JP2011048159A - Toner and image forming method - Google Patents

Abstract

The present invention provides a toner capable of forming a high-quality toner image excellent in environmental stability, member contamination, and development durability.
[Solution]
A toner having a toner particle containing at least a binder resin and a colorant and a metal oxide, the metal oxide having an adsorption moisture amount at a relative humidity of 10% RH on a moisture adsorption isotherm at 30 ° C. (Mass%), when the amount of adsorbed moisture at a relative humidity of 90% RH is M90 (mass%), (M90-M10) / (90-10) is 0.0001 or more and 0.0070 or less, and When the wettability with respect to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, the methanol concentration when the transmittance is 50% is 40.0% by volume or less.
[Selection] Figure 1

Description

  The present invention relates to a toner and an image forming method for developing an electrostatic image used in an image forming method such as electrophotography and electrostatic printing.

  Temperature and humidity have a great influence on the fluctuation of the toner charge amount, and one of the causes is the amount of moisture adsorbed on the surface of the toner and the member. Since surface adsorbed moisture lowers the chargeability of toner and external additives used for toner surface treatment, stable surface adsorbed water content is an effective index to improve environmental stability in a wide range of environments. Become.

  Further, in the examination for evaluating the surface property of the toner, the wettability of the external additive used for the treatment of the toner or the toner surface with respect to the mixed solvent is an effective index.

  As a toner in which the material present in the toner particles is uniform, a magnetic toner that defines the transmittance and molecular weight in wettability with respect to a mixed solvent of water and methanol is disclosed (see Patent Document 1).

  However, the toner has some problems as a toner excellent in low-temperature fixability, environmental stability, and durability that are currently required.

  In addition, in a toner having inorganic fine particles as an external additive on the toner particle surface, a toner is disclosed in which the difference between the wettability of toner particles without the inorganic fine particles to water and the wettability of the toner to water is defined (patent) Reference 2).

  However, the toner is contaminated with components such as an anti-static roller, a photosensitive drum and a developing roller due to embedding external additives in a high-speed system, and there are some problems as a toner excellent in low-temperature fixability, environmental stability, and development durability. Have

  Furthermore, a toner having fine alumina powder on the surface of the toner particles is disclosed in which the CuKα characteristic X-ray diffraction and the isothermal adsorption moisture amount of the fine alumina powder are defined (see Patent Document 3).

  However, the amount of moisture adsorbed by the toner due to the relative humidity fluctuation is large, and there are some problems as a toner excellent in environmental stability such as member contamination and density fluctuation due to toner charge amount change.

JP 2002-278147 A JP 2003-202700 A JP 2008-145489 A

An object of the present invention is to provide a toner and an image forming method that solve the above problems. More specifically, the amount of moisture adsorbed on the surface is stable even in a wide range of environments, and by adding a metal oxide having specific methanol wettability, it has high environmental stability, component contamination, and development durability. An object of the present invention is to provide a toner capable of forming a high-quality toner image and an image forming method.

In order to achieve the above object, an invention according to the present application is a toner having toner particles containing at least a binder resin and a colorant and a metal oxide, wherein the metal oxide has a moisture adsorption measured at 30 ° C. On the isotherm, when the amount of adsorbed water at a relative humidity of 10% RH is M10 (mass%) and the amount of adsorbed water at a relative humidity of 90% RH is M90 (mass%), (M90-M10) /
(90-10) is 0.0001 or more and 0.0070 or less, and when the wettability with respect to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, the transmittance is 50%. The methanol concentration is 40.0% by volume or less.

  According to the present invention, by specifying the wettability of the metal oxide moisture adsorption isotherm and the mixed solvent of the metal oxide with methanol and water, it has high environmental stability, component contamination, and development durability. A toner capable of forming a high-quality toner image and an image forming method can be provided.

It is a figure which shows an example of the moisture adsorption isotherm of a metal oxide. It is a figure which shows the molecular weight distribution measured by GPC of the THF soluble part of a toner. In FIG. 2, it is a figure which shows molecular weight distribution when converting the height of a peak into h (M1) [mV] = 1.00. In FIG. 3, the integrated values S1, S2, and S3 of three molecular weight regions are shown. It is a figure which shows the reversing heat flow curve measured by the differential scanning calorimeter (DSC) of the toner. It is a schematic diagram which shows an example of the preferable image development apparatus used for the image forming method. FIG. 2 is a schematic configuration diagram illustrating an example of a process cartridge and an image forming apparatus.

  Hereinafter, the present invention will be described in detail. The present invention is a toner having toner particles containing at least a binder resin and a colorant and a metal oxide, and is characterized by the metal oxide. In the present invention, in the examination for evaluating the surface property of the metal oxide, the moisture adsorption isotherm of the metal oxide and the wettability of the metal oxide with respect to the mixed solvent of methanol and water are measured. The amount of moisture adsorbed on the surface per 1% relative humidity of the metal oxide indicates the degree of moisture adsorption / desorption. When the moisture adsorption / desorption degree of the metal oxide is small in environmental fluctuations, that is, under low and high humidity, the metal oxide exhibits particularly excellent performance in charging stability and component contamination. On the other hand, because the wettability (precipitation degree) of the metal oxide to the mixed solvent of methanol and water is easy to wet, the original performance of the metal oxide surface is sufficiently exhibited, the charging characteristics of the toner are stabilized, the environmental stability, Excellent performance in component contamination and development durability.

The graph of the moisture adsorption isotherm of the metal oxide in the present invention is shown in FIG. In the moisture adsorption isotherm measured at 30 ° C., the metal oxide of the present invention has an adsorption moisture amount of M10 (mass%) at a relative humidity of 10% RH, and an adsorption moisture quantity of 90% relative humidity at an M90 (mass%). ), (M90-M10) / (90-10) is 0.0001 or more and 0.0070 or less. (M9
0-M10) / (90-10) represents the adsorbed moisture content of the metal oxide with respect to 1% relative humidity. When (M90-M10) / (90-10) is 0.0001 or more and 0.0070 or less, performance excellent in environmental stability, development durability, member contamination, and stop stripes is exhibited. More preferably, (M90-M10) / (90-10) is 0.0001 or more and 0.0050 or less. When (M90-M10) / (90-10) is 0.0001 or more and 0.0050 or less, it shows excellent performance in member contamination, particularly development streaks, under high temperature and high humidity. More preferably, (M90-M10) / (90-10) is 0.0001 or more and 0.0040 or less. Excellent performance in fog and component contamination under high temperature and high humidity.
When (M90-M10) / (90-10) is smaller than 0.0001, the chargeability tends to be excessive in a low temperature environment, and the development durability is deteriorated. (M90-M10) / (9
When 0-10) is larger than 0.0070, fog and member contamination are deteriorated in a high humidity environment.

  The method for measuring the moisture adsorption isotherm of the metal oxide in the present invention will be described later. The reason why the moisture adsorption isotherm was measured under the condition of 30 ° C. in the present invention is that the moisture adsorption isotherm is highly dependent on the relative humidity and less temperature dependent. Therefore, the measurement was performed in an atmosphere of 30 ° C. where the stability of the moisture adsorption amount measuring apparatus was the best. In addition, the reason why the surface adsorbed water amount per 1% relative humidity was measured by the values of 10% and 90% relative humidity on the moisture adsorption isotherm of the metal oxide in the present invention is that the relative humidity is 1% in a wide range of humidity environments. This is to show the amount of moisture adsorbed on the surface. In particular, the rate of change in the amount of moisture adsorbed on the surface often increases from a relative humidity of 20% or less and a relative humidity of 80% or more. Therefore, evaluation was performed with numerical values of 10% relative humidity, which is an average value of 0 to 20% relative humidity, and 90% relative humidity, which is an average value of 80% to 100% relative humidity.

In the present invention, the value of (M90-M10) / (90-10) of the metal oxide is determined by repeating the treatment in a high oxygen state or the high temperature treatment step on the surface of the metal oxide, the unmodified silicone varnish, or various modifications. It is adjusted by a surface treatment agent such as silicone varnish, unmodified silicone oil, various modified silicone oils, silane compounds, and silane coupling agents.

  Next, the methanol wettability of the metal oxide of the present invention will be described. When the wettability of a metal oxide to a mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, the region where the transmittance exceeds 90% indicates that the metal oxide is hardly wetted with methanol. The region where the transmittance is lower than 10% indicates that the metal oxide is almost completely wetted. And the area | region whose transmittance | permeability is 50% represents that the metal oxide is wetted with methanol on average. The metal oxide of the present invention has a methanol concentration of 40.0 vol. When the transmittance is 50% when the wettability of the metal oxide to a mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm. % Or less. By setting the methanol concentration when the transmittance is 50% to 40.0% by volume or less, the charging characteristics of the toner are stabilized, and stop streaks, filming, fogging, member contamination, and image density are improved. More preferably, it is 20.0 volume% or less. By making it 20.0 vol% or less, stop streaks and filming under high temperature and high humidity are improved. More preferably, it is 10.0 volume% or less. By making it 10.0% by volume or less, stop streaks, filming, and member contamination under high temperature and high humidity are further improved. When it is larger than 40.0% by volume, the image density is lowered.

  The metal oxide satisfying the above methanol concentration shows that most of the particles are easily wetted at a low methanol concentration as defined in the present invention, and the metal oxide is treated with an oil or a silane coupling agent. It is an indicator to show that. Since the surface treatment of the metal oxide is very small, the charging characteristics of the toner are stabilized, and a toner excellent in environmental stability, development durability, and member contamination can be obtained.

  In the present invention, the methanol wettability of the metal oxide is determined by adding a surface treatment agent such as a modified or unmodified silicone varnish, a modified or unmodified silicone oil, a silane compound, and a silane coupling agent to the metal oxide. Can be adjusted. In addition, the measuring method of the wettability in this invention is mentioned later.

  As described above, the rate of change in the amount of adsorbed water per 1% relative humidity on the adsorbed water isotherm is small, so that the toner slides between the regulating blade and the toner carrier, and between the toner carrier and the toner supply roller even in a wide range of environments. Even if it is rubbed and charged, the charge removal due to moisture can be reduced. Furthermore, the surface treatment of metal oxides with surface treatment agents such as oil and silane coupling agents is extremely small or not, so that environmental stability and components over a long period of time are not affected by the surface treatment agent performance and durability. The metal oxide surface performance of excellent contamination is exhibited, and a stable high-quality image can be obtained.

  In the present invention, when the metal oxide is surface-treated, the content of unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, and various modified silicone oils per 100 parts by mass of the metal oxide is 2.0 mass. Part or less is preferred. If it is larger than 2.0 parts by mass, the member contamination, image density, stop streaks, filming and fogging over a long period tend to deteriorate. Preferably it is 1.0 mass part or less, More preferably, it is 0.1 mass part or less. Component contamination is further improved.

  Further, the content of the silane compound and the silane coupling agent per 100 parts by mass of the metal oxide is preferably 10.0 parts by mass or less. When it is larger than 10.0 parts by mass, image density, stop streaks, filming, and fog over a long period tend to deteriorate. Preferably it is 5.0 mass parts or less, More preferably, it is 2.0 mass parts or less. Component contamination is further improved.

  When the surface is treated with a large amount of the surface treatment agent, the surface treatment agent on the surface of the metal oxide is continuously rubbed on the surface of the member such as a developing roller, a toner supply roller, and a regulating blade. Decreases and the metal oxide or toner is fused to the surface of the member. For example, if the toner is fused to the surface of the developing roller, the chargeability of the toner is hindered, causing problems such as image fogging and streak images.

  In the present invention, the zeta potential (mV) in the zeta potential measurement in a state where the metal oxide is dispersed in methanol is preferably -10.0 mV or more and 60.0 mV or less. If it is smaller than -10.0, charging under low humidity becomes excessive, and there is a tendency that image density is lowered and poor regulation tends to occur. Moreover, when it is larger than 60.0 mV, fog and density reduction are likely to occur in a high humidity environment. Preferably they are 0.0 mV or more and 40.0 mV or less, More preferably, they are 0.0 mV or more and 35.0 mV or less.

  The zeta potential (mV) of the metal oxide in methanol in the present invention is determined by repeating the treatment of the metal oxide in a high oxygen state or the high temperature treatment step on the surface of the metal oxide, or the unmodified silicone varnish or various modified silicone varnishes. It is adjusted by a surface treatment agent such as unmodified silicone oil, various modified silicone oils, silane compounds, and silane coupling agents. A method for measuring the zeta potential in the present invention will be described later.

  The metal oxide of the present invention preferably has an adsorption moisture amount of 0.60% by mass or less at a relative humidity of 90% RH in a moisture adsorption isotherm at a temperature of 30 ° C. When it is larger than 0.60% by mass, contamination of members such as fogging and development streaks tends to occur under high humidity. Preferably it is 0.40 mass% or less, More preferably, it is 0.30 mass% or less. Although a lower limit is not specifically limited, It is preferable that it is 0.10 mass% or more.

  In the moisture adsorption isotherm at a temperature of 30 ° C. of the metal oxide, the amount of moisture adsorbed at a relative humidity of 90% RH is determined by repeating the treatment of the metal oxide in a high oxygen state or the high temperature treatment process on the surface of the metal oxide. It is adjusted by a surface treatment agent such as unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, and silane coupling agents.

  In the present invention, the volume-based median diameter (D50) in a laser diffraction particle size distribution meter measured in metal oxide water is preferably 0.10 μm or more and 1.00 μm or less. If the volume-based median diameter is smaller than 0.10 μm, fog and image density fluctuation tend to occur. On the contrary, when it exceeds 1.00 μm, the metal oxide tends to be present unevenly on the surface of the toner particles, so that the member contamination tends to occur.

  The median diameter (D50) of the metal oxide can be adjusted by the flow rate of an inert gas when the metal oxide is produced by a vapor phase oxidation method.

  The content of the metal oxide used in the present invention is preferably 0.05 to 2.00 parts by mass, more preferably 0.10 to 1.00 parts by mass with respect to 100 parts by mass of the toner particles. It is. When the content of the metal oxide is larger than 2.00 parts by mass, the charge balance of the toner is lost and the density tends to decrease. In addition, when the content of the metal oxide is less than 0.01 parts by mass, the amount of addition to the toner decreases, and the metal oxide effect may not be obtained.

  In the present invention, the average circularity with an equivalent circle diameter of 0.80 μm or more and 1.98 μm or less measured by a metal oxide flow particle image analyzer is preferably 0.950 or more and 1.000 or less. If the average circularity is 0.950 or less, the rolling property is poor and the stagnation tends to occur, so that member contamination tends to occur. The average circularity or mode circularity can be adjusted by, for example, a hybridization system (manufactured by Nara Machinery Co., Ltd.).

  In the present invention, the method for producing the metal oxide is not particularly limited as long as it has a desired amount of moisture adsorbed on the surface and wettability, but it is preferably produced by a gas phase oxidation method. Products manufactured by methods other than the vapor phase oxidation method have many functional groups such as hydroxyl groups and alkoxy groups on the metal oxide surface, or become porous, so that many surface treatment agents are required, and component contamination tends to deteriorate. It is in. Further, conventional oxide production methods such as the Bayer method, the alkoxide pyrolysis method, and the alum pyrolysis method tend to have a large number of pores and a non-uniform surface.

  In the present invention, as a result of examining a production method with few surface pores and few surface functional groups, it was preferable to use a gas phase oxidation method in which a metal oxide was obtained by directly oxidizing a metal with oxygen in the gas phase. A preferred metal oxide according to the present invention can be obtained by directly oxidizing the metal oxide with oxygen. More preferably, a gas phase oxidation method is used in which a metal is directly oxidized with oxygen under high concentration oxygen to obtain a metal oxide.

  In particular, in order to obtain the metal oxide according to the present invention, there is a manufacturing method in which the metal oxide is transported into a combustion flame formed in a reaction furnace with an inert gas as a transport medium, and the metal oxide is combusted and oxidized. Preferably used. Examples of the inert gas include nitrogen gas, argon gas, helium gas, neon gas, and the like.

In the gas phase oxidation method, the inside of the reaction system can be instantaneously brought to the melting point of the metal oxide or more, and the surface pores can be reduced. In the gas phase oxidation reaction, it is possible to reduce the number of reactive functional groups in which the reaction proceeds instantaneously, and further, high oxygen and high LPG (Liquid petr).
moisture adsorption amount per 1% of relative humidity, which is a feature of the present invention, by direct oxidation in the state of oleum gas) or polycondensation treatment of the surface of the metal oxide with a polycondensation catalyst such as combustion oxidation or acid-base. It is considered that a metal oxide having a small amount of surface pores can be obtained. The fine pore state and particle size are adjusted by changing the flow rate of the inert gas supplying the metal oxide or the supply amount of the metal oxide.

In the present invention, the volume resistivity of the metal oxide is preferably 1 × 10 ⁶ Ω · cm or more and 1 × 10 ¹³ Ω · cm or less. When it exceeds 1 × 10 ¹³ Ω · cm, the chargeability under low humidity becomes excessive, and the image density tends to be lowered. If it is less than 1 × 10 ⁶ Ω · cm, the toner charge is likely to leak to the member under high humidity, and fog and image density reduction are likely to occur. More preferably, it is 1 × 10 ⁷ Ω · cm or more and 1 × 10 ¹⁰ Ω · cm or less. The low product specific resistance of the metal oxide can be adjusted by the metal species and the surface treatment agent.

  Aluminum, titanium, zirconium, strontium titanate, magnesium titanate, barium titanate, or the like can be used as the main metal species forming the metal oxide. Of these, aluminum and titanium are preferably used in order to keep the chargeability of the toner within an appropriate range throughout the durability. In addition to the main metal species, other metal species may be included. At this time, it is preferable that the element ratio of the main metal species and the other metal species group, that is, the proportion of other metals in the entire metal is less than 30%.

  Preferred metal oxides are aluminum oxide, titanium oxide, zirconium oxide, strontium titanate, magnesium titanate and barium titanate, including at least one selected from these groups, and most preferred is oxidation Aluminum and titanium oxide. Fog, member contamination, and image density are improved.

  Further, in the toner of the present invention, in the endothermic chart measured by differential scanning calorimetry (DSC), the heat amount integral value Q represented by the endothermic area in the range of 40 to 130 ° C. is 10 to 35 J per 1 g of toner. Is preferred. In the present invention, the endothermic area can be adjusted by the wax species and the amount of wax.

  The metal oxide of the present invention is characterized by having a specific methanol wettability under a specific condition and having a water change amount per 1% of relative humidity in a water adsorption isotherm within a specific range. The toner containing such a metal oxide preferably has a heat quantity integral value Q represented by an endothermic area in the range of 40 to 130 ° C. in the endothermic chart of DSC measurement of 10 to 35 J per 1 g of toner. By setting the heat quantity integral value Q to 10 to 35 J per gram of toner, good releasability can be exhibited even at low temperature fixing. Further, when wax is added to the toner, the intermolecular force between the polymer chains of the binder resin is moderately relaxed, and softening of the toner due to heat absorption during fixing and curing of the resin due to heat dissipation of the toner form an appropriate state. be able to. The heat quantity integral value Q represented by the endothermic area can be adjusted by appropriately selecting the type of wax, its content, and the like. A method for calculating the heat quantity integral value Q will be described later. The heat quantity integral value Q is more preferably 15 to 35 J per 1 g of toner.

  When the heat quantity integral value Q represented by the endothermic area is less than 10 J per 1 g of toner, the fixability tends to deteriorate and the gloss of the fixed image tends to be low. The suppression is not expected. On the other hand, if the heat quantity integral value Q represented by the endothermic area exceeds 35 J per gram of toner, the plastic effect of the wax becomes too great and the offset resistance tends to deteriorate.

  The toner of the present invention preferably has a viscosity at 100 ° C. of 3,000 to 40,000 Pa · s, more preferably 5,000 to 30,000 Pa · s, as measured by a constant load extrusion type capillary rheometer. The value of the viscosity of the toner by the constant load extrusion type capillary rheometer in the present invention is determined by the following method.

As an apparatus, for example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: About 1.0 g of toner is weighed, and this is applied for 1 minute with a load of 100 kg / cm ^2.
A sample is molded using an intermediate pressure molding machine.
-Die hole diameter: 1.0 mm
-Die length: 1.0 mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
・ Measurement mode: Temperature rising method ・ Temperature rising speed: 4.0 ° C./min
By the above method, the viscosity (Pa · s) of the toner at 50 to 200 ° C. is measured to obtain the viscosity (Pa · s) at 100 ° C. The value obtained here is the viscosity at 100 ° C. in the capillary rheometer measurement of the toner constant load extrusion method.

  By setting the viscosity at 100 ° C. in the above-described constant load extrusion type capillary rheometer measurement to 3,000 to 40,000 Pa · s, more preferably 5,000 to 30,000 Pa · s, low temperature fixability and image gloss can be obtained. An image excellent in low temperature fixability is obtained. If it is less than 3000 Pa · s, the gloss decreases due to the penetration of the toner into the medium, which is not preferable. Specifically, with use over a long period of time, the inorganic fine powder added as an external additive is buried in the surface of the toner particles, or the toner particles are deformed and the triboelectric charging characteristics become non-uniform. For this reason, a phenomenon in which toner adheres to the non-image area on the transfer material (hereinafter referred to as fogging) tends to occur, which is not preferable. If it is higher than 40,000 Pa · s, the toner particles cannot be sufficiently deformed during the fixing step in high-speed and low-temperature printing, and the toner image tends to be peeled off when the surface of the fixed image is rubbed. In the present invention, the 100 ° C. viscosity measured by a constant load extrusion type capillary rheometer can be adjusted by the amount of the low molecular weight resin, the monomer type at the time of producing the binder resin, the amount of the initiator, the reaction temperature and the reaction time. it can.

  The viscosity at 100 ° C. is related to the toner fixing property (gross). By reducing the viscosity change due to the temperature change, it is possible to reduce the gloss unevenness due to the temperature change of the fixing device and the environmental change during use such as temperature and humidity.

  Preferred ranges for the molecular weight distribution of the tetrahydrofuran (THF) soluble component of the toner in the present invention will be described below.

<GPC-RI (gel permeation chromatography-refractometer) measurement>
Examples of molecular weight distribution charts measured for the tetrahydrofuran (THF) soluble content of the toner in the present invention are shown in FIGS.

  In the molecular weight distribution chart measured by GPC of the tetrahydrofuran (THF) soluble part of the toner, the molecular weight at the main peak p (M1) is M1, and the height at that time is h (M1) [mV]. The molecular weight distribution is shown in FIG. Here, h (4,000) represents the height at a molecular weight of 4,000.

FIG. 3 shows a molecular weight distribution chart when the height is converted into h (M1) [mV] = 100 in the molecular weight distribution chart measured by GPC of the THF soluble portion of the toner shown in FIG. .
In FIG. 3, the height at the main peak P (M1) is indicated by H (M1) (the molecular weight at the main peak is M1). In FIG. 3, the height at a molecular weight of 4,000 is indicated by H (4,000).
FIG. 4 shows the same molecular weight distribution chart as FIG. 3, where S1 is the integral value of the region having a molecular weight of 500 to 2,500, S2 is the integral value of the region having the molecular weight of 2,500 to 15,000. The integrated value in the region of 15,000 to 1,000,000 is indicated by S3.
The toner satisfying the molecular weight distribution defined by the present invention as shown in FIGS. 2 to 4 has the effects described below.

In the chart of molecular weight distribution measured by GPC of the THF soluble content of the toner, the toner containing a component having a molecular weight of 4,000 to 15,000 is effective for low-temperature fixability and has a low melt viscosity. A high gloss image can be obtained.
Here, it is preferable that H (4,000) and H (M1) satisfy H (4,000): H (M1) = (0.100 to 0.950): 1.00. When H (4,000) is less than 0.100 with respect to H (M1), the low-temperature fixability is deteriorated. In particular, when H (4,000) is less than 0.100 with respect to H (M1), it means that the amount of low molecular weight components effective for improving gloss is small, and gloss is reduced. There is a tendency. Moreover, when H (4,000) exceeds 0.950 with respect to H (M1), offset resistance deteriorates, which is not preferable. Further, H (4,000): H (M1) = (0.200 to 0.750): 1.00 is preferable. In the present invention, the value of H (4000) and the value of H (M1) can be adjusted by the amount of low molecular weight resin, the amount of initiator at the time of producing the binder resin, the reaction temperature, and the reaction time.

  In the present invention, in the molecular weight distribution chart measured by GPC of the THF soluble content in the toner, the integrated value (S1) in the region where the molecular weight is 300 to 2,000 and the molecular weight 2,000 to 15, The ratio of the integral value (S2) in the region of 1,000 to the integral value (S3) in the region of molecular weight 15,000 to 1,000,000 is S1: S2: S3 = (0.01 to 0.95): 1. 00: (1.00 to 8.00) is preferable. Since S1: S2: S3 = (0.01 to 0.95): 1.00: (1.00 to 8.00), the components contained in the toner are contained in a well-balanced state. Further improvement in fixing property, offset resistance and high gloss of a fixed image can be achieved.

  When S2 is 1.00 and S1 is less than 0.01 or S3 exceeds 8.00, the low-temperature fixability may be deteriorated. On the contrary, S1 exceeds 0.95. When S3 is less than 1.00, the offset resistance may deteriorate.

  In the present invention, a charge control agent can be used at the time of toner production, and a known one can be used as the charge control agent. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and their metal compounds. Other examples include resin charge control agents.

  Examples of toners that are positively charged include the following. Modified products of nigrosine by nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and lake pigments thereof Triphenylmethane dyes and lake pigments thereof; metal salts of higher fatty acids; resin-based charge control agents.

Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.
The addition amount of these charge control agents is preferably 0.01 to 10.00% by mass with respect to the binder resin or polymerizable monomer.

Furthermore, in order to fully exhibit the effects of the present invention, it is preferable to contain a sulfur element-containing polymer as a charge control agent. The dispersion of the colorant is stabilized by the polarity of the sulfur element-containing polymer, the uniformity of the toner surface state is further improved, and a stable image density can be obtained.
Furthermore, the sulfur element-containing polymer preferably has a certain acid value. In general, in combination with a colorant often having basicity, the acid of the polymer and the base on the surface of the colorant are combined, so that the colorant is in a surface-treated state. This suppresses charge leakage using the colorant as a charge leakage point, makes the toner charge amount distribution more uniform, and maintains high transferability even when continuous image output is performed. .

  The sulfur element-containing polymer is preferably a polymer having a sulfonic acid group. By containing the sulfonic acid group in the polymer, a more stable state is obtained with metals such as magnesium, calcium, barium, zinc, aluminum and phosphorus. Further, the dispersion of the colorant in the toner particles is further promoted, and in addition, the dispersion of a part of the wax due to the dispersion of the colorant is also improved. Further, the glass transition point (Tg) of the sulfur element-containing polymer is preferably 50 ° C to 100 ° C. More preferably, it is higher than 70 ° C and not higher than 100 ° C, and more preferably 73 ° C to 100 ° C.

As the monomer containing elemental sulfur used for producing the elemental sulfur-containing polymer, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid vinyl Examples thereof include sulfonic acid, methacrylsulfonic acid, and maleic acid amide derivatives, maleimide derivatives, and styrene derivatives having the following structures. Preferred is (meth) acrylamide containing a sulfonic acid group.
The sulfur element-containing polymer according to the present invention may be a homopolymer of the above monomer, but is preferably a copolymer of the above monomer and another monomer. As the monomer that forms a copolymer with the above monomer, polymerizable monomers such as vinyl aromatic hydrocarbons and (meth) acrylic acid esters are preferably used.

The sulfur element-containing polymer is preferably contained in an amount of 0.01 to 15.00 parts by mass, more preferably 0.1 to 10.00 parts by mass, per 100 parts by mass of the binder resin.
In the above binder resin, the presence of a unit derived from a monomer having a sulfur element and the molar ratio thereof can be determined by a fluorescent X-ray apparatus or a mass spectrometer.
Further, the content of the sulfur element-containing polymer in the toner can be measured using capillary electrophoresis or the like.
As for the molecular weight of the sulfur element-containing polymer, the weight average molecular weight (Mw) is preferably 500 to 100,000. More preferably, it is 1,000 to 70,000, and still more preferably 5,000 to 50,000.
In addition, when obtaining the physical properties as described above, if extraction of the sulfur element-containing polymer from the toner is required, the extraction method is not particularly limited, and any method can be used.

  A production method for producing the toner of the present invention is a method for producing a toner directly in a medium (hereinafter also referred to as a polymerization method) such as a suspension polymerization method, an interfacial polymerization method and a dispersion polymerization method. preferable. The toner obtained by this polymerization method (hereinafter also referred to as “polymerized toner”) has high transferability because the shape of individual toner particles is almost spherical and the distribution of charge amount is relatively uniform. In particular, among the above polymerization methods, a suspension polymerization method is preferable as a production method for producing the toner of the present invention.

In the suspension polymerization method, a polymerizable monomer composition containing a polymerizable monomer, a colorant, and, if necessary, a wax, a polar resin, and a low molecular weight resin is dispersed in an aqueous medium. A granulating step of granulating a polymerizable monomer composition to produce polymerizable monomer composition particles; a polymerization step of polymerizing the polymerizable monomer in the polymerizable monomer composition particles; This is a polymerization method for producing toner particles by at least passing. Can be added to the monomer composition as desired.

  In the toner of the present invention, the resin component may have a reactive functional group for the purpose of improving the viscosity change of the toner at a high temperature. Examples thereof include a double bond, an isocyanate group, an epoxy group, an amino group, a carboxylic acid group, and a hydroxyl group.

  In the production of the toner of the present invention, a polar resin can be added to the monomer composition for the purpose of improving the shape of the toner particles, the dispersibility and fixing properties of the material, and the image characteristics. For example, hydrophilic functions such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used because monomers are water-soluble and dissolve in aqueous suspension to cause emulsion polymerization. When it is desired to introduce a monomer component containing a group into the toner, a random copolymer of these and a vinyl compound such as styrene or ethylene, a copolymer such as a block copolymer, and a graft copolymer, a polyester, and a polyamide Can be used in the form of polycondensates such as, or addition polymers such as polyethers and polyimines.

  In addition to the above, examples of the low molecular weight resin that can be added to the monomer composition include homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene; 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- Styrenes such as dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer Copolymer; polymethyl methacrylate, polyb Methacrylate, such as polyvinyl acetate can be used singly or in combination.

  Among the low molecular weight resins, the glass transition point (Tg) of the low molecular weight resin is preferably 40 to 100 ° C. The glass transition point of the low molecular weight resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoints of low temperature fixability and high gloss image. The weight average molecular weight (Mw) is preferably 2,000 to 6,000. The addition amount of the low molecular weight resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles.

In producing the toner of the present invention, an addition reactive resin having a double bond is preferably used. As the addition-reactive resin having a double bond, a styrene resin is preferable. For example, in a styrene resin produced by polymerization at a high temperature of 170 ° C. or more, double bonds of 4.6 to 4.9 ppm and 5.0 to 5.2 ppm are measured in ¹ H-NMR measurement using a deuterated chloroform solvent. A peak derived from is observed. That is, the addition-reactive resin obtained as described above has double bonds, and these double bonds are crosslinked during the production of toner particles. Thus, by introducing a small amount of a crosslinked structure in the toner particles, the rate of change in the viscosity of the toner at a high temperature can be reduced more effectively.

The addition-reactive resin having a double bond preferably has a weight average molecular weight of 1,500 or more and 6,000 or less. In this case, the molecular weight is high and the reactivity is gentle compared to a low molecular crosslinking agent such as divinylbenzene, which has been conventionally used. A toner having a thermal characteristic with a small viscosity change rate is obtained. The glass transition point (Tg) of the addition-reactive resin is preferably 40 to 100 ° C. The glass transition point of the addition-reactive resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoint that low temperature fixability and a high gloss image can be obtained.
The addition amount of the addition reactive resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles.

  The toner of the present invention is preferably a toner containing toner particles having at least a core portion and a shell portion. By adopting such a structure, it is possible to prevent charging failure and blocking in each environment due to deposition of the core portion on the toner surface.

The material constituting the surface layer portion preferably has a molecular chain polar structure. In the present invention, the molecular chain polar structure refers to a molecular structure in which atoms in the molecule have many δ + or δ− electron density states.
Resin molecules are composed of a plurality of types of atoms, and the constituent atoms have inherent electronegativity, and the values differ greatly depending on the atoms. Due to this difference in electronegativity, electrons are localized in the molecule. In this localization, the state changes depending on the type, number, and bonding mode of the atoms to be configured, and the polarity of the molecular chain changes.

What is preferable as the molecular chain polar structure is, for example, a bond structure formed by condensation polymerization or addition polymerization. Specifically, ester bonds (—COO—), ether bonds (—O—), amide bonds (—CONH—), imine bonds (—NH—), urethane bonds (—NHCOO—), urea bonds ( -NHCONH-).
For example, in an ether chain (—CH ₂ —O—CH ₂ —) or the like, electrons on carbon atoms are slightly deficient (δ ⁺ ), and electrons on oxygen atoms are slightly excessive (δ ⁻ ), Furthermore, a bond angle with an oxygen atom as a vertex is in a state. Thus, if there are many polarized molecular chains, the polarity of the molecule, that is, the resin will increase, and if there are few polarized molecular chains, it will decrease. In general, molecules composed of hydrocarbons have low polarity.

  When the surface layer portion has a molecular chain polar structure, charging stability is improved. In addition, when toner particles are produced in a polar solvent such as an aqueous or hydrophilic medium, the surface layer portion having a molecular chain polar structure is more uniformly formed in the vicinity of the toner surface. Underlying charging stability and durability during high-speed printing are improved.

  From the above viewpoint, the toner of the present invention preferably contains a polyester resin as a resin for forming the surface layer portion. The polyester resin can be constituted by a known production method from a polyhydric alcohol and a polyvalent carboxylic acid component. Among the monomers constituting the polyester resin, polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, bisphenol A propylene. Examples thereof include oxide and bisphenol A ethylene oxide. These polyhydric alcohols may be used alone or in a mixed state. However, it is not limited to these, and other trivalent or higher alcohol components can be used as the crosslinking component.

  Among the monomers constituting the polyester resin, the polyvalent carboxylic acid component includes naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid and other dicarboxylic acids; phthalic anhydride, maleic anhydride And dicarboxylic acid anhydrides such as dimethyl terephthalate, dimethyl maleate, and dimethyl adipate. In particular, the main component is preferably a lower alkyl ester of a dicarboxylic acid such as dimethyl terephthalate, dimethyl maleate, dimethyl adipate or a derivative thereof.

The polyester resin may be cross-linked by using the following trivalent or higher acid component.
Examples of crosslinking components include trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, and tri-n-hexyl 1,2,4-tricarboxylate. 1,2,4-benzenetricarboxylic acid triisobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl and tricarboxylic acid lower alkyl ester Can be used. However, it is not limited thereto, and other trivalent or higher acid components or trivalent or higher carboxylic acid lower alkyl esters can be used as the crosslinking component.
Moreover, you may use a monovalent | monohydric carboxylic acid component and a monovalent alcohol component to such an extent that the characteristic of the polyester resin which can be used for this invention is not impaired.

The polyester resin is particularly preferably a vinyl-modified polyester resin modified with a vinyl monomer. The vinyl-modified polyester resin has a structure in which a polyester and a vinyl polymer are bonded to each other, the internal protection performance is given by a polyester skeleton, and the charging stability can be improved by a vinyl polymer unit.
The vinyl-modified polyester resin preferably contains 1 to 60% by mass of a vinyl monomer as a monomer component constituting the resin, more preferably 10 to 50% by mass, and further 15 to 40% by mass. It is preferable to contain.
The vinyl-based monomer that can be used to produce the vinyl-modified polyester resin used in the present invention is a vinyl-based polymerizable monomer that can be copolymerized with styrene, and is used when constituting the shell. The polymerizable monomer which can be used can be used.

  The shell portion of the toner is preferably composed of a vinyl resin formed from a vinyl polymerizable monomer. Among these vinyl polymers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is preferable from the viewpoint of efficiently covering the wax mainly forming the inside or the central portion.

  Examples of the polymerizable monomer that can be used to form the resin or the binder resin for forming the shell portion of the present invention include vinyl polymerizable monomers. Preferred examples of the vinyl polymerizable monomer include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; the above acrylic polymerizable monomers A modified body acrylate to methacrylate; methylene aliphatic monocarboxylic esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl Ethers, vinyl ethers such as vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

The material constituting the core of the toner of the present invention is preferably wax. Examples of wax components that can be used in the toner according to the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to the Fischer-Tropsch method, polyethylene, Polyolefin waxes such as polypropylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant-based waxes, animal waxes, and silicone resins can also be used. .

  The wax is preferably added in an amount of 2 to 30% by mass in the toner particles. When the content is less than 2% by mass, the high temperature offset resistance is lowered, and further, the image on the back surface may show an offset phenomenon when fixing a double-sided image. When the amount is more than 30% by mass, toner particles are likely to be coalesced during granulation in the production by the polymerization method, and those having a wide particle size distribution are likely to be generated.

  In the present invention, a polymerization initiator can be used in the polymerization of the toner particles. The following are mentioned as a polymerization initiator used when manufacturing a toner particle by a polymerization method. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20.0% by mass relative to the polymerizable monomer, and may be used alone or in combination.

The binder resin of the toner particles is preferably a vinyl resin. The vinyl resin is produced by polymerization of the vinyl polymerizable monomer described above.
In order to control the molecular weight of the binder resin of the toner particles, a chain transfer agent may be added. A preferred addition amount is 0.001 to 15,000 mass% of the polymerizable monomer.

  In order to control the molecular weight of the binder resin of the toner particles, a crosslinking agent may be added. Examples of the crosslinkable monomer include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, and those obtained by changing the above acrylates to methacrylates.

  The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferred addition amount is 0.001 to 15,000 mass% of the polymerizable monomer.

In the present invention, when the medium used in the polymerization is an aqueous dispersion medium, the following dispersion stabilizers for the monomer composition particles may be used. Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

  In the present invention, when preparing an aqueous medium using a poorly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable that it is 2.0 mass parts. In the present invention, it is preferable to prepare an aqueous medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the monomer composition.

  In order to obtain dispersion stabilizer particles having a fine and uniform particle size, an aqueous medium may be prepared by producing a poorly water-soluble inorganic dispersant in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

In the present invention, various inorganic fine powders can be contained in the toner in addition to the metal oxide of the present invention for the purpose of imparting various properties. The inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles. As inorganic fine powders for the purpose of imparting these properties, for example, the following are used.
1) Fluidity imparting agent: metal oxide (for example, silica, alumina, titanium oxide), carbon black and carbon fluoride. Each of them is more preferably hydrophobized.
2) Abrasive: metal oxide (eg strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (eg silicon nitride), carbide (eg silicon carbide), metal salt (eg calcium sulfate, barium sulfate) , Calcium carbonate).
3) Lubricant: Fluorine resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
4) Charge controllable particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

  Hydrophobic treatment of the inorganic fine powder makes it possible to adjust the chargeability of the toner and improve the characteristics in a high-humidity environment. Therefore, it is preferable to use an inorganic fine powder that has been hydrophobized.

  Examples of the treatment agent for the hydrophobic treatment of the inorganic fine powder include unmodified or modified silicone varnish, unmodified or modified silicone oil, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination. Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is treated with silicone oil simultaneously with or after the hydrophobic treatment with the coupling agent. The hydrophobized inorganic fine powder treated with silicone oil is good for maintaining a high charge amount of the toner even in a high humidity environment and reducing selective developability.

The degree of hydrophobicity, which indicates the degree of hydrophobic treatment of the inorganic fine powder contained in the toner of the present invention, is the wettability of the inorganic fine powder with respect to a mixed solvent of methanol and water.
The wettability of the inorganic fine powder to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, a methanol dropping transmittance curve is prepared, and the methanol concentration (volume%) when the transmittance is 50% is determined. The degree of hydrophobicity. As a measuring apparatus, for example, a powder wettability tester WET-101P manufactured by REHSCA (Resca) can be used.

  These inorganic fine powders are preferably used in an amount of 0.1 to 10 parts by weight, and more preferably 0.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner particles. These inorganic fine powders may be used alone or in combination.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 2.0 to 12.0 μm, more preferably 4.0 to 9.0 μm, and still more preferably 5.0 to 8.0 μm. It is.

  The glass transition point (Tg) of the toner of the present invention is 40 to 100 ° C., preferably 40 to 80 ° C. More preferably, it is 45 to 70 ° C. When the glass transition point is lower than 40 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 100 ° C., the low temperature offset resistance of the toner and the transparency of the transmitted image of the OHP film are lowered.

The content of insoluble content of tetrahydrofuran (THF) in the toner of the present invention is preferably less than 16.0% by mass with respect to toner components other than the toner colorant and inorganic fine powder. More preferably, it is 0.0 mass% or more and less than 10.0 mass%, Most preferably, it is 0.0 mass% or more and less than 5.0 mass%. When it is larger than 16.0% by mass, the low-temperature fixability tends to be lowered.
The THF-insoluble content of the toner refers to the mass ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. The THF-insoluble content of the toner is defined by the values measured as follows.

1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), subjected to a Soxhlet extractor, extracted for 20 hours using 200 ml of THF as a solvent, and soluble components extracted by the solvent are extracted. After evaporation, vacuum drying is performed at 40 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W2 g). The weight of a component other than the resin component such as a pigment in the toner is (W3 g). The THF-insoluble content can be obtained from the following formula.
THF insoluble matter (mass%) = (W1− (W3 + W2)) / (W1−W3) × 100
The THF-insoluble content of the toner can be adjusted by the degree of polymerization and the degree of crosslinking of the binder resin.

  The weight average molecular weight of the toner in the present invention (hereinafter also referred to as the weight average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner) (Mw) is 10,000 to 80,000. It is preferable that When the weight average molecular weight in gel permeation chromatography (GPC) of the soluble content of tetrahydrofuran (THF) in the toner is less than 10,000, the blocking resistance and durability are likely to deteriorate, and the weight average molecular weight exceeds 80,000. Then, it becomes difficult to obtain a low-temperature fixability and a high gloss image. Such toner exhibits good environmental stability and durability stability. Furthermore, it is preferable that the weight average molecular weight in the gel permeation chromatography (GPC) of the soluble part of tetrahydrofuran (THF) in the toner is 10,000 to 60,000. In the present invention, the weight average molecular weight (Mw) of the toner depends on the addition amount and weight average molecular weight of the low molecular resin, the reaction temperature at the time of toner production, the reaction time, the initiator amount, the chain transfer agent amount, and the crosslinking agent amount. Can be adjusted.

  In the present invention, the ratio Mw / Mn of the weight average molecular weight and the number average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is preferably 5 to 100. More preferably, Mw / Mn is 5 to 30. When Mw / Mn is less than 5, the fixable temperature range is narrow, and when it exceeds 100, the low-temperature fixability is deteriorated.

As the colorant used in the present invention, a known pigment, dye or the like, or magnetic powder can be used. These colorants can be used alone or in combination, and further in a solid solution state.
As a preferred method for treating the dye, a polymerizable monomer is previously polymerized in the presence of these dyes, and the resulting colored polymer is added to the monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  During the toner particle production process, the temperature may be raised in the latter half of the polymerization reaction. Further, in order to remove the unreacted polymerizable monomer or by-product, it is preferable to partially distill off the dispersion medium from the reaction system in the latter half of the reaction or after the completion of the polymerization reaction. After completion of the reaction, the produced toner particles are washed, collected by filtration, and dried.

  A method for measuring and evaluating physical properties of the toner and metal oxide of the present invention will be described below.

<Measurement of moisture absorption of metal oxide>
The amount of adsorbed moisture of the metal oxide in the present invention can be measured by, for example, an adsorption equilibrium measuring device (“EAM-02” manufactured by JT Toshi). This is a device that reaches solid-gas equilibrium under conditions where only the target gas (water in the present invention) exists, and measures the solid weight and vapor pressure at this time.

  The actual measurement of the adsorption isotherm is automatically performed by a computer from the measurement of the amount of dry matter and the degassing of dissolved air in the water to the measurement of the isotherm of adsorption and desorption. The outline of the measurement is described in the operation manual issued by JT Toshi Co., Ltd. and is as follows. In the present invention, water is used as the solvent liquid, and the relative humidity and the relative vapor pressure are the same.

First, about 5 g of metal oxide was filled in the sample container in the adsorption tube, and then the thermostat temperature and the sample part temperature were set to 30 ° C. Thereafter, the air valves V1 (main valve) and V2 (exhaust valve) are opened to operate the evacuation unit, and the vacuum vessel is evacuated to about 0.01 mmHg to dry the sample. The mass when the mass change of the sample ceases is defined as “dry matter amount”.
Since air is dissolved in water as a solvent solution, it is necessary to deaerate. First, water is put into a liquid reservoir, the evacuation unit is operated, and the air valves V2 and V3 (liquid reservoir valves) are alternately opened and closed to remove dissolved air. The above operation is repeated several times, and the deaeration ends when no more bubbles are seen in the water.
Following the measurement of the amount of dry matter and deaeration of dissolved air in water, water vapor is introduced from the reservoir by closing the air valves V1, V2 and opening the air valve V3 while keeping the inside of the vacuum vessel under vacuum, Close the air valve. Next, the solvent vapor is introduced into the vacuum vessel by opening the air valve V1, and the pressure is measured by the pressure sensor. When the pressure in the vacuum vessel does not reach the set pressure, the above operation is repeated to set the pressure in the vacuum vessel to the set pressure. When the equilibrium is reached, the pressure and weight in the vacuum vessel become constant, and the pressure and temperature at that time and the sample weight are measured as equilibrium data.

By operating as described above, the adsorption isotherm can be measured by changing the water vapor pressure. In actual measurement, a relative vapor pressure (relative humidity) for measuring the amount of adsorption is set in advance. For example, when the set pressure is 5% RH, 10% RH, 30% RH, 50% RH, 70% RH, 80% RH, 90% RH, and 95% RH, the moisture adsorption amount is sequentially increased from 5% RH. Measure and measure the isotherm.
In this apparatus, the pressure is set by the relative vapor pressure (% RH), and the adsorption isotherm is displayed by the adsorption amount (%) and the relative vapor pressure (% RH). The calculation formulas for the adsorption amount and relative vapor pressure are shown below.
M = {(Wk−Wc) / Wc} × 100
Pk = (Q / Q ₀ ) × 100
(Where M is the amount of moisture adsorbed (%), Pk is the relative vapor pressure (% RH), Wk (mg) is the mass of the sample, Wc (mg) is the amount of dry matter in the sample, and Q ₀ (mmHg) is the (The saturated vapor pressure of water determined by the Antoine equation from the temperature Tk (° C.) at the time of desorption equilibrium, and Q (mmHg) indicates the pressure measured as the equilibrium data.)

<Wettability of metal oxide to mixed solvent of methanol and water>
The wettability of the metal oxide with respect to the mixed solvent of methanol and water was measured by the transmittance of light having a wavelength of 780 nm, a methanol dropping transmittance curve was prepared, and the methanol concentration when the transmittance was 50% was determined as the degree of hydrophobicity ( Volume%). As a measuring apparatus, for example, a powder wettability tester WET-101P manufactured by REHSCA (Resca) Co., Ltd. can be used, and specific measuring operations include the methods exemplified below.

First, 70 ml of a hydrated methanol solution composed of 40% by volume of methanol and 60% by volume of water is placed in a container and dispersed with an ultrasonic disperser for 5 minutes to remove bubbles and the like in the solution. In this solution, 0.5 g of a metal oxide as a specimen is added and suspended, and a sample solution for measuring the hydrophobic properties of the metal oxide is prepared. As a container for preparing and measuring a sample solution, a glass flask having a circular diameter of 5 cm and a height of 88 mm can be used.
Next, while stirring the prepared sample liquid for measurement at a speed of 6.67 s ⁻¹ , methanol was added at 1.3 ml / min. Are continuously added at a dropping rate of 1 to disperse the suspended metal oxide in the solvent. While dropping methanol, the transmitted light intensity of light having a wavelength of 780 nm of the measurement sample is measured to obtain the transmittance, and a methanol dropping transmittance curve is created. Here, the stirring can be performed using a magnetic stirrer (for example, a spindle having a length of 25 mm and a maximum diameter of 8 mm and having a Teflon (registered trademark) coating). Then, the methanol concentration when the transmittance is 50% is calculated as Dm of the metal oxide.
When the degree of hydrophobicity of the metal oxide sample is less than 60%, when the sample is added to a hydrous methanol solution consisting of 60% by volume of methanol and 40% by volume of water, the sample is immediately dispersed in the solvent. A transmission curve cannot be obtained. For this reason, when the Dm of the metal oxide sample was less than 60%, the measurement was performed with the methanol concentration of the initial solution set to 0%.
When the metal oxide was measured under the above conditions, the methanol concentration when the transmittance was 50% was defined as Dm volume%.

<Particle size and particle size distribution of metal oxide>
The volume-based median diameter (D50) of the metal oxide used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting the measurement conditions and analyzing the measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.
The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, optical axis adjustment, optical axis fine adjustment, and blank measurement are performed.
(7) Put about 60 ml of ion-exchanged water in a glass 100 ml flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass is added.
(8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of metal oxide is added little by little to the aqueous solution in the beaker and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In this case, the metal oxide may solidify and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the solid is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(11) The aqueous solution in which the metal oxide prepared in the above (10) is dispersed is immediately added little by little to a batch type cell, taking care not to enter bubbles, and the transmittance of the tungsten lamp is 90% to 95%. Adjust so that Then, the particle size distribution is measured. The volume-based median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

<Zeta potential of metal oxide in methanol>
The zeta potential in the present invention was measured by the following method.
The solvent used is a methanol reagent (purity 99% or more, manufactured by Wako Pure Chemical Industries), and 0.1% with a dehydrating agent (Molecular Sieve 3A, Kanto Chemical) for the purpose of removing the influence of moisture on the zeta potential. The dehydrated product was used below.
The zeta potential was measured by adding 5 mg of a metal oxide in 20 mL of a methanol reagent and dispersing it with ultrasonic dispersion (BRANSON 3510) for 3 minutes to obtain a zeta potential measurement sample. The obtained sample was measured using a maintenance-free capillary zeta potential cell using a zeta sizer nano ZS (manufactured by Sysmex Corporation), which is a zeta potential measuring device by a dynamic light scattering method. The measurement conditions were 23 ° C. and an applied voltage of 120V.

<Volume resistivity of metal oxide>
The sample is molded into tablets using a tablet molding machine. First, about 0.3 g of a sample is placed in a tablet molding chamber. Next, the push rod is inserted into the tablet molding chamber and pressurized with a hydraulic pump at 250 kg / cm 2 for 5 minutes to mold pellet-shaped tablets having a diameter of about 13 mm and a height of about 2 to 3 mm. The tablets obtained here are coated with a conductive agent on the front and back surfaces as necessary. For example, the temperature is 23.5 ° C. and the humidity is 65% RH using, for example, 16008A RESISTIVITYCELL manufactured by HEWLETT PAKARD; or 4329A HIGH RESISTANCE METER manufactured by Hewlett-Packard The resistance value R (Ω) when a voltage of 1000 V is applied in the environment is measured, and the specific electrical resistance value ρ (Ω · cm) is obtained by the following calculation formula (4).
ρ = R × S / l (4)
(In the formula, S represents the cross-sectional area (cm 2) of the sample, and l represents the height (cm) of the sample.)

<Measurement of molecular weight>
The molecular weight of the chromatogram obtained by GPC (gel permeation chromatography) of the present invention is measured under the following conditions.
<Measurement conditions>
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G 807 (diameter 8.0mm, length 30cm) 7 stations ・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration: 10 μl of 0.1% by mass sample

For sample preparation, a toner sample to be measured is placed in tetrahydrofuran (THF), 0.04 g of a resin for toner is dispersed in 20 ml of THF, dissolved, and allowed to stand for 24 hours. -25-2 (manufactured by Tosoh Corporation), Excro Disc 25CR Gelman (manufactured by Science Japan), etc. can be preferably used), and the filtrate is used as a sample. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample. As a standard polystyrene sample for preparing a calibration curve, for example, TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-40, F-20, F-10, manufactured by Tosoh Corporation Calibration curves can be created using F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, and at least about 10 standard polystyrene samples are used. Is appropriate.
In general, in the measurement of the molecular weight distribution of GPC, the chromatogram rises from the baseline on the high molecular weight side and starts measurement from the starting point, and the molecular weight is measured up to about 400 on the low molecular weight side.

<DSC measurement>
In the present invention, M-DSC (trade name, manufactured by TA Instruments) was used as a differential scanning calorimeter (DSC). Weigh accurately 6 mg of the toner sample to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The maximum glass transition point Tg (° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

  In addition, in the endothermic chart at the time of temperature rise measured by DSC, the calorific integral value Q (J / g) obtained by converting the endothermic amount (J) represented by the peak area of the endothermic main peak into the amount of heat per gram of toner is measured. did. An example of a reversing heat flow curve obtained by DSC measurement of the toner is shown in FIG. The calorie integral value Q (J / g) is obtained using the reversing heat flow curve obtained from the above measurement. For the calculation, analysis software Universal Analysis Ver. Using 2.5H (manufactured by TA Instruments) and using the function of Integral PeakLinear, the heat value integral value Q (J / g) from the region surrounded by the straight line connecting the measurement points at 35 ° C and 135 ° C and the endothermic curve Ask for.

<Measurement of toner weight average particle diameter (D4)>
Measurement of particle size distribution of toner As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.11 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml of the electrolytic aqueous solution, and 5 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 minute, and the measuring device is used to measure the volume and number of toner particles for each channel using a 100 μm aperture as the aperture. The volume distribution and the number distribution are calculated. Then, the weight-based toner weight average particle diameter (D4) obtained from the volume distribution of the toner particles (the median value of each channel is a representative value for each channel) is obtained.

  Channels are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00 to 40.30 μm are used.

<Measuring method of average circularity and circularity standard deviation of toner particles>
A suitable amount of a surfactant, preferably an alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added. A desktop ultrasonic cleaner with an oscillation frequency of 50 kHz and an electric output of 150 watts. Using a disperser (for example, “VS-150” (manufactured by Velvo Crea Co., Ltd.), a dispersion treatment was performed for 2 minutes to obtain a dispersion liquid for measurement. It cooled suitably so that it might become.
The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow type particle image analyzer, 3,000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is set. The analysis particle diameter was limited to 1.98 μm or more and 19.92 μm or less, and the average circularity and circularity standard deviation of the toner particles were determined.
In measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5100A diluted with ion-exchanged water) before the start of measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

<Measurement of average circularity of metal oxide>
When measuring a metal oxide, change the amount of the measurement sample to “0.02 g” to “0.01 g”, change to “standard objective lens (10 ×)” and “high magnification imaging unit (objective lens)” (20 times)) ”. Further, the analysis particle diameter is changed to “equivalent circle diameter of 1.98 μm or more and 19.92 μm or less” to be “equivalent circle diameter of 0.80 μm or more and 1.98 μm or less”. It went by the method of.

Next, the image forming method of the present invention will be described. The image forming method of the present invention comprises a charging step of charging an electrostatic latent image carrier with a charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, toner layer regulation An image forming method comprising: a step of regulating toner on a toner carrier with a member; and a development step of developing the electrostatic latent image with toner to form a toner image on the electrostatic latent image carrier. In the image forming method of the present invention, the so-called non-magnetic one-component contact developing system in which the developer carrying member has a cylindrical shape and the surface thereof is provided in contact with the surface of the photoreceptor is most preferable. In the contact development method, since toner is directly supplied to the latent image carrier, adverse effects such as scattering on the image hardly occur, and lines and characters can be printed with good reproducibility. The image forming apparatus of the present invention is not limited to the non-magnetic one-component contact development method, although it is preferable for maintaining the image quality.
As a contact one-component developing method, it is possible to develop using non-magnetic toner, for example, using a developing device 90 as shown in FIG.

The developing device 90 includes a developing container 91 that stores a one-component developer 98 (hereinafter simply referred to as “developer”) that is a non-magnetic toner, and a one-component developer 98 that is stored in the developing container 91. Developer carrier 92 for transporting the toner to the developing area, supply roller 95 for supplying the developer onto the developer carrier, and the thickness of the developer layer on the developer carrier. An elastic blade 96 as a developer layer thickness regulating member and a stirring member 97 for stirring the developer 98 in the developing container 91 are provided.
As the developer carrier 92, it is preferable to use an elastic roller having an elastic layer 94 formed of an elastic member such as rubber or resin having elasticity such as foamed silicone rubber on the roller base 93.
The elastic roller 92 is in electrostatic contact with a surface of a photoconductor 99 as a photoconductor serving as a latent image holding member, and is formed on the photoconductor by a one-component developer 98 applied to the surface of the elastic roller. The latent image is developed, and unnecessary one-component developer 98 present on the photosensitive member after the transfer is recovered. At the time of development, a DC and / or AC development bias is applied to the elastic roller.

  In the present invention, the developer carrying member 92 is substantially in contact with the surface of the photoreceptor 99. This means that when the one-component developer is removed from the developer carrier, the developer carrier is in contact with the photoreceptor. At this time, an image having no edge effect is obtained through the developer by an electric field acting between the photosensitive member and the developer carrying member, and at the same time, cleaning is performed. It is necessary that the surface of the elastic roller as the developer carrying member or the vicinity of the surface has an electric potential between the surface of the photosensitive member and the surface of the elastic roller. Therefore, it is possible to use a method in which the elastic rubber of the elastic roller is resistance controlled to the middle resistance region to keep the electric field while preventing conduction with the surface of the photoconductor, or a method of providing a thin dielectric layer on the surface layer of the conductive roller. . Furthermore, there is a configuration in which a conductive resin sleeve in which the surface that contacts the surface of the photoreceptor is covered with an insulating material on the conductive roller or a conductive layer is provided on the surface that does not contact the photoreceptor with an insulating sleeve. Is possible.

  The elastic roller carrying the one-component developer may rotate in the same direction as the photoconductor or in the opposite direction. When the rotation is in the same direction, the peripheral speed ratio is preferably greater than 100% with respect to the peripheral speed of the photoreceptor. The higher the peripheral speed ratio is, the more developer is supplied to the development site, the more frequently the developer is desorbed from the electrostatic latent image, and the unnecessary part of the developer is scraped off. An image faithful to the electrostatic latent image is obtained by repeatedly applying the developer to the portion.

  The developer layer thickness regulating member 96 is not limited to an elastic blade as long as it is in pressure contact with the surface of the developer carrying member 92 by an elastic force, and an elastic roller can also be used. As the elastic blade and elastic roller, rubber elastic bodies such as silicone rubber, urethane rubber and NBR; synthetic resin elastic bodies such as polyethylene terephthalate; metal elastic bodies such as stainless steel and steel can be used. Furthermore, even those complexes can be used.

  The supply roller 95 is made of a foam material such as polyurethane foam, and rotates with a relative speed other than 0 in the forward or reverse direction with respect to the developer carrier, and supplies the one-component developer on the developer carrier. The developer after development (undeveloped developer) is also stripped off.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

<Production example of metal oxide 1>
Oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG (Liquid Petroleum gas) was supplied at 2 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, aluminum powder (average particle size of about 60 μm, supply rate of 18 kg / h) was supplied from the metal oxide powder supply apparatus to the reactor along with nitrogen gas (supply rate of 1.8 m ³ (standard state) / h) through the combustor. . In the reactor, the metal oxide was burned by a flame and oxidized to obtain metal oxide 1. Table 1 shows the physical properties of the metal oxide.

<Production example of metal oxide 2>
As shown below, hexamethyldisilazane [Silane coupling agent Z-6079 (trade name) manufactured by Toray Dow Corning Co., Ltd.] is used as a silane coupling agent having a silicon-nitrogen bond in the molecule using metal oxide 1. Then, surface treatment with a silane coupling agent and preparation of a solid-liquid dispersion were performed.
100 parts by mass of metal oxide 1 was put in a Henschel mixer, and while stirring at 100 ° C. at a rotation speed of 1,600 rpm, 1.0 part by mass of a 1: 1 mixture of hexamethyldisilazane and toluene was added. The metal oxide 1 was sprayed while being atomized using an air spray, and the metal oxide 1 was surface-treated with a silane coupling agent. Furthermore, after stirring the said processing mixture for 15 minutes at a rotational speed of 1500 rpm, the metal oxide 2 was obtained by drying at 120 degreeC for 3 hours. By the surface treatment with the silane coupling agent, the particle surface of the metal oxide 1 was coated with the silane coupling agent. At this time, the surface treatment amount of the silane coupling agent (the coating amount of the silane coupling agent) was 1.0% by mass with respect to the metal oxide 1.

<Production example of metal oxide 3>
The metal oxide 1 was used in the same manner as in the production example of the metal oxide 2 except that the amount of the mixture liquid of hexamethyldisilazane and toluene having a mass ratio of 1: 1 was 3.0 parts by mass. Oxide 3 was obtained. At this time, the surface treatment amount of the silane coupling agent (the coating amount of the silane coupling agent) was 3.0% by mass with respect to the metal oxide 1.

<Production example of metal oxide 4>
The metal oxide 1 was used in the same manner as in the production example of the metal oxide 2 except that the amount of the mixed liquid of hexamethyldisilazane and toluene having a mass ratio of 1: 1 was 4.8 parts by mass. Oxide 4 was obtained. At this time, the surface treatment amount of the silane coupling agent (the coating amount of the silane coupling agent) was 4.8% by mass with respect to the metal oxide 1.

<Production example of metal oxide 5>
The oxygen supply rate to the combustor is from 180 (standard condition) m ³ / h to 160 m ³ (standard condition) / h, and the LPG and nitrogen gas supply rates are 1.8 m ³ (standard condition) / h to 2.0 m ^A metal oxide 5 was obtained in the same manner as the metal oxide 1 except for changing to ³ / h (standard state).

<Production example of metal oxide 6>
The oxygen supply amount to the combustor is 180 m ³ (standard state) / h to 140 m ³ (standard state) / Hr, LPG, and nitrogen gas supply amounts are 1.8 m ³ (standard state) / h to 2.0 ( Standard state) A metal oxide 6 was obtained in the same manner as the metal oxide 1 except that it was changed to m ³ / h.

<Production example of metal oxide 7>
Oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 1 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, metal oxide 1 (average particle size of about 0.7 μm, supply rate: 10 kg / h) is supplied from the metal powder supply device to the reactor through the combustor together with nitrogen gas (supply rate: 1.8 m ³ (standard state) / h). did. In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 7.

<Production example of metal oxide 8>
A metal oxide 8 having a median diameter of 0.67 μm is obtained by strictly classifying and removing ultrafine powder and coarse powder simultaneously with a multi-division classifier using the Coanda effect (elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.). Obtained.

<Production example of metal oxide 9>
Using a hybridization system manufactured by Nara Machinery Co., Ltd., the metal oxide 1 was fed from the metal oxide 1 (supply amount 10 kg / h) until the discharge valve was opened (cycle time) and the rotational speed of the dispersion rotor. Surface treatment of the metal oxide was performed at a speed of 1.2 × 10 ⁵ mm / second and a cycle time of 55 to 60 seconds to obtain a metal oxide 9.

<Production example of metal oxide 10>
Oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 2 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, aluminum powder (average particle size: about 60 μm, supply amount: 2 kg / h) was supplied from the metal oxide powder supply device together with nitrogen gas (supply amount: 2.0 m ³ (standard state) / h) to the reactor through the combustor. In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 10.

<Production example of metal oxide 11>
Oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 2 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, aluminum powder (average particle size: about 60 μm, supply amount: 6 kg / h) was supplied from the metal oxide powder supply apparatus together with nitrogen gas (supply amount: 1.8 m ³ (standard state) / h) to the reactor through the combustor. In the reaction furnace, the metal powder was burned by a flame and oxidized to obtain a metal oxide 11.

<Production example of metal oxide 12>
Oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 2 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, aluminum powder (average particle size: about 60 μm, supply rate: 40 kg / h) was supplied from the metal oxide powder supply device together with nitrogen gas (supply rate: 2.0 m ³ (standard state) / h) to the reactor through the combustor. In the reactor, the metal powder was burned by a flame and oxidized to obtain metal oxide 12.

<Production example of metal oxide 13>
A mixed gas of titanium tetrachloride and oxygen was preheated to 1,050 ° C. to obtain titanium dioxide A at a reaction temperature of 1,600 ° C. The obtained titanium dioxide A had a particle size of 0.71 μm. Next, oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 2 m ³ (standard state) / h to form a flame for ignition of titanium dioxide A. Next, titanium dioxide A (average particle size of about 0.70 μm, supply amount: 8 kg / h) was supplied from the metal powder supply device together with nitrogen gas (supply amount: 2.0 m ³ (standard state) / h) to the reactor through the combustor. . In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 13.

<Production example of metal oxide 14>
After meta-titanic acid obtained by the sulfuric acid method is deiron-bleached and bleached, 4.0N aqueous sodium hydroxide solution is added to adjust the pH to 9.0, followed by desulfurization, and then neutralized to pH 5.4 with 6.0N hydrochloric acid and filtered. Washed with water. Water was added to the washed cake to make a 1.25 mol / liter slurry 1 as TiO ₂ , and 6.0N hydrochloric acid was added to adjust the pH to 1.1 to perform peptization. 0.156 mol of this peptized hydrous titanium oxide was collected as TiO ₂ and charged into a 3 liter reaction vessel, and a strontium chloride aqueous solution having a SrO / TiO ₂ molar ratio of 1.15 was added to the peptized hydrous titanium oxide slurry 1. Then, the TiO ₂ concentration was adjusted to 0.156 mol / liter, nitrogen gas was blown in, and the mixture was left for 20 minutes to replace the inside of the reaction vessel with nitrogen gas. Next, while flowing nitrogen into the reaction vessel and further stirring and mixing, the mixed solution of metatitanic acid and strontium chloride was heated to 90 ° C., and then 150 mL of 2.5N aqueous sodium hydroxide solution was added over 24 hours. Thereafter, stirring was continued at 90 ° C. for 1 hour to complete the reaction. After the reaction, the mixture was cooled to 40 ° C., the supernatant was removed under a nitrogen atmosphere, decantation was performed by adding 2.5 liters of pure water, and washing was repeated twice. Then, it filtered with Nutsche, and the obtained cake was dried in 110 degreeC air | atmosphere for 8 hours, and strontium titanate A was obtained. Next, oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 2 m ³ (standard state) / h to form a flame for ignition of titanium dioxide A. Next, strontium titanate A (average particle size of about 0.70 μm, supply rate: 8 kg / h) is supplied from the metal powder supply device together with nitrogen gas (supply rate: 2.0 m ³ (standard state) / h) to the reactor through the combustor. did. In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 14.

<Production example of metal oxide 15>
100 parts by weight of metal oxide 14 was put into a Henschel mixer, and while stirring at 100 ° C. at a rotation speed of 1,600 rpm, 2.0 parts by weight of a mixed solution of hexamethyldisilazane and toluene in a mass ratio of 1: 1 was added. The metal oxide 14 was sprayed while being atomized using an air spray, and the metal oxide 14 was surface-treated with a silane coupling agent. Furthermore, after stirring the said processing mixture for 15 minutes at a rotational speed of 1500 rpm, the metal oxide 15 was obtained by drying at 120 degreeC for 3 hours.

<Production Example of Metal Oxide 16>
Oxygen was supplied to the combustor at 180 m ³ (standard state) / h, and LPG was supplied at 1 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, the metal oxide 7 (supply amount 10 kg / h) was supplied from the metal powder supply apparatus to the reactor together with nitrogen gas (supply amount 1.8 m ³ (standard state) / h) through the combustor. In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 16.

<Production example of metal oxide 17>
Oxygen was supplied to the combustor at 120 m ³ (standard state) / h, and LPG was supplied at 2 m ³ (standard state) / h to form a flame for ignition of aluminum powder. Next, aluminum powder (average particle size: about 60 μm, supply amount: 10 kg / h) was supplied from the metal oxide powder supply apparatus together with nitrogen gas (supply amount: 2.0 m ³ (standard state) / h) to the reactor through the combustor. In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 17.

<Production example of metal oxide 18>
While mixing 100 parts by mass of metal oxide 1 in a Henschel mixer and stirring at 100 ° C. at a rotation speed of 1,600 rpm, 16.4 parts by mass of the mixture of hexamethyldisilazane and toluene in a mass ratio of 1: 1 was added. The metal oxide 1 was sprayed while being atomized using an air spray, and the metal oxide 1 was surface-treated with a silane coupling agent. Furthermore, after the said processing mixture was stirred for 15 minutes at the rotational speed of 1500 rpm, the metal oxide 18 was obtained by drying at 120 degreeC for 3 hours.

<Production Example of Metal Oxide 19>
The metal oxide 5 was put into a mixer, stirring was started at a mixer internal temperature of 260 ° C. and a peripheral speed of 100 m / s, and nitrogen was circulated. 10.0 parts by weight of dimethyl silicone oil (viscosity: 50 cSt) was sprayed with 100 parts by weight of metal oxide 5 using a two-fluid nozzle to adhere to metal oxide 1. Furthermore, stirring of the mixer was continued under the same conditions and held for 60 minutes to obtain a metal oxide 19.

<Production Example of Metal Oxide 20>
As a conventionally used method, a flame for igniting aluminum powder was formed by supplying oxygen to the combustor at 50 m ³ (standard state) / h and LPG (Liquid Petroleum gas) at 2 m ³ (standard state) / h. . Next, aluminum powder (average particle size of about 60 μm)
m supply amount 20 kg / h) was supplied from the metal oxide powder supply apparatus together with nitrogen gas (supply amount 15.0 m ³ (standard state) / h) to the reactor through the combustor. In the reactor, the metal powder was burned by a flame and oxidized to obtain a metal oxide 20.

<Production example of metal oxide 21>
Hydrous titanium oxide obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with pure water until the supernatant had an electric conductivity of 1,150 μS / cm to obtain slurry 3. Next, an aqueous sodium hydroxide solution was added to adjust the pH of the slurry 3 to 9.0, and stirring was performed for 30 minutes to obtain a slurry 4. After completion of the stirring, hydrochloric acid was added dropwise to adjust the pH of the slurry 4 to 7, and then the slurry was washed with pure water until the supernatant had an electric conductivity of 250 μS / cm to obtain a slurry 5.
Thereafter, hydrochloric acid was added to slurry 5 to adjust the pH to 1.5, and 1 liter of titania sol having anatase type crystal structure of 120 g / liter as TiO ₂ was obtained. After adding 22.0 ml of a 250 g / liter zirconium oxychloride aqueous solution as ZrO ₂ , the mixture was stirred for 1 hour. Thereafter, an aqueous sodium hydroxide solution was added to adjust the pH of the slurry 5 to 7. The supernatant was washed with pure water until the electric conductivity of the supernatant reached 60 μS / cm, filtered and dried. This dried product was fired at 900 ° C. for 1 hour to obtain fine powder A having a median diameter of 0.05 μm.
Next, 100 parts by weight of fine powder A was put into a Henschel mixer, and stirred at 100 ° C. at a rotation speed of 1,600 rpm, 30.0 parts by weight of a mixture of hexamethyldisilazane and toluene in a mass ratio of 1: 1. Was subjected to a surface treatment with a silane coupling agent of fine powder A while atomizing using an air spray. Furthermore, after the said processing mixture was stirred for 15 minutes at the rotational speed of 1,500 rpm, fine powder B was obtained by drying at 120 degreeC for 3 hours. The fine powder B was put into a mixer, stirring was started at a mixer internal temperature of 260 ° C. and a peripheral speed of 100 m / s, and nitrogen was circulated. 5.0 parts by weight of dimethyl silicone oil (viscosity: 50 cSt) was sprayed with respect to 100 parts by weight of fine powder B using a two-fluid nozzle, and adhered to fine powder B. Furthermore, stirring of the mixer was continued under the same conditions and held for 60 minutes to obtain metal oxide 21.

<Production Example of Metal Oxide 22>
The combustion-supporting gas supply pipe is opened and oxygen gas (60 m ³ (standard state) / h) is supplied to the burner. After igniting the ignition burner, the combustible gas supply pipe is opened and hydrogen gas (60 m ³ (standard State) / h) is supplied to a burner to form a flame, and silicon tetrachloride (200 kg / h) is gasified and supplied to this by an evaporator, and a flame hydrolysis reaction is performed to obtain fine powder C. It was.
Next, the fine powder C was put into a mixer, stirring was started at a mixer internal temperature of 260 ° C. and a peripheral speed of 100 m / s, and nitrogen was circulated. The dimethyl silicone oil (viscosity 50 cSt) of 5.0 parts by weight with respect to 100 parts by weight of the fine powder C was sprayed using a two-fluid nozzle to adhere to the fine powder C. Furthermore, stirring of the mixer was continued under the same conditions and held for 60 minutes to obtain a metal oxide 22. Tables 1-1 and 1-2 show the physical properties of the metal oxides 1 to 22.

{Resin synthesis example}
(Production example of styrene resin (1))
40 parts by mass of xylene was placed in a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 210 ° C. The pressure at this time was 0.32 MPa. A mixture of 100 parts by mass of styrene monomer, 0.12 parts by mass of n-butyl acrylate and 3.4 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel and added to xylene at 210 ° C. over 3.5 hours. It was dripped under pressure (0.32 MPa). After the dropping, the reaction was further carried out at 180 ° C. for 2 hours to complete the solution polymerization, and xylene was removed. The resulting styrene resin had a weight average molecular weight of 2,650 and a Tg of 56 ° C. This is designated as styrene resin (1).

(Production example of styrene resin (2))
In a reactor equipped with a dropping funnel, a Liebig cooler, a nitrogen-filled tube (nitrogen flow rate 100 ml / min) and a stirrer, 700 parts by mass of xylene was added and the temperature was raised to 145 ° C. A mixture of 100 parts by mass of styrene monomer and 8.1 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel and dropped into xylene at 145 ° C. over 1.5 hours at normal pressure. Further, the reaction was carried out for 2 hours under reflux of xylene (137 ° C. to 145 ° C.) to complete solution polymerization, and xylene was removed. The resulting styrene resin had a weight average molecular weight of 8,000 and Tg of 60 ° C. This is designated as styrene resin (2).

(Production example of styrene resin (3))
A mixture of 20 parts by mass of xylene, 80 parts by mass of styrene, 20 parts by mass of n-butyl acrylate and 2.2 parts by mass of di-tert-butyl peroxide as an initiator was charged into a reactor equipped with a Liebig cooler and a stirrer. Polymerization was carried out at a temperature of 100 ° C. for 24 hours. Thereafter, xylene was removed to obtain a styrene resin (3). The obtained styrene resin had a weight average molecular weight of 380,000 and a Tg of 62 ° C. This is designated as a styrene resin (3).
Table 2 shows the physical properties of the styrene resins (1) to (3) obtained above.

<Measurement of ¹ H-NMR (nuclear magnetic resonance) spectrum>
The NMR spectrum shown in Table 2 was measured under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10000 times Measurement temperature: 60 ° C
Sample: 50 mg of a measurement sample is put into a sample tube having a diameter of 5 mm, CDCl ₃ is added as a solvent, and this is dissolved in a constant temperature bath at 60 ° C. to prepare.

Determination of proton abundance ratio of methylene group (CH ₂ ═C (C ₆ H ₅ ) —) derived from double bond by ¹ H-NMR measurement: 4.6 to 4.9 ppm hydrogen in ¹ H-NMR spectrum The intensity ratio between the signal of (each 1H equivalent) and the signal of 5.0 to 5.2 ppm hydrogen (each 1H equivalent), S _4.6-4.9 / S _5.0-5.2, is determined.
A: With peak B: Without peak

(Example of production of negative charge control resin 1)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 255 parts by mass of methanol, 145 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As a monomer, 88 parts by mass of styrene, 6.2 parts by mass of 2-ethylhexyl acrylate, and 5.1 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature while stirring. A solution prepared by diluting 1.0 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution prepared by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.

Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, the particles are dissolved by adding MEK (methyl ethyl ketone) to a concentration of 10%.
The above solution was gradually poured into 20 times the amount of MEK in methanol for reprecipitation. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.

Further, MEK was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the above solution was gradually poured into n-hexane 20 times the amount of MEK for reprecipitation. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The polar polymer thus obtained has a Tg of about 83 ° C., a main peak molecular weight (Mp) of 21,400, Mn of 11,100, Mw of 33,200, and an acid value of 14.5 mgKOH / g. there were. Further, ¹ H-NMR (EX-400 manufactured by JEOL Ltd.
: 400 MHz), the composition measured was as charged. The obtained resin is referred to as negative charge control resin 1.

(Example of production of polyester resin (1))
-Terephthalic acid: 11.2 mol-Bisphenol A-propylene oxide 2-mol adduct (PO-BPA): 10.2 mol
The polyester monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device are attached to the autoclave. The reaction was performed until Tg reached 70 ° C. to obtain a polyester resin (1). Table 3 shows the physical properties.

(Production example of toner particle 1)
In a four-necked vessel, 720 parts by weight of ion-exchanged water, 950 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by weight of a 1.0 mole aqueous HCl solution are added, and a high-speed stirring device TK is added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 90 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 64.0 parts by mass n-butyl acrylate 16.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.50 parts by mass Styrenic resin (1) 20 parts by mass (Mw = 2650, Mw / Mn = 1) .63)
Polyester resin (1) 5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts by mass negative charge control resin 1 0.5 parts by mass wax [Fischer-Tropsch wax, endothermic main peak temperature 78.2 ° C.]
10 parts by mass 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 9.0, which is a polymerization initiator, in the monomer mixture 1 obtained by dispersing the monomer mixture for 3 hours with an attritor The monomer composition to which part by mass (toluene solution 50%) was added was put into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotational speed of the high-speed stirrer at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. The raw materials and polymerization conditions are shown in Table 4.

Next, the temperature in the container was raised to 80 ° C. and maintained for 3 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain toner particle slurry 1. Dilute hydrochloric acid was added to the container containing the toner particle slurry 1 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 1) having a weight average particle diameter of 5.7 μm. Table 5 shows the raw materials and polymerization conditions.
Table 5 shows the physical properties of the toner particles.

(Production example of toner particle 2)
Styrene resin (2) 60 parts by mass Styrenic resin (3) 40 parts by mass Polyester resin (1) 5 parts by mass Copper phthalocyanine pigment 6.5 parts by mass Negative charge control agent (3,5-di-tert-butyl Aluminum compound of salicylic acid)
0.5 parts by mass negative charge control resin (1) 0.5 parts by mass wax [Fischer-Tropsch wax, endothermic main peak temperature 78 ° C.]
10 parts by mass After the above materials are mixed with a Henschel mixer, melt kneading is performed at 130 ° C. with a twin-screw kneading extruder, the kneaded product is cooled, and then coarsely pulverized with a cutter mill and using a fine pulverizer using a jet stream. After pulverization and further classification using an air classifier, polymer particles (toner particles 2) having a weight average particle diameter of 5.9 μm were obtained.

(Production example of toner particle 3)
64.0 parts by mass of styrene monomer in production example of toner particle 1 54.0 parts by mass, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 9.0 parts by mass 11.5 parts by mass The toner particles 3 were obtained in the same manner as in the production example of the toner particles 1 except that the toner particles were changed to parts.

<Example 1>
Henschel contains 100 parts by mass of toner particles 1 with 1.2 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method and a hydrophobicity of 81, and 0.15 parts by mass of metal oxide 1. It was mixed for 140 seconds with a mixer (Mitsui Mining Co., Ltd.) (mixing step 1). Then, it rested for 120 seconds (pause process 1). Immediately after the 120-second pause, mixing was resumed and mixed for 160 seconds (mixing step 2). Then, it rested for 120 seconds (pause process 2). Immediately after the 120-second pause, mixing was resumed and mixed for 150 seconds (mixing step 3). Then, it rested for 120 seconds (pause process 3). Immediately after the 120-second pause, mixing was resumed and mixed for 150 seconds (mixing step 4). The maximum temperature reached in the tank by repeating the mixing step and the pause step as described above was about 30 ° C. The toner thus obtained is referred to as Toner 1.

Using a toner cartridge of a tandem Canon laser beam printer LBP5500 having the configuration as shown in FIG. 7, 250 g of toner 1 was loaded. And 1.0% printing in each environment of low temperature and low humidity (15 ° C / 10% RH), normal temperature and normal humidity (25 ° C / 55% RH), and high temperature and high humidity (32.5 ° C / 85% RH) Print out the ratio image up to 17,500 sheets, solid image density and fog at the initial and 17,500 output, filming, stop streak, development streak, and drum fusion at the 17,500 output Was evaluated. The results are shown in Table 6, Table 7, and Table 8.

<Image density measurement>
For the image density, using a Macbeth densitometer (RD-914; manufactured by Macbeth), using an SPI auxiliary filter, low temperature and low humidity (L / L) (15 ° C./10% RH), normal temperature and normal humidity (N / N) ) The image density of the fixed image portion of the image output in an environment of (25 ° C./55% RH) and high temperature and high humidity (H / H) (32.5 ° C./85% RH) was measured.
With regard to the durable image density, after being left in each environment for 2 days, it is set in a toner cartridge, and up to 17,500 images with a printing ratio of 1.0% are used on recording paper (75 mg / cm ² ). Printed out. Then, evaluation of the solid image density at the initial stage and when 17,500 sheets were output was performed according to the following evaluation criteria.
Rank A: 1.40 or higher Rank B: 1.30 to 1.39
Rank C: 1.20 to 1.29
Rank D: 1.10 to 1.19
Rank E: 1.00 to 1.09
Rank F: 0.99 or less

<Development streak evaluation>
The development streak was evaluated according to the following criteria from a halftone image (toner applied amount 0.25 mg / cm ² ) obtained after printing 17,500 sheets.
A: A vertical streak in the paper discharge direction, which appears as a development streak, is not seen on the developing roller or the halftone image.
B: Although there are one or two circumferential thin stripes at both ends of the developing roller, no vertical stripe in the paper discharge direction that appears as a developing stripe on the halftone image.
C: Although there are 3 to 5 thin circumferential streaks at both ends of the developing roller, no vertical streak in the paper discharge direction, which appears as a developing streak, is seen on the halftone image. However, it can be erased by image processing.
D: There are 6 to 20 fine circumferential streaks at both ends of the developing roller, and several fine developing streaks can be seen on the halftone image. It cannot be erased even with image processing.
E: 20 or more development streaks are seen on the developing roller and the image of the halftone portion, and cannot be erased even by image processing.

<Fixing test>
Process spin by remodeling the fixing device to the fixing temperature of the fixing unit Canon laser beam printer LBP5500 tandem was modified so as to be adjusted to have a configuration shown in FIG. 7 - undetermined 0.5 mg / cm ² in de 170 mm / sec The toner image was heated and pressed without oil on the image receiving paper to form a fixed image on the image receiving paper.
The fixability is obtained by rubbing the fixed image 10 times with a Kimwipe [S-200 (Crecia Co., Ltd.)] with a load of 75 g / cm ² , and the temperature at which the density reduction rate before and after rubbing is less than 5% is defined as the low temperature offset end temperature. Used for evaluation of fixability.

<Fog>
The fog density (%) is calculated from the difference between the whiteness of the white portion of the printed image and the whiteness of the transfer paper measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), and the image fog is evaluated according to the following criteria. did.
A: Less than 1.0% B: 1.0% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4.0% or more, less than 5.5% E: 5. 5% or more, less than 7.0% F: 7.0% or more

<Stop line>
Stop streaks (also called cleaning blade set traces) are low temperature and low humidity (15 ° C / 10% RH), normal temperature and normal humidity (25 ° C / 55% RH), and high temperature and high humidity (32.5 ° C / 85% RH). After the endurance of 17,500 sheets, the toner cartridge was removed and left for 15 days in each environment. Thereafter, the toner cartridge was set again, a solid image (toner applied amount 0.35 mg / cm ² ) was output, and the presence or absence of a stop streak (a streak perpendicular to the paper discharge direction) was visually evaluated.
A: No cleaning blade set trace perpendicular to the paper discharge direction is seen on the photoconductor or the solid image.
B: Although there is a cleaning blade set trace perpendicular to the circumferential direction on the photoconductor, no cleaning blade set trace perpendicular to the paper discharge direction is seen on the solid image.
C: There is a cleaning blade set trace perpendicular to the circumferential direction on the photosensitive member, and a slight cleaning blade set trace perpendicular to the paper discharge direction is seen on the solid image. However, it can be erased by image processing.
D: A cleaning blade set trace perpendicular to the circumferential direction is present on the photoreceptor, and a cleaning blade set trace perpendicular to the paper discharge direction is seen on the solid image. It cannot be erased even with image processing.

<Filming>
Filming is 17,500 sheets durable under low temperature and low humidity (15 ° C / 10% RH), normal temperature and normal humidity (25 ° C / 55% RH), and high temperature and high humidity (32.5 ° C / 85% RH). Evaluation was made after the delivery. At that time, the degree of contamination of the developing roller on the solid black image and after the solid white image was produced was evaluated. The evaluation levels are shown below.
A: The surface state of the developing roller is extremely uniform.
B: Although the surface state of the developing roller is uniform, a ripple pattern is seen in a very small part.
C: A ripple pattern is seen on a part of the surface of the developing roller.
D: A ripple pattern appears on the entire surface of the developing roller.
E: Ripples on the surface of the developing roller grow and some irregularities are clearly seen.
F: Unevenness on the surface of the developing roller spreads over the entire surface and is clearly understood.

<Photosensitive drum fusion>
Photosensitive drum fusion was evaluated based on the following evaluation criteria by visually observing the surface of the photosensitive drum after the endurance of 17,500 sheets in the durability test and further observing image defects.
A: No fusion occurs during the durability.
B: During the endurance, 1 to 2 points are generated but disappear. Does not appear in the image.
C: After the end of durability, several points of fusion occur but disappear. Level that causes slight unevenness in the image.
D: After the end of durability, several points of fusion occur and do not disappear. Unevenness also occurs in the image.
E: Fusion of 10 points or more occurred.
F: Fusion occurs on the entire surface.

<Examples 2 to 19 and Comparative Examples 1 to 5>
In Examples, Toners 2 to 24 were produced in the same manner except that the toner particles and metal oxides used were changed as shown in Tables 6 to 8, and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 6-8.

Claims (10)

A toner having at least a binder resin and a colorant and toner particles and a metal oxide,
In the moisture adsorption isotherm measured at 30 ° C., the metal oxide has an adsorption moisture amount of M10 (mass%) at a relative humidity of 10% RH, and an adsorption moisture quantity of 90 ° RH at a relative humidity of 90%. (M90-M10) / (90-10) is 0.0001 or more and 0.0070 or less, and the wettability with respect to the mixed solvent of methanol and water was measured by the transmittance of light having a wavelength of 780 nm. In this case, the toner has a methanol concentration of 40.0% by volume or less when the transmittance is 50%.   2. The toner according to claim 1, wherein the metal oxide has a zeta potential (mV) in a zeta potential measurement in a state of being dispersed in methanol of −10.0 mV to 60.0 mV.   3. The toner according to claim 1, wherein the metal oxide has an adsorption moisture amount of 0.60% by mass or less at a relative humidity of 90% RH on a moisture adsorption isotherm at 30 ° C. 3.   4. The metal oxide according to claim 1, wherein a volume-based median diameter in a laser diffraction particle size distribution meter measured in water is 0.10 μm or more and 1.00 μm or less. 5. The toner described.   The metal oxide has an average circularity of 0.950 or more and 1.000 or less with an equivalent circle diameter of 0.80 μm or more and 1.98 μm or less as measured by a flow particle image analyzer. The toner according to any one of Items 4 to 4.   The toner according to claim 1, wherein the metal oxide is manufactured by a gas phase oxidation method. 7. The toner according to claim 1, wherein the metal oxide has a volume resistivity of 1 × 10 ⁶ Ω · cm to 1 × 10 ¹³ Ω · cm.   8. The metal oxide according to claim 1, wherein the metal oxide includes at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, strontium titanate, magnesium titanate, and barium titanate. The toner according to claim 1.   The toner particles are polymerizable by adding a polymerizable monomer composition containing at least a polymerizable monomer and a colorant to an aqueous medium, and granulating the polymerizable monomer composition in the aqueous medium. It is obtained by forming monomer composition particles and polymerizing a polymerizable monomer contained in the polymerizable monomer composition particles. Toner. A charging step of charging the electrostatic latent image carrier with charging means; an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image; and a toner on the toner carrier with a toner layer regulating member In the image forming method, the image forming method includes a developing step of developing the electrostatic latent image with toner to form a toner image on the electrostatic latent image carrier, and the toner contains at least a binder resin and a colorant. A toner having toner particles and a metal oxide,
In the moisture adsorption isotherm measured at 30 ° C., the metal oxide has an adsorption moisture amount of M10 (mass%) at a relative humidity of 10% RH, and an adsorption moisture quantity of 90 ° RH at a relative humidity of 90%. When (M90-M10) / (90-10) is 0.0001 or more and 0.0070 or less, and the wettability test for a mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm. In the image forming method, the methanol concentration when the transmittance is 50% is 40.0% by volume or less.

Images