JP2016114675A - Image formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image formation method that is excellent in transfer efficiency even after used for a long period of time in a high-speed copying machine, and is excellent in scattering and roughening, selected developability, and line/solid ratio.SOLUTION: In an image formation method configured to: charge a static charging image carrier; form a static charging image on the static charging image carrier; develop the static charging image by toner to form a toner image; and transfer the toner image to a transfer material, the static charging image carrier is an electro-photographic photoreceptor that has a surface layer composed of at least a photoconduction layer and hydrogenation amorphous silicon carbide on the photoconduction layer, in which a sum of atomic density of a silicon atom in the surface layer and the atomic density of a carbon atom therein is equal to or more than 6.60×10atom/cm, and defect density of the surface layer to be obtained by electron spin resonance measurement is equal to or less than 2.2×10spins/cm, the toner is toner that has binder resin, and the binder resin has a polyester part having a specific aliphatic compound condensed in a terminal.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an image forming method applied to an image forming apparatus such as an electrophotographic system or an electrostatic recording system, such as an electrophotographic system or an electrostatic recording system, in which an electrostatic charge image formed on an electrophotographic photoreceptor is visualized. It is about.

In recent years, as image forming apparatuses such as copiers and printers have become widespread, the performance required of image forming apparatuses is required to be higher image quality, higher speed, and longer life, and also to reduce running costs. It has been demanded.
As an electrophotographic photoreceptor for achieving high image quality, high speed, and long life, an amorphous silicon photoreceptor using amorphous silicon such as hydrogenated amorphous silicon in a photoconductive layer is known. Amorphous silicon is hereinafter also expressed as “a-Si”. Further, the electrophotographic photoreceptor is also simply referred to as “photoreceptor”.
As a configuration example of the a-Si photosensitive member, a configuration in which a lower charge injection blocking layer, a photoconductive layer, and a surface layer are sequentially laminated on a substrate can be given. Among these, a-Si photoreceptors using hydrogenated amorphous silicon carbide as a material for the surface layer are known. The hydrogenated amorphous silicon carbide is hereinafter also referred to as “a-SiC”. Since the a-SiC surface layer is excellent in wear resistance, it is mainly used in an electrophotographic apparatus having a high process speed.
For example, according to Patent Document 1, the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is set to 6.60 × 10 ²² (atoms / cm ³ ) or more. It is known that the wear resistance can be increased and a long life can be achieved.

On the other hand, in order to reduce the running cost of copying machines and printers, it is important to reduce the consumption of toner, which is a consumable item.
In a copying machine and a printer, an electrostatic latent image on a photoreceptor is developed with toner, and an image is obtained through a process of transferring the toner image on the photoreceptor to a transfer material.
At this time, in order to obtain a high-quality image while suppressing toner consumption, the electrostatic latent image on the photosensitive member is developed with a minimum amount of toner, and the toner image is transferred to a transfer material with high transfer efficiency. There is a need.
When developing an electrostatic latent image on a photoreceptor, if a toner with poor charging uniformity is used, the line / solid ratio tends to increase. The line / solid ratio is a value indicating the ratio of toner consumption between the line portion and the solid black portion. Generally, a line portion such as a character tends to consume more toner than a solid black portion due to an edge effect of an electric field of an electrostatic latent image. Therefore, keeping the line / solid ratio low is important for reducing the toner consumption while maintaining a high image density. Further, toner with poor charging uniformity also tends to deteriorate selective developability. Selective developability is a phenomenon in which fine powder that tends to have a high charge amount is selectively developed, and toner having a large particle size accumulates in the developing device. If the selective developability is poor, the ratio of the toner having a large particle diameter increases with long-term use, and the image quality tends to deteriorate.

In addition, when the transfer efficiency is low, in order to obtain a high-quality image, more toner than necessary is developed on the photoconductor, which increases the consumption of toner necessary to obtain one image. End up.
In the transfer process, an electrostatic transfer bias is formed by applying a voltage having a polarity opposite to that of the toner to the transfer material, and the toner image is transferred from the photoreceptor to the transfer material. The transfer efficiency increases as the electrostatic force that the toner receives from the transfer bias increases.
However, if the voltage applied to the transfer material is increased in order to increase the transfer efficiency, a discharge occurs between the transfer material and the photosensitive member, resulting in a decrease in transfer bias and conversely a decrease in transfer efficiency. Are known. Furthermore, the discharge start voltage varies depending on the type of transfer material and the temperature and humidity of the external environment.
Therefore, high transfer efficiency is indispensable for obtaining high-quality images regardless of the type of transfer material and the temperature and humidity of the external environment.
In order to improve transfer efficiency, it is necessary to reduce the adhesion between the photoreceptor and the toner. In particular, since the non-electrostatic adhesion force is proportional to the contact area between the toner and the photoconductor, various studies have been conducted for the purpose of reducing the contact area.

For example, in Patent Document 2, an inorganic fine particle having a large particle size is externally added to a toner to act as a spacer between the toner and the photoreceptor, thereby reducing the contact area between the toner and the photoreceptor and improving the transfer efficiency. It is known. However, in this method, when the external additive is embedded due to durability or the spacer particles move to the concave portions of the toner particles, the transfer efficiency may be significantly reduced.
On the other hand, a method of making the toner shape spherical to reduce the contact area is also known, but it is preferable that the toner is non-spherical considering the cleaning property of the photosensitive member by the blade.

In order to solve these problems, proposals have been made to control the unevenness of the toner particle surface. For example, Patent Document 3 discloses a case where the circularity of the toner is 0.930 or more and 0.980 or less, and the unevenness of the toner particle surface is defined by a waviness motif average value. In this method, by controlling the unevenness of the non-spherical toner particles, the spacer particles that remain in the recesses can be reused, and the transfer efficiency can be maintained.
However, since higher speed is required in the future, and the stress that the toner is subjected to in the developing device is high, it is difficult to suppress a decrease in transfer efficiency due to embedding of the external additive, and there is room for improvement. .

JP 2010-49241 A JP 2002-108001 A JP 2013-148760 A

  An object of the present invention is to provide an image forming method that has good transfer efficiency even after long-term use in a high-speed copying machine, good selective developability, excellent image quality, low line / solid ratio, and low toner consumption. That is.

The electrostatic image carrier is charged, an electrostatic image is formed on the charged electrostatic image carrier, the electrostatic image is developed with toner to form a toner image, and the electrostatic image on the electrostatic image carrier In an image forming method for transferring the toner image to a transfer material,
The electrostatic charge image carrier is an electrophotographic photosensitive member having at least a photoconductive layer and a surface layer composed of hydrogenated amorphous silicon carbide on the photoconductive layer,
The sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is 6.60 × 10 ²² atoms / cm ³ or more,
The defect density determined by electron spin resonance measurement of the surface layer is 2.2 × 10 ¹⁹ spins / cm ³ or less, the toner is a toner having a binder resin, and the binder resin is an aliphatic monolith The present invention relates to an image forming method characterized by having a polyester portion condensed at the terminal with at least one aliphatic compound selected from the group consisting of carboxylic acid and aliphatic monoalcohol.

  According to the present invention, there is provided an image forming method in which a transfer efficiency is good after a long period of use in a high-speed copying machine, an excellent selective developability, an excellent image quality, a low line / solid ratio and a low toner consumption. be able to.

Schematic sectional view of an electrophotographic photosensitive member that can be used in the present invention Schematic sectional view of an electrophotographic apparatus that can be used in the present invention Examples of film forming equipment that can produce electrophotographic photoreceptors Schematic diagram of chart used for image memory evaluation

As a result of earnestly examining the method for reducing the non-electrostatic adhesion between the photosensitive member and the toner in order to improve the transfer efficiency,
The electrostatic image bearing member comprises an electrophotographic photosensitive member (at least a photoconductive layer and a hydrogenated amorphous silicon) having at least a photoconductive layer and a surface layer composed of hydrogenated amorphous silicon carbide on the photoconductive layer. An electrophotographic photosensitive member sequentially laminated with a surface layer composed of carbide),
The sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is 6.60 × 10 ²² atoms / cm ³ or more,
The defect density determined by electron spin resonance measurement of the surface layer is 2.2 × 10 ¹⁹ spins / cm ³ or less. The toner is a toner having a binder resin, and the binder resin is an aliphatic monocarboxylic acid. It has been found that an unprecedented transfer efficiency can be obtained by using an image forming method having a polyester moiety in which at least one aliphatic compound selected from the group consisting of an acid and an aliphatic monoalcohol is condensed at the terminal.

The reason why this configuration provides an unprecedented superior effect is not clear, but is probably as follows.
The defect density of the surface layer of the photoreceptor used in the present invention is 2.2 × 10 ¹⁹ spins / cm ³ or less.
The defect density is a value calculated from a signal considered to be mainly caused by dangling bonds by an electron spin resonance (ESR) method. A dangling bond is an unpaired electron, and is considered to be a chemically highly active and unstable portion. That the defect density is 2.2 × 10 ¹⁹ spins / cm ³ or less indicates that the surface layer of the photoconductor has a more stable state than before, and the surface free energy of the photoconductor is It is considered low. Furthermore, since the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is 6.60 × 10 ²² atoms / cm ³ or more, the wear resistance and oxidation resistance are high. It is possible to maintain stability for a long time.
On the other hand, the toner used in the present invention is characterized by having a polyester portion in which an aliphatic compound is condensed at the terminal. It is known that condensation of an aliphatic compound to a polyester site improves the low-temperature fixability of the toner, but it is not common to improve transfer efficiency. The aliphatic compound itself is a compound having lower cohesive energy and surface free energy than the polyester part. For this reason, the condensation of the aliphatic compound at the end of the polyester site facilitates the transfer of the aliphatic group-derived alkyl group to the surface of the toner, and as a result, it is presumed that the surface free energy of the toner is lowered. However, in an experiment using a conventional photoconductor, a significant improvement in transfer efficiency as in the present invention has not been obtained.
That is, an improvement in transfer efficiency that has not been achieved in the past has been found for the first time by using a toner having a low surface free energy in combination with a photoreceptor having a low surface free energy in the present invention.

First, the layer structure of the electrophotographic photosensitive member of the present invention will be described.
Hereinafter, the atomic density of silicon atoms is also expressed as “Si atomic density”. The atomic density of carbon atoms is also expressed as “C atomic density”. The sum of the atomic density of silicon atoms and the atomic density of carbon atoms is also expressed as “Si + C atomic density”.
FIG. 1A is a schematic diagram showing a layer structure of an a-Si photosensitive member. A lower charge injection blocking layer 102, a photoconductive layer 103, and a surface layer 104 are sequentially stacked on the substrate 101. This layer structure is mainly applied to an a-Si photosensitive member for positive charging.
FIG. 1B is a schematic diagram showing a layer structure of an a-Si photosensitive member in which an intermediate layer 105 is provided between the photoconductive layer 103 and the surface layer 104. By applying a charge injection blocking capability to the intermediate layer 105, the present invention can also be applied to a negatively charged a-Si photoreceptor.
FIG. 1C is a schematic diagram of a layer structure of an a-Si photosensitive member in which a plurality of intermediate layers 106 are provided between the photoconductive layer 103 and the surface layer 104. This configuration can also be applied to an a-Si photosensitive member for negative charging by imparting a charge injection blocking capability to any of the plurality of intermediate layers 106.
FIG. 1D is a schematic diagram of a layer configuration of an a-Si photosensitive member in which a change layer 107 is provided between the photoconductive layer 103 and the surface layer 104. This configuration can also be applied to a negatively charged a-Si photosensitive member by imparting charge injection blocking ability to a part of the change layer 107.

Next, each layer and substrate constituting the photosensitive member having the above-described layer structure will be described.
(Surface layer)
The surface layer can obtain the effect of the present invention by satisfying the following requirements.
The sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is 6.60 × 10 ²² atoms / cm ³ or more,
The defect density calculated | required by the electron spin resonance measurement of the said surface layer shall be 2.2 * 10 < ¹⁹ > spins / cm < ³ > or less.
The a-SiC surface layer is repeatedly charged at the time of image output, whereby the outermost surface is oxidized and a polar group is generated. When the polar group is generated, the surface free energy increases, so that the adhesion between the toner and the photoreceptor increases, and the transfer efficiency deteriorates. That is, in order to improve transfer efficiency, it is effective to suppress oxidation of the a-SiC surface layer.
In order to suppress the oxidation of the a-SiC surface layer, the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the a-SiC surface layer is 6.60 × 10 ²² atoms / cm ³ or more. To do. By doing in this way, the bond strength of the silicon atom and carbon atom which form the frame | skeleton of an a-SiC surface layer becomes strong, and oxidation resistance improves. As a result, transfer efficiency is improved.
The Si + C atom density is preferably 6.60 × 10 ²² atoms / cm ³ or more and 7.24 × 10 ²² atoms / cm ³ or less, and 6.90 × 10 ²² atoms / cm ³ or more and 7.24 × 10 ^22. More preferably, it is at most atoms / cm ³ .

Further, the defect density of the a-SiC surface layer affects the adhesion between the toner and the photoreceptor. When the defect density of the a-SiC surface layer increases, the surface layer becomes chemically unstable, and the surface free energy may increase. That is, in order to improve the transfer efficiency, it is necessary to reduce the defect density of the a-SiC surface layer to keep the surface free energy low. In the present invention, it has been found that the transfer efficiency is improved by setting the defect density of the a-SiC surface layer to 2.2 × 10 ¹⁹ spins / cm ³ or less.
When the defect density exceeds 2.2 × 10 ¹⁹ spins / cm ³ , the surface free energy of the photoreceptor increases, and the non-electrostatic adhesion between the toner and the photoreceptor increases. Transfer toner cannot be improved by using a toner containing a condensed polyester moiety. It has also been found that the resistivity of the surface layer changes depending on the defect density, which also affects the image memory. Image memory is a phenomenon in which an afterimage of an image formed on the photoconductor on the first round of the photoconductor appears in the image formation process on the second round. When the defect density of the surface layer is lowered, the resistivity tends to increase. Since the image memory has a lower surface layer resistivity, the defect density is 9.0 × 10 ¹⁸ spins / cm ³ or more and 2.2 × 10 in order to achieve both transfer efficiency and suppression of the image memory. It is preferably controlled to ¹⁹ spins / cm ³ or less, more preferably 1.1 × 10 ¹⁹ spins / cm ³ or more and 1.8 × 10 ¹⁹ spins / cm ³ or less.

On the other hand, in improving the light transmittance of the a-SiC surface layer, the number of carbon atoms relative to the sum of the number of silicon atoms (Si) and the number of carbon atoms (C) in the a-SiC surface layer ( The ratio C) (C / (Si + C)) is preferably in the range of 0.50 to 0.65, and C / (Si + C) is more preferably in the range of 0.55 to 0.63. . By setting it within this range, the sensitivity characteristic of the photoconductor is improved, and the occurrence of roughness due to uneven wear of the surface of the photoconductor is suppressed.
Furthermore, from the viewpoint of transfer efficiency, the ratio (a ₂ / a ₁ ) of the absorbance a ₂ having a wave number of 2960 cm ^{−1 to} the absorbance a _{1 having} a wave number of 2890 cm ⁻¹ in the infrared absorption spectrum of the a-SiC surface layer is 0.52 or less. More preferred. Absorptions at a wavenumber of 2960 cm ^-1 in the infrared absorption ^spectrum, a peak due to absorption by sp 3 -CH _3, absorptions at a wavenumber of 2890cm ^{-1 is} a peak due to absorption by sp 3 -CH. That _is, as _a 2 / a ₁ is low, it means that a methyl group is less contained in the a-SiC surface layer.
In particular, when the number of methyl groups in the a-SiC surface layer is reduced, local discontinuity of the network of silicon atoms and carbon atoms is reduced. Therefore, the Si + C atom density is set to 6.60 × 10 ²² atoms / cm ³ or more, and a ₂ / a ₁ is controlled to be low, so that the silicon atoms and carbon atoms in the a-SiC surface layer are included in the network. Locally weak parts are difficult to form. As a result, it is considered that the a-SiC skeleton is further strengthened, the surface free energy is lowered, and the transfer efficiency is improved. Of course, the bonding state between the silicon atom and the hydrogen atom also affects the skeleton of the a-SiC.

However, since the energy of the C—H bond and the Si—H bond is 98.8 (kcal / mol) and 70.4 (kcal / mol), respectively, the C—H bond is actually higher than the Si—H bond. There is a tendency for more bonds. That is, the change in the way hydrogen atoms are incorporated into the a-SiC surface layer appears significantly in the C—H bond. Therefore, in the present invention, focusing on the state of the hydrogen atoms bonded to a carbon atom, the ratio _a 2 / _{a 1} absorbance _{a 2} of wavenumber 2960 cm ^-1 to the absorbance _{a 1} wavenumber 2890cm ^-1 in the infrared absorption spectrum In order to improve transfer efficiency, it is more preferable to set it to 0.52 or less.
Further, the a ₂ / a ₁ is more preferably from 0.10 to 0.52, and further preferably from 0.46 to 0.52. The a ₂ / a ₁ can be controlled by adjusting the flow rate of the raw material gas and the reaction pressure.
In addition, the film thickness of the surface layer is preferably 0.1 μm or more and 2.5 μm or less.

(Middle layer)
In the present invention in which the light transmittance of the a-SiC surface layer is improved, it is preferable to provide an intermediate layer composed of a-SiC between the a-SiC surface layer and the photoconductive layer.
In the present invention, in order to improve the light transmittance, C / (Si + C) is preferably set to 0.50 or more and 0.65 or less. That is, it is preferable that the a-SiC surface layer has a wide optical band gap. In this case, unless the band gap of the photoconductive layer is changed, the difference in optical band gap between the surface layer and the photoconductive layer is increased. As the optical band gap difference increases, band mismatch increases, and charge transfer between the surface layer and the photoconductive layer may not be smooth.

In such a case, by providing an intermediate layer with an optimized composition of a-SiC, the photocarrier generated by exposure can be easily moved to the surface layer, so that a good electrostatic latent image can be easily maintained and better. It becomes possible to obtain a good image quality. For this purpose, (C of the a-SiC intermediate layer is used.
/ (Si + C)) is preferably set lower than (C / (Si + C)) of the a-SiC surface layer.
Of course, a plurality of layers in which (C / (Si + C)) is changed in stages are provided in the a-SiC intermediate layer, or (C / (Si + C)) in the a-SiC intermediate layer is continuously changed. May be. In this case, it is preferable that the (C / (Si + C)) of the a-SiC intermediate layer is monotonously increased from the photoconductive layer to the a-SiC surface layer. The monotonic increase means that (C / (Si + C)) does not have a region where the photoconductive layer is substantially lowered toward the surface layer.
Further, in the case of a negatively charged photoreceptor, it is effective for obtaining charging characteristics to impart charge injection blocking ability to the intermediate layer. In order to improve the charge injection stopping ability, it is effective to include the group 13 of the periodic table in the a-SiC intermediate layer. Among atoms belonging to Group 13 of the periodic table, a boron atom, an aluminum atom, and a gallium atom are preferable. The intermediate layer imparted with the charge injection blocking ability is hereinafter also referred to as “upper blocking layer”.

(Photoconductive layer)
In the present invention, the photoconductive layer may be any photoconductive layer as long as it has photoconductive characteristics that can satisfy the electrophotographic characteristics. From the viewpoint of durability and stability, a-Si light is used. A conductive layer is preferred.
In the present invention, when a photoconductive layer composed of a-Si is used as the photoconductive layer, in order to compensate for dangling bonds in a-Si, halogen atoms can be contained in addition to hydrogen atoms. .
The total content (H + X) of the hydrogen atom (H) and the halogen atom (X) is 10 atom% with respect to the sum (Si + H + X) of the silicon atom (Si), the hydrogen atom (H), and the halogen atom (X). It is preferable that it is above, and it is more preferable that it is 15 atomic% or more. On the other hand, it is preferably 30 atomic% or less, and more preferably 25 atomic% or less.

In the present invention, the photoconductive layer preferably contains atoms for controlling conductivity as required. Atoms for controlling conductivity may be contained in the photoconductive layer in a uniformly distributed state, or there may be a portion containing in a non-uniform distribution state in the film thickness direction. May be.
As atoms for controlling conductivity, so-called impurities in the semiconductor field can be given. That is, an atom belonging to Group 13 of the periodic table giving p-type conductivity or an atom belonging to Group 15 of the periodic table giving n-type conductivity can be used. Among atoms belonging to Group 13 of the periodic table, a boron atom, an aluminum atom, and a gallium atom are preferable. Among atoms belonging to Group 15 of the periodic table, a phosphorus atom and an arsenic atom are preferable.
The content of atoms for controlling the conductivity contained in the photoconductive layer is preferably 1 × 10 ⁻² atom ppm or more with respect to silicon atoms (Si). On the other hand, it is preferably 1 × 10 ² atom ppm or less.

In the present invention, the film thickness of the photoconductive layer is preferably 15 μm or more and 60 μm or less from the viewpoint of electrophotographic characteristics and cost. If the film thickness of the photoconductive layer is 15 μm or more, the amount of current passing through the charging member is unlikely to increase and deteriorate.
If the thickness of the photoconductive layer is 60 μm or less, an abnormal growth site of a-Si (for example, a site of 50 μm or more and 150 μm or less in the horizontal direction and a site of 5 μm or more and 20 μm or less in the height direction) is difficult to increase. Damage to the rubbing member is suppressed, and the occurrence of image defects is suppressed.
The photoconductive layer may be composed of a single layer or a plurality of layers (for example, a charge generation layer and a charge transport layer).

(Lower charge injection blocking layer)
In the present invention, it is preferable to provide a charge injection blocking layer having a function of blocking charge injection from the substrate side between the substrate and the photoconductive layer. The lower charge injection blocking layer is hereinafter also referred to as “lower blocking layer”. The lower blocking layer is a layer having a function of blocking the injection of charges from the substrate to the photoconductive layer when the surface of the photoreceptor is subjected to a charging process with a certain polarity. In order to provide such a function, the lower blocking layer should be based on the material constituting the photoconductive layer and contain a relatively large number of atoms for controlling conductivity compared to the photoconductive layer. Is preferred.
The atoms contained in the lower blocking layer for controlling the conductivity may be contained in the lower blocking layer in a uniformly distributed state or in a non-uniform distribution state in the film thickness direction. There may be a part that does. If the distribution concentration is non-uniform, it is preferable to contain it so that it is distributed more on the substrate side. In any case, it is preferable that atoms for controlling conductivity are contained in the lower blocking layer in a uniform distribution in the in-plane direction parallel to the surface of the substrate from the viewpoint of uniform characteristics. .
As atoms to be contained in the lower blocking layer in order to control conductivity, atoms belonging to Group 13 or 15 of the periodic table can be used depending on the charge polarity.

Furthermore, the adhesion between the lower blocking layer and the substrate can be improved by containing at least one kind of carbon atom, nitrogen atom and oxygen atom in the lower blocking layer.
At least one kind of carbon atom, nitrogen atom, and oxygen atom contained in the lower blocking layer may be contained in a uniformly distributed state in the lower blocking layer. Moreover, although contained uniformly in the film thickness direction, there may be a part contained in a non-uniform distribution in the in-plane direction. In any case, the atoms for controlling the conductivity are contained in the charge injection blocking layer in a uniform distribution in the in-plane direction parallel to the surface of the substrate from the viewpoint of achieving uniform characteristics. preferable.

  The film thickness of the lower blocking layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.3 μm or more and 5 μm or less from the viewpoint of electrophotographic characteristics and cost. By setting the film thickness to 0.1 μm or more, the charge injection ability from the substrate can be sufficiently obtained, and a preferable charging ability can be obtained. On the other hand, when the thickness is 5 μm or less, it is possible to suppress an increase in manufacturing cost due to the extension of the formation time of the lower blocking layer.

(Substrate)
The substrate preferably has conductivity (conductive substrate), and preferably can hold the photoconductive layer formed on the surface and the surface layer. Examples of the material of the base include metals such as aluminum and iron, and alloys thereof. Note that a conductive substrate (conductive substrate) is hereinafter also referred to as a “conductive substrate”.

(Electrophotographic apparatus having electrophotographic photosensitive member of the present invention)
An image forming method using an electrophotographic apparatus having an a-Si photoreceptor will be described with reference to FIG.
First, the photosensitive member 201 is rotated, and the surface of the photosensitive member 201 is uniformly charged by the main charger (charging unit) 202. Thereafter, the electrostatic latent image forming means (exposure means) 203 irradiates the surface of the photoconductor 201 with image exposure light to form an electrostatic latent image on the surface of the photoconductor 201, and then the developing device (developing means) 204. Development is performed using the supplied toner. As a result, a toner image is formed on the surface of the photoreceptor 201.
Then, the toner image is transferred to an intermediate transfer member 205 which is an example of a transfer unit, secondarily transferred from the intermediate transfer member 205 to a transfer material (not shown) such as paper, and the toner image is transferred by a fixing unit (not shown). Is fixed on the transfer material.
On the other hand, toner remaining on the surface of the photoconductor 201 to which the toner image has been transferred is removed by a cleaner (cleaning means) 206, and then the surface of the photoconductor 201 is exposed by a pre-exposure device 207. In this way, the remaining carriers in the electrostatic latent image in the photoconductor 201 are neutralized. Image formation is continuously performed by repeating this series of processes.

(Manufacturing apparatus and manufacturing method for manufacturing the electrophotographic photosensitive member of the present invention)
The method for producing the electrophotographic photosensitive member of the present invention may be any method as long as it can form a layer that satisfies the above-mentioned regulations. Specific examples include plasma CVD, vacuum deposition, sputtering, and ion plating. Among these, the plasma CVD method is preferable from the viewpoint of easy supply of raw materials.
Below, the manufacturing apparatus and manufacturing method using plasma CVD method are demonstrated.

FIG. 3 is a diagram schematically showing an example of a photoconductor deposition apparatus by RF plasma CVD using a high-frequency power source for producing the a-Si photoconductor of the present invention.
This deposition apparatus is roughly composed of a deposition apparatus 3100 having a reaction vessel 3110, a source gas supply device 3200, and an exhaust device (not shown) for depressurizing the inside of the reaction vessel 3110.
In the reaction vessel 3110 in the deposition apparatus 3100, a substrate 3112, a substrate heating heater 3113, and a source gas introduction pipe 3114 connected to the ground are installed. Further, a high frequency power source 3120 is connected to the cathode electrode 3111 via a high frequency matching box 3115.
The source gas supply device 3200 includes source gas cylinders 3221 to 3225, valves 3231 to 3235, pressure regulators 3261 to 3265, inflow valves 3241 to 3245, outflow valves 3251 to 3255, and mass flow controllers 3211 to 3215. A gas cylinder filled with each source gas is connected to a source gas introduction pipe 3114 in the reaction vessel 3110 via an auxiliary valve 3260. 3116 is a gas pipe, 3117 is a leak valve, and 3121 is an insulating material.

Next, a method for forming a deposited film using this apparatus will be described. First, the substrate 3112 that has been degreased and washed in advance is placed in the reaction vessel 3110 via a cradle 3123. Next, an exhaust device (not shown) is operated to exhaust the reaction vessel 3110. While viewing the display of the vacuum gauge 3119, when the pressure in the reaction vessel 3110 reaches a predetermined pressure of, for example, 1 Pa or less, power is supplied to the substrate heating heater 3113 to cause the substrate 3112 to have a temperature of, for example, 50 ° C. or more and 350 ° C. or less. Heat to a predetermined temperature. At this time, an inert gas such as Ar or He can be supplied from the gas supply device 3200 to the reaction vessel 3110 and heated in an inert gas atmosphere.
Next, a gas used to form a deposited film is supplied from the gas supply device 3200 to the reaction vessel 3110. That is, if necessary, the valves 3231 to 3235, the inflow valves 3241 to 3245, and the outflow valves 3251 to 3255 are opened, and the flow rate is set to the mass flow controllers 3211 to 3215. When the flow rate of each mass flow controller is stabilized, the main valve 3118 is operated while viewing the display of the vacuum gauge 3119 to adjust the pressure in the reaction vessel 3110 to a desired pressure.

When a desired pressure is obtained, high-frequency power is applied from the high-frequency power source 3120 and simultaneously the high-frequency matching box 3115 is operated to generate plasma discharge in the reaction vessel 3110. Thereafter, the high frequency power is quickly adjusted to a desired power, and a deposited film is formed.
When the formation of the predetermined deposited film is finished, the application of the high frequency power is stopped, the valves 3231 to 3235, the inflow valves 3241 to 3245, the outflow valves 3251 to 3255, and the auxiliary valve 3260 are closed, and the supply of the raw material gas is finished. . At the same time, the main valve 3118 is fully opened, and the inside of the reaction vessel 3110 is exhausted to a pressure of 1 Pa or less, for example.
The formation of the deposited film is completed as described above. When a plurality of deposited films are formed, the above procedure is repeated again to form each layer. The bonding region can also be formed by changing the flow rate of the source gas, the pressure, and the like in a certain time toward the conditions for forming the photoconductive layer.
After all the deposited films are formed, the main valve 3118 is closed, an inert gas is introduced into the reaction vessel 3110, and after returning to atmospheric pressure, the substrate 3112 is taken out.

For the formation of the a-SiC surface layer, silanes such as silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) can be suitably used as a source gas for supplying silicon atoms. As the source gas for the carbon atoms supplied, for example, methane _(CH 4), acetylene _(C 2 _{H 2)} gas or the like can be suitably used. By adjusting the mixing ratio of these raw material gases, (C / (Si + C)) of a-SiC can be adjusted.
In the formation of the a-SiC surface layer according to the present invention, hydrogen (H ₂ ) dilution is a useful method for adjusting the Si + C atom density and the defect density. By diluting the raw material gas with hydrogen, the amount of hydrogen atoms contained in the formed a-SiC surface layer is once greatly reduced and then slightly increased. In the region where the amount of hydrogen atoms contained in the a-SiC surface layer decreases, the Si + C atom density increases as the amount of hydrogen atoms contained in the a-SiC surface layer decreases.

Further, in a region where the amount of hydrogen atoms contained in the a-SiC surface layer is slightly increased by increasing the amount of dilution by hydrogen atoms (hereinafter also referred to as “hydrogen dilution amount”), it is contained in the a-SiC surface layer. As the amount of hydrogen atoms increases slightly, the defect density decreases. In other words, the Si + C atom density and the defect density can be controlled by optimizing the hydrogen dilution amount.
As other parameters, reducing the flow rate of the source gas, increasing the high frequency power, or increasing the temperature of the substrate can increase the Si + C atom density. On the other hand, the defect density can be lowered by increasing the pressure in the reaction vessel (hereinafter also referred to as “reaction pressure”). What is necessary is just to set combining these conditions suitably.

For the formation of the intermediate layer, the same method as that for forming the surface layer can be employed. And it forms by setting conditions, such as quantity of source gas etc. which are supplied to a reaction container, high frequency electric power, reaction pressure, and temperature of a substrate if needed. In order to impart charge injection blocking capability to the intermediate layer, the intermediate layer may be formed by adding a source gas containing atoms belonging to Group 13 or 15 of the periodic table depending on the charge polarity. Examples of the source gas containing atoms belonging to Group 13 or Group 15 of the periodic table include phosphine (PH ₃ ) and diborane (B ₂ H ₆ ).
For the formation of the photoconductive layer, for example, silanes such as silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) can be suitably used as the source gas for supplying silicon atoms. In addition to the above silanes, for example, hydrogen (H ₂ ) can be suitably used as the source gas for supplying hydrogen atoms.
In addition, when a photoconductive layer such as the above-described halogen atom, atom for controlling conductivity, carbon atom, oxygen atom, nitrogen atom or the like is included, a gaseous or easily gasifiable substance containing each atom is used. What is necessary is just to use suitably as a material.

(Measurement of surface layer thickness)
First, the center part of the longitudinal direction in the arbitrary circumferential directions of the reference photoconductor was cut out with a 15 mm square to prepare a reference sample.
Next, the photoreceptor on which the lower blocking layer, the photoconductive layer, the upper blocking layer, and the surface layer were formed was cut out in the same manner to prepare a measurement sample.
The reference sample and the measurement sample were measured by spectroscopic ellipsometry (manufactured by JA Woollam: high-speed spectroscopic ellipsometry M-2000) to determine the film thickness of the surface layer.
Specific measurement conditions of spectroscopic ellipsometry are incident angles: 60 °, 65 °, 70 °, measurement wavelengths: 195 nm to 700 nm, and beam diameter: 1 mm × 2 mm.
First, for the reference sample, the relationship between the wavelength, the amplitude ratio Ψ, and the phase difference Δ was determined at each incident angle by spectroscopic ellipsometry.

Next, using the measurement result of the reference sample as a reference, the relationship between the wavelength, the amplitude ratio Ψ, and the phase difference Δ was determined at each incident angle by spectroscopic ellipsometry, similarly to the reference sample.
Further, a lower blocking layer, a photoconductive layer, an upper blocking layer, and a surface layer were sequentially formed. Then, using the layer structure having the roughness layer where the surface layer and the air layer coexist on the outermost surface as a calculation model, the volume ratio of the surface layer to the air layer of the roughness layer is changed by analysis software, and each incident angle is changed. The relationship between the wavelength, the amplitude ratio Ψ, and the phase difference Δ was calculated. Then, the mean square error of the relationship between the wavelength, the amplitude ratio Ψ and the phase difference Δ obtained by the above calculation at each incident angle and the relationship between the wavelength, the amplitude ratio Ψ and the phase difference Δ obtained by measuring the measurement sample is minimized. The calculation model was selected.
The film thickness of the surface layer was calculated using the selected calculation model, and the obtained value was taken as the film thickness of the surface layer. The analysis software is J.I. A. Woolase WVASE32 was used. The volume ratio of the surface layer to the air layer of the roughness layer was calculated by changing the ratio of the air layer in the roughness layer by 1 from 10: 0 to 1: 9 in the surface layer: air layer.
In the positively charged a-Si photosensitive member produced under each film forming condition of this example, the wavelength and amplitude obtained by calculation when the volume ratio of the surface layer of the roughness layer to the air layer is 8: 2. The mean square error of the relationship between the ratio Ψ and the phase difference Δ and the relationship between the wavelength, the amplitude ratio Ψ and the phase difference Δ obtained by measurement was minimized.

(Measurement of (C / (Si + C)) and Si + C atom density)
After the measurement by spectroscopic ellipsometry was completed, the number of silicon atoms and carbon atoms in the surface layer in the RBS measurement area was measured by RBS (Rutherford backscattering method) using the following apparatus for the measurement sample. .
Backscattering measurement apparatus: AN-2500 Nisshin High Voltage Co., Ltd. (C / (Si + C)) was determined from the number of atoms of silicon atoms and carbon atoms measured. Next, Si atom density, C atom density, and Si + C atom density were determined using the surface layer thickness determined by spectroscopic ellipsometry for silicon atoms and carbon atoms determined from the RBS measurement area.
The intermediate layer (C / (Si + C)) was analyzed in the depth direction by simulation analysis of the RBS measurement results.
Specific measurement conditions for RBS are incident ions: ⁴ He ⁺ , incident energy: 2.3 MeV, incident angle: 75 °, sample current: 35 nA, and incident beam length: 1 mm. The RBS detector was measured with a scattering angle of 160 ° and an aperture diameter of 8 mm, and the HFS detector was measured with a recoil angle of 30 ° and an aperture diameter of 8 mm + Slit.

(Defect density measurement)
The defect density of the a-SiC surface layer was measured by an electron spin resonance (ESR) method using the following apparatus.
Body: BRUKER Elexsys E580,
Gauss meter: ER036TM manufactured by BRUKER
Cryostat: ESR900 manufactured by OXFORD.
The measurement sample was cut into a strip (20 mm × 3 mm) at the center in the longitudinal direction in an arbitrary circumferential direction of the photoreceptor, and ESR measurement was performed under the following conditions.
A reference sample was similarly cut out from the reference photoreceptor. Similarly, ESR measurement was performed for the reference sample, and the number of defects due to the surface layer was calculated from the difference between the measurement sample and the reference sample. In addition, the defect density (spin density) of the a-SiC surface layer was calculated from a signal (g value = 2.020-2.0030 vicinity) considered to be mainly caused by dangling bonds on C. The defect density was calculated | required using the film thickness of the surface layer calculated | required by spectroscopic ellipsometry with respect to the number of defects calculated | required from the measurement area of ESR.
Specific measurement conditions of the ESR method were as follows.
Measurement temperature: 30K, central magnetic field: 3369G, magnetic field sweep range: 200G,
Modulation: 100 kHz, 20 G, microwave: 9.43 GHz, 2 μW,
Sweep time: 83.886s × 10times, time constant: 163.84ms,
Number of data points: 1024 points, cavity: TE011, cylindrical type.

(FT-IR-ATR method)
The functional group of the a-SiC surface layer was measured by the FT-IR-ATR (Fourier transform infrared spectroscopy-attenuated total reflection) method using the following apparatus.
Bio-Rad Digilab: FT-IR equipment FTS-55A
As a measurement sample, a central portion in the longitudinal direction in an arbitrary circumferential direction of the photosensitive member was cut out as a 15 mm square, and FT-IR-ATR measurement was performed under the following conditions.
Specific measurement conditions of the FT-IR-ATR method were as follows.
Light source: special ceramics, detector: HgCdTe, resolution: 4 cm ⁻¹ ,
Integration count: 256 times, IRE: Ge, incident angle: 60 degrees,
Attachment: Attachment for single reflection ATR (Seagull).
When the refractive index of the a-SiC surface layer is 1.9 to 2.5 under the above conditions, the measurement depth of the ATR method is 2000 cm ⁻¹ and a maximum of 0.2 μm. Therefore, by laminating the a-SiC surface layer by 0.3 μm or more, the influence of the lower layer than the a-SiC surface layer can be ignored.
It performs baseline correction of the measured waveform to determine the ratio _a 2 / _{a 1} absorbance _{a 2} of wavenumber 2960 cm ^-1 to the absorbance _{a 1} wavenumber 2890cm ^-1.

Next, the toner in the present invention will be described. First, the binder resin will be described.
The binder resin is characterized in that it has a polyester moiety in which at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid and an aliphatic monoalcohol is condensed at the terminal. By using the toner containing the binder resin together with the photoconductor, transfer efficiency unprecedented can be obtained.
It is important that the aliphatic compound used in the present invention is a monocarboxylic acid or a monoalcohol. Since the functional group is monovalent, the aliphatic compound is bonded to the end of the polyester portion. The alkyl group derived from the aliphatic compound bonded to the terminal is more likely to move to the surface because the molecular movement is easier than the alkyl group bonded to the inside of the molecular chain, effectively reducing the surface free energy of the toner. Contribute to.

The aliphatic compound used for the binder resin preferably has 30 to 102 carbon atoms, more preferably 50 to 80 carbon atoms. The aliphatic compound may be a mixture of aliphatic compounds having different carbon numbers. In the case of a mixture of aliphatic compounds having different carbon numbers, the average value of the carbon numbers preferably has the above range. By setting the number of carbons in the above range, transfer efficiency is improved. The reason why the transfer efficiency is improved by setting the carbon number within the specified range is not clear, but can be considered as follows.
By setting the number of carbon atoms to 30 or more, the alkyl group derived from the aliphatic compound bonded to the molecular chain of the binder resin has a certain size, so that the adhesive force between the toner and the photoreceptor can be effectively reduced. The size is sufficient and transfer efficiency is good. Further, the colorant and the charge control agent can be effectively dispersed in the binder resin, so that the micro charge uniformity of the toner is improved and the scattering is improved. Scattering means that when developing an electrostatic latent image on a photosensitive member with toner, toner with non-uniform charge cannot sufficiently follow the development bias, and therefore toner is also applied to the non-image area around the image area. It is a phenomenon that develops as if scattered.
By setting the number of carbon atoms to 102 or less, it is considered that the molecular weight does not become too large and can move freely to some extent in the binder resin, and tends to be biased to the surface. As a result, the adhesion force between the toner and the photoconductor can be effectively reduced, and the transfer efficiency is improved. Further, it is considered that good charge uniformity can be obtained without hindering the interaction between the charge control agent and the binder resin, and the scattering is improved.

In the present invention, the binder resin has a polyester moiety. In the present invention, the “polyester part” means a part derived from polyester, and the resin having a polyester part includes, for example, a polyester resin and a hybrid resin in which a polyester part and other resin units are bonded. Examples of other resins include vinyl resins, polyurethane resins, epoxy resins, and phenol resins.
More preferably, the binder resin contains a polyester resin in which an aliphatic compound is condensed at the terminal. By containing the polyester resin, the charge amount is increased, and the line / solid ratio is improved.

The component which comprises the said polyester part is explained in full detail. In addition, the following components can use 1 type, or 2 or more types according to a kind and a use.
Examples of the divalent acid component constituting the polyester moiety include the following dicarboxylic acids or derivatives thereof. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or their anhydrides or lower alkyl esters thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides or The lower alkyl ester; alkenyl succinic acid or alkyl succinic acid having 1 to 50 carbon atoms, or an anhydride thereof, or a lower alkyl ester thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or the like Anhydride or its lower alkyl ester.

  On the other hand, the following are mentioned as a bivalent alcohol component which comprises a polyester site | part. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenation Bisphenol A, bisphenol represented by formula (I-1) and its derivatives: and diols represented by formula (I-2).

（式中、Ｒはエチレン又はプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less.)

（式中、Ｒ’はエチレン又はプロピレン基であり、ｘ’、ｙ’はそれぞれ０以上の整数であり、かつ、ｘ’＋ｙ’の平均値は０以上１０以下である。）

(In the formula, R ′ is an ethylene or propylene group, x ′ and y ′ are each an integer of 0 or more, and the average value of x ′ + y ′ is 0 or more and 10 or less.)

The constituent component of the polyester part used in the present invention contains a trivalent or higher carboxylic acid compound and a trivalent or higher alcohol compound as a constituent component in addition to the above divalent carboxylic acid compound and divalent alcohol compound. May be.
Although it does not restrict | limit especially as a trivalent or more carboxylic acid compound, Trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. are mentioned. Examples of the trihydric or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.

The polyester moiety in the binder resin used in the present invention preferably contains 1 mol% or more and 30 mol% or less of an aliphatic polyhydric alcohol as an alcohol component, and more preferably contains 5 mol% or more and 30 mol% or less. Examples of the aliphatic polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and neopentyl glycol. 1,4-cyclohexanedimethanol (CHDM) and the like.
By containing the aliphatic polyhydric alcohol in the above range, the molten state between the toners after fixing becomes more uniform, and the roughness is improved. The roughness of the output image is affected by the molten state of the toner after fixing. That is, if the toner is in a uniformly melted state, a smooth image can be obtained even by visual evaluation, and the roughness is good. By containing the aliphatic polyhydric alcohol, the melt viscosity of the toner is likely to decrease in the toner fixing temperature region, so that the toners are easily melted more uniformly.

  In the present invention, the method for producing the polyester moiety is not particularly limited, and a known method can be used. For example, the aforementioned divalent carboxylic acid compound and divalent alcohol compound are charged simultaneously with an aliphatic monocarboxylic acid or an aliphatic monoalcohol, polymerized through an esterification reaction or a transesterification reaction, and a condensation reaction, and the polyester portion is To manufacture. Alternatively, the above-mentioned divalent carboxylic acid compound and divalent alcohol compound are charged, and after polymerization through esterification reaction or transesterification reaction and condensation reaction, an aliphatic monocarboxylic acid or aliphatic monoalcohol is added, and Polymerization may produce a polyester moiety. The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C. or higher and 290 ° C. or lower. In the polymerization of the polyester moiety, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, and germanium dioxide can be used.

  The binder resin preferably contains a polyester portion obtained by condensation polymerization in the presence of a titanium-based catalyst. A line / solid ratio is improved by using a polyester portion subjected to condensation polymerization in the presence of a titanium-based catalyst. The reason for this is not clear, but it is presumably because the catalyst residue remaining in the binder resin affects the charging uniformity of the binder resin.

Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃
N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₁ (C ₃ H ₇ O) ₃ ], titanium monopropyl tris (tri such as ethanol aminate) _{[Ti (C 6 H 14 O 3} N) 3 (C 3 H 7 O) 1 ] and the like, titanium diisopropylate bistriethanolaminate among them, titanium diisopropylate bis diethanol aminate And titanium dipentylate bistriethanolamate are preferred.
Specific examples of other titanium catalysts include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetra-n-
Butyl titanate, tetrapropyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred.

  These can be obtained, for example, by reacting titanium halide with the corresponding alcohol. Moreover, it is more preferable that a titanium compound contains an aromatic carboxylic acid titanium compound. The aromatic carboxylic acid titanium compound is preferably obtained by reacting an aromatic carboxylic acid and a titanium alkoxide. The aromatic carboxylic acid is preferably a divalent or higher valent aromatic carboxylic acid (that is, an aromatic carboxylic acid having two or more carboxyl groups) and / or an aromatic oxycarboxylic acid. Examples of the divalent or higher aromatic carboxylic acid include dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, trimellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, and naphthalene tetracarboxylic acid. Examples thereof include polyvalent carboxylic acids such as acids, anhydrides thereof, and esterified products. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxycarboxylic acid, gallic acid, mandelic acid, and tropic acid. Among these, as the aromatic carboxylic acid, it is more preferable to use a divalent or higher carboxylic acid, and it is particularly preferable to use isophthalic acid, terephthalic acid, trimellitic acid, or naphthalenedicarboxylic acid.

  In the present invention, when a hybrid resin of polyester and vinyl resin is used, at least styrene is used as a vinyl monomer for generating a vinyl polymerization site (or vinyl copolymerization site) in the hybrid resin. Preferably it is. Since styrene has a large proportion of aromatic rings in the molecular structure, durability stability is more advantageous. The content of styrene is preferably 70 mol% or more, and more preferably 85 mol% or more in the vinyl monomer.

Examples of the vinyl monomer for generating a vinyl polymerization site other than styrene include the following styrene monomer and acrylic acid monomer.
Styrene monomers include o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl. Styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3,4 -Styrene derivatives such as dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene.
Examples of acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, dodecyl acrylate, and 2-ethylhexyl acrylate. , Acrylic acid and acrylic esters such as stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n-butyl, methacrylic acid Such as isobutyl, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate - methylene aliphatic monocarboxylic acids and their esters; acrylonitrile, methacrylonitrile and acrylic acid or methacrylic acid derivatives such as acrylamide.

  Furthermore, as a monomer constituting the vinyl polymerization site, acrylic acid or methacrylic acid ester such as 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) And monomers having a hydroxyl group such as styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

  Various monomers capable of vinyl polymerization can be used in combination with the vinyl polymerization site as required. Examples of such monomers include ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl halides such as; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether: vinyl vinyl ketone, vinyl hexyl ketone, Vinyl ketones such as methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; further maleic acid, citraconic acid Unsaturated dibasic acids such as itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated dibasic acid anhydrides such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Products: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester Unsaturated basic acid half ester such as methyl fumarate half ester and methyl mesaconic acid half ester; Unsaturated basic acid ester such as dimethylmaleic acid and dimethyl fumaric acid; Α, β-unsaturated acid anhydrides such as: anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their acid anhydrides and these And a monomer having a carboxyl group such as a monoester.

  The vinyl polymerization site may be a polymer cross-linked with a cross-linkable monomer as exemplified below if necessary. Crosslinkable monomers include, for example, aromatic divinyl compounds, diacrylate compounds linked by alkyl chains, diacrylate compounds linked by alkyl chains containing ether bonds, and chains containing aromatic groups and ether bonds. And diacrylate compounds, polyester-type diacrylates, and polyfunctional crosslinking agents.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.
Examples of the diacrylate compounds linked by the alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1, Examples include 6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate.

  Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Examples include dipropylene glycol diacrylate and those obtained by replacing acrylate of the above compound with methacrylate.

As the diacrylate compounds linked by a chain containing the aromatic group and the ether bond,
For example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and the above compounds And those obtained by replacing acrylate with methacrylate. Examples of polyester diacrylates include trade name MANDA (Nippon Kayaku).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing acrylates of the above compounds with methacrylate. Triallyl cyanurate, triallyl trimellitate; and the like.

  The vinyl polymerization site may be a resin produced using a polymerization initiator. These polymerization initiators are preferably used in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

  Examples of such a polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile) 2-carbamoylazoisobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis Ketone peroxides such as (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butylperoxide Oxide, t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3, 5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di- 2 Ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, di-t -Butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxy Azelate, and the like.

As described above, the hybrid resin is a resin in which a polyester site and a vinyl polymerization site are chemically bonded.
Therefore, it is preferable to perform polymerization using a compound that can react with any of the monomers of both resins (hereinafter referred to as “both reactive compounds”). Examples of such a bireactive compound include compounds such as fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate in the monomer of the condensation polymerization resin and the monomer of the addition polymerization resin. Is mentioned. Of these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

As a method of obtaining a hybrid resin, it can be obtained by reacting a raw material monomer at a polyester site and a raw material monomer at a vinyl polymerization site simultaneously or sequentially. For example, when a raw material monomer at a polyester site is subjected to a condensation polymerization reaction after an addition polymerization reaction of a vinyl polymer monomer, the molecular weight can be easily controlled.
In the hybrid resin, the mixing ratio (mass ratio) of the polyester portion and the vinyl-based polymerization portion is preferably 50/50 to 90/10 from the viewpoint of controlling the crosslinked structure at the molecular level, and 50/50 to 80/20. Is more preferable. When the polyester part is contained in an amount of 50% by mass or more, the low-temperature fixing property is improved, and when the vinyl polymerization part is contained in an amount of 10% by mass or more, the charging stability is improved.

The aliphatic compound used in the present invention is preferably an aliphatic monocarboxylic acid or aliphatic monoalcohol having a specific carbon number, and the others are not particularly limited. For example, any of grade 1, 2 and 3 can be used.
Specifically, examples of the aliphatic monocarboxylic acid include melissic acid, lacteric acid, tetracontanoic acid, pentacontanoic acid and the like.
Examples of the aliphatic monoalcohol include merisyl alcohol and tetracontanol.

In addition, the aliphatic compound used in the present invention is an aliphatic monocarboxylic acid or an aliphatic monoalcohol having a carbon number specified in the present invention, and a modified wax obtained by modifying an aliphatic hydrocarbon wax ( For example, an acid-modified aliphatic hydrocarbon wax or an alcohol-modified aliphatic hydrocarbon wax) can also be used.
These modified waxes do not impair the effects of the present invention as long as 50% by mass or more of a monovalent modified wax is contained in a mixture in which zero-valent, monovalent and polyvalent components are mixed.
Specific examples of the acid-modified aliphatic hydrocarbon wax and the alcohol-modified aliphatic hydrocarbon wax include the following.
The acid-modified aliphatic hydrocarbon wax in the present invention is preferably one in which polyethylene or polypropylene is modified with a monovalent unsaturated carboxylic acid such as acrylic acid.

Among the alcohol-modified aliphatic hydrocarbon waxes in the present invention, the primary alcohol-modified aliphatic hydrocarbon wax may be produced by, for example, polymerizing ethylene using a Ziegler catalyst and oxidizing the polymer after completion of the polymerization. Then, after producing an alkoxide of a catalyst metal and polyethylene, a method of hydrolyzing is mentioned.
In addition, as a process for producing a secondary alcohol-modified aliphatic hydrocarbon wax, for example, an aliphatic hydrocarbon wax is preferably formed in a liquid phase with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. Obtained by oxidation. The obtained hydrocarbon wax may be further subjected to purification by a press sweat method, purification using a solvent, hydrogenation treatment, and treatment with activated clay after washing with sulfuric acid. A mixture of boric acid and boric anhydride can be used as the catalyst. The mixing ratio of boric acid and boric anhydride (boric acid / boric anhydride) is a molar ratio, preferably 1.0 or more and 2.0 or less, more preferably 1.2 or more and 1.7 or less. When the proportion of boric anhydride is less than the above range, excess boric acid tends to cause an aggregation phenomenon. On the other hand, when the proportion of boric anhydride is more than the above range, the powder substance derived from boric anhydride is recovered after the reaction, and excess boric acid does not contribute to the reaction and is not preferable from the economical viewpoint.

The amount of boric acid and boric anhydride to be used is preferably 0.001 mol or more and 10 mol or less with respect to 1 mol of the aliphatic hydrocarbon as a raw material when the mixture is converted into boric acid. More preferred is a mole or more and 1 mole or less.
In addition to boric acid / boric anhydride, metaboric acid and pyroboric acid can also be used. Examples of those that form esters with alcohols include boron oxyacids, phosphorus oxyacids, and sulfur oxyacids. Specific examples include boric acid, nitric acid, phosphoric acid, and sulfuric acid.
As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used. The gas preferably has an oxygen concentration of 1% by volume to 30% by volume, more preferably 3% by volume to 20% by volume.
The liquid phase oxidation reaction is usually carried out in the molten state of the starting aliphatic hydrocarbon without using a solvent. The reaction temperature is 120 ° C. or higher and 280 ° C. or lower, preferably 150 ° C. or higher and 250 ° C. or lower. The reaction time is preferably 1 hour or more and 15 hours or less.

Boric acid and boric anhydride are preferably mixed in advance and added to the reaction system. If only boric acid is added alone, the dehydration reaction of boric acid tends to occur. Moreover, the addition temperature of the mixed catalyst of boric acid and boric anhydride is preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 110 ° C. or higher and 160 ° C. or lower. As a result, the catalytic ability of boric anhydride tends to decrease.
After completion of the reaction, water is added to the reaction mixture, and the resulting boric acid ester of the aliphatic hydrocarbon wax is hydrolyzed and purified to obtain an alcohol-modified aliphatic hydrocarbon wax having a desired functional group.

The aliphatic compound used in the present invention is preferably an aliphatic monoalcohol. The carboxyl group of the polyester terminal tends to form a stronger hydrogen bond than the hydroxyl group. That is, when a carboxyl group is present on the toner surface, the surface free energy is increased, but by capping the carboxyl group with an aliphatic monoalcohol, it is possible to effectively weaken the polyester terminal interaction. As a result, the surface free energy of the toner can be effectively reduced, and the transfer efficiency is improved.
The method for condensing the aliphatic compound to the terminal of the binder resin is not particularly limited. As a preferred embodiment, when the binder resin is produced, it is preferable to perform polycondensation by simultaneously adding an aliphatic compound to the monomer constituting the polyester portion of the binder resin. Thereby, the aliphatic compound can be sufficiently condensed at the terminal of the polyester part of the binder resin.

  The content of the aliphatic compound is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and further preferably 2% by mass in the binder resin. % To 7% by mass. When the addition amount is 0.1% by mass or more, the surface free energy can be effectively reduced, and the transfer efficiency is improved. In addition, when the amount is 10% by mass or less, it is possible to minimize the plastic effect of the aliphatic compound on the binder resin, and it is possible to suppress deformation of the toner due to stress during development, and contact between the toner and the photoreceptor. It is considered that the increase in area is suppressed and transfer efficiency is improved.

The binder resin of the present invention may contain a plurality of binder resins. For example, a polyester resin or a hybrid resin in which a polyester portion and other resin units are combined may be used in combination.
The binder resin preferably contains, for example, a binder resin A which is a polyester resin and a binder resin B which is a hybrid resin of a polyester site and a vinyl polymerization site. In addition, the binder resin A and the binder resin B are terminated with at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid and an aliphatic monoalcohol (preferably having 30 to 102 carbon atoms). More preferably, it contains a condensed polyester moiety. Since the aliphatic compound is present in the binder resin A and the binder resin B, the transfer efficiency is improved.

The binder resin preferably contains 60% by mass or more and 100% by mass or less of the polyester portion in the binder resin. By containing 60% by mass or more of the polyester part, it effectively interacts with the charge control agent and the charge uniformity is improved.
When a plurality of binder resins are used in combination as described above (for example, containing the binder resin A and the binder resin B), it is preferable to use a high softening point resin and a low softening point resin. The high softening point resin preferably has a softening point of 120 ° C. or higher and 170 ° C. or lower, more preferably 120 ° C. or higher and 145 ° C. or lower. Further, the low softening point resin preferably has a softening point of 70 ° C. or higher and lower than 120 ° C., more preferably 80 ° C. or higher and lower than 100 ° C.
Such a system is preferable because the molecular weight distribution of the toner can be designed relatively easily and a wide fixing region can be provided.

When one kind of binder resin is used alone, the softening point is preferably 95 ° C or higher and 170 ° C or lower. More preferably, it is 120 degreeC or more and 160 degrees C or less. When the softening point is within the above range, the balance between high temperature offset resistance and low temperature fixability is good.
The softening point is measured as follows. The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent in the flow curve is the sum of X and Smin is the melting temperature Tm in the 1/2 method.
As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

The glass transition temperature (Tg) of the binder resin is preferably 45 ° C. or higher from the viewpoint of storage stability. Further, from the viewpoint of low-temperature fixability, Tg is preferably 75 ° C. or less, and particularly preferably 65 ° C. or less.
The glass transition temperature (Tg) of the binder resin for toner is measured under normal temperature and humidity according to ASTM D3418-82 using a differential scanning calorimeter (DSC) and MDSC-2920 (manufactured by TA Instruments). To do. As a measurement sample, a precisely weighed about 3 mg of binder resin is used. This is put in an aluminum pan and an empty aluminum pan is used as a reference. The measurement temperature range is 30 ° C. or more and 200 ° C. or less, once the temperature is increased from 30 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min, then the temperature is decreased from 200 ° C. to 30 ° C. at a temperature decrease rate of 10 ° C./min. The temperature is raised to 200 ° C. at a temperature rising rate of 10 ° C./min. In the DSC curve obtained in the second temperature raising process, the intersection point between the baseline intermediate line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of the resin.

Next, the charge control agent will be described.
In the toner according to the present invention, a known charge control agent can be used as the charge control agent. For example, azo iron compound, azo chromium compound, azo manganese compound, azo cobalt compound, azo zirconium compound, carboxylic acid derivative chromium compound, carboxylic acid derivative zinc compound, carboxylic acid derivative aluminum compound, carboxylic acid Derivative zirconium compounds are mentioned. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid. A charge control resin can also be used. The charge control agent is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
The toner according to the present invention has the following formula [1] as a charge control agent.

(In the formula, A ₁ , A ₂ and A ₃ each independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. M Represents an Fe atom, a Cr atom, or an Al atom, and X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.
It is preferable to contain the compound shown by these. By containing the compound represented by the formula [1], the charge amount of the toner becomes high, the line / solid ratio becomes good, and the consumption amount becomes good even when printing a line image like a character.

  The pyrazolone monoazo metal compound represented by the formula [1] can be produced using a known method for producing a monoazo complex compound. A typical production method is described below. First, a mineral acid such as hydrochloric acid or sulfuric acid is added to a diazo component such as 4-chloro-2-aminophenol. It is dropped while maintaining the following. 4-Chloro-2-aminophenol is diazotized by reacting with stirring at 10 ° C. or lower for 30 minutes to 3 hours. Add sulfamic acid, and confirm that nitrous acid does not remain excessively with potassium iodide starch paper.

Next, a coupling component which is 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone, an aqueous solution of sodium hydroxide, sodium carbonate and an organic solvent are added and dissolved by stirring at room temperature. The diazo compound is added thereto and stirred at room temperature for several hours to perform coupling. After stirring, it is confirmed that there is no reaction between the diazo compound and resorcin, and the reaction is completed. Stir well after adding water, let stand and separate. Further, an aqueous sodium hydroxide solution is added, washed with stirring, and liquid separation is performed. Thereby, a solution of the monoazo compound is obtained.

  As the organic solvent used in the above coupling, monohydric alcohols, dihydric alcohols, and ketone organic solvents are preferable. Monovalent alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, n-amyl alcohol, isoamyl alcohol, ethylene glycol monoalkyl (1 to 4 carbon atoms). ) Ether. Examples of the divalent alcohol include ethylene glycol and propylene glycol. Examples of ketones include methyl ethyl ketone and methyl isobutyl ketone.

Next, a metallization reaction is performed. Water, salicylic acid, n-butanol, and sodium carbonate are added to the monoazo compound solution and stirred. When iron is used as the coordination metal, an aqueous ferric chloride solution and sodium carbonate are added.
The liquid temperature is raised to 30 ° C. or higher and 40 ° C. or lower, and the reaction is followed by TLC. After the reaction for 5 hours or more and 10 hours or less, it is confirmed that the raw material spots have disappeared, and the reaction is completed. After stopping stirring, stop and separate the liquid. Further, water, n-butanol, and an aqueous sodium hydroxide solution are added to perform alkali cleaning. Filter and remove the cake and wash with water.
The cake washed with water is dissolved in an organic solvent. The organic solvent used at this time is preferably dimethyl sulfoxide, N, N-dimethylformamide, monohydric alcohol, or dihydric alcohol. Monovalent alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, n-amyl alcohol, isoamyl alcohol, and ethylene glycol monoalkyl (1 to 4 carbon atoms). Ether. Examples of the divalent alcohol include ethylene glycol and propylene glycol.
The solution is heated to 50 ° C., and water is added while stirring to gradually precipitate the charge control agent. If an antifoaming agent is added to water beforehand, the charge control agent can be made uniform by removing bubbles generated in the system. After cooling and filtering, the pyrazolone monoazo metal compound of the present invention can be obtained by washing the cake with water and further vacuum drying the cake.
The charge control agent is preferably a monoazo iron compound represented by the following formula [2].

(In the formula, A ₁ , A ₂ and A ₃ each independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X ^{+ Represents} a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.
That is, the coordination metal is preferably iron. By using iron as the coordination metal, the toner can be provided with stable charging performance over a long period of time. As a result, the line / solid ratio is good.
The charge control agent is more preferably a monoazo iron compound represented by the following formula [3].

(In the formula, X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.)
By adopting the structure shown in Formula [3], a toner having a sharper charge amount distribution can be obtained, and the line / solid ratio can be improved.
The charge control agent preferably has a volume average particle size of 0.5 μm or more and 3.0 μm or less. By setting the volume average particle size within this range, the dispersibility in the binder resin is improved.

A method for measuring the particle size distribution of the charge control agent in the present invention will be described.
The particle size of the charge control agent is measured using a Coulter LS-230 type particle size distribution meter (manufactured by Coulter, Inc.) of a laser diffraction type particle size distribution meter. Ethanol is used as a measurement solvent. Wash and replace the measurement system of the particle size distribution analyzer several times with ethanol and execute the background function.
Next, a sample solution is obtained as follows, and the sample solution is gradually added into the measurement system of the measuring device, and the PIDS (concentration) on the screen of the device is measured to be 45% to 55%. Measurement is performed by adjusting the sample concentration in the system, and the frequency ratio is obtained from the distribution calculated from the volume distribution.
The measurement was performed with the refractive index of ethanol as 1.36 as the device coefficient and 1.08 (real part) -0.00i (imaginary part) as the optical model. The particle size measurement range of the Coulter LS-230 type particle size distribution meter of the laser diffraction type particle size distribution meter in the present invention is 0.040 or more and less than 2000 μm. The measurement temperature was 20 ° C. or more and 25 ° C. or less.

As a sample preparation method, 0.4 g of the fine powder to be measured is weighed, put into a beaker containing 100 ml of ethyl alcohol, and stirred for 1 minute with a stirrer. Transfer the beaker to the ultrasonic vibration layer and treat for 3 minutes. Immediately after completion of the treatment, the dispersion solution is added to the measurement part filled with ethanol until the measurement allowable concentration is reached, and measurement is started.
In addition, as the ultrasonic vibration layer in the present invention, ULTRASONIC CLEANER VS-150 type (frequency 50 kHz, maximum output 150 W) manufactured by Inoue Seieido Co., Ltd. was used.
The sample concentration in this measurement is suitable for observing the aggregation and dispersion of the fine powder, and is a concentration at which the particle size distribution of the fine powder can be accurately observed. When measuring a sample having a small particle size or a low cohesiveness, the sample amount may be 0.2 g and the amount of ethyl alcohol may be 50 ml.
In the Coulter LS-230 type particle size distribution analyzer, the particle size of each particle is first determined and distributed to the following channels. Then, assuming that the center diameter of each channel is the representative value of the channel and the sphere having the representative value as the diameter is assumed, the volume-based particle size distribution is obtained based on the volume of the sphere.

Furthermore, the charge control agent may contain an acetate ester, preferably 1 ppm to 1000 ppm, more preferably 1 ppm to 500 ppm, and still more preferably 1 ppm to 300 ppm. By containing an acetic acid ester in the above range in the charge control agent, the chargeability of the toner becomes very good and the selective developability becomes better. The reason for this is not clear, but it is thought as follows.
Most of the acetate contained in the pyrazolone monoazo metal compound is volatilized in the kneading process of the toner manufacturing process. When the acetic acid ester volatilizes, it volatilizes from the interface between the charge control agent and the binder resin contained in the toner, so that the adhesion between the binder resin and the charge control agent is weakened. Therefore, it is easy to be crushed at the interface between the binder resin and the charge control agent in the pulverization step, and the charge control agent is likely to be exposed on the toner surface. As a result, it is considered that the effect of the charge control agent becomes more remarkable, and the selective developability is improved.
Preferable acetic acid esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate and the like, and particularly butyl acetate, more preferably n-butyl acetate is used.

The measurement of the content of acetate contained in the charge control agent is performed as follows.
<Measurement method of acetate content>
The acetate content is calculated as the amount of organic volatile component in terms of toluene of the charge control agent by organic volatile component analysis at a heating temperature of 120 ° C. by the headspace method. Specifically, it can be measured as follows.
A 50 mg charge control agent is precisely weighed in a head space vial (volume: 22 ml), and sealed with a crimp cap and a fluororesin-coated septum using a crimper. This vial is set in a headspace sampler, and gas chromatogram (GC) analysis is performed under the following conditions. And the total area value of the peak of the obtained GC chart is calculated by data processing. At this time, an empty vial in which no charge control agent is sealed is also measured simultaneously as a blank, and the measurement value in the blank measurement is subtracted from the charge control agent measurement data.
On the other hand, several vials (for example, 0.1 μl, 0.5 μl, 1.0 μl) prepared by precisely weighing toluene are prepared in the vial, and measured under the following analysis conditions before measuring the charge control agent sample. Then, a calibration curve is created from the amount of toluene charged and the toluene area value.
The amount of organic volatile component in terms of toluene is obtained by converting the area value of the organic volatile component of the charge control agent to the mass of toluene based on this calibration curve, and further converting it to an amount based on the mass of the charge control agent. It is done.

(Measurement equipment and measurement conditions)
Headspace sampler: Turbo Matrix HS40 (manufactured by PerkinElmer Japan)
Oven temperature: 120 ° C
Transfer line temperature: 125 ° C
Needle temperature: 125 ° C
Insulation time: 60 minutes Cycle time: 65 minutes Pressurization time: 2.5 minutes Injection time: 0.08 minutes Carrier gas: He
GC: TRACE GC Ultra (manufactured by Thermo Fisher Scientific Co., Ltd.)
MS: ISQ (manufactured by Thermo Fisher Scientific Co., Ltd.)
Column: HP-5MS (inner diameter: 0.25 mm, film thickness: 0.25 μm, column length: 60 m
)
Temperature rise conditions: (1) 40 ° C .: hold for 3 minutes, (2) heat up to 70 ° C. at 2 ° C./min, (3) temperature rise to 150 ° C. at 5 ° C./min, (4) at 10 ° C./min Hold for 1 minute after heating up to 300 ° C.
Inlet condition Temperature: 200 ℃
Pressure: 150kPa
Split flow: 10mL
Split ratio: 7

The charge control agent preferably has an electric conductivity of 300 μS / cm or less (more preferably 200 μS / cm or less, more preferably 100 μS / cm or less) when dispersed in ion exchange water by 1% by mass. The electric conductivity represents the content of water-soluble ions and the like contained in the charge control agent, and the higher the electric conductivity is, the more substances such as ions are contained. By reducing the amount of water-soluble ions contained in the charge control agent, the charge control agent and the binder resin interact more effectively, and the charge amount of the toner can be maintained high. Good line / solid ratio.
As a method of adjusting the electric conductivity of the charge control agent to 300 μS / cm or less, there is a method of repeatedly washing and filtering using a sufficient amount of water, and examples of the filtering method include a filter press and centrifugal filtration. Furthermore, there are a method using a reverse osmosis membrane and a semipermeable membrane, or a purification method by crystallization operation in which a charge control agent is dissolved and crystals are reprecipitated.

The method for measuring electrical conductivity in the present invention is performed as follows.
Disperse 1.5 g of the dried charge control agent in 150 ml of ion exchange water and boil for 15 minutes. After cooling to room temperature with running water, filter with 5A filter paper. For this filtrate, the distilled water is adjusted to 150 ml with ion-exchanged water and measured with an electric conductivity meter (HORIBA conductivity meter ES-14).
The specific surface area of the charge control agent is preferably 3.0 m ² / g or more and 30.0 m ² / g or less.
Examples of the method for incorporating the charge control agent into the toner include the following methods. A method of adding a kneading agent to a binder resin together with a colorant, kneading and pulverizing (pulverized toner), or adding a monoazo metal compound to a polymerizable monomer monomer and polymerizing it (polymerized toner). As described above, a method in which toner particles are added (internally added) in advance;

The toner of the present invention can be used as any one of magnetic one-component toner, non-magnetic one-component toner, and non-magnetic two-component toner.
When used as a magnetic one-component toner, magnetic iron oxide particles are preferably used as the colorant. Magnetic iron oxide particles contained in the magnetic one-component toner include magnetic iron oxides such as magnetite, maghemite and ferrite, and magnetic iron oxides including other metal oxides; metals such as Fe, Co and Ni, or Alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and these A mixture is mentioned.
Examples of the colorant when used as the non-magnetic one-component toner and the non-magnetic two-component toner include the following.

As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black is used, and magnetic powder such as magnetite and ferrite is also used.
As a colorant suitable for the yellow color, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Butt yellow 1,3,20 is mentioned. Examples of the dye include C.I. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 etc. are mentioned. These are used alone or in combination of two or more.

  As a colorant suitable for cyan, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc. I. Bat Blue 6, C.I. I. Acid Blue 45 is exemplified. Examples of the dye include C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 etc. are mentioned. These are used alone or in combination of two or more.

A pigment or dye can be used as a colorant suitable for magenta. Examples of the pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc. I. Pigment violet 19; C.I. I. Buttred 1, 2, 10, 13, 15, 23, 29, 35 may be mentioned. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. basic dye etc. are mentioned. These are used alone or in combination of two or more.

  In order to impart releasability to the toner, the toner preferably contains a release agent (wax). As the wax, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferably used because of easy dispersion in the toner and high releasability. If necessary, one or two or more kinds of waxes may be used together in a small amount. Examples include the following:

  Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate wax; Deoxidized part or all of fatty acid esters such as acid carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Saturated fatty acid bisamides such as ethylene biscapric amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-diole Unsaturated fatty acid amides such as luadipic acid amide and N, N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bis-stearic acid amide and N, N-distearyl isophthalic acid amide; calcium stearate , Fatty acid metal salts such as calcium laurate, zinc stearate and magnesium stearate (generally called metal soap); grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid A partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oils and fats.

  Examples of waxes that are particularly preferably used in the present invention include aliphatic hydrocarbon waxes. Examples of such aliphatic hydrocarbon waxes include the following. Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen Synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained from the gas by the age method and synthetic hydrocarbon waxes obtained by hydrogenating them; press sweating method, solvent method, vacuum Wax separated by use of distillation or fractional crystallization.

Examples of the hydrocarbon as the base of the aliphatic hydrocarbon wax include the following. Carbonization synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, the Gintor method, Hydrocol method (using a fluidized catalyst bed)) Hydrogen compounds); hydrocarbons having up to about several hundred carbon atoms obtained by the age method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. Specific examples include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industry Co., Ltd.); High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) Sazol H1, H2, C80, C105, C77 (Sazol Corporation); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiwa Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite); wood wax, beeswax, rice wax, candelilla wax, carnauba wax (Co., Ltd.) Celerica NODA).

  When the toner is prepared by the pulverization method, the release agent may be added at the time of melt-kneading, or may be at the time of producing the binder resin. These release agents may be used alone or in combination. The release agent is preferably added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, a normal carrier such as ferrite or magnetite or a resin-coated carrier can be used. A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.
The resin-coated carrier is composed of carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles. Examples of the resin used for the coating material include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; acrylic resins such as acrylic acid ester copolymers and methacrylic acid ester copolymers. Fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; aminoacrylate resins. Other examples include ionomer resins and polyphenylene sulfide resins. These resins can be used alone or in combination.

In the toner of the present invention, silica fine powder is preferably externally added to the toner particles in order to improve transfer efficiency, charging stability, developability, fluidity, and durability. The silica fine powder preferably has a specific surface area of 30 m ² / g or more and 500 m ² / g or less, more preferably 50 m ² / g or more and 400 m ² / g or less by the BET method by nitrogen adsorption. The silica fine powder is preferably used in an amount of 0.01 to 8.00 parts by mass, and more preferably 0.10 to 5.00 parts by mass with respect to 100 parts by mass of the toner particles.
The BET specific surface area of the fine silica powder is determined by using, for example, a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI 2360/2375 (manufactured by Micrometric), Tristar 3000 (manufactured by Micrometric). Nitrogen gas is adsorbed on the surface of the powder, and calculation can be performed using the BET multipoint method.
Silica fine powder has unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane coupling agents, and functional groups for the purpose of hydrophobization and triboelectric charge control as required. It is also preferable that it is treated with a treating agent such as a silane compound or other organosilicon compound or in combination with various treating agents.

Furthermore, you may add another external additive to the toner of this invention as needed. Examples of such external additives include charging aids, conductivity-imparting agents, fluidity-imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, abrasives, and fine resin particles. An inorganic fine powder is mentioned. Examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. Of these, strontium titanate powder is preferable.

  As a method for producing the toner, the following method can be used. The binder resin and, if necessary, the colorant, charge control agent, wax, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The mixture is melt kneaded using a thermal kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder. At that time, wax, magnetic iron oxide particles, and a metal-containing compound may be added. The melt-kneaded product is cooled and solidified, and then pulverized and classified to obtain toner particles. Further, if necessary, the toner particles and the external additive can be mixed with a mixer such as a Henschel mixer to obtain a toner.

The following are mentioned as a mixer. Henschel mixer (made by Mitsui Mining); Super mixer (made by Kawata); Ribocorn (made by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (made by Hosokawa Micron); A Ladige mixer (manufactured by Matsubo).
Examples of the kneader include the following. KRC kneader (manufactured by Kurimoto Tekkosho); Bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel); PCM kneader (Ikegai) Steel mill); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); kneedex (manufactured by Mitsui Mining); MS-type pressure kneader, nider ruder (manufactured by Moriyama Seisakusho); Banbury mixer (Kobe Steel) (Made by the company).

Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.) SK; jet mill (manufactured by Seishin Enterprise Co., Ltd.); kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turboe Corporation); super rotor (manufactured by Nisshin Engineering Co., Ltd.).
Examples of the classifier include the following. Classifier, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Engineering Co., Ltd.); YM Microcut (manufactured by Yaskawa Corporation).
Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokusu Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Micro shifter (manufactured by Hadano Sangyo Co., Ltd.); circular vibrating sieve

Next, the method for measuring the particle size distribution of the toner according to the present invention will be described.
<Measurement of toner weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measure with 25,000 effective measurement channels, analyze and calculate the measurement data.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) 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 electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the (1) round bottom beaker installed in the sample stand, the (5) electrolytic aqueous solution in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited at all by these. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Example of production of a-Si photoreceptors 1 to 7>
Using the plasma processing apparatus of FIG. 3, a lower blocking layer, a photoconductive layer, an upper blocking layer, and a surface layer are sequentially formed on a cylindrical substrate under the conditions shown in Table 2 below, and a-Si for negative charging is formed. Photoconductors 1 to 7 were produced. As the cylindrical substrate, a cylindrical aluminum conductive substrate having a diameter of 84 mm, a length of 371 mm, and a thickness of 3 mm was used.
The raw material gas flow rate, reaction pressure, high-frequency power, and substrate temperature (substrate temperature) during the surface layer formation were as shown in Table 3 below. Two photoconductors were prepared under each film forming condition (layer forming condition). In addition, one reference photoreceptor having only the lower blocking layer, the photoconductive layer and the upper blocking layer shown in Table 2 was prepared.

※表面層の条件については、表３に示す。

* Table 3 shows the surface layer conditions.

Using one photoconductor under each film formation condition, the Si atom density, the C atom density, the Si + C atom density, (C / (Si + C)), the absorbance ratio a ₂ / a _1, and the defect density are determined according to the above analysis method. Determined by The evaluation results are shown in Table 4.

<Example of production of binder resin A-1>
Bisphenol A ethylene oxide (2.2 mol adduct): 45.0 mol parts Bisphenol A propylene oxide (2.2 mol adduct): 40.0 mol parts Ethylene glycol: 15.0 mol parts Terephthalic acid: 100.0 mol parts 95 parts by mass of the monomer constituting the polyester part and 5 parts by mass of an aliphatic monoalcohol having 50 carbon atoms (wax having a hydroxyl group at one end of polyethylene) were charged into a 5-liter autoclave together with 500 ppm of tetra-n-butyl titanate. A reflux condenser, a water separator, an N ₂ gas introduction pipe, a thermometer, and a stirring device were attached thereto, and a polycondensation reaction was performed at 230 ° C. while introducing N ₂ gas into the autoclave. The reaction time was adjusted so that the desired softening point was obtained. After completion of the reaction, the reaction time was taken out from the container, cooled and pulverized to obtain a binder resin A-1. Table 5 shows Tg and Tm.

<Example of production of binder resins A-2 to A-4>
Binder resin, except that the mol parts of ethylene glycol (described in the table as EG) and bisphenol A ethylene oxide (2.2 mol adduct) (described in the table as BPA-EO) are changed as shown in Table 5. Binder resins A-2 to A-4 were obtained according to the production example of A-1.

<Example of production of binder resin B-1>
(Polyester part prescription)
-Bisphenol A ethylene oxide (2.2 mol adduct): 100.0 mol parts-Terephthalic acid: 65.0 mol parts-Trimellitic anhydride: 25.0 mol parts-Acrylic acid: 10.0 mol parts Monomers constituting the polyester part Into a four-necked flask, 55 parts by mass of a mixture of the above and 5 parts by mass of an aliphatic monoalcohol having 50 carbon atoms were charged, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. And stirred at 160 ° C.
There, 40 parts by mass of a vinyl copolymer monomer (90.0 mol part of styrene and 10.0 mol part of 2-ethylhexyl acrylate) constituting the vinyl copolymer site and 1 part by mass of benzoyl peroxide as a polymerization initiator are added to a dropping funnel. The solution was added dropwise over 4 hours and reacted at 160 ° C. for 5 hours.
Thereafter, the temperature was raised to 230 ° C., 0.2 parts by mass of tetra-n-butyl titanate was added to the total amount of monomer components constituting the polyester portion, and the polymerization reaction was performed until the desired softening point was reached. . After completion of the reaction, the reaction product was taken out from the container, cooled and pulverized to obtain a binder resin B-1.

<Example of production of binder resins B-2 to B-7>
Binder except that 0.2 parts by mass of dibutyltin oxide is used instead of 0.2 parts by mass of titanium tetrabutoxide, and the parts by mass, carbon number and type of the aliphatic compound are changed as shown in Table 6. According to the production example of resin B-1, binder resins B-2 to B-7 were obtained.

<Production Example 1 of Charge Control Agent>
Into a mixed solution of 580 parts of water and 84 parts of 35% hydrochloric acid, 57.4 parts of 4-chloro-2-aminophenol was added and stirred under cooling. Cool on ice, maintain the temperature of the solution between 0 ° C. and 5 ° C., drop 28.2 parts of sodium nitrite dissolved in 50.7 parts of water into aqueous hydrochloric acid and stir for 2 hours to diazotize. did. To this, excess nitrous acid was eliminated with sulfamic acid, followed by filtration to obtain a diazo solution.
Next, 101 parts of 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone was added to and dissolved in a mixed solution of 475 parts of water, 95 parts of sodium carbonate, and 840 parts of n-butanol. The said diazo solution was added there, and it stirred at the temperature of 20 degreeC or more and 22 degrees C or less for 4 hours, and performed the coupling reaction. Thereafter, 43.5 parts of 25% aqueous sodium hydroxide solution was added and washed with stirring, and the lower aqueous layer was separated and removed.
Next, 226 parts of water, 29 parts of salicylic acid, 823.7 parts of n-butanol, and 242.4 parts of 15% sodium carbonate were added to the reaction solution and stirred. Further, 89.6 parts of 38% ferric chloride aqueous solution was added, and the temperature of the solution was raised to 30 ° C., followed by stirring for 8 hours to perform a complexing reaction, and the reaction product was filtered. The operation of washing the filtrate with 1000 parts of water was repeated 5 times. Vacuum drying at a temperature of 60 ° C. for 24 hours gave 98.8 parts of a monoazo metal compound. This is designated as charge control agent 1.
When the structure of the charge control agent 1, infrared absorption spectrum, the visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, was identified from the mass spectrum, X in the compound of formula (3) ⁺
Was confirmed to be a hydrogen ion.
When the particle size distribution of the charge control agent 1 was measured, the ratio of particles having a volume average particle size of 5.5 μm, 4.0 μm or more was 73%. Furthermore, the electrical conductivity when the charge control agent 1 was dispersed in 1% by mass in ion-exchanged water was 560 μS / cm.

<Production Example 2 of Charge Control Agent>
The charge control agent 1 obtained in Production Example 1 of the charge control agent was added and dissolved in 80 parts by mass and 320 parts by mass of dimethyl sulfoxide. There, a mixed solution of 5 parts by mass of antifoaming agent KF995 (cyclic dimethyl silicone), 0.005 parts by mass of n-butyl acetate and 5000 parts by mass of water was dropped to precipitate a monoazo metal compound. After completion of the dropwise addition, the obtained precipitate was washed with 1000 parts by mass of water, and then vacuum-dried at a temperature of 60 ° C. for 24 hours to obtain the charge control agent 2 as the target compound.
The structure of the charge control agent 2, the infrared absorption spectrum, the visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, was identified from the mass spectrum, X ⁺ is hydrogen with a compound of formula (3) It was confirmed to be an ion.
When the particle size distribution of the charge control agent 2 was measured, the ratio of particles having a volume average particle size of 0.9 μm, 4.0 μm or more was 6%. Further, the content of n-butyl acetate was 10 ppm. Furthermore, the electric conductivity when the charge control agent 2 was dispersed in 1% by mass in ion-exchanged water was 21 μS / cm.

<Production Example 3 of Charge Control Agent>
In the charge control agent production example 2, the charge control agent 3 was obtained in the same manner except that 0.001 part by mass of n-butyl acetate was used and the deposition speed was adjusted by the dropping rate.
The structure of the charge control agent 3, the infrared absorption spectrum, the visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, was identified from the mass spectrum, X ⁺ is hydrogen with a compound of formula (3) It was confirmed to be an ion.
When the particle size distribution of the charge control agent 3 was measured, the proportion of particles having a volume average particle size of 1.8 μm, 4.0 μm or more was 12%. Further, the content of n-butyl acetate was 1 ppm. Furthermore, the electric conductivity when the charge control agent 3 was dispersed in 1% by mass in ion-exchanged water was 17 μS / cm.

<Production Example 4 of Charge Control Agent>
In the charge control agent production example 2, the charge control agent 4 was obtained in the same manner except that n-butyl acetate was 0.2 parts by mass and the deposition speed was adjusted by the dropping speed.
The structure of the charge control agent 4, the infrared absorption spectrum, the visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, was identified from the mass spectrum, X ⁺ is hydrogen with a compound of formula (3) It was confirmed to be an ion.
When the particle size distribution of the charge control agent 4 was measured, the ratio of particles having a volume average particle diameter of 2.0 μm and 4.0 μm or more was 13%. The n-butyl acetate content was 300 ppm. Furthermore, the electric conductivity when the charge control agent 4 was dispersed in 1% by mass in ion-exchanged water was 14 μS / cm.

<Production Example 5 of Charge Control Agent>
In the charge control agent production example 2, the charge control agent 5 was obtained in the same manner except that n-butyl acetate was 0.3 parts by mass and the deposition speed was adjusted by the dropping speed.
The structure of the charge control agent 5, the infrared absorption spectrum, the visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, was identified from the mass spectrum, X ⁺ is hydrogen with a compound of formula (3) It was confirmed to be an ion.
When the particle size distribution of the charge control agent 5 was measured, the proportion of particles having a volume average particle size of 0.5 μm, 4.0 μm or more was 2%. The n-butyl acetate content was 500 ppm. Further, when the charge control agent 5 is dispersed in 1% by mass in ion exchange water, the electric conductivity is 33 μS.
/ Cm.

<Production Example 6 of Charge Control Agent>
In the charge control agent production example 5, the charge control agent 6 was obtained in the same manner except that n-butyl acetate was 0.1 parts by mass and water was 500 parts by mass, and the deposition rate was adjusted by the dropping rate. It was.
The structure of the charge control agent 6, infrared absorption spectrum, the visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, was identified from the mass spectrum, X ⁺ is hydrogen with a compound of formula (3) It was confirmed to be an ion.
When the particle size distribution of the charge control agent 6 was measured, the proportion of particles having a volume average particle size of 2.2 μm, 4.0 μm or more was 16%. The n-butyl acetate content was 1000 ppm. Furthermore, the electrical conductivity when the charge control agent 6 was dispersed in 1% by mass in ion-exchanged water was 293 μS / cm.

<Production Example 7 of Charge Control Agent>
In the charge control agent production example 5, the charge control agent 7 was obtained in the same manner except that the n-butyl acetate was 0.1 parts by mass and the water was 200 parts by mass, and the deposition rate was adjusted by the dropping rate. It was.
The structure of the charge control agent 7 was identified by infrared absorption spectrum, visible absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, and mass spectrum. As a result, X ⁺ is hydrogen in the compound of formula (3). It was confirmed to be an ion.
When the particle size distribution of the charge control agent 7 was measured, the ratio of particles having a volume average particle size of 2.3 μm, 4.0 μm or more was 18%. The n-butyl acetate content was 1100 ppm. Furthermore, the electrical conductivity when the charge control agent 7 was dispersed in 1% by mass in ion-exchanged water was 365 μS / cm.

<Production Example of Toner 1>
Binder resin A-1: 30 parts by mass Binder resin B-1: 70 parts by mass Fischer-Tropsch wax: 4 parts by mass (manufactured by Sasol, C105, melting point 105 ° C.)
Magnetic iron oxide particles (average particle size 0.15 μm, Hc = 11.5 kA / m, σs = 88 Am ²
/ Kg, σr = 14 Am ² / kg) 75 parts by mass / charge control agent 2: 2 parts by mass The above materials were premixed with a Henschel mixer and then melt kneaded with a biaxial kneading extruder. At this time, the residence time was controlled so that the temperature of the kneaded resin was 150 ° C. The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then pulverized with a turbo mill, and the finely pulverized powder obtained is a multi-division classifier using the Coanda effect (elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.) Was used to obtain a toner having a weight average particle diameter (D4) of 7.3 μm. To 100 parts by mass of the toner, 1.0 part by mass of hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ² / g, hexamethyldisilazane treatment as hydrophobic treatment) and strontium titanate ( The toner 1 was obtained by externally mixing 3.0 parts by mass of a volume average particle diameter of 1.6 μm and sieving with a mesh having an opening of 150 μm.

<Production Example of Toners 2 to 15>
Toners 2 to 15 were prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 7.
In addition, T77 of the charge control agent in Table 7 is a monoazo iron complex (Hodogaya Chemical Co., Ltd.) represented by the following formula [4].

<Example 1>
For the evaluation, a modified machine of a digital electrophotographic apparatus “image RUNNER ADVANCE 8105 Pro” (trade name) manufactured by Canon Inc. was used. The modified machine is configured to apply primary charging and developing bias from an external power source, and the DC component of the primary charging and developing bias is changed to negative charging. The photoconductor of this remodeling machine was changed to the photoconductor 1, and the reversal development process in which the exposed portion of the photoconductor was reversed and the toner was developed on the exposed portion of the photoconductor was changed. At this time, it carried out on the conditions which turn on a photoconductor heater. Further, toner 1 was supplied to the developing device, and various evaluations were performed under the following conditions.

[Transfer efficiency]
In an environment with a temperature of 30 ° C. and a humidity of 80 RH% (hereinafter also referred to as an H / H environment), the transfer efficiency after initial and after endurance of 100,000 sheets was evaluated. As the transfer paper, CS-680, A4 paper (basis weight 68 g / m ² ) was used which was left in an H / H environment overnight to absorb water sufficiently. Transfer efficiency is 10
A solid black patch of cm ² was passed through, and the weight of the untransferred toner and the pre-transfer toner on the photoreceptor was measured, calculated and evaluated.
A: Very good (98% or more)
B: Good (95% or more and less than 98%)
C: Normal (92% to less than 95%)
D: Slightly bad (90% or more and less than 92%)
E: Bad (less than 90%)

[Spattering]
In endurance use in an H / H environment, a lattice pattern (1 cm interval) on a 100 μm (latent image) line was printed after 100,000 sheets, and the scattering was visually evaluated using an optical microscope.
(Evaluation criteria)
A (very good): the line is very sharp and hardly splattered B (good): the line is sharply scattered to the extent that it is slightly scattered C (normal): the splatter is slightly large but the line is relatively sharp D (bad) ): There is a lot of splattering, and the lines feel dull

[Line / solid ratio]
In an H / H environment, the DC voltage _VDC was adjusted so that the amount of toner loaded on the paper of the FFH image (hereinafter, solid portion) was 0.9 mg / cm ² after the endurance use of 100,000 sheets.
With the solid black patch 1 cm long and 7 cm wide developed on the drum, the main body is stopped, and the amount of toner (Mb) applied to the solid black portion on the drum is measured.
Next, the main body is stopped in a state where a patch (line: solid white = 4: 8) in which 20 lines of 170 μm are written in a range of 1 cm in length and 7 cm in width is developed on the drum, and the toner on the line portion on the drum is stopped. The applied amount (Ml) is measured.
The applied amount of the line part (Ml / (7 * 4/12)) / the applied amount of the solid black part (Mb / 7) was calculated and evaluated.
(Evaluation criteria)
A (very good): less than 1.30 B (good): 1.30 or more and less than 1.40 C (normal): 1.40 or more and less than 1.50 D (bad): 1.50 or more

[Evaluation of gastling]
A halftone (30H) image was formed, this image was visually observed, and the roughness was evaluated based on the following criteria. The 30H image is a value obtained by displaying 256 gradations in hexadecimal, and is a halftone image when 00H is solid white (non-image) and FFH is solid black (entire image). This evaluation was performed after endurance use of 100,000 sheets in a temperature of 23 ° C. and a humidity of 5 RH% (hereinafter also referred to as N / L environment), and evaluated according to the following criteria.
(Evaluation criteria)
A (very good): It does not feel rust and is smooth.
B (good): There is not much feeling of roughness.
C (ordinary): Although there is a slight roughness, it is at a level where there is no practical problem.
D (Poor): There is a feeling of roughness and is a problem.

[Selective developability]
In the durable use under H / H environment, the particle size distribution of the toner in the developing unit was measured at the initial stage and after 100,000 sheets, and the change of the volume average particle diameter was evaluated based on the following criteria.

(Evaluation criteria)
A (very good): less than 0.20 B (good): 0.20 or more and less than 0.30 C (normal): 0.30 or more and less than 0.40 D (bad): 0.40 or more

[Image memory]
The image data was configured so that it could be output directly without using a printer driver, and the test chart of A3 shown in FIG. 4 was output. This test chart has a repetitive pattern of solid white and solid black on the leading end side of the image, and is then formed with a halftone of an area ratio of 25% of 1 dot 1 space of 600 dpi. A photoconductor part in which a solid white solid black image is formed on the first round of the photoconductor, and a halftone is formed on the second round, and a solid white is formed on the first round of the halftone part. The density difference between the density of the part corresponding to the part and the density of the part corresponding to the part where solid black is formed in the first round is expressed by a reflection densitometer (manufactured by X-Rite Inc: 504).
The image density was measured with a spectral densitometer.
In this evaluation, evaluation was performed according to the following criteria from the concentration difference.
A (very good): density difference is less than 0.010 B (normal): density difference is 0.010 or more and less than 0.020 C (bad): density difference is 0.020 or more

In each of the above evaluation items, all the configurations of Example 1 were A determinations.

<Examples 2 to 14>
Evaluation was performed in the same manner as in Example 1 except that the photoreceptor and toner were changed as shown in Table 8. The evaluation results are shown in Table 8.

Examples 2 to 4 were the same evaluation results as Example 1. Although the amount of butyl acetate contained in the charge control agent is slightly different, it is considered that there is no problem. In Example 3, the absorbance ratio a ₂ / a ₁ of the photoreceptor was 0.52, but the transfer efficiency was A evaluation.
In Example 5, the transfer efficiency after endurance use of 100,000 sheets was evaluated as B. Since the absorbance ratio a ₂ / a ₁ of the photoreceptor is 0.54, it is considered that the surface layer of the photoreceptor has changed slightly due to durability. The selective developability was also evaluated as B. Since the amount of butyl acetate contained in the charge control agent 6 is as large as 1000 ppm, the selective developability is considered to be slightly deteriorated. Furthermore, the image memory was also evaluated as B. Since the defect density of the photosensitive member 5 is as low as 9.0 × 10 ¹⁸ spins / cm ³ , it is considered that the resistance of the photosensitive member is increased and the image memory is slightly deteriorated.
In Examples 6 and 7, the roughness was B and the selective developability was C. It is considered that the amount of the aliphatic polyhydric alcohol in the binder resin A has an effect, and the interaction between the binder resin, the ester group concentration, and the charge control agent has been lowered, which has slightly affected the roughness. The amount of butyl acetate is 1
Since it is as high as 100 ppm, it is considered that selective developability was affected.
In Example 8, the roughness was evaluated as C. Since the amount of the aliphatic polyhydric alcohol in the binder resin A is as large as 35 mol%, it is considered that the roughness was deteriorated.

In Example 9, the line / solid ratio was B evaluation. By changing the polymerization catalyst of the polyester part of the binder resin from a titanium catalyst to a tin catalyst, it is considered that the charging uniformity of the binder resin slightly deteriorated and slightly affected the line / solid ratio.
In Example 10, the line / solid ratio was C evaluation. It is considered that the charge amount was reduced by changing the charge control agent to T77, and the line / solid ratio was slightly deteriorated.
In Examples 11 and 12, the initial transfer efficiency was B evaluation, and the scattering was B evaluation. In Example 11, since the content of the aliphatic compound having 30 carbon atoms is as small as 0.1% by mass, the effect of suppressing the adhesion between the toner and the photoreceptor is weak, and the initial transfer efficiency is considered to be slightly deteriorated. Furthermore, regarding the scattering, it is considered that the effect of dispersing the colorant and the charge control agent in the binder resin is weak and the charging uniformity is deteriorated. In Example 12, since the amount of the aliphatic compound having 102 carbon atoms is as large as 10% by mass, the toner is somewhat easily deformed, and the contact area between the toner and the photoreceptor and the charging uniformity are deteriorated, thereby affecting the scattering. It is done.
In Examples 13 and 14, the transfer efficiency after endurance use of 100,000 sheets was C evaluation, and the scattering was also C evaluation. In Examples 13 and 14, since the amount of the aliphatic compound is as large as 11% by mass, the toner is easily deformed, and the adhesion between the toner and the photosensitive member is increased.

<Comparative Examples 1-3>
Evaluation was performed in the same manner as in Example 1 except that the photoreceptor and toner were changed as shown in Table 9. Table 9 shows the evaluation results.

In Comparative Example 1, the initial transfer efficiency was C evaluation, and the transfer efficiency after 100,000 sheets was D evaluation. Since the defect density of the photosensitive member 6 is as high as 2.5 × 10 ¹⁹ spins / cm ³ , it is considered that the adhesion between the photosensitive member and the toner is increased and the transfer efficiency is deteriorated.
In Comparative Example 2, the initial transfer efficiency was D evaluation. Furthermore, scattering, line / solid ratio, roughness and selective developability were evaluated as D. Since the binder resin does not contain an aliphatic compound, the adhesion between the toner and the photosensitive member is increased, and the initial transfer efficiency is considered to have deteriorated. In addition, since it does not contain an aliphatic compound, it is considered that the charging performance has changed and the image quality has deteriorated by one rank.
In Comparative Example 3, the transfer efficiency after 100,000 sheets was E evaluation. Since the surface density of the photoconductor 7 is as low as 6.50 × 10 ²² atoms / cm ^{3 in the} surface layer, the surface layer of the photoconductor changes due to endurance use, and the adhesion between the photoconductor and the toner increases. It is done.

101: Substrate, 102: Lower charge injection blocking layer, 103: Photoconductive layer, 104: Surface layer, 105: Intermediate layer, 106: Multiple intermediate layers, 107: Change layer

201: electrophotographic photosensitive member, 202: main charger, 203: electrostatic latent image forming means (image exposure means), 204: developing device, 205: intermediate transfer member, 206: cleaner, 207: pre-exposure device

3100: Deposition device, 3110: Reaction vessel, 3200: Raw material gas supply device,
3111: Cathode electrode, 3112: Substrate, 3113: Heater for substrate heating, 3114: Source gas introduction pipe, 3115: High-frequency matching box, 3116: Gas pipe, 3117: Leak valve, 3118: Main valve, 3119: Vacuum gauge, 3120 : High frequency power supply, 3121: insulating material, 3123: cradle,
3221 to 3225: raw material gas cylinder, 3231 to 3235: valve, 3261 to 3265: pressure regulator, 3241 to 3245: inflow valve, 3251 to 3255: outflow valve, 3211 to 3215: mass flow controller, 3260: auxiliary valve

Claims (7)

The electrostatic image carrier is charged, an electrostatic image is formed on the charged electrostatic image carrier, the electrostatic image is developed with toner to form a toner image, and the electrostatic image on the electrostatic image carrier In an image forming method for transferring the toner image to a transfer material,
The electrostatic charge image carrier is an electrophotographic photosensitive member having at least a photoconductive layer and a surface layer composed of hydrogenated amorphous silicon carbide on the photoconductive layer,
The sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is 6.60 × 10 ²² atoms / cm ³ or more,
The defect density determined by electron spin resonance measurement of the surface layer is 2.2 × 10 ¹⁹ spins / cm ³ or less,
The toner is a toner having a binder resin, and the binder resin has a polyester portion where a terminal is condensed with at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acid and aliphatic monoalcohol. An image forming method.   The image forming method according to claim 1, wherein the aliphatic compound is at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 30 to 102 carbon atoms and an aliphatic monoalcohol.   The image forming method according to claim 1, wherein the content of the aliphatic compound in the binder resin is 0.1% by mass or more and 10% by mass or less. The image forming method according to claim 1, wherein the toner contains a charge control agent, and the charge control agent is a compound represented by the following formula [1].

(In the formula, A ₁ , A ₂ and A ₃ each independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. M Represents an Fe atom, a Cr atom, or an Al atom, and X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.   The electrophotographic photosensitive member has a ratio (C / (Si + C)) of the number of carbon atoms (C) to the sum of the number of silicon atoms (Si) and the number of carbon atoms (C) in the surface layer. The image forming method according to claim 1, wherein the image forming method is 0.50 or more and 0.65 or less. The defect density is 9.0 × 10 ¹⁸ spins / cm ³ or more and 2.2 × 10 ¹⁹ spi.
The image forming method according to claim 1, wherein the image forming method is ns / cm ³ or less. In the electrophotographic photosensitive member, a ratio (a ₂ / a ₁ ) of an absorbance a ₂ having a wave number of 2960 cm ^{−1 to} an absorbance a _{1 having} a wave number of 2890 cm ⁻¹ in an infrared absorption spectrum of the surface layer is 0.52 or less. Item 7. The image forming method according to any one of Items 1 to 6.

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