JP2012093562A - Toner, image forming method, and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that retains a fixed image under a high temperature and humidity environment (for example, temperature of 45°C, humidity of 80%), prevents carrier spent under high temperature and humidity, and reduces adhesion of toner to a fixing member, as well as a developer including the toner and a carrier, and an image forming method that reliably accommodates to high-speed printing using the developer.SOLUTION: The toner includes a core that contains at least a crystalline polyester, an amorphous polyester, a colorant, and a mold release agent; and a core-shell structure that is formed of a shell containing vinyl resin. The toner has thermal hardness of 0.5 or more to 2.5 or less, and a softening index of 40°C or higher to 79°C or lower.

Description

  The present invention relates to a toner, an image forming method, and a developer.

  In an image forming apparatus such as an electrophotographic apparatus or an electrostatic recording apparatus, an electrostatic latent image formed on a photoreceptor is developed with a developer containing toner to form a toner image. After being transferred to a recording medium such as paper, the image is formed by fixing by heating. Further, when forming a full-color image, generally, development is performed using toners of four colors of black, yellow, magenta, and cyan. After the toner images of the respective colors are transferred onto a recording medium and superimposed, heating is performed. To fix at the same time.

  At this time, if the softening property of the toner is lowered in order to improve the low-temperature fixability, the low-temperature melting component of the toner adheres to the carrier when an image is output in a high-temperature and high-humidity environment, and the charging ability of the carrier is reduced. The problem was that a high temperature and high humidity carrier spent that could not be maintained occurred.

  In the technology for improving low-temperature fixability, a core-shell toner containing a release agent, a colorant, a binder resin and a filler is disclosed as a toner for developing an electrostatic image (Patent Document 1). The toner obtained in the above literature has a flow tester 1/2 outflow temperature of 60 ° C. or higher and 100 ° C. or lower, and the shell contains a thermoplastic resin. However, this proposed technique has not solved the problem of high temperature and high humidity carrier spent. In addition, the evaluation of fixing retention in a high temperature and high humidity environment has not been made.

  Further, as a trade-off relationship between low-temperature fixability and pressure fixability, it is necessary to reduce toner adhesion to the fixing member. In order to prevent toner adhesion to the fixing member, it is necessary to achieve not only the function of wax but also appropriate viscoelastic property control of the toner resin and a high balance with the fixing pressure, but this has been difficult to achieve so far. .

  The present invention relates to a toner that achieves a high degree of compatibility between fixed image retention in a high-temperature and high-humidity environment, high-temperature and high-humidity carrier spent, and reduced toner adhesion to a fixing member, a developer having the toner and carrier, An object of the present invention is to provide an image forming method that uses the developer to ensure high-speed printing compatibility.

According to the present invention, it has a core-shell structure comprising a core containing a crystalline polyester, an amorphous polyester, a colorant and a release agent, and a shell containing a vinyl resin,
The thermal hardness is 0.5 or more and 2.5 or less,
A toner having a softening index of 40 ° C. or higher and 79 ° C. or lower is provided.

  The present invention has the following effects.

  Toner that achieves high compatibility between fixing image retention in high temperature and high humidity environment, high temperature and high humidity carrier spent and reduction of toner adhesion to fixing member, developer having the toner and carrier, and developer Can be used to provide an image forming method ensuring high-speed printing compatibility.

FIG. 1 is a schematic diagram showing an apparatus for measuring a toner outflow start temperature (Tfb) according to the present invention, and an example of a flow curve for obtaining Tfb. FIG. 1 (a) is a schematic view showing an apparatus for measuring the outflow start temperature (Tfb) of the toner of the present invention. FIG. 1B is a diagram showing an example of a flow curve for obtaining the toner outflow start temperature (Tfb) of the present invention. FIG. 2 is a schematic configuration diagram illustrating an example of a process cartridge of an image forming apparatus using the toner of the present invention. FIG. 3 is a schematic configuration diagram showing an example of a dandem type color image forming apparatus according to the direct transfer system of the present invention. FIG. 4 is a schematic configuration diagram showing an example of a dandem type color image forming apparatus in the indirect transfer system of the present invention. FIG. 5 is a schematic configuration diagram showing another example of the color image forming apparatus of the present invention. FIG. 6 is a schematic configuration diagram showing another example of the color image forming apparatus of the present invention.

  Hereinafter, the present invention will be described in detail.

  The present invention has a core-shell structure comprising a core containing crystalline polyester, amorphous polyester, colorant and release agent, and a shell containing vinyl resin, and has a thermal hardness of 0.5 to 2.5. By using a toner having a softening index of 40 ° C. or higher and 79 ° C. or lower, in a pressure fixing system, a fixed image retention property in a high temperature and high humidity environment, a high temperature and high humidity carrier spent, It has been found that a toner that achieves a high level of reduction in toner adhesion to the fixing member and an image forming apparatus, a process cartridge, and a developer containing the toner and ensuring high-speed printing compatibility can be provided.

  The mechanism is estimated as follows.

  First, the toner has a core-shell structure, so that the outer shell layer has a bad influence on the spent on the carrier and the developing member, such as a release agent such as wax, a coloring agent such as a pigment, a poorly charged component, and a low-melting component. Protect. On the other hand, the toner can be designed using a resin with low softening properties in order to cope with low-temperature fixability due to the internal core portion. In this case, it is more preferable that the toner contains at least a vinyl resin as a binder resin for the shell in terms of thermal hardness design and viscoelastic property design of the shell layer resin. In addition, since the toner contains at least a crystalline polyester resin, the viscoelastic property of the resin can be designed to be a sharp melt, which is effective in a core-shell structure toner based on an appropriate thermal hardness design of the present invention. It is possible to demonstrate the function. In addition, since the toner is a toner containing at least a urea-modified polyester resin, it is possible to give the resin a complicated cross-linked structure, and the design range of the thermal characteristics and viscoelastic characteristics of the toner is further expanded, which is more preferable. . Further, since the toner contains not only the urea-modified polyester resin but also at least an unmodified polyester resin, the low-temperature fixability and the glossiness and gloss uniformity when used in a full-color apparatus are improved.

  Further, the toner is characterized in that the thermal hardness St evaluated by a flow tester is 0.5 to 2.5 and the softening index Ct is 40 ° C. to 79 ° C. Here, the thermal hardness St is defined as follows.

  The load of the flow tester is changed from 2 to 25 kgf, and the toner outflow start temperature Tfb at the load is evaluated. The load at that time is plotted on the xy plane with the x-axis (the unit of x-axis is kgf) and the outflow start temperature is the y-axis (the unit of y-axis is temperature (° C.)). Then, a linear function is derived from these plots by the method of least squares. The absolute value of the slope of the derived linear function is defined as St. The softening index Ct defines the outflow start temperature Tfb at a load of 25 kgf as Ct.

  Although it is the meaning of each characteristic value, the thermal hardness St is mainly attributed to the viscoelastic characteristics of the shell layer of the toner, and can be evaluated as a characteristic value indicating the ease of melting of the toner with respect to the load. It shows that the fall of outflow start temperature is large with respect to load, so that St is large. That is, a large St value indicates that the entire toner is difficult to thermally soften unless a high load is applied. It is thought that the softening temperature is lowered only when the shell structure is destroyed by the load. Therefore, it can be evaluated that the thermal hardness of the shell layer is hard. On the other hand, if the load dependency is small (not) on the outflow start temperature, it indicates that the meltability hardly changes even when a load is applied. In other words, since the meltability is greatly dependent on the amount of heat, the thermal hardness of the shell is soft, indicating that the shell melts even when the load is small.

  On the other hand, the softening index Ct indicates the viscoelastic characteristics of the entire toner, particularly the core. It is defined by the outflow start temperature Tfb at a load of 25 kgf. The load of 25 kgf is sufficient to break the core-shell structure in the core-shell structure toner. That is, it can be evaluated as the softening property of the toner when a sufficient load is applied. That is, Ct is considered to be a toner outflow start temperature in a state where the shell structure is destroyed by pressure fixing.

  It is important for the thermal hardness St of the shell layer to be in the range of 0.5 to 2.5 in order to ensure heat-resistant storage stability and development durability. In addition, a sufficient amount and state of Wax bleed out from the inside of the toner to the surface to exhibit a releasing effect for fixing wrapping, but if the thermal hardness of the shell layer is not properly controlled, A sufficient release effect cannot be exhibited. Therefore, it is necessary to highly balance the St value.

  When the softening index Ct of the core portion is 40 ° C. to 79 ° C., sufficient low-temperature fixability in pressure fixing can be ensured. When the temperature is lower than 40 ° C., although the toner core is covered with a shell layer, the heat-resistant storage stability is lowered due to the influence of heat and humidity of the external environment. Furthermore, carrier spent is generated in the use in a high temperature and high humidity environment which is more severe in heat. On the other hand, when it exceeds 79 ° C., the core is difficult to soften and sufficient low-temperature fixability is insufficient.

  Further, the fixing device of the image forming apparatus is used in an apparatus including a fixing system using heat and pressure at least at a fixing member surface temperature of 40 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C. Is more preferable because of improved image quality.

  More preferably, the thickness of the shell layer is highly controlled in the range of 0.01 μm to 2 μm. When the shell layer thickness is less than 0.01 μm, the layer effect is not sufficient, which is not preferable. On the other hand, if the thickness exceeds 2 μm, the shell layer is too thick, and the color developability by the colorant inside the core and the exuding property of the wax deteriorate, which is not preferable. Further, it is not preferable because the low-temperature fixability of the shell layer cannot be sufficiently secured.

The fixing pressure ^{30N / cm 2 ~4000N / cm 2} , more preferably ^{50N / cm 2 ~2000N / cm 2} , more preferably of ^60N / cm ^{2 ~1000N} / cm 2 surface pressure a visible image on a recording medium By controlling the pressure at the above, appropriate pressure fixing can be achieved in combination with the toner of the present invention. When the fixing pressure is less than 30 N / cm ² , the fixing pressure is not sufficient and the toner is not sufficiently deformed by pressure, and the fixability to a recording medium (paper, sheet such as OHP, resin, fiber, etc.) is lowered. On the other hand, if it exceeds 4000 N / cm ² , the pressure is too high and toner adheres to the fixing member (roller, belt, film, etc.), which is not preferable because it becomes the same phenomenon as hot offset.

  Further, it is more preferable that the toner has a mean circular diameter E of 0.93 to 0.99, and a core-shell structure can be secured in a shape close to a sphere appropriately.

  In addition, since the toner has a shape factor SF-1 value of 100 to 150 and a shape factor SF-2 value of 100 to 140, the core-shell structure has an appropriately spherical shape. Is more preferable.

The toner preferably has a weight average particle diameter D ₄ of 2 to 7 μm, more preferably 2 to 5 μm. The ratio D ₄ / Dn of the weight average particle diameter D ₄ and the number average particle diameter Dn is 1.00 to 1.25, more preferably 1.00 to 1.15. As a result, it is possible to form toner particles having a uniform core-shell structure while ensuring the charge developing property, transfer property, and fixing property of the toner.

  In addition, by using a two-component developer characterized by containing the toner described above and at least a magnetic carrier, the charging potential, which is reduced when the toner is made into a core-shell structure, is sufficient for frictional charging in a short time. It is possible to ensure a good rise and maintain a sufficiently sharp charge amount distribution. Further, the developer can sufficiently cope with the carrier spent problem.

In addition, in an image forming apparatus including a fixing device that fixes a visible image on a recording medium by at least pressure, it is a tandem development system in which at least four or more development units having different development colors are arranged in series. The color image forming apparatus is characterized in that the pressure is 200 to 3000 mm / sec, the pressing surface pressure during fixing is 30 N / cm ^{2 to} 4000 N / cm ² , and the fixing nip time is 30 ms to 400 ms. is there. By using this image forming device, it is possible to properly develop, transfer, and fix even in areas where the system speed is high, and control toner deformation and melting and fixing to recording media (paper, etc.) under high pressure. At the same time, it has a fixing characteristic that does not cause hot offset. Further, by appropriately designing the fixing nip time, it is possible to provide an image forming method that can control an appropriate pressure and heat amount for fixing the toner, consume less power, and ensure appropriate image quality.

  Further, the fixing device of the image forming apparatus is provided with a fixing system using at least the heat and pressure of the fixing medium surface temperature of 40 ° C. to 100 ° C. preferable.

(Confirmation of toner shell layer and thickness evaluation)
The toner of the present invention has a core-shell structure comprising a core containing crystalline polyester, amorphous polyester, colorant and release agent, and a shell containing vinyl resin.

  The core makes it possible to design a resin having a low softening property and a toner to cope with low-temperature fixability. The shell can protect the carrier and the developing unit from the core wax, pigment, and poorly charged components that adversely affect the spent on the carrier and the developing unit.

  The confirmation and layer thickness of the toner shell layer in the present invention can be evaluated by the following method using a TEM (transmission electron microscope). The thickness of the shell layer was evaluated by measuring 10 particles extracted at random and averaging them.

  First, the toner is embedded and cured in an epoxy resin about one full spatula. The sample is gas-exposed for 1 minute to 24 hours with ruthenium tetroxide, osmium tetroxide, or another staining agent to distinguish and dye the shell layer and the core interior. The exposure time is appropriately adjusted according to the contrast during observation. Next, a section is cut out with a knife, and an ultrathin section (200 nm thickness) of toner is prepared with an ultramicrotome (Leica, ULTRACUT UCT, using a diamond knife). Thereafter, observation is performed with a TEM (transmission electron microscope, H7000, manufactured by Hitachi High-Tech) at an acceleration voltage of 100 kV. Depending on the composition of the shell layer and the core portion, there may be cases in which it can be identified without staining, in which case the evaluation is performed without staining. It is also possible to give a composition contrast by other means such as selective etching, and it is also possible to evaluate the shell layer by TEM observation after such pretreatment.

(Toner thermal hardness St, softening index Ct)
The thermal hardness St, softening index Ct, and thermal retention Ht of the toner of the present invention are preferably evaluated by the following methods.

  Evaluation was performed using an elevated flow tester (manufactured by Shimadzu Corporation, CFT-500D). The device is a technique for evaluating the viscoelastic properties (temperature dependence) of the toner by elevating the temperature while applying a load to the tableted toner and allowing the molten toner to flow out of the die hole and evaluating the amount of plunger drop. Yes (Fig. 1 (a)). In general, the temperature at which the amount of descent reaching the end of the outflow changes greatly is defined as the outflow start temperature Tfb. The outflow end temperature is defined as Tend (FIG. 1 (b)).

  Usually, the outflow start temperature Tfb or T1 / 2 temperature at a certain constant load is generally evaluated as a characteristic value related to thermal fixability. In the present invention, the outflow start temperature when the load is changed is set. It has been found that the characteristics corresponding to the thermal hardness St of the toner shell layer can be evaluated by the evaluation. St indicates the pressure dependence of the outflow start temperature, and can be evaluated as the thermal hardness of the shell layer. St is defined as a value obtained by multiplying the slope of the graph when the load (2 kgf to 25 kgf) is plotted on the horizontal axis and the outflow start temperature is plotted on the vertical axis, minus.

Further, the softening index Ct of the core layer is defined by an outflow start temperature Tfb at a load of 25 kgf (after a sufficient load is applied and the shell layer is broken).
1) Sample 1 g of toner was used after being pressure-molded into a cylindrical tablet with a diameter of 1 cm.
2) Temperature conditions 50 ° C to 3 ° C / min.
3) Die hole diameter 0.5mm
4) Die length 10mm
5) Heating time 200s
(Average circularity E)
The average circularity E of the toner is defined by the circularity E = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. The average circularity was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation; “FPIA-2100”) and analyzed using analysis software (FIPA-2100 Data Processing Program for FPIA version 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 g to 0.5 g was added, and the mixture was stirred 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.). Using the FPIA-2100, the dispersion was measured for toner shape and distribution until a density of 5000 / μL to 15000 / μL was obtained.

  In this measurement method, it is important that the concentration of the dispersion liquid is 5000 / μL to 15000 / μL from the viewpoint of measurement reproducibility of 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 it is small for small particle sizes and needs to be increased for large particle sizes. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0.3. By adding 5 g, the dispersion concentration can be adjusted to 5000 / μL to 15000 / μL.

(Shape factors SF-1 and SF-2)
The shape factors SF-1 and SF-2 used in the present invention were randomly sampled 300 FE-SEM images of toner obtained by measurement with FE-SEM (manufactured by Hitachi, S-4200), The image information was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco through an interface and analyzed, and the values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.
SF-1 = (L ² / A) × (π / 4) × 100
SF-2 = (P ² / A) × (1 / 4π) × 100
Here, the absolute maximum length of the toner is L, the projected area of the toner is A, and the maximum peripheral length of the toner is P. In the case of a true sphere, all become 100, and from a spherical shape to an indefinite shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (ellipse, sphere, etc.), and SF-2 represents a shape factor representing the degree of surface irregularities.

(Weight average particle diameter, D ₄ / Dn (ratio of weight average particle diameter / number average particle diameter))
The weight average particle diameter (D ₄ ), the number average particle diameter (Dn), and the ratio (D ₄ / Dn) of the toner can be measured by the following method. The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Beckman Coulter, Inc.) or the like. In particular, Coulter Multisizer II is used in the present invention. The measurement method is described below.

  First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% by mass NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Beckman Coulter, Inc.) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(System speed)
In the present invention, the system linear velocity was measured as follows. When A4 paper, longitudinal paper passage (length of paper passage paper: 297 mm), continuous 100 sheets, output by the corresponding image forming apparatus, the output time from start to end is Xsec, and the system speed is Y, the following The system speed was calculated by the equation.

Y (mm / sec) = 100 sheets × 297 mm ÷ Xsec
(Fixing pressure surface pressure)
The fixing pressure surface pressure in the present invention can be measured by using a pressure distribution measuring device PINCH (manufactured by Nitta Corporation).

(Fixing nip time)
The fixing nip time was calculated from the measurement of the linear velocity and the fixing nip width.

(Process cartridge)
FIG. 2 is a schematic diagram showing a configuration of an image forming apparatus including a process cartridge that can be applied to an apparatus used in the image forming method of the present invention. In FIG. 2, a represents the entire process cartridge, b represents a photosensitive member, c represents a charging unit, d represents a developing unit, and e represents a cleaning unit.

  In the present invention, at least the photosensitive member b and the developing unit d are integrally combined as a process cartridge among the above-described components such as the photosensitive member b, the charging device unit c, the developing unit d, and the cleaning unit e. The process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

(Crystalline polyester resin)
In this invention, it is more preferable to contain the crystalline polyester resin shown below. The melting point of the crystalline polyester resin needs to be in the range of 50 to 100 ° C, more preferably in the range of 55 to 90 ° C, and still more preferably in the range of 60 to 85 ° C. When the melting point is less than 50 ° C., it becomes difficult to store the toner such as blocking the stored toner and to store the fixed image after fixing. Further, when the melting point exceeds 100 ° C., sufficient low-temperature fixability cannot be obtained. In addition, melting | fusing point of the said crystalline polyester resin was calculated | required as the peak temperature of the endothermic peak obtained by the said differential scanning calorimetry (DSC).

  The crystalline polyester resin used in the toner of the present invention is synthesized from, for example, a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present embodiment, a commercially available product may be used as the crystalline polyester resin, or a synthesized product may be used.

  Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid Aromatic dicarboxylic acids such as dibasic acids such as, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.

  Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as an acid component, the dicarboxylic acid component which has a sulfonic acid group other than the said aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained. Furthermore, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.

  As the polyhydric alcohol component, an aliphatic diol is preferable, and a linear aliphatic diol having 7 to 20 carbon atoms in the main chain portion is more preferable. If the aliphatic diol is branched, the crystallinity of the polyester resin is lowered, and the melting point may be lowered. Further, when the main chain portion has less than 7 carbon atoms, when polycondensation with an aromatic dicarboxylic acid, the melting temperature becomes high and fixing at low temperature may be difficult, while the main chain portion has 20 carbon atoms. Exceeding the above range makes it difficult to obtain practical materials. The number of carbon atoms in the main chain portion is more preferably 14 or less.

  Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester used in the toner of the present invention include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5. -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12- Examples include, but are not limited to, dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, considering availability, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are desirable.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

  Among the polyhydric alcohol components, the content of the aliphatic diol is preferably 80 mol% or more, and more preferably 90% or more. When the content of the aliphatic diol is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. .

  If necessary, a polycarboxylic acid or a polyhydric alcohol may be added at the final stage of the synthesis for the purpose of adjusting the acid value or the hydroxyl value. Examples of polycarboxylic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, alkenyl Aliphatic carboxylic acids such as succinic anhydride and adipic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid.

  Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc. And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct.

  The crystalline polyester resin can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is depressurized as necessary, and the reaction is carried out while removing water and alcohol generated during the condensation.

  When the polymerizable monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a polymerizable monomer having poor compatibility in the copolymerization reaction, the polymerizable monomer having poor compatibility and the polymerizable monomer and the acid or alcohol to be polycondensed are condensed in advance. And then polycondensation with the main component.

  Catalysts usable in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, germanium and the like Metal compounds; phosphorous acid compounds; phosphoric acid compounds; and amine compounds.

  Specifically, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxy , Titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetra Butoxide, Zirconium naphthenate, Zirconyl carbonate, Zirconyl acetate, Zirconyl stearate, Zirconyl octylate, Germanium oxide, Trif Alkenyl phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  The acid value of the crystalline polyester resin used in the present invention (mg number of KOH required to neutralize 1 g of resin) is preferably in the range of 3.0 to 30.0 mgKOH / g, and 6.0 to 25 More desirably, it is in the range of 0.0 mgKOH / g, and further desirably in the range of 8.0 to 20.0 mgKOH / g.

  When the acid value is lower than 3.0 mgKOH / g, the dispersibility in water is lowered, and thus it may be very difficult to produce particles by a wet process. In addition, since stability as polymerized particles during aggregation is significantly reduced, it may be difficult to produce an efficient toner. On the other hand, when the acid value exceeds 30.0 mgKOH / g, the hygroscopicity as a toner increases and the toner may be easily affected by the environment.

  The crystalline polyester resin preferably has a weight average molecular weight (Mw) of 6,000 to 35,000. If the molecular weight (Mw) is less than 6,000, the toner may soak into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the strength of the fixed image against bending resistance may decrease. On the other hand, when the weight average molecular weight (Mw) exceeds 35,000, the viscosity at the time of melting becomes too high, and the temperature for reaching a viscosity suitable for fixing may be increased, resulting in the deterioration of the low-temperature fixability. There is a case.

  The weight average molecular weight can be measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC was performed with a THF solvent using a Tosoh column / TSKgel Super HM-M (15 cm) using a Tosoh GPC / HLC-8120 as a measuring device. The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  The content of the crystalline polyester resin in the toner is preferably in the range of 3 to 40% by mass, more preferably in the range of 4 to 35% by mass, and still more preferably in the range of 5 to 30% by mass. When the content of the crystalline polyester resin is less than 3% by mass, sufficient low-temperature fixability may not be obtained. When the content is more than 40% by mass, sufficient toner strength and fixed image strength cannot be obtained. There is a case where an adverse effect on the charging property is also caused.

(Amorphous polyester resin)
In the present invention, it is preferable to contain at least the following amorphous polyester resin as a binder resin for the toner. The amorphous polyester resin includes a urea-modified polyester resin and an unmodified polyester resin, and it is more preferable to contain both of them.

(Urea-modified polyester resin)
In the present invention, the following urea-modified polyester resins can be used as the polyester resin. Specifically, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol And alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) and the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, the urea content in the urea-modified polyester is lowered, and the hot offset resistance is deteriorated. The content of the polyisocyanate (3) component in the polyester prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. When the number is less than 1 per molecule, the molecular weight of the urea-modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

  The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1 / 1.5 to 1.5 / 1, more preferably 1 / 1.2 to 1.2 / 1. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates.

(Unmodified polyester)
In the present invention, not only the polyester prepolymer (A) having an isocyanate group is used alone but also an unmodified polyester (C) is contained as a toner binder component together with the polyester prepolymer (A) having an isocyanate group. It is more preferable. By using the unmodified polyester (C) in combination, the low-temperature fixability and the glossiness and gloss uniformity when used in a full-color apparatus are improved. Examples of the unmodified polyester (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as those of the polyester component of the polyester prepolymer (A) having an isocyanate group. The same as the polyester prepolymer (A) having an isociate group. In addition, it is preferable in terms of low-temperature fixability and hot offset resistance that the polyester prepolymer (A) having an isocyanate group and the unmodified polyester (C) are at least partially compatible. Therefore, the polyester component of the polyester prepolymer (A) having an isocyanate group and the unmodified polyester (C) preferably have similar compositions. When the unmodified polyester (C) is contained, the weight ratio of the prepolymer (A) having an isocyanate group to the unmodified polyester (C) is usually 5/95 to 75/25, preferably 10/90 to 25 / 75, more preferably 12/88 to 25/75, and particularly preferably 12/88 to 22/78. When the weight ratio of the polyester prepolymer (A) having an isocyanate group is less than 5% by mass, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat resistant storage stability and low temperature fixability.

  The peak molecular weight of the unmodified polyester (C) is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of the unmodified polyester (C) is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g to 120 mg KOH / g, and particularly preferably 20 mg KOH / g to 80 mg KOH / g. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of the unmodified polyester (C) is usually 0.5 mgKOH / g to 40 mgKOH / g, preferably 5 mgKOH / g to 35 mgKOH / g. By giving the acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

In the present invention, the glass transition point (Tg) of the toner is usually 40 ° C. to 70 ° C., preferably 45 ° C. to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner, the temperature (TG ′) at which 10000 dyne / cm ² is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 ° C. to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 ° C. to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Vinyl resin)
In the present invention, the toner preferably contains the following vinyl resin, and more preferably contains the following vinyl resin as a binder resin for the shell. The vinyl resin is not particularly limited as long as it is dispersed in an aqueous medium, and a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer is used. Examples of the monomer in this case include vinyl homopolymers containing acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride. It is done. In addition, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylate 3- Chloro-2-hydroxypropyl, methacrylic acid 3-chloro-2-monohydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide A (meth) acrylic homopolymer containing a hydroxyl group such as can also be used. Furthermore, vinyl alcohols such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether or ethers with vinyl alcohol, and esters of vinyl alcohol such as pinyl acetate, pinyl propionate, vinyl butyrate and compounds containing carboxyl groups Homopolymers can also be used. Acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride and methacrylic acid chloride, those having a nitrogen atom such as pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, or heterocyclic rings thereof Homopolymers can also be used.

(Coloring agent)
All known dyes and pigments can be used as the colorant of the present invention. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL , Isoindolinone yellow, bengara, red lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phise red, parachlor ortho nitroaniline red, risor fast scarlet G, Reliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine Range, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Bull Foley, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Titanium, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1% to 15% by weight, preferably 3% to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As binder resin kneaded with the production of the master batch or the master batch, in addition to the above-mentioned urea-modified polyester resin and non-modified polyester resin, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and substituted products thereof. Polymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-Chlormetac Methyl formate copolymer, Styrene-acrylonitrile copolymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid Styrene copolymers such as copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type and can also be used in mixture of 2 or more types.

  This master batch can be obtained by mixing and kneading the master batch resin and the colorant with high shearing force to obtain a master batch. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a coloring agent, is a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
There is no restriction | limiting in particular as a mold release agent of this invention, It can select suitably from well-known things. For example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax, etc. can be mentioned. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) ); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The wax content in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, phenolic condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP 1415 (above, Hodogaya Chemical Co., Ltd.), No. 4 Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst AG), LRA-901, LR which is a boron complex -147 (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene Quinacridone, azo pigment, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. More preferably, the range is 0.2 to 5 parts by weight. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, and the effect of the main charge control agent is diminished. As a result, the electrostatic attraction force with the developing roller increases, leading to a decrease in developer fluidity and a decrease in image density. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent. May be.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles or hydrophobic treated inorganic fine particles can be used. It is more desirable to include at least one kind of inorganic fine particles having an average particle diameter of 1 nm to 100 nm, more preferably 5 nm to 70 nm. Further, it is more preferable that the hydrophobized primary particles have at least one inorganic fine particle having an average particle size of 20 nm or less and at least one inorganic fine particle having a particle size of 30 nm or more. In addition, the specific surface area by BET method is preferably 20m ² / g~500m ² / g.

  Any of them can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above manufactured by Hoechst AG), R972, R974, RX200, RY200, R202, R805, R812 (above Nippon Aerosil Co., Ltd.). Made). Moreover, as titania fine particles, P-25 (made by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (made by Titanium Industry Co., Ltd.), TAF-140 (made by Fuji Titanium Industry Co., Ltd.), MT- 150W, MT-500B, MT-600B, MT-150A (manufactured by TEIKA CORPORATION) and the like. In particular, as hydrophobized titanium oxide fine particles, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF-1500T (and above) Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (above Teika Co., Ltd.), IT-S (Ishihara Sangyo Co., Ltd.), and the like.

  In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. It can be obtained by processing. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic-modified silicone oil, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, etc. can be used . Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred.

  The addition amount may be 0.1% to 5% by weight, preferably 0.3% to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nmn or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.

  Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.

  Such a fluidizing agent is subjected to surface treatment to increase hydrophobicity, thereby preventing deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 μm to 1 μm.

(Resin fine particles)
In the present invention, vinyl-based resin fine particles can be contained as required. The resin fine particles used preferably have a glass transition point (Tg) of 40 to 100 ° C. and a weight average molecular weight of 3,000 to 300,000. As described above, when the glass transition point (Tg) is less than 40 ° C. and / or the weight average molecular weight is less than 3,000, the storage stability of the toner deteriorates, and blocking occurs during storage and in the developing machine. There is. When the glass transition point (Tg) is 100 ° C. or higher and / or the weight average molecular weight is 300,000 or higher, the resin fine particles inhibit the adhesion between the toner and the fixing paper, and the fixing minimum temperature increases. May end up.

  The residual ratio of the resin fine particles to the toner particles is preferably in the range of 0.5 wt% to 5.0 wt%. When the residual ratio is less than 0.5% by weight, the storage stability of the toner is deteriorated, and blocking is observed during storage and in the developing machine. On the other hand, if the residual amount is 5.0% by weight or more, the resin fine particles inhibit the exudation of the wax, the effect of releasing the wax cannot be obtained, and the occurrence of offset is observed.

  The content of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

Further, when synthesizing the resin fine particles, it is also preferable to contain a small amount of polylactic acid in order to control the viscoelastic properties of the toner.

(Production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Subsequently, this is made to react with polyisocyanate (3) at 40 to 140 degreeC, and the polyester prepolymer (A) which has an isocyanate group is obtained.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
The aqueous phase used in the present invention is more preferably used by adding resin fine particles in advance. The resin fine particles function as a particle size controlling agent, so that they are arranged around the toner and finally cover the toner surface and function as a shell layer. Since the function as a sufficient shell layer is influenced by the particle size and composition of the resin fine particles, the dispersant (surfactant) in the aqueous phase, the solvent, and the like, detailed control is required.

  The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The toner particles are obtained by forming a dispersion composed of a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase and reacting with amines (B). As a method for stably forming a dispersion composed of a polyester prepolymer (A) having an isocyanate group in an aqueous phase, the polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase can be used. And a method of adding a toner raw material composition to be dispersed by a shearing force. A polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), a colorant masterbatch, a release agent, a charge control agent, The unmodified polyester resin or the like may be mixed when forming the dispersion in the aqueous phase, but after mixing the toner raw material in advance and then dissolving or dispersing in the organic solvent, the mixture is added to the aqueous phase. It is more preferable to disperse. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. It may be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 μm to 20 μm, a high-speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 5000 rpm to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 minutes to 5 minutes. The temperature during dispersion is usually 0 ° C. to 150 ° C. (under pressure), preferably 40 ° C. to 98 ° C. Within the above temperature range, a higher temperature is preferable in that the dispersion of the polyester prepolymer (A) having an isocyanate group has a low viscosity and is easily dispersed.

  The amount of the aqueous phase to be used with respect to 100 parts of the toner composition containing the polyester prepolymer (A) having an isocyanate group is usually 50 parts by weight to 2000 parts by weight, preferably 100 parts by weight to 1000 parts by weight. When the amount of the aqueous phase used is less than 50 parts by weight, the toner composition is not well dispersed and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Amine salt surfactants such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Quaternary ammonium salt type cationic surfactants, nonionic surfactants such as fatty acid amide derivatives, polyhydric alcohol derivatives, alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N -Alky Over N, amphoteric surfactants such as N-dimethylammonium betaine.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 31- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) mono-N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid and metal Salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,
As the trade names of the surfactants having a fluoroalkyl group, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Manufactured by Sumitomo 3M Co., Ltd.), Unidyne DS-1101, DS-102, (manufactured by Taikin Kogyo Co., Ltd.), Megafuck F-110, F-120, F1-113, F-191, F-812, F-833 (Manufactured by Dainippon Ink & Chemicals, Inc.), Xtop EF 1102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products Co., Ltd.), Footgent F- 100, F150 (manufactured by Neos Co., Ltd.) and the like.

  Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and aliphatics such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-21 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS -202 (manufactured by Daikin Industries Co., Ltd.), MegaFuck F-150, F-824 (manufactured by Dainippon Ink Chemical Co., Ltd.), Xtop EF-32 (manufactured by Tochem Products Co., Ltd.), Manufactured by Neos Co., Ltd.).

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. can do. In addition, calcium phosphate can be removed from the fine particles by an operation such as enzymatic degradation.

  When a dispersant is used, the dispersant may remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The reaction time for the elongation and / or cross-linking reaction is selected depending on the reactivity depending on the combination of the isocyanate group structure of the prepolymer (A) and the amines (B), but usually 10 minutes to 40 hours, preferably 2 hours. ~ 24 hours. The reaction temperature is generally 0 ° C to 150 ° C, preferably 40 ° C to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire reaction system is gradually raised and the organic solvent in the droplets is completely removed by evaporation can be employed. Alternatively, a method of spraying the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles and evaporating and removing the aqueous dispersant together is also possible. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. By using a spray dryer, belt dryer, rotary kiln or the like, the desired quality can be obtained in a short time.

  Further, as a method for removing the organic solvent, air can be blown away by a rotary evaporator or the like.

  Thereafter, rough separation is performed by centrifugation, the emulsified dispersion is washed in a washing tank, and the drying process is repeated in a hot air drier to remove the solvent and dry the toner base.

  After that, it is more preferable to add a further aging step. The aging temperature is preferably 30 ° C. to 55 ° C. (more preferably 40 ° C. to 50 ° C.), and more preferably 5 hours to 36 hours (more preferably 10 hours to 24 hours).

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.

  In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.

  The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  Finally, an external additive such as inorganic fine particles and a toner are mixed with a Henschel mixer or the like, and coarse particles are removed with an ultrasonic sieve or the like to obtain a final toner.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 part by weight of toner to 100 parts by weight of carrier. 10 parts by weight is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 μm to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins such as polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Tandem type color image forming device)
In the present invention, a color image forming apparatus of a tandem type development system in which at least four development units having different development colors are arranged in series can be used. An example of an embodiment of a tandem type color image forming apparatus will be described. As shown in FIG. 3, the tandem type electrophotographic apparatus includes a direct transfer system in which an image on each photoconductor 1 is sequentially transferred onto a sheet s conveyed by a sheet conveying belt 3 by a transfer apparatus 2. As shown in FIG. 4, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2 and then the image on the intermediate transfer member 4 is transferred to the sheet s by the secondary transfer device 5. There are indirect transfer systems that perform batch transfer. The transfer device 5 is a transfer conveyance belt, but there is also a roller-shaped method.

  Comparing the direct transfer type and the indirect transfer type, the former has a sheet feeding device 6 arranged upstream of the tandem type image forming apparatus t in which the photoreceptors 1 are arranged, and a fixing device 7 arranged downstream. There is a drawback in that the size increases in the sheet conveying direction.

  On the other hand, the latter can set the secondary transfer position relatively freely. Therefore, there is an advantage that the paper feeding device 6 and the fixing device 7 can be arranged so as to overlap the tandem type image forming apparatus t, and the size can be reduced.

  In the former, in order not to increase the size in the sheet conveyance direction, the fixing device 7 is disposed close to the tandem type image forming apparatus t. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the sheet s can bend. As a result, an impact when the leading edge of the sheet s enters the fixing device 7 (particularly noticeable with a thick sheet), and a speed between the sheet conveying speed when passing through the fixing device 7 and the sheet conveying speed by the transfer conveying belt. Due to the difference, there is a drawback that the fixing device 7 tends to affect the upstream image formation.

  On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 can hardly affect the image formation.

  For the reasons described above, recently, among the tandem type electrophotographic apparatuses, the indirect transfer type has been attracting attention.

  In this type of color electrophotographic apparatus, as shown in FIG. 4, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 5 shows an embodiment of the present invention, which is a tandem indirect transfer type electrophotographic apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.

  Then, as shown in FIG. 5, in the illustrated example, it can be rotated and conveyed clockwise in the figure by being wound around three support rollers 14, 15, and 16.

  In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.

  Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.

  An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.

  A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.

  The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.

  In the illustrated example, under such a secondary transfer device 22 and a fixing device 25, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet in parallel with the tandem image forming device 20 described above. Is provided.

  When a copy is made using this color electrophotographic apparatus, the original is set on the original table 30 of the automatic original conveying apparatus 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is placed on the other contact glass 32. When set, the scanner 300 is immediately driven to travel on the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source, and the reflected light from the document surface is further reflected toward the second traveling body 34 and reflected by the mirror of the second traveling body 34 to form the imaging lens 35. The reading sensor 36 receives the light and reads the contents of the document. Further, one of the support rollers 14, 15, and 16 is driven to rotate by a drive motor (not shown), and the other two support rollers are also driven to rotate, thereby rotating and conveying the intermediate transfer member 10. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10. Further, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, the sheets are fed out from one of the paper cassettes 44 provided in the paper bank 43 in multiple stages, and are separated one by one by the separation roller 45 to feed the paper. Then, the sheet is conveyed to the sheet feeding path 48 in the copying machine main body 100 and abutted against the registration roller 49 to stop the sheet.

  Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.

  The sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22 by rotating the registration roller 49 in synchronization with the timing, and the composite color image formed on the intermediate transfer member 10 is transferred to the secondary transfer device 22. The color image is recorded on the sheet by transferring the image.

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image. Are discharged and stacked on the discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

  On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.

  Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  Now, in the tandem image forming apparatus 20 described above, the individual image forming means 18 includes, for example, a charging device 60, a developing device 61, and a primary device around a drum-shaped photoreceptor 40 as shown in FIG. The image forming apparatus includes a transfer device 62, a photoconductor cleaning device 63, a charge removal device 64, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to the following Example.

  Hereinafter, a part shows a weight part.

(Evaluation machine)
As the evaluation machines, evaluation machines G1 to G8, H1, and H2 of imagio MP C6000 manufactured by Ricoh Co., Ltd., which are mainly modified fixing parts, were used. Table 1 shows the changed evaluation conditions. The linear velocity was set by changing or adjusting all of the development, transfer, cleaning unit, and transport unit. The fixing unit of the fixing unit adjusted the fixing surface pressure, the fixing nip time, and the fixing member surface temperature. The fixing member surface was coated with tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), molded, and surface-adjusted.

（2成分現像剤評価）
2成分系現像剤で画像評価する場合は、以下のように、シリコーン樹脂により0.5μｍの平均厚さでコーティングされた平均粒径35μｍのフェライトキャリアを用い、キャリア１００重量部に対し各色トナー7重量部を、容器が転動して攪拌される型式のターブラーミキサーを用いて均一混合し帯電させて、現像剤を作製した。
（キャリアの製造）
・芯材
Mnフェライト粒子（重量平均径：35μｍ）・・・５,０００部
・コート材
トルエン・・・４５０部
シリコーン樹脂ＳＲ２４００（東レ・ダウコーニング・シリコーン株式会社製、不揮発分５０％）
・・・４５０部
アミノシランＳＨ６０２０（東レ・ダウコーニング・シリコーン株式会社製）・・・１０部
カーボンブラック・・・１０部
上記コート材を１０分間スターラーで分散してコート液を調整し、このコート液と芯材を流動床内に回転式底板ディスクと攪拌羽根を設けた旋回流を形成させながらコートを行うコーティング装置に投入して、当該コート液を芯材上に塗布した。得られた塗布物を電気炉で２５０℃、２時間焼成し、上記キャリアを作製した。

(Two-component developer evaluation)
When evaluating an image using a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin with an average thickness of 0.5 μm is used as follows. The developer was uniformly mixed and charged using a tumbler mixer of a type in which the container was rolled and stirred to prepare a developer.
(Carrier production)
・ Core
Mn ferrite particles (weight average diameter: 35 μm): 5,000 parts, coating material: Toluene: 450 parts Silicone resin SR2400 (manufactured by Toray Dow Corning Silicone Co., Ltd., nonvolatile content 50%)
... 450 parts Aminosilane SH6020 (Toray Dow Corning Silicone Co., Ltd.) ... 10 parts Carbon black ... 10 parts The coating material is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and this coating liquid The core material was put into a coating apparatus for coating while forming a swirling flow having a rotating bottom plate disk and a stirring blade provided in the fluidized bed, and the coating liquid was applied onto the core material. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to produce the carrier.

Example 1
-Synthesis of resin fine particle emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 10 parts of polylactic acid, 60 of styrene Parts, 100 parts of methacrylic acid, 70 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to form a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 280 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 59 ° C., and the weight average molecular weight was 60,000.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This was designated as [Aqueous Phase 1].
-Synthesis of amorphous low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 339 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 80 parts adipic acid, 10 parts of acid and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 5 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 mmHg to 15 mmHg, and then 35 parts of trimellitic anhydride were placed in a reaction vessel at 180 ° C. The mixture was reacted at normal pressure for 1 hour to obtain [Amorphous low molecular weight polyester 1]. [Amorphous low molecular weight polyester 1] had a number average molecular weight of 1,800, a weight average molecular weight of 3,500, Tg of 38 ° C., and an acid value of 25 mg KOH / g.

-Synthesis of amorphous intermediate polyester-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 162 parts of terephthalic acid, trimellitic anhydride 122 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 7 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 1400, a weight average molecular weight of 5300, Tg of 40 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g.

  Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight percentage of 1.53%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.
-Synthesis of master batch (MB)-
Add 1200 parts of water, 540 parts of carbon black (PrIintex 35, manufactured by Degussa AG) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], 1200 parts of polyester resin, and add Henschel mixer (former Mitsui Mining Co., Ltd. Manufactured by Kogyo Co., Ltd.), and the mixture was kneaded at 110 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

-Synthesis of crystalline polyester resin-
After putting 1200 parts of 1,6-hexanediol, 1200 parts of decanedioic acid, and 0.4 parts of dibutyltin oxide as a catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, The air in the container was made an inert atmosphere with nitrogen gas by depressurization, and stirring was performed at 180 rpm for 5 hours by mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became viscous, it was air-cooled to stop the reaction to obtain [Crystalline Polyester 1]. [Crystalline Polyester 1] had a number average molecular weight of 3700, a weight average molecular weight of 16000, and a melting point of 69 ° C.

-Creation of oil phase-
178 parts of [Amorphous low molecular weight polyester 1], 120 parts of paraffin WAX (melting point 90 ° C.), 1400 parts of crystalline polyester and 947 parts of ethyl acetate are charged in a container equipped with a stir bar and a thermometer and stirred for 80 The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw Material Solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by IMEX Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / second, and a volume of 0.5 mm zirconia beads of 80 volumes. Carbon black and WAX were dispersed under the conditions of% filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [Amorphous low molecular weight polyester 1] was added, and the mixture was passed through a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

-Emulsification-> Solvent removal-
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 120 parts, [Ketimine Compound 1] 3.5 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 5 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at a rotation speed of 10,000 rpm for 1.5 hours to obtain [Emulsion Slurry 1].

  [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 40 ° C for 72 hours to obtain [Dispersion slurry 1].

−Washing → Drying−
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure, and then washed and dried according to the following procedures (1) to (4).
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake obtained in (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake obtained in (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion exchanged water to the filter cake of (3), mix with a TK homomixer (rotation speed 12,000 rpm for 10 minutes) and then filter twice, and filter cake 1 Obtained.

  [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, sieved with a mesh of 75 μm, [toner base particle 1] was obtained.

  Thereafter, 100 parts of [toner base particle 1] and 1 part of hydrophobized silica having a particle diameter of 13 nm were mixed with a Henschel mixer to obtain a toner. The physical properties of the obtained toner are shown in Table 2, and the evaluation results using the evaluation machine A are shown in Table 3.

(Examples 2 to 8)
In Example 1, it evaluated similarly to Example 1 except having changed the used evaluation machine into G2-G8.
The result evaluated with each evaluation machine was made into Examples 2-8, respectively. The obtained evaluation results are shown in Table 3.

Example 9
A toner was obtained in the same manner as in Example 1 except that the resin fine particle emulsion used in Example 1 was changed as follows. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.
-Synthesis of resin fine particle emulsion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.), 10 parts of polylactic acid, 60 of styrene Parts, 100 parts of methacrylic acid, 70 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 20 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 3 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 65 ° C. for 12 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 2] was obtained. The volume average particle diameter of [fine particle dispersion 2] measured by LA-920 was 390 nm. A portion of [Fine Particle Dispersion 2] was dried to isolate the resin component. The Tg of the resin was 60 ° C., and the weight average molecular weight was 70,000.

(Example 10)
A toner was obtained in the same manner as in Example 1 except that the resin fine particle emulsion and the amorphous low molecular weight polyester used in Example 1 were changed as follows. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

-Synthesis of resin fine particle emulsion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.), 10 parts of polylactic acid, 60 of styrene Parts, 100 parts of methacrylic acid, 70 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 2000 rpm for 20 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 3 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 65 ° C. for 12 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 3] was obtained. The volume average particle diameter of [fine particle dispersion 3] measured by LA-920 was 640 nm. A portion of [Fine Particle Dispersion 3] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 120,000.

-Synthesis of amorphous low molecular weight polyester-
430 parts of bisphenol A propylene oxide 2-mole adduct, 300 parts of propylene oxide 3-mole adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid Then, 10 parts of maleic anhydride and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted for 8 hours while distilling off the generated water under a nitrogen stream at 220 ° C. Subsequently, the pressure was reduced to 5 mmHg to 20 mmHg, and the acid value was 7 mg KOH / g. The acid value was taken out, cooled to room temperature, and pulverized to obtain [Amorphous Low Molecular Polyester 3]. The number average molecular weight was 6,020, the weight average molecular weight was 25,600, Tg was 59 ° C., and the acid value was 8 mg KOH / g.

(Example 11)
A toner was obtained in the same manner as in Example 1 except that the aqueous phase used in Example 1 was changed to the following and that the amorphous low molecular polyester used was changed to the following. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

-Adjustment of aqueous phase-
1,013 parts of water, 60 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries), 90 parts of ethyl acetate After mixing and stirring, a milky white liquid was obtained. This was used as the [aqueous phase].

-Synthesis of amorphous low molecular weight polyester-
430 parts of bisphenol A propylene oxide 2-mole adduct, 300 parts of propylene oxide 3-mole adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid Then, 10 parts of maleic anhydride and 2 parts of titanium dihydroxybis (triethanolaminate) were added as a condensation catalyst, and the reaction was carried out for 8 hours while distilling off the water produced under a nitrogen stream at 220 ° C. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value reached 7 mgKOH / g, the reaction mixture was taken out, cooled to room temperature and pulverized to obtain [Amorphous Low Molecular Polyester 3]. The number average molecular weight was 6,020, the weight average molecular weight was 25,600, Tg was 59 ° C., and the acid value was 8 mg KOH / g.

(Example 12)
A toner was obtained in the same manner as in Example 1 except that the resin fine particle emulsion used in Example 1 was changed as follows. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

-Synthesis of resin fine particle emulsion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 10 parts of polylactic acid, 70 of styrene Parts, 90 parts of methacrylic acid, 60 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The mixture was heated to raise the temperature in the system to 75 ° C. and reacted for 3 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and then an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 4] was obtained. The volume average particle diameter of the [fine particle dispersion 4] measured by LA-920 was 153 nm. A portion of [Fine Particle Dispersion 4] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 15,000.

(Comparative Examples 1-2)
In Example 1, it evaluated similarly to Example 1 except having changed the used evaluation machine into H1 and H2.
The result evaluated with each evaluation machine was set as Comparative Examples 1 and 2, respectively. The obtained evaluation results are shown in Table 3.

(Comparative Example 3)
A toner was obtained in the same manner as in Example 1 except that the resin fine particle emulsion used in Example 1 was changed as follows. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

-Synthesis of resin fine particle emulsion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.), 10 parts of polylactic acid, 60 of styrene Parts, 100 parts of methacrylic acid, 70 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and then an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 5] was obtained. The volume average particle diameter of [fine particle dispersion 5] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 5] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 140,000.

(Comparative Example 4)
A toner was obtained in the same manner as in Example 1 except that the aqueous phase used in Example 1 was changed to the following. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

-Adjustment of aqueous phase-
1,013 parts of water, 60 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether sodium disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This was used as the [aqueous phase].

(Comparative Example 5)
A toner was obtained in the same manner as in Example 1 except that the resin fine particle emulsion used in Example 1 was changed as follows. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

-Synthesis of resin fine particle emulsion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.), 10 parts of polylactic acid, 60 of styrene Parts, 100 parts of methacrylic acid, 70 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 1500 rpm for 20 minutes to obtain a white emulsion. The mixture was heated to raise the temperature in the system to 75 ° C. and reacted for 3 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 65 ° C. for 12 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 6] was obtained. The volume average particle diameter of the [fine particle dispersion 6] measured by LA-920 was 720 nm. A portion of [Fine Particle Dispersion 6] was dried to isolate the resin component. The Tg of the resin was 57 ° C., and the weight average molecular weight was 120,000.

(Comparative Example 6)
A toner was obtained in the same manner as in Example 1 except that the amorphous low molecular weight polyester used in Example 1 was changed to the following. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.
-Synthesis of amorphous low molecular weight polyester-
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of ethylene oxide 2-mole adduct of bisphenol A, 326 parts of propylene oxide 3-mole adduct of bisphenol A, 278 parts of terephthalic acid, phthalic anhydride 40 parts and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 220 ° C. for 8 hours while distilling off the water generated under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 mmHg to 20 mmHg. When the acid value becomes 2 mgKOH / g or less, it is cooled to 180 ° C., 62 parts of trimellitic anhydride is added, and the mixture is reacted for 2 hours under normal pressure sealing and then taken out. The mixture was cooled to room temperature and pulverized to obtain [Amorphous low molecular weight polyester 4]. The number average molecular weight was 4,020, the weight average molecular weight was 93,800, Tg was 68 ° C., and the acid value was 35 mgKOH / g.

(Comparative Example 7)
-Production of crystalline polyester resin-
In a heat-dried three-necked flask, 124 parts of ethylene glycol, 22.2 parts of sodium dimethyl 5-sulfoisophthalate, 213 parts of dimethyl sebacate, and 0.3 part of dibutyltin oxide as a catalyst were added, and then the container was subjected to decompression. The inside air was placed under an inert atmosphere of nitrogen gas, and stirring was performed at 180 ° C. for 5 hours by mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, the mixture was stirred for 2 hours, and when it became viscous, the reaction was stopped by air cooling to synthesize 220 parts of crystalline polyester resin. The number average molecular weight was 5,400, the weight average molecular weight was 9,700, and Tg was 60 ° C.

-Preparation of resin particle dispersion-
150 parts of the above-mentioned crystalline polyester resin was put into 850 parts of distilled water and mixed and stirred with a homogenizer (manufactured by IKA Japan, Ultra Tarax) while heating to 85 ° C. to obtain a resin particle dispersion.

-Preparation of amorphous polymer dispersion (B)-
The amorphous polymer dispersion (B) was prepared as follows. That is, in a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, 50 mol of terephthalic acid as an acid component, 50 mol of isophthalic acid and 60 mol of bisphenol A ethylene oxide 2 mol adduct as an alcohol component, ethylene glycol 40 mol was added, and the inside of the reaction vessel was replaced with dry nitrogen gas, 0.04 mol of dibutyltin oxide was added, and the mixture was allowed to stir at about 195 ° C. for about 6 hours under a nitrogen gas stream. After raising the temperature to 0 ° C. and allowing the reaction to stir for about 6.0 hours, the pressure in the reaction vessel was reduced to 10.0 mmHg and the reaction was allowed to stir for about 0.5 hours under reduced pressure to obtain a polyester resin. Tg was 64 ° C., the weight average molecular weight was 19,000, the number average molecular weight was 5,000, and the acid value was 16 mgKOH / g.

Subsequently, the obtained amorphous polymer was dispersed using a disperser in which Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) was modified to a high temperature and high pressure type. The composition ratio is 80% by weight of ion-exchanged water and the concentration of amorphous polyester resin is 20% by weight. The pH is adjusted to 8.5 with ammonia, the rotational speed of the rotor is 60 Hz, the pressure is 5 kg / cm ² , the heat The Cavitron was operated under the conditions of heating at 140 ° C. using an exchanger to obtain an amorphous polymer dispersion (B). An amorphous polyester polymer dispersion (B) having a volume average particle size of 150 nm was prepared.

-Preparation of amorphous polymer dispersion (C)-
[Production of resin particles]
· Styrene · · · 200 parts · Methyl methacrylate · · 120 parts · n-butyl acrylate · · · 40 parts · Acrylic acid · · · 4 parts · Dodecanethiol · · 24 parts · Carbon tetrabromide · · · 4 parts The above raw material components were mixed and dissolved, and 6 parts of a nonionic surfactant (Sanyo Kasei Kogyo Co., Ltd., Nonipol 400) and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen) SC) Disperse and emulsify 10 parts in ion exchanged water 560 parts in a flask, mix slowly for 10 minutes, and add 50 parts of ion exchanged water in which 4 parts of ammonium persulfate is dissolved. After nitrogen substitution, the contents in the flask were heated with an oil bath until the contents reached 70 ° C. while stirring, and emulsion polymerization was continued for 5 hours. In this way, an amorphous polymer dispersion (C) in which resin particles having a volume average particle diameter of 180 nm, a glass transition point of 73 ° C., a weight average molecular weight of 15,000, and a number average molecular weight of 7,000 are dispersed. Resin particle concentration 40 mass%) was prepared.

-Preparation of colorant dispersion (2)-
After mixing and dissolving 250 parts of a cyan pigment (Daiichi Seika Kogyo Co., Ltd., ECB-301), 20 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK), and 730 parts of ion-exchanged water. Then, a colorant dispersion (2) was prepared by dispersing using a homogenizer (Ultra Tarax, manufactured by IKA Japan Co., Ltd.) and dispersing a colorant (cyan pigment).

-Preparation of release agent dispersion-
A release agent (paraffin wax, melting point 90 ° C.) 350 parts, an anionic surfactant 15 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and ion-exchanged water 635 parts are mixed, and 90 ° C. on a water bath. The mixture was dispersed using a homogenizer (manufactured by IKA Japan Co., Ltd., Ultra Tarax) while being heated to prepare a release agent dispersion.

-Preparation of toner-
-Resin particle dispersion (2) ... 680 parts-Polyester amorphous polymer dispersion (B) (Tg 66.0 ° C, weight average molecular weight 9,000, number average molecular weight 4,000, solid content concentration 30%) ... 340 Part / resin dispersion (A)-(a)
(Superester NS100H (trade name, Tg 61.7 ° C., weight average molecular weight 1,800, number average molecular weight 1,400, manufactured by Arakawa Chemical Industries, Ltd.) 120 parts / colorant dispersion (2) 52 parts, release agent dispersion liquid: 66 parts The above dispersion liquid is mixed, and further 5 parts of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 650 parts of ion-exchanged water, and further polyester amorphous high After adding 340 parts of the molecular dispersant (B) and placing it in a round stainless steel flask, the mixture was heated to 60 ° C. with stirring in an oil bath for heating, held at 60 ° C. for 3 hours, and then subjected to an optical microscope. It was confirmed that aggregated particles having a volume average particle diameter of about 5.0 μm were formed, and the mixture was further heated and stirred at 60 ° C. for 1 hour and then observed with an optical microscope. The average particle size is about 5. It was confirmed that aggregated particles having a size of 5 μm were formed.

  The pH of this aggregated particle dispersion was 3.8. Accordingly, an aqueous solution obtained by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by mass was gently added to adjust the pH to 5.0. The aggregated particle dispersion was heated to 80 ° C. and kept for 30 minutes while continuing to stir, and then observed with an optical microscope, and coalesced spherical particles were observed. Thereafter, the temperature was lowered to 30 ° C. at a rate of 1 ° C./min while adding ion-exchanged water to solidify the particles.

  Thereafter, the obtained reaction product was filtered, washed with 2000 parts of ion-exchanged water, and filtered again to obtain 560 parts of a toner cake of SC 50% core particles 1.

  After putting the toner cake of core particles 1 into a 3 L flask, 100 parts of amorphous polymer dispersion (C) was added and stirring was started. After 10 minutes, 250 g of ion-exchanged water was added so that the solid content was 35%, and then the pH was adjusted to 3.0 by gradually adding a 0.3 mol / L nitric acid aqueous solution. After 30 minutes, 0.28 parts of polyaluminum chloride was added, and after another 30 minutes, the temperature was raised to 48 ° C. at a rate of 0.5 ° C./1 minute. After 2 hours at 48 ° C, the temperature was raised to 57 ° C at a rate of 0.1 ° C / 1 minute. Since the pH at this time was 7.3, the pH was adjusted to 7.5 by gradually adding a 0.5 mol / L aqueous sodium hydroxide solution, and heating was continued for 10 hours. After 10 hours, it was confirmed by electron microscope (SEM) photography that a coating layer of attached particles was formed on the surface of the core particles, and then the temperature was lowered to 20 ° C. in 30 minutes.

After cooling, the reaction product was filtered, sufficiently washed with ion exchange water, and then dried using a vacuum dryer to obtain colored particles.
100 parts of colored particles and 1 part of hydrophobized silica having a particle diameter of 13 nm were mixed with a Henschel mixer to obtain a toner. The physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

（評価項目）
−高温高湿環境下での定着画像保持性評価−
得られた二成分現像剤と各評価機を用いて温度４５℃、湿度８０％の高温高湿環境下にて、３％画像面積チャートを１０,０００枚出力した後、画像出しをし、定着画像保持性を測定した。転写紙はリコーフルカラーＰＰＣ用紙タイプ６２００を用いた。

(Evaluation item)
-Evaluation of fixed image retention in high temperature and high humidity environment-
Using the obtained two-component developer and each evaluation machine, in a high-temperature and high-humidity environment at a temperature of 45 ° C. and a humidity of 80%, output 10,000 sheets of a 3% image area chart, and then image and fix. Image retention was measured. Ricoh full color PPC paper type 6200 was used as the transfer paper.

  A print image having an image density of 1.2 by X-Rite 938 was output to obtain a fixed image. The obtained image was rubbed 50 times with a clock meter equipped with a sand eraser, and the image density before and after that was measured. Fixing retention was determined by the following formula.

Fixing retention (%) = [(image density after 10 times of sand eraser) / (previous image density)] × 100
[Criteria]
A: Fixing retention is 80% or more, which is very excellent.

    ○: Excellent fixing retention is 70% or more and less than 80%.

Δ: Fixation retention is 60% or more and less than 70%, and minimum retention is ×: Fixation retention is less than 60%.

-Evaluation of carrier spent property under high temperature and high humidity environment-
Using the obtained two-component developer and each evaluation machine, 100,000 sheets of a 20% image area chart were output in a high temperature and high humidity environment at a temperature of 45 ° C. and a humidity of 80%. Thereafter, the developer was taken out, and the developer was put into a cylindrical cage with metal meshes at both ends. The toner was detached from the developer with high-pressure air, and only the carrier was collected. The spent property of the obtained carrier was evaluated from the cross section of the carrier. After embedding the carrier in a resin, a cross section of the carrier is created by a cross section polisher (manufactured by JEOL Ltd., IB-09010CP), and spent by FE-SEM (scanning electron microscope, Ultra 55, Carl Zeiss NTS GmbH). Objects were evaluated for observation. The cut carrier 10 particles were selected at random, and the spent layer thickness was analyzed by image processing software, and the spent property was evaluated as follows.

[Criteria]
A: The spent layer cannot be observed.

○: Spent layer thickness of 100 nm or less Δ: Spent layer thickness of 100 nm or more and 200 nm or less ×: Spent layer thickness of more than 200 nm −Evaluation of toner adhesion to a fixing member in a high temperature and high humidity environment−
Using the obtained two-component developer and each evaluation machine, after outputting 10,000 sheets of a 3% image area chart in a high temperature and high humidity environment at a temperature of 45 ° C. and a humidity of 80%, the image is output and fixed. The toner adhesion to the member was evaluated. Ricoh full color PPC paper type 6200 was used as the transfer paper.

  An image with an image density of 1.2 by X-Rite 938 was output, and the toner adhesion to the fixing member was evaluated based on the presence or absence of an offset image generated at the second week position in the cycle corresponding to the fixing roll diameter. .

[Criteria]
(Double-circle): There is no toner adhesion and it is very excellent.

    ◯: Although toner adhesion cannot be confirmed on the image, slight toner adhesion can be confirmed on the fixing member.

    Δ: Slight toner adhesion can be confirmed on the image.

    X: The toner adheres clearly on the image and is inferior.

a charging unit b photosensitive member c charging unit d developing unit e cleaning unit s sheet t image forming apparatus 1 photosensitive member 2 transfer device 3 sheet conveying belt 4 intermediate transfer member 5 secondary transfer device 6 paper feeding device 7 fixing device 8 photosensitive member Cleaning device 9 Intermediate cleaning device 100 Transfer device body 200 Paper feed table 300 Scanner 400 Automatic document feeder

JP 2006-267231 A

Claims (8)

A core comprising a crystalline polyester, an amorphous polyester, a core containing a colorant and a release agent, and a shell containing a vinyl resin;
The thermal hardness is 0.5 or more and 2.5 or less,
A toner having a softening index of 40 ° C. or higher and 79 ° C. or lower.   The toner according to claim 1, wherein the toner has a shell layer thickness of 0.01 μm to 2 μm.   At least a solution obtained by dissolving or dispersing the crystalline polyester, a polyester prepolymer having an isocyanate group, a compound having an amino group, a colorant and a material containing a release agent in an organic solvent, the particles of the vinyl resin. The toner according to claim 1, wherein the toner is formed by emulsifying or dispersing in an aqueous medium containing the organic solvent, and then removing the organic solvent.   The toner according to claim 1, wherein the average circularity E is 0.93 to 0.99.   The toner according to claim 1, wherein the shape factor SF-1 value is 100 to 150 and the shape factor SF-2 value is 100 to 140.   6. The weight average particle diameter D4 is 2 to 7 μm, and the ratio D4 / Dn of the weight average particle diameter D4 and the number average particle diameter Dn is 1.00 or more and 1.25 or less. The toner according to any one of the above.   A two-component developer comprising at least the toner according to claim 1 and at least a carrier having magnetism. Using an image forming apparatus including a fixing device for fixing the pressure of a visible image on a recording medium at least ^{30N / cm 2 ~4000N / cm 2} , the image forming method using the developer according to claim 7 .

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