the values measured twice. When the amount of N element was less than 0.5 wt% 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 portion 800 ° C, catalyst portion 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.

(Urea binding amount measurement conditions)
The presence of a urea-soluble urea bond in the toner can be performed by ¹³ C-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 ¹³ C-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. 7 shows a ¹³ C-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.

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

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

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

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

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

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 1 mass%-20 mass% are preferable, and 3 mass%-10 mass% are more preferable. . When the content is less than 1% by mass, the hot offset resistance tends to deteriorate, and when it exceeds 20% by mass, the heat resistant storage stability, chargeability, transferability, and stress resistance tend to deteriorate. It is not preferable.

―Colorant―
There is no restriction | limiting in particular as a coloring agent used for the toner of this invention, According to the objective, it can select suitably from a well-known coloring agent.
The color of the colorant of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, Each color toner can be obtained by appropriately selecting the type of colorant, but is preferably a color toner.

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

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

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

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but from the viewpoint of compatibility with the binder resin in the present invention, the binder resin of the present invention or a resin having a structure similar to the binder resin of the present invention should be used. Is preferred.
The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

―Charge control agent―
Further, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount exceeds 5% by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image The density may be lowered, and if it is less than 0.01% by mass, the charge start-up property and the charge amount are not sufficient, and the toner image may be easily affected.

<Organic modified layered inorganic mineral>
In the present invention, the toner can contain an organically modified layered inorganic mineral.
The organically modified layered inorganic mineral is an organically modified layered inorganic mineral in which at least some of the ions present between the layers of the layered inorganic mineral are modified with organic ions. The layered inorganic mineral is a layered inorganic mineral formed by overlapping layers having a thickness of several nm. The term “modified” is synonymous with introducing organic ions into ions existing between layers of the layered inorganic mineral, and in a broad sense is intercalation.
By containing an organically modified layered inorganic mineral in which at least some of the ions present between the layers of the layered inorganic mineral are modified with organic ions, it functions as a crystal nucleating agent for the crystalline resin and increases the crystallinity of the toner. Alternatively, by dispersing in the toner oil phase, it functions as a filler and has a function of making the toner shape indefinite.
In addition, the layered inorganic mineral produces the greatest effect by being arranged in the vicinity of the toner surface layer. However, it is known that the organically modified layered inorganic mineral in the present invention is uniformly arranged in the vicinity of the toner surface layer without any gap. . For this reason, the structural viscosity of the binder resin in the vicinity of the toner surface layer is efficiently increased, and the image is sufficiently protected even in the state of an image having a low resin hardness just after fixing. Further, since the effect can be efficiently exhibited even with a small addition amount, it is considered that there is almost no hindrance to fixability.

Here, the presence state of the organically modified layered inorganic mineral in the toner is determined by cutting a sample in which toner particles are embedded in an epoxy resin with a micromicrotome or an ultramicrotome, and scanning the cross section of the toner with a scanning electron microscope (SEM) or the like. It can be confirmed by observation. In the case of observation by SEM, it is preferable to confirm by a reflected electron image, and it is preferable because the presence of the organically modified layered inorganic mineral can be observed with a strong contrast. Further, using FIB-STEM (HD-2000, manufactured by Hitachi, Ltd.), a sample in which toner particles are embedded in an epoxy resin or the like may be cut with an ion beam, and the cross section of the toner may be observed. Also in this case, it is preferable to confirm with a reflected electron image because of easy visual recognition.
Further, the vicinity of the toner surface in the present invention refers to a toner image obtained by cutting a sample in which toner particles are embedded in an epoxy resin with a micro-microtome, an ultra-microtome, or an FIB-STEM. It is defined as a region of 0 nm to 300 nm from the surface to the inside of the toner.

The layered inorganic mineral is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include smectite group clay minerals (montmorillonite, saponite, hectorite, etc.), kaolin group clay minerals (kaolinite, etc.), bentonite. Attapulgite, magadiaite, and kanemite. These may be used individually by 1 type and may use 2 or more types together.
The organically modified layered inorganic mineral is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least a part of the ions existing between the layers of the layered inorganic mineral are modified with organic ions. Examples include organically modified layered inorganic minerals. Among these, those in which at least part of ions between layers of the smectite group clay mineral having a smectite-based basic crystal structure are modified with an organic cation are preferable from the viewpoint of dispersion stability in the vicinity of the toner surface, and between the layers of montmorillonite. Particularly preferred are those in which at least some of the ions have been modified with an organic cation, and those in which at least some of the ions between bentonite layers have been modified with an organic cation.

The organic modified layered inorganic mineral can be confirmed by gas chromatography mass spectrometry (GCMS) that at least some of the ions present between the layers of the layered inorganic mineral are modified with organic ions, for example, A method of filtering a solution obtained by dissolving a binder resin in a toner as a sample with a solvent, pyrolyzing the obtained solid with a pyrolyzer, and identifying the structure of the organic substance with GCMS is preferable. . Specifically, as a thermal decomposition apparatus, Py-2020D (manufactured by Frontier Laboratories) is used, and after thermal decomposition at 550 ° C., a method of identifying with a GCMS apparatus QP5000 (manufactured by Shimadzu Corporation) is mentioned. It is done.
Further, as the organic modified layered inorganic mineral, a metal anion is introduced by replacing a part of the divalent metal of the layered inorganic mineral with a trivalent metal, and at least a part of the metal anion is converted into an organic anion. And a layered inorganic compound modified with (1).

A commercially available product can be used as the organically modified layered inorganic mineral. Examples of the commercially available products include Bentone 3, Bentone 38, Bentone 38V (manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL (manufactured by Southern Clay), and the like. Quartium 18 bentonite; Stearalkonium bentonite such as Bentone 27 (manufactured by Leox), Thixogel LG (manufactured by United catalyst), Clayton AF, Clayton APA (above, manufactured by Southern Clay), etc .; Clayton HT, Clayton PS (above, Quartium 18 / Benzalkonium bentonite such as Southern Clay) Organically modified montmorillonite such as Clayton HY (Southern Clay); Lucentite SPN (Coop Chemical Co.) ) Organic modified Sukumetaito the like, such as. Among these, Clayton AF, Clayton APA, and Lucentite SPN are particularly preferable.
As examples of the organic-modified layered inorganic mineral, a DHT-4A (manufactured by Kyowa Chemical Industry _{Co.), R1 (OR2) nOSO 3} M ( however, R1 number 13 alkyl group carbon, R2 is 2 to 6 carbon atoms Particularly preferred is a group modified with a compound having an organic ion represented by the following formula: alkylene groups, n is an integer of 2 to 10, and M is a monovalent metal element. Examples of the compound having the organic ion represented by R1 (OR2) nOSO ₃ M, for example, HITENOL 330T (produced by Dai-ichi Kogyo Seiyaku Co., Ltd.).

The organically modified layered inorganic mineral may be mixed with a resin and used as a composite master batch. There is no restriction | limiting in particular as this resin, According to the objective, it can select suitably from well-known things.
The content of the organically modified layered inorganic mineral with respect to the toner is preferably 0.1% by mass to 3.0% by mass, more preferably 0.5% by mass to 2.0% by mass, and 1.0% by mass to 1.5% by mass is particularly preferred. When the content is less than 0.1% by mass, the effect of the layered inorganic mineral is hardly exhibited, and when it exceeds 3.0% by mass, the low-temperature fixability tends to be inhibited.

There is no particular limitation on the organic ion modifier, which is a compound having the organic ions and capable of modifying at least some of the ions present between the layers of the layered inorganic mineral into organic ions, and is appropriately selected according to the purpose. For example, quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts; branched, unbranched or cyclic alkyls having 1 to 44 carbon atoms, branched, unbranched or cyclic alkenyl atoms having 1 to 22 carbon atoms, Sulfates having a skeleton such as branched, unbranched or cyclic alkoxy having 8 to 32 carbon atoms, branched or unbranched or cyclic hydroxyalkyl having 2 to 22 carbon atoms, ethylene oxide, propylene oxide, sulfonates having the skeleton, Examples thereof include a carboxylate having the skeleton and a phosphate having the skeleton. Among these, quaternary alkyl ammonium salts and carboxylic acids having an ethylene oxide skeleton are preferable, and quaternary alkyl ammonium salts are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

―External additive―
Various external additives can be added to the toner for purposes such as fluidity modification, charge amount adjustment, and electrical property adjustment. The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, stearin) Metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Also manufactured by Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

  Hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles are obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination, but at least two kinds of inorganic fine particles having an average particle size of hydrophobized primary particles of 20 nm or less are included, and 30 nm or more. More preferably, it contains at least one kind of inorganic fine particles. Moreover, it is preferable that the specific surface area by BET method of the said inorganic fine particle is 20-500 m < ² > / g.
The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.

Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced.
The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

-Toner production method-
The toner production method and materials in the present invention can be any known ones as long as they satisfy the conditions, and are not particularly limited. There is a so-called chemical method of granulating.
Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); Phase inversion emulsification method in which water is added to a solution composed of an emulsifier; the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Aggregation And the like. Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.) by the crystalline resin, and the production method described above. The toner obtained in (I) is more preferable.
In the following, a detailed description of these production methods will be given.

  The kneading and pulverizing method is, for example, a method of producing the toner base particles by pulverizing and classifying a toner material having at least a colorant, a binder resin, and a release agent melted and kneaded.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, and a Kneader manufactured by Buss Co., Ltd. are suitable. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

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

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. This is a method for producing toner base particles by dispersing or emulsifying in a medium.

The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl. Ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol solvents, such as ethyl hexyl alcohol and benzyl alcohol, and these 2 or more types of mixed solvents are mentioned.

In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary.
As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkyl benzene sulfonic acid, phosphate ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), an amphoteric surfactant (carbon carboxyl). Acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.
Examples of the water-soluble polymer include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan. , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid) , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  The toner of the present invention comprises at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a release agent in a dissolution suspension method. The oil phase composition is dispersed or emulsified in an aqueous medium containing resin fine particles, the active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium, and the reactive group-containing prepolymer, It is preferable to obtain the toner base particles by a method of reacting the toner (production method (I)).

The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm or more than 300 nm, the particle size distribution of the toner may be deteriorated.

  The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the concentration is too low, the productivity of the toner decreases.

  The toner composition other than the binder resin such as the colorant and the release agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. May be.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The dispersion or emulsification method in the aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

  As a method of washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification, and the like. The colorant particle dispersion and the release agent particle dispersion are obtained by a known wet dispersion method. It can be obtained by dispersing a colorant or a release agent in an aqueous medium.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, The monovalent metal which comprises salts, such as sodium and potassium; The bivalent metal which comprises salts, such as calcium and magnesium; The trivalent metal which comprises salts, such as aluminum, etc. Is mentioned.
Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and complexes and multimers thereof are preferable. .
In addition, heating between the agglomeration and after completion of the agglomeration can promote fusion of the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.
As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used.

Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above.
For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. It is preferable to have a ratio (volume average particle diameter / number average particle diameter) to the average particle diameter.
The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles. For example, 0.950 to 0.980 is preferable, and 0.960 to 0 is preferable. .975 is more preferred. In addition, it is preferable that the average circularity is less than 0.95.
When the average circularity is less than 0.950, satisfactory transferability and a high-quality image free from dust may not be obtained. When the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning on the photoconductor and transfer belt occurs, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.

  The average circularity was measured using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIAversion 00-10). Specifically, 0.1 to 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner 0 is added. 0.1 to 0.5 g was added, and the mixture was mixed with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the concentration of the dispersion reached 5,000 to 15,000 / μL. In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the concentration of the dispersion, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0.00 g. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μl to 15,000 / μl.

  There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3 micrometers-10 micrometers are preferable, and 4 micrometers-7 micrometers are more preferable. When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. Therefore, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, and more preferably 1.00 to 1.15.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). Then, measurement was performed with an aperture diameter of 100 μm, and analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. The mixture was stirred with a micropartel, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

The ratio Tsh2nd / Tsh1st of the maximum endothermic peak shoulder temperature Tsh1st of the first temperature rise by the differential scanning calorimeter (DSC) of the toner and the maximum endothermic peak shoulder temperature Tsh2nd of the second temperature rise is 0.90 or more. It is preferable that it is 1.10 or less.
The shoulder temperature (Tsh1st, Tsh2nd) of the maximum endothermic peak of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). That is, first, 5.0 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. In the obtained DSC curve, the endothermic peak temperature at the first temperature rise is Tm1st, and the endothermic peak temperature at the second temperature rise is Tm2nd. At this time, when there are a plurality of endothermic peaks, the one with the largest endothermic amount is selected. For each endothermic peak, the intersections of the base line on the lower temperature side than the endothermic peak and the tangent line on the low temperature side forming the endothermic peak are denoted as Tsh1st and Tsh2nd, respectively.

In the X-ray diffraction measurement of the toner, the ratio (C) / ((C) where 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 value of (+ (A)) is preferably 0.15 or more, more preferably 0.20 or more, still more preferably 0.30 or more, and particularly preferably 0.45 or more. When the crystallinity value is less than 0.15, the influence of the amorphous part contained in the toner is increased, and the sharp viscoelastic response to heat unique to the crystalline resin is impaired, and the low temperature fixability is reduced. Deterioration of heat resistance and heat storage stability may occur.
To control the crystallinity of the toner, for example, change the mixing ratio of the crystalline resin and the amorphous resin, or change the crystallinity of the crystalline resin (change the monomer composition, For example, by changing the ratio of the crystalline part to the amorphous part of the block resin having a crystalline part).

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, the filming of the toner on the developing roller as the developer carrying member, and the thinning of the toner are performed. There is no fusion of toner to a layer thickness regulating member such as a blade for layering, and good and stable developability and images can be obtained even when the developing means is used for a long time (stirring). Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

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

―Carrier core material―
The core material is not particularly limited as long as it has magnetic particles, and suitable examples include ferrite, magnetite, iron, and nickel. In addition, when considering adaptability to environmental aspects that have been remarkably advanced in recent years, if it is a ferrite, it is not a conventional copper-zinc ferrite, but, for example, manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese- It is preferable to use magnesium-strontium ferrite, lithium ferrite, or the like.

―Coating layer―
The coating layer contains at least a binder resin, and may contain other components such as inorganic fine particles as necessary.

[Binder resin]
The binder resin for forming the coating layer of the carrier is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, polyolefin (for example, polyethylene, polypropylene, etc.) or a modified product thereof , Crosslinkable copolymer containing styrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; silicone resin composed of organosiloxane bond or modified product thereof (for example, alkyd resin, polyester resin, Polyamide; Polyester; Polyurethane; Polycarbonate; Urea resin; Melamine resin; Benzoguanamine resin; Epoxy resin; Ionomer resin; Polyimide resin and derivatives thereof Body, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

There is no restriction | limiting in particular as said silicone resin, According to the objective from the silicone resin generally known, it can select suitably according to the objective, For example, straight silicone resin which consists only of organosiloxane bonds, alkyd, polyester , Silicone resins modified with epoxy, acrylic, urethane and the like.
Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Specific examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

  The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

[Fine particles]
The coating layer may contain fine particles as necessary. The fine particles are not particularly limited and can be appropriately selected from conventionally known materials according to the purpose. , Tin oxide, zinc oxide, silica, titanium oxide, alumina, potassium titanate, barium titanate, aluminum borate and other inorganic fine particles, polyaniline, polyacetylene, polyparaphenylene, poly (para-phenylene sulfide), polypyrrole, parylene For example, conductive polymers such as carbon black, organic fine particles such as carbon black, and the like may be used.
The fine particles may be further subjected to a conductive treatment on the surface. As a method of such a conductive treatment, aluminum, zinc, copper, nickel, silver, or an alloy thereof, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin are formed on the surface of the fine particles. And indium oxide doped with antimony, tin oxide doped with antimony, zirconium oxide, and the like in the form of a solid solution or fusion. Among these, a method of conducting a conductive treatment using tin oxide, indium oxide, or indium oxide doped with tin is preferable.

The content of the coating layer in the carrier is preferably 5% by mass or more, and more preferably 5% by mass or more and 10% by mass or less.
The thickness of the coating layer is preferably 0.1 μm to 5 μm, and more preferably 0.3 μm to 2 μm.
Here, the thickness of the coating layer is, for example, a carrier cross section of 50 points or more using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) after creating a carrier cross section with FIB (focused ion beam). Can be calculated as an average value of the obtained film thicknesses.

―Method of forming carrier coating layer―
The method for forming the coating layer on the carrier is not particularly limited, and a conventionally known coating layer forming method can be used, and the above-described coating layer raw materials including the binder resin or the binder resin precursor are dissolved. The method of apply | coating a coating layer solution on the surface of a core material using the spraying method or the immersion method etc. is mentioned. It is preferable to promote the polymerization reaction of the binder resin or the binder resin precursor by applying the coating layer solution on the surface of the core material and heating the carrier on which the coating layer is formed. The heat treatment may be performed subsequently in the coating apparatus after the coating layer is formed, or may be performed by another heating means such as a normal electric furnace or a firing kiln after the coating layer is formed.
The heat treatment temperature varies depending on the constituent material of the coating layer to be used, and is not generally determined. The decomposition temperature of the coating layer constituting material is preferably an upper limit temperature up to about 220 ° C., and the heat treatment time is preferably about 5 minutes to 120 minutes.

―Physical properties of the carrier―
The volume average particle diameter of the carrier is preferably in the range of 10 to 100 μm, and more preferably in the range of 20 to 65 μm.
If the volume average particle size of the carrier is less than 10 μm, carrier adhesion due to the decrease in uniformity of the core material particles may occur, and if it exceeds 100 μm, the reproducibility of image details is poor. It is not preferable because a fine image may not be obtained.
The method for measuring the volume average particle size is not particularly limited as long as it is a device capable of measuring the particle size distribution. Can do.

The volume resistivity of the carrier is preferably 9 [log (Ω · cm)] or more and 16 [log (Ω · cm)] or less, preferably 10 [log (Ω · cm)] or more and 14 [log (Ω · cm)]. cm)]] or less.
When the volume resistivity is less than 9 [log (Ω · cm)], carrier adhesion occurs in the non-image area, and when the volume resistivity is more than 16 [log (Ω · cm)], it is not preferable at the edge portion during development. The so-called edge effect, in which the image density is enhanced, is not preferable. The volume resistivity can be arbitrarily adjusted within this range by adjusting the film thickness of the carrier coating layer and the content of the conductive fine particles as necessary.

The volume resistivity is measured by filling a cell made of a fluororesin container containing electrodes 1a and 1b having a distance between electrodes of 0.2 cm and a surface area of 2.5 cm × 4 cm, and dropping height: Tapping is performed under the conditions of 1 cm, tapping speed: 30 times / min, and tapping frequency: 10 times. Next, a DC voltage of 1000 V was applied between both electrodes, and a resistance value r [Ω] after 30 seconds was measured with a high resistance meter 4329A (manufactured by Yokogawa Hewlett-Packard Co., Ltd .: High Resistance Meter). The volume resistivity R [log (Ω · cm)] can be calculated by calculating as (3).
R = Log [r × (2.5 cm × 4 cm) /0.2 cm] (3)

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably such that the mass ratio of the toner to the carrier is 2.0 to 12.0% by mass, More preferably, it is 2.5-10.0 mass%.

(Toner container, image forming apparatus)
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a schematic configuration diagram showing a main part of a color laser printer showing an example of an image forming apparatus using a toner container or a replenishment developer container according to an embodiment of the present invention.
This printer includes four photoreceptors 1Y, 1C, 1M, and 1K for forming toner images of respective colors of yellow, cyan, magenta, and black (hereinafter referred to as Y, C, M, and K). A transfer device 5 is provided below the photoreceptors 1Y, 1C, 1M, and 1K arranged in the horizontal direction.

Each color image forming unit provided with the photoreceptors 1Y, 1C, 1M, and 1K has substantially the same configuration except that the color of the toner to be formed is different. In this case, in order to form a Y toner image. The Y image forming unit will be described.
The Y image forming unit includes a uniform charging device 2Y, an optical writing unit 3Y, a developing device 4Y, a cleaning device 6Y, and the like around a drum-shaped photoreceptor 1Y that is driven to rotate counterclockwise in the drawing. These are held by a common casing and are integrally attached to and detached from the printer main body.
The photoreceptor 1 </ b> Y is obtained by coating an organic photosensitive layer on an element tube such as aluminum.

The uniform charging device 2Y uniformly charges, for example, a negative polarity on the surface of the photoreceptor 1Y that is rotationally driven in the direction of arrow A (counterclockwise direction) in the drawing.
The optical writing unit 3Y has a light source composed of a laser diode or the like, a regular hexahedral polygon mirror, a polygon motor for rotationally driving the mirror, an fθ lens, a lens, a reflection mirror, and the like.
A laser beam L emitted from a light source driven based on image information sent from a personal computer (not shown) or the like is reflected on the polygon mirror surface and deflected as the polygon mirror rotates, so that the photoreceptor 1Y. To reach.
As a result, the surface of the photoreceptor 1Y is optically scanned, and an electrostatic latent image for Y is formed on the surface of the photoreceptor 1Y.

The developing device 4Y for Y has a first developing roll 41Y and a second developing roll 42Y that expose a part of the peripheral surface from an opening provided in the casing.
Each of these developing rolls has a developing sleeve formed of a non-magnetic pipe that is driven to rotate by a driving means (not shown), and a magnet roller (not shown) that is included so as not to be rotated.
In the developing device 4Y, a Y developer (not shown) including a magnetic carrier and a negatively chargeable Y toner is included.
The Y developer is agitated and conveyed by three conveying screws (not shown), and while the Y toner is triboelectrically charged, it is carried on the developing sleeves of these developing rolls and used for development.

In the developing region where the developing sleeve and the photoreceptor 1Y face each other, a negative polarity is provided between the developing sleeve to which a negative developing bias output from a power source (not shown) is applied and the electrostatic latent image on the photoreceptor 1Y. The developing potential for electrostatically moving the Y toner from the sleeve side to the latent image side acts.
In addition, a non-development potential that electrostatically moves negative Y toner from the background side to the sleeve side acts between the developing sleeve and the uniformly charged portion (background portion) of the photoreceptor 1Y.

The Y toner in the Y developer on the developing sleeve is separated from the sleeve by the action of the developing potential and is transferred onto the electrostatic latent image on the photoreceptor 1Y.
By this transfer, the electrostatic latent image on the photoreceptor 1Y is developed into a Y toner image.
The Y toner image on the photoreceptor 1Y is transferred onto an intermediate transfer belt 7 that runs in the direction of arrow B by a transfer device 5 described later.

The developing device 4Y has a toner concentration sensor as a magnetic permeability sensor that outputs a voltage corresponding to the magnetic permeability of the Y developer contained therein. The toner concentration sensor outputs a voltage corresponding to the toner concentration. Output.
This output voltage value is sent to a supply control unit (not shown).
The replenishment control unit includes a storage unit such as a RAM, in which M Vtref, which is a target value of the output voltage from the Y toner density sensor, and a toner density sensor mounted on another developing device. Vtref data for C, M, and K, which are target values of the output voltage from.
For the Y developing device 4Y, the value of the output voltage from the Y toner density sensor is compared with the Y Vtref, and the developer replenishing device 10 described later is driven for a time corresponding to the comparison result.
Thus, the replenishing Y developer is replenished to the developing device 4Y.
By controlling in this way, an appropriate amount of Y developer is replenished to the Y developer whose Y toner concentration has been reduced with development, and the Y toner concentration of the Y developer in the developing device 4Y is within a predetermined range. Maintained.
The same replenishment control is performed for the developing devices 4C, M, and K.

The Y toner image developed on the photoreceptor 1Y is transferred to the front surface of an intermediate transfer belt 7 described later.
Untransferred toner that has not been transferred onto the intermediate transfer belt 7 adheres to the surface of the photoreceptor 1Y that has undergone the transfer process.
This transfer residual toner is removed by the cleaning device 5Y.
The surface of the photoreceptor 1Y from which the transfer residual toner has been removed in this manner is discharged by a discharging lamp (not shown), and then uniformly charged by the uniform charging device 2Y.
Although the Y image forming unit has been described in detail, C, M, and K toner images are formed on the surfaces of the photoreceptors 1C, M, and K by the same process in the image forming units for other colors.

The transfer device 5 is disposed in the loop of the endless intermediate transfer belt 7 below the photoreceptors 1Y, 1C, 1M, and 1K in the drawing.
The Y, C, M, and K toner images formed on the photosensitive members 1Y, 1C, 1M, and 1K of the respective colors are sequentially superimposed and transferred onto the intermediate transfer belt 7 by the transfer device 5.
As a result, a four-color superimposed toner image (hereinafter referred to as a four-color toner image) is formed on the intermediate transfer belt 7.
One of the rollers around which the intermediate transfer belt 7 is wound, in this example, the lowermost roller is configured as a secondary transfer bias roller 71, and the secondary transfer bias roller 71 includes a power source and wiring (not shown). A secondary transfer bias is applied by the voltage applying means.

The printer includes a paper feeding cassette (not shown), and accommodates a recording paper bundle in which a plurality of recording papers 8 are stacked therein.
Then, the uppermost recording paper 8 is sent out to the paper feed path at a predetermined timing.
The sent recording paper 8 is sent out at a timing that can be synchronized with the four-color toner image on the intermediate transfer belt 7 through a pair of registration rollers (not shown) disposed at the end of the paper feeding path. By the action of the transfer bias roller 71, the image is secondarily transferred onto the recording paper 8.
The recording paper 8 on which the full-color image is formed in this way is discharged from the secondary transfer nip, and then sent to a fixing device (not shown) to fix the full-color image.

FIG. 2 is a schematic diagram illustrating a configuration example of the toner replenishing device 10 having a toner storage unit.
In FIG. 2, a toner replenishing device 10 includes a toner bottle 11 as a replaceable toner container for storing toner, a transport pump 12 as means for transporting the replenishing toner stored in the toner bottle 11, and a transport pump thereof 12 includes a sub hopper 13 (toner container) that temporarily stores the toner conveyed through 12 and a conveying screw 14 as a toner replenishing unit that replenishes the toner stored in the sub hopper 13 to the developing device.

The toner replenishing device 10 replenishes the toner consumed by the printing operation from the sub hopper 13 to the developing device 4 via the conveying screw 14.
The sub hopper 13 is provided with a sensor 15. When the toner stored in the sub hopper 13 is reduced, the toner is transported from the toner bottle 11 via the transport pump 12, and the sensor 15 is attached to the sub hopper 13. The amount of toner up to the detected position is controlled so that it always exists.

Since the toner replenishing device 10 configured as described above includes the sub hopper 13, even if the toner in the toner bottle becomes empty and the bottle needs to be replaced, printing can be performed for a certain period. The bottle can be changed at a short time.
Furthermore, since the toner is replenished from the sub hopper 13 using the conveying screw 14, it is easy to supply the toner to the developing device with high accuracy.

By the way, in the above embodiment, as shown in FIG. 2, a transport pump 12 that transports toner by generating a negative pressure is used as the toner transport means.
As shown in FIG. 3, the conveying pump 12 is a suction type uniaxial eccentric powder pump commonly called a MONO pump, and its configuration is made into a screw shape eccentric with a material having rigidity such as metal. The rotor 20, a stator 21 made of an elastic body such as rubber, and a stator 21 made of a double screw, and a case 22 made of a resin material that encloses the stator 21. The stator 21 is fixed to the case 22. Installed.

The rotor 20 is rotationally driven via a supply clutch 23 that is drivingly connected to a drive source (not shown) and a shaft joint 24.
In the transport pump 12 configured in this manner, when the replenishment clutch 23 is turned on and the rotor 20 is rotated, a strong self-suction force is generated in the pump, and the toner is sucked from the suction portion at the tip of the case 22, and the sucked toner is removed. It becomes possible to send out to the sub hopper 13 from a discharge portion (not shown) in the vicinity of the shaft joint 24.

Furthermore, since the silicon tube 16 is used for the transport path from the toner bottle 11 to the transport pump 12, it is easier to roll inside the machine than when a screw is used for transport.
As a result, the degree of freedom in layout increases and it becomes easy to realize downsizing of the machine.

In addition, the screw stresses the toner and deteriorates the quality when the conveying path becomes long, whereas in the case of conveying by the conveying pump 12, the influence of the length of the conveying path is hardly seen.
Further, since the conveyance amount per unit time of the uniaxial eccentric powder pump is substantially constant, the remaining amount of the toner bottle 11 can be known from the operation time.
Furthermore, the conveyance from the toner bottle 11 to the sub hopper 13 is not affected even if there is some variation, but the toner to be replenished to the developing device 4 is high in order to keep the toner concentration in the developing device 4 appropriate. Precision resolution is required. Therefore, toner can be replenished with high resolution by using the conveying screw 14 for replenishment from the sub hopper 13 to the developing device 4.

(Toner container screw structure)
In order to achieve the above object, according to the present invention, a replaceable toner container, a transporting means for transporting toner stored in the toner container, and a toner for temporarily storing toner transported through the transporting means are provided. An image forming apparatus having a conveying screw for supplying toner to the developing device, wherein the toner accommodating portion is disposed at a portion lower than an axis of the conveying screw and an outer peripheral end of the conveying screw. The gap between the inner wall of the toner storage portion is 2.0 mm or less.
The gap between the outer peripheral end of the conveying screw and the inner wall of the toner container is preferably small, and more preferably 0.8 mm or less.

In the present invention, in order to make the gap between the outer peripheral end of the conveying screw and the inner wall of the toner accommodating portion 2.0 mm or less, a clearance prevention member that fills the gap is attached to the inner wall of the toner accommodating portion to convey the toner. A gap preventing member may be interposed between the outer peripheral end of the screw and the inner wall of the toner containing portion.
The gap prevention member includes a first surface that is mounted on the inner wall of the toner storage portion, and a second surface that is located on the opposite side of the first surface and faces the outer peripheral end of the conveying screw. Has an elastic member that contacts the outer peripheral end of the conveying screw in a deformed state. A friction reducing member may be provided between the second surface of the elastic member and the outer peripheral end of the conveying screw.

(Example of screw configuration)
(First Embodiment) As shown in FIG. 4B, the gap S between the inner wall 57Ya and the outer peripheral end 56Ya1 of the conveying screw 56Ya is substantially zero at a portion lower than the axis of the conveying screw of the toner accommodating portion 57Y. The diameter of the inner wall 57Ya of the toner containing portion 57Y is larger than the outer diameter R of the conveying screw 56Ya by 0 to 0.1 mm.
With such a configuration, the toner T replenished in the toner containing portion 57Y is conveyed to the developer containing portion without forming the non-moving layer 90, and is dispersed and charged with the carrier at the tip.
However, considering the manufacturing accuracy of the conveying screw 56Ya and the manufacturing error of the toner accommodating portion 57Y, the clearance S between the inner wall 57Ya of the toner accommodating portion 57 and the outer peripheral end 56Ya1 of the conveying screw 56Ya is low-cost. It is difficult to make it 2.0 mm or less.

(Second Embodiment) Therefore, in this embodiment, as shown in FIG. 4C, the inner wall 57Ya of the toner containing portion 57Y is 2.0 mm, for example, at a portion lower than the outer diameter R of the conveying screw 56Ya at a portion lower than the axis of the conveying screw. In order to make the gap S larger, the gap prevention member 83Y is disposed between the inner wall 57Ya and the outer peripheral end 56Ya1 of the conveying screw 56Ya along the inner wall 57Ya of the toner containing portion 57Y.
The gap preventing member 83Y includes a first surface 81Ya mounted on the inner wall 57Ya, and a second surface 81Yb that is located on the opposite side of the first surface 81Ya and faces the outer peripheral end 56Ya1 of the conveying screw. The outer surface 56Ya1 and the second surface 81Yb of the conveying screw are bonded to the second surface 81Yb of the sponge 81Y and the sponge 81Y that is an elastic member that contacts the outer surface 56Ya1 of the conveying screw in a deformed state. And a thin resin (PET) film member 82Y serving as a friction reducing member interposed therebetween.
With this configuration, the sponge 81Y and the film member 82Y on the sponge 81Y are always in close contact with each other so as to push up the conveying screw 56Ya, and the inner wall 57Ya and the conveying screw 56Ya of the toner accommodating portion 57Y are located below the axis of the conveying screw. Can be set to 2.0 mm or less.

Further, if the surface of the conveying screw 56Ya that contacts the outer peripheral end 56Ya1 is the sponge 81Y, resistance during rotation of the conveying screw 56Ya increases, and the load on the drive motor 75Y increases. It is conceivable that the sponge piece is broken by the rotation of 56 Ya and the broken sponge piece is mixed into the developer G.
However, in this embodiment, since the thin film member 82Y is interposed between the conveying screw 56Ya and the sponge member 81, the resistance when the conveying screw 56Ya rotates is small, and the load on the driving motor 75Y is reduced, and the sponge member 81 Durability is enhanced and sponge pieces are not mixed into the developer G.
Of course, for the purpose of eliminating the gap S, the gap prevention member 83Y may be formed of the sponge member 81Y alone without the film member 82Y.

  Further, as shown in FIG. 4A, in the conventional developing device, 2.0 mm is provided between the outer peripheral end of the conveying screw 56Ya and the inner wall 57Ya of the toner containing portion 57Y in a portion lower than the axis of the conveying screw. There is a gap S that exceeds the above, but the conventional configuration can be developed only by mounting the gap prevention member 83Y constituted by the sponge 81Y and the film member 82Y or the gap prevention member 83Y constituted by the sponge 81Y alone. The parts of the apparatus can be used, and the cost can be further reduced.

  In the present invention, a developer replenishing device having a replenishment developer accommodating portion having a similar structure can be provided except that the toner in the toner replenishing device having the toner accommodating portion is changed to a developer.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Production Example 1)
<Production of crystalline polyurethane resin A-1>
In a reaction vessel equipped with a stirrer and a thermometer, 45 parts by mass of 1,4-butanediol (0.50 mol), 59 parts by mass of 1,6-hexanediol (0.50 mol), and methyl ethyl ketone (hereinafter referred to as MEK) 200 parts by mass was added. To this solution, 250 parts by mass (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 maximum peak temperature of heat of fusion 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 introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 15 parts by mass (0.10 mol) of adipic acid, 177 parts by mass of 1,6-hexanediol (1 .50 mol) and 0.5 parts by mass of tetrabutoxy titanate as a condensation catalyst were added, and the reaction was carried out for 8 hours at 180 ° C. under a nitrogen stream 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 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 mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( (MDI) 30 parts by mass (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 Mw 22,000 and a maximum peak temperature of heat of fusion of 62 ° C.

(Production Example 3)
<Production of urethane-modified crystalline polyester resin A-3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by mass (1.00 mol) of sebacic acid, 189 parts by mass of 1,6-hexanediol (1.60 mol), and dibutyltin oxide as a condensation catalyst 0.5 part by mass 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 6 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 Mw of 6,000.
Subsequently, the obtained [crystalline polyester resin A′-3] was transferred into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and 300 parts by mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 38 parts by mass (0.15 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 A-3]. The obtained [urethane-modified crystalline polyester resin A-3] had Mw 10,000 and the maximum peak temperature of heat of fusion was 64 ° C.

(Production Example 4)
<Production of urethane-modified crystalline polyester resin A-4>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 185 parts by mass (0.91 mol) of sebacic acid, 13 parts by mass (0.09 mol) of adipic acid, 106 parts by mass of 1,4-butanediol (1 .18 mol) and 0.5 parts by mass of titanium dihydroxybis (triethanolamate) as a condensation catalyst were 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 1,4-butanediol produced under a nitrogen stream, and the Mw was approximately 14 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin A′-4] was obtained. The obtained [Crystalline polyester resin A′-4] was Mw 14,000.
Subsequently, the obtained [crystalline polyester resin A′-4] was transferred into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and 250 parts by mass of ethyl acetate and 12 parts by mass of hexamethylene diisocyanate (HDI). Part (0.07 mol) was added and 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-4]. The obtained [urethane-modified crystalline polyester resin A-4] had an Mw of 39,000 and a maximum peak temperature of heat of fusion of 63 ° C.

(Production Example 5)
<Production of urethane-modified crystalline polyester resin A-5>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 166 parts by mass (0.82 mol) of sebacic acid, 26 parts by mass (0.18 mol) of adipic acid, 131 parts by mass of 1,4-butanediol (1 .45 mol) and 0.5 parts by mass of titanium dihydroxybis (triethanolamate) as a condensation catalyst were 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 1,4-butanediol produced under a nitrogen stream, and the Mw was about 8 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [Crystalline Polyester Resin A′-5] was obtained. The obtained [Crystalline Polyester Resin A′-5] was Mw 8,000.
Subsequently, the obtained [crystalline polyester resin A′-5] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 250 parts by mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 33 parts by mass (0.13 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-5]. The obtained [urethane-modified crystalline polyester resin A-5] had Mw of 17,000 and a maximum peak temperature of heat of fusion of 54 ° C.

(Production Example 6)
<Production of urethane-modified crystalline polyester resin A-6>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 18 parts by mass (0.12 mol) of adipic acid, 139 parts by mass of 1,6-hexanediol (1 .18 mol) and 0.5 parts by mass 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 about 18 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin A′-6] was obtained. The obtained [Crystalline polyester resin A′-6] was Mw 18,000.
Subsequently, the obtained crystalline polyester resin A′-6 was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts by mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate (MDI). 15 parts by mass (0.06 mol) was added and 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-6]. The obtained [urethane-modified crystalline polyester resin A-6] had Mw 42,000 and a maximum peak temperature of heat of fusion of 62 ° C.

(Production Example 7)
<Production of urethane-modified crystalline polyester resin A-7>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by mass (1.00 mol) of sebacic acid, 149 parts by mass (1,26 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst 0.5 part by mass 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 9 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin A′-7] was obtained. The obtained [Crystalline polyester resin A′-7] was Mw 9,000.
Subsequently, the obtained [crystalline polyester resin A′-7] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 250 parts by mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 28 parts by mass (0.11 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-7]. The obtained [urethane-modified crystalline polyester resin A-7] had an Mw of 30,000 and a maximum peak temperature of heat of fusion of 67 ° C.

(Production Example 8)
<Production of urethane-modified crystalline polyester resin A-8>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by mass (1.00 mol) of sebacic acid, 191 parts by mass of 1,6-hexanediol (1.62 mol), and tetrabutoxy titanate as a condensation catalyst 0.5 part by mass 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 4 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin A′-8] was obtained. [Crystalline polyester resin A′-8] obtained had Mw of 4,000.
Subsequently, the obtained [crystalline polyester resin A′-8] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 300 parts by mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 35 parts by mass (0.14 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 A-8]. The obtained [urethane-modified crystalline polyester resin A-8] had Mw of 8,500 and a maximum peak temperature of heat of fusion of 64 ° C.

(Production Example 9)
<Production of crystalline polyurea resin A-9>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 123 parts by mass (1.40 mol) of 1,4-butanediamine, 212 parts by mass (1.82 mol) of 1,6-hexanediamine, methyl ethyl ketone (MEK) ) After adding 100 parts by mass and stirring, 336 parts by mass of hexamethylene diisocyanate (HDI) (2.00 mol) was added and reacted at 60 ° C. for 5 hours under a nitrogen stream. Next, MEK was distilled off under reduced pressure to obtain [Crystalline Polyurea Resin A-9]. The obtained [Crystalline polyurea resin A-9] had Mw of 23,000 and a maximum peak temperature of heat of fusion of 64 ° C.

(Production Example 10)
<Production of crystalline polyester resin A-10>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 185 parts by mass (0.91 mol) of sebacic acid, 13 parts by mass (0.09 mol) of adipic acid, 125 parts by mass of 1,4-butanediol (1 .39 mol) and 0.5 parts by mass 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 1,000,000 to obtain [Crystalline Polyester Resin A-10]. The obtained [Crystalline Polyester Resin A-10] had Mw 9,500 and the maximum peak temperature of heat of fusion was 57 ° C.

(Production Example 11)
<Production of Crystalline Polyester Resin A-11>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 130 parts by mass (1,10 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst. 0.5 part by mass 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 30 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the value reached 1,000, and [Crystalline Polyester Resin A-11] was obtained. The obtained [Crystalline Polyester Resin A-11] had Mw 27,000 and a maximum peak temperature of heat of fusion of 62 ° C.

(Production Example 12)
<Manufacture of Block Resin A-12 Composed of Crystalline Part and Amorphous Part>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 25 parts by mass (0.33 mol) of 1,2-propylene glycol and 170 parts by mass of methyl ethyl ketone (MEK) were added and stirred, and then 4,4 ′ -147 mass parts (0.59 mol) of diphenylmethane diisocyanate (MDI) was added and reacted at 80 ° C for 5 hours to obtain a MEK solution of [amorphous part c-1] having an isocyanate group at the terminal.
Separately, in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 160 parts by mass (1.35 mol) of 1,6-hexanediol, and tetracondensation as a condensation catalyst. Butoxytitanate 0.5 mass part was put, and it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under 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 9 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin A′-12] was obtained. The obtained [Crystalline Polyester Resin A′-12] had Mw of 8,500 and a maximum peak temperature of heat of fusion of 63 ° C.
Next, a solution obtained by dissolving 320 parts by mass of [crystalline polyester resin A′-12] in 320 parts by mass of MEK as a crystalline part was added to 340 parts by mass of the [amorphous part c-1]. The reaction was performed at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, MEK was distilled off under reduced pressure to obtain [Block Resin A-12]. The obtained [Block Resin A-12] had Mw of 26,000 and a maximum peak temperature of heat of fusion of 62 ° C.

(Production Example 13)
<Production of Block Resin A-13 Composed of Crystalline Part and Amorphous Part>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 39 parts by mass (0.51 mol) of 1,2-propylene glycol and 270 parts by mass of methyl ethyl ketone (MEK) were added and stirred, and then 4,4 ′ -228 mass parts (0.91 mol) of diphenylmethane diisocyanate (MDI) was added, and it was made to react at 80 degreeC for 5 hours, and the MEK solution of [amorphous part c-2] which has an isocyanate group at the terminal was obtained.
Separately, in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 160 parts by mass (1.35 mol) of 1,6-hexanediol, and tetracondensation as a condensation catalyst. Butoxytitanate 0.5 mass part was put, and it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under 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 8 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the value reached 1,000, to obtain [Crystalline Polyester Resin A′-13]. The obtained [Crystalline polyester resin A′-13] had Mw of 7,500 and the maximum peak temperature of heat of fusion was 62 ° C.
Next, a solution obtained by dissolving 320 parts by mass of [crystalline polyester resin A′-12] in 320 parts by mass of MEK was added as a crystalline part to 540 parts by mass of the MEK solution of [amorphous part c-2]. The reaction was performed at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, MEK was distilled off under reduced pressure to obtain [Block Resin A-13]. The obtained [Block Resin A-13] had Mw of 23,000 and the maximum peak temperature of heat of fusion was 61 ° C.

(Production Example 14)
<Production of urethane-modified crystalline polyester resin B-1>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 113 parts by mass (0.56 mol) of sebacic acid, 109 parts by mass of dimethyl terephthalate (0.56 mol), 132 parts by mass of 1,6-hexanediol ( 1.12 mol) and 0.5 parts by mass of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 180 ° C. for 8 hours while distilling off generated water and methanol 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 35 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 34,000.
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 mass of ethyl acetate and 10 parts by mass of hexamethylene diisocyanate (HDI). Part (0.06 mol) was added and 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 63,000 and a maximum peak temperature of heat of fusion of 65 ° C.

(Production Example 15)
<Production of urethane-modified crystalline polyester resin B-2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 204 parts by mass (1.01 mol) of sebacic acid, 13 parts by mass (0.09 mol) of adipic acid, 136 parts by mass of 1,6-hexanediol (1 .15 mol) and 0.5 parts by mass 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′-2] was obtained. The obtained [Crystalline Polyester Resin B′-2] was Mw 20,000.
Subsequently, the obtained [crystalline polyester resin B′-2] was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 200 parts by mass of ethyl acetate, 4,4′-diphenylmethane diisocyanate ( MDI) 15 parts by mass (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-2]. The obtained [urethane-modified crystalline polyester resin B-2] had an Mw of 39,000 and a maximum peak temperature of heat of fusion of 63 ° C.

(Production Example 16)
<Production of crystalline polyurea resin B-3>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 79 parts by mass (0.90 mol) of 1,4-butanediamine, 116 parts by mass (1.00 mol) of 1,6-hexanediamine, methyl ethyl ketone (MEK) ) After adding 600 parts by mass and stirring, 475 parts by mass (1.90 mol) of 4,4′-diphenylmethane diisocyanate (MDI) was added and reacted at 60 ° C. for 5 hours under a nitrogen stream. Next, MEK was distilled off under reduced pressure to obtain [Crystalline Polyurea Resin B-3]. The obtained [crystalline polyurea resin B-3] had Mw of 57,000 and the maximum peak temperature of heat of fusion of 66 ° C.

(Production Example 17)
<Production of crystalline polyester resin B-4>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 230 parts by mass (1.00 mol) of dodecanedioic acid, 118 parts by mass of 1,6-hexanediol (1.00 mol), and tetrabutoxy as a condensation catalyst. 0.5 parts by mass of titanate 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 50 under reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [Crystalline Polyester Resin B-4] was obtained. The obtained [Crystalline polyester resin B-4] had Mw of 52,000 and a maximum peak temperature of heat of fusion of 66 ° C.

(Production Example 18)
<Production of crystalline resin precursor B′-5>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 122 parts by mass (1.03 mol) of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst. (Triethanolaminate) 0.5 parts by mass was added, and the reaction was carried out at 180 ° C. for 8 hours 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 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 introduction tube, and 300 parts by mass of ethyl acetate and 27 parts by mass (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 mass% ethyl acetate solution of [crystalline resin precursor B′-5] having an isocyanate group at the terminal. 10 parts by mass of the obtained [crystalline resin precursor B′-5] in ethyl acetate was mixed with 10 parts by mass of tetrahydrofuran (THF), 1 part by mass of dibutylamine was added thereto, and the mixture was stirred for 2 hours. . As a result of GPC measurement using the obtained solution as a sample, Mw of [crystalline resin precursor B′-5] was 54,000. Moreover, as a result of performing DSC measurement about the sample obtained by removing a solvent from the said solution, the maximum peak temperature of the heat of fusion of [crystalline resin precursor B'-5] was 57 degreeC.

The raw materials used for the production of the crystalline resin and the physical properties of the crystalline resin are summarized in Tables 1 to 3.
In addition, as for the said crystalline resin, all (softening temperature / maximum peak temperature of heat of fusion) was the range of 0.8-1.6.

(Production Example 19)
<Production of Amorphous Resin C-1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube, 222 parts by mass of bisphenol A EO 2 mol adduct, 129 parts by mass of bisphenol A PO 2 mol adduct, 166 parts by mass of isophthalic acid, and 0.5 parts by mass 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, it was cooled to 180 ° C., 35 parts by mass of trimellitic anhydride was added, and the reaction was carried out 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 20)
<Production of Amorphous Resin Precursor C′-2>
720 parts by mass of bisphenol A EO 2 mol adduct, 90 parts by mass of bisphenol A PO2 mol adduct, 290 parts by mass of terephthalic acid, and 1 part by mass of tetrabutoxy titanate are placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube. The reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and [non-crystalline resin] was obtained.
Next, 400 parts by mass of the obtained [amorphous resin], 95 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are put into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen insertion pipe. The mixture was reacted at 80 ° C. for 8 hours to obtain a 50 mass% ethyl acetate solution of [amorphous resin precursor C′-2] having an isocyanate group at the terminal.

[Examples 1 to 26, Comparative Examples 1 to 28]
<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)-
Paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) 50 parts by mass in a container in which a stir bar and a thermometer are set, the above [graft polymer] 30 parts by mass Parts and 420 parts by mass of ethyl acetate, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. in 1 hour, and a bead mill (Ultra Visco Mill, manufactured by IMEX) Using, a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume of 0.5 mm zirconia beads were filled, and dispersion was performed under the conditions of 3 passes to obtain [release agent dispersion liquid (1)]. .

-Preparation of master batches (1), (2), (4), (5), (7)-(13)-
Crystalline polyurethane resin A-1 100 parts by mass Carbon black (Printex 35, manufactured by Degussa) 100 parts by mass (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
-Ion exchange water 50 mass parts 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)].
According to Table 4, [Masterbatch (2)] to [Masterbatch (13)] were produced in the same manner as [Masterbatch (1)] except that the binder resin was changed.

-Preparation of oil phases (1)-(3), (5), (7)-(10), (14)-(17), (21)-
In a container equipped with a thermometer and a stirrer, 31.5 parts by mass of [urethane-modified crystalline polyester resin A-2] is added, ethyl acetate is added in an amount such that the solid content concentration is 50% by mass, and the melting point of the resin It was heated to the above and dissolved well. To this, 100 parts by mass of a 50 mass% ethyl acetate solution of [Amorphous Resin C-1], 60 parts by mass of [Releasing Agent Dispersion (1)], and 12 parts by mass of [Masterbatch (2)] are 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 the production so as not to crystallize.
For the oil phases (2), (3), (5), (7) to (10), (14) to (17), and (21), the type and amount of the crystalline resin A, the crystalline resin B This was prepared in the same manner except that the type / addition amount of amorphous resin C, the addition amount of amorphous resin C, and the type of masterbatch were changed according to Table 5.
In addition, about the crystalline resin B in Table 5, and [amorphous resin precursor C'-2], [B-1], [B-2], [B-3], and [B-4] [B′-5] or [amorphous resin precursor C], which is a binder resin precursor, is used by dissolving and dispersing together with other toner materials in the oil phase preparation stage. When “-2” is used, it was not added at the oil phase preparation stage, but was added to the oil phase at the time of preparation of the toner base described later, and dissolved and dispersed.

-Preparation of oil phase (17-2), (17-3)-
0.06 part by mass of [nucleating agent] (ADEKA STAB NA-11, melting point 400 ° C., manufactured by ADEKA) was added to the oil phase (17) to prepare an oil phase (17-2).
Further, 1.1 parts by mass of [nucleating agent] (ADEKA STAB NA-11, melting point 400 ° C., manufactured by ADEKA) was added to the oil phase (17) to prepare an oil phase (17-3).

-Production of oil phases (22) to (27)-
An oil phase (22) was prepared by adding 1 part by mass of a synthetic smectite compound (Lucentite SPN, manufactured by Co-op Chemical) to the oil phase (1).
2 parts by mass of a synthetic smectite compound (Lucentite SPN, manufactured by Co-op Chemical) was added to the oil phase (1) to prepare an oil phase (23).
An oil phase (24) was prepared by adding 1 part by mass of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) to the oil phase (2).
2 parts by mass of a synthetic smectite compound (Lucentite SPN, manufactured by Co-op Chemical) was added to the oil phase (2) to prepare an oil phase (25).
An oil phase (26) was prepared by adding 1 part by mass of a synthetic smectite compound (Lucentite SPN, manufactured by Corp Chemical Co.) to the oil phase (3).
2 parts by mass of a synthetic smectite compound (Lucentite SPN, manufactured by Co-op Chemical) was added to the oil phase (3) to prepare an oil phase (27).

-Production of oil phase (28)-
60 parts by mass of [Partitioner Dispersion (1)] is added to 100 parts by mass of a 50% by mass ethyl acetate solution of [Amorphous Resin C-1], and a TK homomixer (Special Machine Co., Ltd.) is added at 50 ° C. The oil phase (28) was obtained by stirring at a rotational speed of 5,000 rpm and uniformly dissolving and dispersing.

―Manufacture of aqueous dispersion of resin fine particles―
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts by mass of water, 120 parts by mass of styrene, 100 parts by mass of methacrylic acid, 45 parts by mass of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) When 10 parts by mass and 1 part by mass of ammonium persulfate were charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by mass of a 1% ammonium persulfate aqueous solution was added and 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, manufactured by Sanyo Chemical Industries, Ltd.), and 90 ethyl acetate Mass parts were mixed and stirred to obtain [Aqueous phase (1)].

—Production of Toner Bases (1) to (3), (5), (7) to (10), (14) to (17-3), (21) to (28) —
In another container in which a stirrer and a thermometer were set, 520 parts by mass of [Aqueous phase (1)] was placed and heated to 40 ° C. To 235 parts by mass of [Oil phase (1)] maintained at 50 ° C., 25 parts by mass of an ethyl acetate solution of [crystalline resin precursor B′-5] was added, and a TK homomixer (Special Kika Co., Ltd.) was added. The product was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to prepare [oil phase (1 ′)]. While stirring the above [water phase (1)] kept at 40 to 50 ° C. at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), [oil phase (1 ′)] The resultant 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 mass 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 mass of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1) and mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), followed by filtration under reduced pressure.
(3) 100 parts by mass of 10 mass% 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 mass of ion-exchanged water to the filter cake of (3) above, 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, the toner base (2), (3), (5), (7) to (10), (14) to (17-3), and (21) to (28) are respectively used. 2), (3), (5), (7) to (10), (14) to (17-3), and (21) to (28) were produced.

-Preparation of oil phase (4), (13), (18)-(20)-
In a container equipped with a thermometer and a stirrer, 62 parts by mass of [urethane-modified crystalline polyester resin A-2] and 12 parts by mass of [urethane-modified crystalline polyester resin B-2] are added, and the solid content concentration is 50% by mass. An amount of ethyl acetate was added and heated to a melting point of the resin or higher to dissolve well. To this, 40 parts by mass of a 50% by mass ethyl acetate solution of [Amorphous Resin C-1], 60 parts by mass of [Releasing Agent Dispersion], and 12 parts by mass of [Masterbatch (2)] were added, and the mixture was heated to 50 ° C. The mixture was stirred with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [oil phase (5)]. The temperature of [Oil phase (4)] was kept at 50 ° C. in the container, and was used within 5 hours from the production so as not to crystallize.
For the oil phases (13) and (18) to (20), the type / addition amount of the crystalline resin A, the type / addition amount of the crystalline resin B, the addition amount of the amorphous resin C, and the type of the masterbatch Were prepared in the same manner, only by changing according to Table 6.

-Preparation of aqueous phase (2)-
990 parts by mass of water, 37 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 90 parts by mass of ethyl acetate were mixed and stirred. )].

-Preparation of toner base (4), (13), (18)-(20)-
In another container with a stirrer and a thermometer, 520 parts by mass of [Aqueous Phase (2)] is placed and heated to 40 ° C. and kept at 40-50 ° C. [Oil Phase (4)] was added while stirring at 13,000 rpm, 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 mass 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 mass of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1) and mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), followed by filtration under reduced pressure.
(3) 100 parts by mass of 10 mass% 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 mass of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filter twice, and filter cake (4) Got.
The obtained filter cake (4) was dried at 45 ° C. for 48 hours with a circulating drier. Thereafter, the mixture was sieved with a mesh having a mesh size of 75 μm to prepare a toner base (4).
Similarly, toner bases (13) and (18) to (20) were prepared using oil phases (13) and (18) to (20), respectively.

-Preparation of crystalline resin particle dispersion (A-3)-
60 parts by mass of ethyl acetate was added to 60 parts by mass of [Urethane-Modified Crystalline Polyester Resin A-3] and mixed and stirred at 50 ° C. to dissolve. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution After adding 120 parts by mass of the resin solution to [Aqueous phase] mixed and emulsifying with a homogenizer (IKA, Ultra Tarrax T50), emulsifying with a Manton Gorin high-pressure homogenizer (Gorin), [Emulsified slurry A-3] was obtained.
Next, [Emulsified slurry A-3] is put into a container in which a stirrer and a thermometer are set, and the solvent is removed at 60 ° C. for 4 hours to obtain [crystalline resin particle dispersion (A-3)]. It was. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [crystalline resin particle dispersion liquid (A-3)] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make). .

-Production of crystalline resin particle dispersion (A-6)-
60 parts by mass of ethyl acetate was added to 60 parts by mass of [urethane-modified crystalline polyester resin A-6], and dissolved by mixing and stirring at 50 ° C. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution After adding 120 parts by mass of the resin solution to [Aqueous phase] mixed and emulsifying with a homogenizer (IKA, Ultra Tarrax T50), emulsifying with a Manton Gorin high-pressure homogenizer (Gorin), [Emulsified slurry A-6] was obtained.
Next, [Emulsified slurry A-6] is put into a container in which a stirrer and a thermometer are set, and the solvent is removed at 60 ° C. for 4 hours to obtain [crystalline resin particle dispersion (A-6)]. It was. It was 0.18 micrometer when the volume average particle diameter of the particle | grains in the obtained [crystalline resin particle dispersion liquid (A-6)] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make). .

-Preparation of crystalline resin particle dispersion (B-1)-
60 parts by mass of ethyl acetate was added to 60 parts by mass of [Urethane-Modified Crystalline Polyester Resin B-1], and dissolved by mixing and stirring at 50 ° C. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution After adding 120 parts by mass of the resin solution to [Aqueous phase] mixed and emulsifying with a homogenizer (IKA, Ultra Tarrax T50), emulsifying with a Manton Gorin high-pressure homogenizer (Gorin), [Emulsified slurry B-1] was obtained.
Next, [Emulsified slurry B-1] is put into a container in which a stirrer and a thermometer are set, and the solvent is removed at 60 ° C. for 4 hours to obtain [crystalline resin particle dispersion (B-1)]. It was. It was 0.16 micrometer when the volume average particle diameter of the particle | grains in the obtained [crystalline resin particle dispersion liquid (B-1)] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make). .

-Preparation of non-crystalline resin particle dispersion (C-1)-
[Amorphous resin C-1] 60 parts by mass of ethyl acetate was added to 60 parts by mass, mixed and stirred to dissolve. Next, 120 parts by weight of water, 6 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution After adding 120 parts by mass of the resin solution to [Aqueous phase] mixed and emulsifying using a homogenizer (IKA, Ultra Tarrax T50), emulsifying with a Manton Gorin high-pressure homogenizer (Gorin), [Emulsified slurry C-1] was obtained.
Next, [Emulsified slurry C-1] is put into a container in which a stirrer and a thermometer are set, and the solvent is removed at 60 ° C. for 4 hours to obtain [crystalline resin particle dispersion (C-1)]. It was. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [crystalline resin particle dispersion liquid (C-1)] was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make). .

-Preparation of release agent dispersion (2)-
Paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, melting point 75 ° C.) 25 parts by mass, anionic surfactant (manufactured by Sanyo Chemical Industries: Eleminol MON-7) 5 parts by mass, water 200 parts by mass are mixed, and 95 ° C. And melted. Next, this melt was emulsified with a homogenizer (IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to obtain a release agent dispersion (2).

-Preparation of colorant dispersion-
Carbon black (Printtex35, manufactured by Degussa) 20 parts by mass, anionic surfactant (Eleminol MON-7, manufactured by Sanyo Chemical Industries Co., Ltd.) 2 parts by mass, and water 80 parts by mass were mixed, and a TK homomixer (special machine) To obtain [Colorant Dispersion].

-Preparation of toner base (6)-
[Crystalline resin particle dispersion (A-3)] 190 parts by mass, [Crystalline resin particle dispersion (B-1)] 63 parts by mass, [Amorphous resin particle dispersion (C-1)] 63 parts by mass Part, 46 parts by weight of [release agent dispersion (2)], 17 parts by weight of [colorant dispersion] and 600 parts by weight of water were adjusted to pH 10 with a 2% by weight aqueous sodium hydroxide solution. Subsequently, with stirring, 50 parts by mass of a 10% by mass magnesium chloride aqueous solution was gradually added dropwise to the solution, and the mixture was heated to 60 ° C. The slurry was maintained at 60 ° C. until the volume average particle diameter of the aggregated particles grew to 5.3 μm to obtain [Slurry 6].
The obtained [Slurry 6] was filtered under reduced pressure, and then the above washing treatments (1) to (4) were performed to obtain a filter cake (6). The obtained filter cake (6) was dried at 45 ° C. for 48 hours with a circulating drier. Thereafter, the toner base (6) was prepared by sieving with a mesh of 75 μm.

-Preparation of toner base (11)-
[Crystalline resin particle dispersion (A-6)] 190 parts by mass, [Crystalline resin particle dispersion (B-1)] 63 parts by mass, [Amorphous resin particle dispersion (C-1)] 63 parts by mass Part, 46 parts by weight of [release agent dispersion (2)], 17 parts by weight of [colorant dispersion] and 600 parts by weight of water were adjusted to pH 10 with a 2% by weight aqueous sodium hydroxide solution. Subsequently, with stirring, 50 parts by mass of a 10% by mass magnesium chloride aqueous solution was gradually added dropwise to the solution, and the mixture was heated to 60 ° C. The slurry was maintained at 60 ° C. until the volume average particle diameter of the aggregated particles grew to 5.9 μm to obtain [Slurry 11].
The obtained [Slurry 11] was filtered under reduced pressure, and then the washing treatments (1) to (4) were performed to obtain a filter cake (11). The obtained filter cake (11) was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the toner base (11) was prepared by sieving with a mesh having an opening of 75 μm.

-Preparation of toner base (12)-
[Urethane-modified crystalline polyester resin A-2] 60 parts by mass, [Urethane-modified crystalline polyester resin B-1] 20 parts by mass, [Amorphous resin C-1] 20 parts by mass, paraffin wax (Nippon Seiki Co., Ltd.) After premixing 5 parts by mass, HNP-9, melting point 75 ° C.) and 12 parts by mass of [Masterbatch (2)] using a Henschel mixer (Mitsui Miike Chemical Industries, Ltd., FM10B) The mixture was melted and kneaded at a temperature of 80 ° C. to 120 ° C. with a biaxial kneader (Ikegai, PCM-30). The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 μm to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labojet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the weight average particle size becomes 6.2 ± 0.3 μm. The louver opening is adjusted so that the weight average particle size is 7.0 ± 0.2 μm and the amount of fine powder of 4 μm or less is 10% by number or less with an air classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was performed with appropriate adjustment to obtain [Mother toner (12)].

-Preparation of toners (1) to (28)-
100 parts by weight of the obtained toner base (1) to toner base (28) 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 (Mine Co., Ltd.) was used for 5 cycles of mixing at a peripheral speed of 30 m / sec for 30 seconds and resting for 1 minute, followed by sieving with a mesh having an opening of 35 μm, and toner (1) to toner (28) Was made.

(Average circularity)
The average circularity is measured using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIAversion 00-10). Specifically, 0.1 to 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner 0 is added. Add 1 to 0.5 g and stir with microspatel, then add 80 mL of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using this dispersion, the shape and distribution of the toner are measured using FPIA-2100 until a density of 5,000 to 15,000 / μL is obtained. In this measurement method, the dispersion concentration is preferably 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0.00 g. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μl to 15,000 / μl.

(Toner capacity evaluation)
(1) 10 g of the obtained toners (1) to (28) are weighed and put into a stoppered graduated cylinder (made of Pyrex (registered trademark) glass, standard product with a capacity of 50 mL). Shake strongly and let the toner contain air.
(2) Stand still at the end of swinging and measure the standing time.
(3) Read from the scale of the cylinder which calls the toner capacity at the time of standing for 5 minutes, 20 minutes and 24 hours, and set them as V1, V2 and V3 (mL), respectively.
(4) The bulk density of the toner is calculated from 10 (g) / V3 (mL).
In addition, the measurement of said V1, V2, V3 (mL) evaluated on the same environmental conditions using the sample left to stand at 22 degreeC and 50RH% for 30 minutes.

(Evaluation of replenishability with toner replenishing device)
The obtained toners (1) to (28) were evaluated for replenishability using two types of replenishing devices having different screw portions of the toner container.
The toner container 1 is a container having no gap (gap of 1 mm or less) between the screw and the container wall in FIG.
The toner container 2 is a container in which the screw diameter of the toner container 1 is changed so that a gap of 3 mm is provided between the screw and the container wall.
The toner container 3 is a container in which the screw diameter of the toner container 1 is changed so that a gap of 2 mm is provided between the screw and the container wall.
In an environment of room temperature of 40 ° C. and relative humidity of 70%, 20 g of toner was put into the toner container (volume: 100 ml), left to stand for 1 hour, and then toner discharge was started at a rate of 2 g / min. The toner carried out from the toner container was collected. Next, the same operation was performed using the collected toner, and the stationary-discharge was repeated 10 times in total.
Next, 100 g of this toner was sieved with a stainless sieve having an opening of 75 μm, and the amount and hardness of the toner aggregate remaining on the sieve were evaluated.
○ There are almost no coarse particles. △ Coarse particles are slightly seen. × Many coarse particles are present. A hard aggregate is an aggregate that maintains its shape even when held with a finger. A soft agglomerate is an agglomerate that collapses when held with a finger.

The physical properties of the obtained toners (1) to (28) are shown in Tables 7-1 to 7-2. Tables 8-1 to 8-2 show the combinations of toner and toner containers and evaluation results of toner replenishment in Examples 1 to 26 and Comparative Examples 1 to 28.
In the table, the crystalline binder resin ratio indicates the ratio of the crystalline binder resin to the binder resin.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charging device 3 Optical writing unit 4 Developing device 5 Transfer device 6 Cleaning device 7 Intermediate transfer belt 8 Recording paper 11 Toner bottle 12 Conveyance pump 13 Toner container 14 Conveyance screw 16 Silicon tube 20 Rotor 21 Stator 22 Case 23 Replenishment clutch 24 Shaft joint 56Ya Conveying screw 56Ya1 Outer peripheral end of conveying screw 57Y Toner accommodating portion 57Ya Inner wall of toner accommodating portion 58Y Toner concentration detecting means 71 Secondary transfer bias roller 81Y Sponge 81Ya First surface 81Yb Second surface 82Y Film member 83Y Gap prevention member 90 Non-moving layer

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

Claims (11)

A replaceable toner container; a transport unit that transports toner stored in the toner container; and a toner storage unit that temporarily stores the toner transported through the transport unit; Is an image forming apparatus having a conveying screw for replenishing the stored toner to the developing device,
(1) The gap between the outer peripheral end of the conveying screw and the inner wall of the toner accommodating portion is 2.0 mm or less at a portion lower than the axis of the conveying screw in the toner accommodating portion.
(2) The image forming apparatus, wherein the toner contains a crystalline resin, and the crystalline resin contains a crystalline resin having a urethane bond and / or a urea bond in the main chain.   The maximum endothermic peak T1 of the second temperature increase by the differential scanning calorimeter (DSC) of the toner is in the range of 50 ° C. or more and 70 ° C. or less, and the endothermic amount ΔH (T) of the second temperature increase is 30 J / g or more and 75 J / g. The image forming apparatus according to claim 1, wherein the image forming apparatus is g or less.   The ratio of the molecular weight of 100,000 or more in the toner (tetrahydrofuran) (THF) soluble content of the toner is 100,000 or more is 5% or more, and the weight average molecular weight (Mw) is 20,000 or more and 70,000. The image forming apparatus according to claim 1, wherein:   The second endothermic endothermic amount of the toner in the differential scanning calorimeter (DSC) is ΔH (T) (J / g), and the insoluble content of the toner in the THF / ethyl acetate mixed solvent (mass ratio 50/50). ΔH (H) / ΔH (T) is 0.20 to 1.25, where ΔH (H) (J / g) is the second endothermic amount of temperature rise in the differential scanning calorimeter (DSC). The image forming apparatus according to any one of claims 1 to 3.   In the X-ray diffraction measurement of the toner, the ratio (C) / ((C) where 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 image forming apparatus according to claim 1, wherein + (A)) is 0.15 or more. The maximum endothermic peak T1 at the second temperature increase in the range of 0 to 150 ° C. and the maximum exothermic peak T2 at the time of temperature decrease satisfy the following relational expression (1) in the differential scanning calorimeter (DSC) of the toner. The image forming apparatus according to claim 1.
T1−T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)
(However, the rate of temperature increase from 0 ° C. to 150 ° C. at the time of temperature increase is 10 ° C./min, and the temperature decrease rate from 150 ° C. to 0 ° C. is 10 ° C./min.)   The image forming apparatus according to claim 1, wherein the crystalline resin having a urethane bond and / or a urea bond in the main chain is a resin having a crystalline polyester unit.   As a crystalline resin having a urethane bond and / or a urea bond in the main chain, a first crystalline resin and a second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin, The image forming apparatus according to claim 1, further comprising: The image forming apparatus according to claim 1, wherein the toner satisfies the following relational expression for toner volumes V1 and V2 (mL).
V2 / V1 ≧ 0.79
(Here, V1 and V2 indicate the toner capacity when left for 5 minutes and 20 minutes after stirring.) The toner is
(1) The following relational expressions for the toner volumes V1 and V3 (mL) are satisfied,
V3 / V1 ≧ 0.71
(Here, V1 and V3 indicate the toner capacity when left for 5 minutes and 24 hours after stirring.)
The image forming apparatus according to any one of claims 1 to 9, wherein (2) and the bulk density of the toner at the time of measuring V3 is 0.44 to 0.51 (g / ml). A replaceable replenishment developer container, transport means for transporting the replenishment developer stored in the replenishment developer container, and temporarily replenishment developer transported via the transport means An image forming apparatus including a replenishment developer accommodating portion, and the replenishment developer accommodating portion includes a conveying screw for replenishing the developer developer stored therein to the developing device;
(1) The gap between the outer peripheral end of the conveying screw and the inner wall of the replenishing developer accommodating portion is 2.0 mm or less at a portion lower than the axis of the conveying screw in the replenishing developer accommodating portion.
(2) The toner of the replenishment developer contains a crystalline resin, and the crystalline resin contains a crystalline resin having a urethane bond and / or a urea bond in the main chain. .

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