JP6614896B2 - Image forming method - Google Patents

Description

  The present invention relates to an image forming method employed in an electrophotographic apparatus, an electrostatic recording apparatus, an electrostatic printing apparatus, and the like.

In recent years, full-color image forming apparatuses such as full-color printers and full-color copiers are required to support various transfer materials such as not only plain paper but also recycled paper having a large surface unevenness. In order to meet this demand, a transfer method using an intermediate transfer member has become mainstream as a transfer method employed in a full-color image forming apparatus.
In the transfer method using the intermediate transfer member, a primary transfer step of transferring the toner image from the surface of the photosensitive member (electrophotographic photosensitive member) to the surface of the intermediate transfer member, and the toner image transferred to the surface of the intermediate transfer member A secondary transfer process for transferring the toner onto the transfer material is required. Since the transfer method using the intermediate transfer member has a larger number of times of transfer than the transfer method not using the intermediate transfer member, there is a concern that the dot reproducibility (roughness) decreases and the transfer efficiency decreases.

Many image forming apparatuses are provided with a mechanism for scraping toner (transfer residual toner) remaining on the surface of the photosensitive member or the surface of the intermediate transfer member with a cleaning member such as a cleaning blade. However, when high-speed image output is performed, the residual toner tends to slip through, and the residual toner may stay on the surface of the photoreceptor or the surface of the intermediate transfer material for a long time. As a result, the photosensitive member or the intermediate transfer member may be contaminated with toner.
As a technique for improving the primary transfer property and the contamination resistance of the photosensitive member, the adhesion force of the surface of the intermediate transfer member to the toner is smaller than the adhesion force of the surface of the photosensitive member to the toner, and the toner from the photosensitive member to the intermediate transfer member It has been proposed to smooth the transition.

Patent Document 1 discloses an image forming method in which the contact angle of water on the surface of the intermediate transfer member is smaller than the contact angle of water on the surface of the photoreceptor.
Patent Document 2 discloses that a contact angle of water with a surface contact angle of 95 ° or more and a surface ten-point average roughness Rz of 2 μm or less and a surface contact angle with water of 95 ° or more and a surface ten-point average. An image forming method using an intermediate transfer member having a roughness Rz of 2 μm or less is disclosed.
Patent Document 3 discloses an image forming method using an intermediate transfer belt having a fluorine-based water- and oil-repellent coating with low adhesion on the surface.
However, Patent Document 1 does not disclose the adhesion of the toner itself. The image forming method disclosed in Patent Document 1 exhibits excellent primary transferability in the primary transfer step. However, in the secondary transfer step, the adhesion between the intermediate transfer member and the toner is strong, and the secondary transfer property may not be sufficient. Also, the surface transferability of the intermediate transfer member tends to be insufficient.
Further, in the image forming methods disclosed in Patent Documents 2 and 3, the adhesion of the intermediate transfer member is not sufficiently large and the adhesion between the toners is small as compared with the adhesion of the photosensitive member. For this reason, a uniform toner layer cannot be maintained at the time of primary transfer, and a problem of “missing” is easily generated in which only a central portion such as a thin line, which is one of transfer defects, is not transferred.

JP 2003-202785 A JP 2006-84840 A JP 2009-192901 A

  The object of the present invention is to provide excellent transferability even when performing high-speed image output using a transfer material such as recycled paper having a large surface irregularity, and to stably output a good image even in long-term use. It is an object of the present invention to provide an image forming method capable of

The present invention
A charging step for charging the surface of the photoreceptor;
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the charged photoreceptor;
Developing the electrostatic latent image with toner to form a toner image;
A primary transfer step of transferring the toner image to the surface of the intermediate transfer member;
A cleaning step of removing residual toner remaining on the surface of the photoreceptor after the primary transfer step;
A secondary transfer step of transferring the toner image transferred to the surface of the intermediate transfer member onto a transfer material;
A fixing step of fixing the toner image transferred to the transfer material to the transfer material;
An image forming method comprising:
When the contact angle of water on the surface of the photoreceptor is θ (A) and the contact angle of water on the surface of the intermediate transfer member is θ (B), θ (B) is 100 ° or more and 150 ° or less. The θ (A) and the θ (B) satisfy the relationship of the following formula (1),
−70 ° ≦ θ (A) −θ (B) <0 ° (1)
The toner has toner particles containing a binder resin;
The contact angle of water on the surface of the molded pellet of the toner with respect to water is 60 ° or more and 80 ° or less.

  According to the present invention, it is excellent in transferability even in high-speed image output using a transfer material such as recycled paper having a large unevenness on the surface, and a good image can be stably output even in long-term use. An image forming method can be provided.

The figure of the thermal spheronization processing apparatus used for this invention is shown. It is a schematic diagram which shows an example of the electrophotographic apparatus of this invention. FIG. 2 is a schematic cross-sectional view in the thickness direction of an intermediate transfer member according to the present invention. It is the schematic of the output chart obtained from a microhardness measuring apparatus.

The image forming method of the present invention comprises:
A charging step for charging the surface of the photoreceptor;
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the charged photoreceptor;
Developing the electrostatic latent image with toner to form a toner image;
A primary transfer step of transferring the toner image to the surface of the intermediate transfer member;
A cleaning step of removing residual toner remaining on the surface of the photoreceptor after the primary transfer step;
A secondary transfer step of transferring the toner image transferred to the surface of the intermediate transfer member onto a transfer material;
A fixing step of fixing the toner image transferred to the transfer material to the transfer material;
An image forming method comprising:
When the contact angle of water on the surface of the photoreceptor is θ (A) and the contact angle of water on the surface of the intermediate transfer member is θ (B), θ (B) is 100 ° or more and 150 ° or less. And the θ (
A) and θ (B) satisfy the relationship of the following formula (1),
−70 ° ≦ θ (A) −θ (B) <0 ° (1)
The toner has toner particles containing a binder resin;
The contact angle of water on the surface of the molded pellet of toner is 60 ° or more and 80 ° or less.

The present inventors consider the effects of the present invention as follows.
In order to obtain an effect that the primary transfer property and the secondary transfer property can be maintained at a good level even when the toner image is repeatedly transferred, in the present invention, the contact angle of water on the surface of the photoreceptor and the intermediate Attention was paid to the relationship between the contact angle of the surface of the transfer body with water and the contact angle of the toner surface with water.
Conventional image forming methods have employed a method in which the contact angle of water on the surface of the photoreceptor is larger than the contact angle of water on the surface of the intermediate transfer member. In this case, the primary transferability can be maintained at a good level. However, when images are continuously output to a transfer material such as recycled paper having a large surface unevenness over a long period of time, there is a tendency that the toner is separated from the intermediate transfer member at the time of secondary transfer. In addition, in order to reduce the adhesion of the toner itself, when a toner having a large contact angle with water on the surface of the toner is used, it is difficult to form a uniform toner layer because the toner tends to scatter and fall out during transfer. In some cases, good images could not be obtained.
Therefore, in the present invention, the relationship between the contact angle of water on the surface of the photoreceptor and the contact angle of water on the surface of the intermediate transfer member, and the contact angle of water on the surface of the toner are controlled. As a result, it has become possible to maintain good transferability even when images are continuously output to a transfer material such as recycled paper having a large surface unevenness over a long period of time.

One feature of the present invention is that when the contact angle of water on the surface of the photoreceptor is θ (A) and the contact angle of water on the surface of the intermediate transfer member is θ (B), θ (B) is 100 ° to 150 °, and θ (A) and θ (B) satisfy the relationship of the following formula (1).
−70 ° ≦ θ (A) −θ (B) <0 ° (1)
Generally, the larger the value of the surface contact angle θ with respect to water, the smaller the surface adhesion. Even if the θ (B) is not less than 100 ° and not more than 150 °, if [theta (A) −theta (B)] is less than −70 °, the adhesion force between the surface of the photosensitive member and the toner is increased. On the other hand, since the adhesion force between the surface of the intermediate transfer member and the toner is too small, it is difficult to form a uniform toner layer on the surface of the intermediate transfer member during the primary transfer. Further, even when the θ (B) is 100 ° or more and 150 ° or less, when [theta (A) −the θ (B)] is 0 ° or more, the contact angle of the surface of the photoreceptor with respect to water. Is too large, the contact area between the surface of the photoreceptor and the cleaning member becomes insufficient during cleaning, and slipping through and poor cleaning are likely to occur.
A more preferable range of the θ (A) −the θ (B) is
−60 ° ≦ θ (A) −θ (B) <− 10 ° ( 1 ) ′
It is.
The contact angle θ (A) with respect to water on the surface of the photoreceptor can be controlled by adjusting the surface roughening treatment of the surface of the photoreceptor, for example.
Further, the contact angle θ (B) with respect to water on the surface of the intermediate transfer member is controlled by adjusting the content of perfluoropolyether (hereinafter also referred to as “PFPE”) in the surface layer of the intermediate transfer member, for example. Can do.

In the intermediate transfer member used in the image forming method of the present invention, the θ (B) is 100 ° or more and 150 ° or less. Preferably, it is 115 degrees or more and 130 degrees or less.
When the θ (B) is less than 100 °, in the case of the present invention, the adhesion between the surface of the intermediate transfer member and the toner is large, and the transfer material is excellent for a transfer material having a large surface unevenness during secondary transfer. Next transferability is not obtained. When θ (B) exceeds 150 °, the adhesion between the surface of the intermediate transfer member and the toner is too small, and it is difficult to form a uniform toner layer on the intermediate transfer member at the time of primary transfer.

The intermediate transfer member used in the image forming method of the present invention preferably has a base layer and a surface layer. The surface layer preferably has a matrix-domain structure having a matrix and a domain in a cross section in the thickness direction. The matrix of the matrix-domain structure preferably contains a binder resin. The domain of the matrix-domain structure preferably contains PFPE. PFPE is a material that can reduce toner adhesion.
Since PFPE is contained in the domain of the matrix-domain structure, image output is repeated, and even when the surface layer of the intermediate transfer member is subjected to various chemical deteriorations and physical deteriorations, the PFPE remains in the intermediate transfer member. Continue to exist on the surface. As a result, good transferability can be maintained. When the inventors measured the surface of the intermediate transfer member by X-ray photoelectron spectroscopy (ESCA) after outputting a large number of images using the intermediate transfer member according to the present invention, a peak derived from PFPE was found. It was confirmed that it was detected with the same value as the initial image output.
Further, even when polytetrafluoroethylene (PTFE) particles, which are fluorine compounds as in PFPE, are dispersed in the surface layer of the intermediate transfer member, the effect as in the case of using PFPE cannot be obtained.
The domain may contain different materials other than PFPE. For example, for the purpose of adjusting other characteristics, an additive compatible with PFPE may be contained in the domain. Furthermore, the domain may not be completely filled with PFPE and voids may exist. The content of PFPE in the domain is preferably 10% by mass or more and 50% by mass or less, and more preferably 20% by mass or more and 50% by mass or less.

The domain containing PFPE is phase-separated from the matrix containing the binder resin.
However, even when the phases are separated, the component composition of the matrix and the domain is not always strictly separated. Even in a matrix-domain structure having a clear interface between a matrix and a domain, each phase (matrix and domain) may contain a small amount of components of other phases. It is also academically said that an intermediate composition exists in a very narrow width around 10 nm at the interface between the matrix and the domain.
A matrix-domain in the surface layer of the intermediate transfer member is obtained by cutting out the intermediate transfer member and observing a cross section in the thickness direction of the surface layer of the intermediate transfer member with a scanning electron microscope (hereinafter also referred to as “SEM”). The presence or absence of the structure can be confirmed.
The average major axis of the domain observed by SEM is preferably 30 nm or more and 3000 nm or less, and more preferably 100 nm or more and 1000 nm or less. When the average major axis of the domain is 30 nm or more and 3000 nm or less, that is, the domain has a certain size, adhesion of the intermediate transfer member to the toner can be further reduced. The average major axis of the domain can be controlled by adjusting the amount of the dispersant used when forming the surface layer.

The ratio of the area of the domain in the unit area (15 μm ² ) of the cross section in the thickness direction of the surface layer of the intermediate transfer member is preferably 1% by area to 50% by area with respect to the area of the matrix. More preferably, it is 30 area% or less. The ratio of the area of the domain is not less than 1 area% and not more than 50 area% with respect to the area of the matrix, that is, the domain has a certain ratio, thereby further reducing the adhesion of the intermediate transfer member to the toner. can do.
Whether the domain contains PFPE can be identified by detection using an elemental analysis method such as an energy dispersive X-ray analyzer (EDX), TOF-SIMS, Auger spectroscopy, or the like. For example, when the domain of the intermediate transfer body of the present invention was subjected to elemental analysis by EDX, a fluorine atom could be detected and the domain could be identified as a domain containing PFPE. Moreover, the fragment of the fluorocarbon ether structure derived from PFPE could also be observed from the domain by TOF-SIMS.
Further, as the intermediate transfer member according to the present invention, a belt shape, a drum shape, a roller shape, or other shapes can be used.

[Electrophotographic equipment]
An image forming apparatus 10 shown in FIG. 2 is an electrophotographic full color image forming apparatus (full color laser printer).
The image forming apparatus 10 shown in FIG. 2 includes an intermediate transfer belt 7 that is a belt-shaped intermediate transfer member. Then, an image forming unit that is an image forming unit for each color component of yellow (Y), magenta (M), cyan (C), and black (K) in order along the plane portion of the intermediate transfer belt 7 in the moving direction. Py, Pm, Pc, and Pk are provided. Since the basic configuration of each image forming unit is the same, the details of the image forming unit will be described only for the yellow image forming unit Py.
The yellow image forming unit Py includes a photosensitive drum 1Y which is a drum-shaped electrophotographic photosensitive member (electrostatic latent image carrier). The photosensitive drum 1Y is formed by laminating a charge generation layer, a charge transport layer, and a surface protective layer in order on an aluminum cylinder as a base.
The yellow image forming unit Py includes a charging roller 2Y as a charging unit. By applying a charging bias to the charging roller 2Y, the surface (circumferential surface) of the photosensitive drum 1Y is uniformly charged.

Above the photosensitive drum 1Y, a laser exposure device 3Y as an image exposure unit is disposed. The laser exposure device 3Y performs scanning exposure according to image information on the uniformly charged surface of the photosensitive drum 1Y to form an electrostatic latent image of a yellow color component on the surface of the photosensitive drum 1Y.
The electrostatic latent image formed on the photosensitive drum 1Y is developed with toner as a developer by a developing device 4Y as developing means. The developing device 4Y includes a developing roller 4Ya as a developer carrying member and a regulating blade 4Yb as a developer amount regulating member, and contains yellow toner as a developer. The developing roller 4Ya supplied with the yellow toner is in light pressure contact with the photosensitive drum 1Y in the developing portion, and is rotated with a speed difference in the forward direction with respect to the photosensitive drum 1Y. The yellow toner conveyed to the developing unit by the developing roller 4Ya adheres to the electrostatic latent image formed on the photosensitive drum 1Y by applying a developing bias to the developing roller 4Ya. As a result, a toner image (yellow toner image) is formed on the photosensitive drum 1Y.

The intermediate transfer belt 7 is stretched around a driving roller 71, a tension roller 72, and a driven roller 73, and is moved (rotated and driven) in the direction of the arrow in FIG. 2 while being in contact with the photosensitive drum 1Y. Then, the yellow toner image that has reached the primary transfer portion Ty is transferred onto the intermediate transfer belt 7 by the primary transfer roller 5Y as a primary transfer member pressed against the photosensitive drum 1Y via the intermediate transfer belt 7. Is done.
Similarly, the image forming operation described above is performed in each of the magenta (M), cyan (C), and black (K) units Pm, Pc, and Pk as the intermediate transfer belt 7 is moved, and the image is formed on the intermediate transfer belt 7. Four toner images of yellow, magenta, cyan, and black are superimposed. The four color toner images are conveyed along with the movement of the intermediate transfer belt 7, and are transferred at a predetermined timing by the secondary transfer roller 8 serving as a secondary transfer unit in the secondary transfer portion T ′. All images are transferred onto S. In secondary transfer, a transfer voltage of several kV is often applied in order to ensure a sufficient transfer rate, but at that time, discharge may occur near the nip of the secondary transfer portion. This discharge contributes to chemical deterioration of a transfer member such as an intermediate transfer member.

The transfer material S is stored in a cassette 12 which is a transfer material storage unit, picked up by a pickup roller 13, and transferred to the surface of the intermediate transfer belt 7 by a transport roller pair 14 and a registration roller pair 15. The toner image is conveyed to the secondary transfer portion T ′ in synchronization with the toner image.
The toner image transferred to the transfer material S is fixed by a fixing device 9 as fixing means, and becomes a full-color image. The fixing device 9 includes a fixing roller 91 and a pressure roller 92 provided with a heating unit, and heats and presses an unfixed toner image on the transfer material S to fix it on the transfer material S.
Thereafter, the transfer material S is discharged out of the image forming apparatus by the conveyance roller pair 16 and the discharge roller pair 17.
A cleaning blade 11 as a cleaning unit for the intermediate transfer belt 7 is disposed downstream of the secondary transfer portion T ′ in the rotational driving direction of the intermediate transfer belt 7, and is transferred to the transfer material S at the secondary transfer portion T ′. The toner (transfer residual toner) remaining on the surface of the intermediate transfer belt 7 without being removed is removed.

  As described above, the toner image transfer process from the photoconductor to the intermediate transfer belt and from the intermediate transfer belt to the transfer material is repeated. Further, by repeating recording on a large number of transfer materials, the transfer process is further repeated.

According to the study by the present inventors, the intermediate transfer member disclosed in Japanese Patent Application Laid-Open No. 2009-192901 has good image quality at the initial stage of image output.
However, when image output is continued, the transferability of the intermediate transfer member gradually decreases, and the image quality may deteriorate to the same level as when an intermediate transfer member not coated with a fluorine compound is used. It was.

This phenomenon is considered to occur because the fluorine compound having water repellency and oil repellency coated on the surface of the intermediate transfer member is deteriorated by repeating the transfer process.
This deterioration is considered to be caused by the following (i) and (ii).
(I) Chemical deterioration of the surface of the intermediate transfer member due to discharge caused by application of a high voltage during transfer.
(Ii) Physical deterioration of the surface of the intermediate transfer member due to scratches on the surface layer due to cleaning or the like.
The above consideration is based on the following experimental facts.
First, a decrease in transferability of the intermediate transfer member after long-term use was a phenomenon that is often seen when pulverized toner is used among toners. For this reason, it is considered that the surface properties of the intermediate transfer member are changed by the wax exposed on the surface of the toner particles being attached to the intermediate transfer member.
However, after repeatedly outputting an image, even if the wax on the surface of the intermediate transfer member was carefully wiped with a solvent, the deterioration in image quality was not recovered.

Second, when the surface of the intermediate transfer member is measured by X-ray photoelectron spectroscopy (XPS), immediately after the surface of the intermediate transfer member is coated with a fluorine compound, 10-30 atomic% of fluorine atoms are present on the surface of the intermediate transfer member. Existed.
However, after output of 1000 or more images, only a few atomic percent or less of fluorine atoms were present on the surface of the intermediate transfer member.
Third, when the contact angle of the surface of the intermediate transfer member with respect to hexadecane was measured, it was 40 ° or more immediately after the surface of the intermediate transfer member was coated with a fluorine compound.
However, after repeatedly outputting several thousand or more images, the angle was 20 ° or less.

FIG. 3 is a view showing a preferred embodiment of the intermediate transfer body 200 according to the present invention, and is a sectional view in the thickness direction.
The intermediate transfer member 200 has a base layer 201 and a surface layer 203. The surface layer 203 has a matrix-domain structure having a matrix 203-1 and a domain 203-3 existing in the matrix 203-1 in the thickness direction. Here, the matrix 203-1 contains a binder resin, and the domain 203-3 contains PFPE.
The surface of the intermediate transfer member 200, that is, the surface of the surface layer 203 on which the toner image is carried, preferably has a micro hardness measured by an ultra micro hardness meter of 50 MPa or more.

According to the intermediate transfer member having such a configuration, excellent transferability is maintained even by repeated image formation, and a high-quality image can be stably output over a long period of time.
The above effect is
(1) microhardness of the surface of the intermediate transfer member, and
(2) The present inventors consider that this is due to a surface layer having a matrix-domain structure in the thickness direction.

[Micro hardness]
The surface of the intermediate transfer member according to the present invention preferably has a micro hardness measured by an ultra micro hardness meter of 50 MPa or more.
The transferability of the intermediate transfer member is affected by the adhesion force of the toner to the surface. The adhesion force of the toner to the surface of the intermediate transfer member increases as the contact area between the surface of the intermediate transfer member and the toner increases.
When the micro hardness of the surface of the intermediate transfer member measured by the ultra-micro hardness meter is 50 MPa or more, the contact area between the surface of the intermediate transfer member and the toner can be reduced. As a result, the adhesion force of the toner to the surface of the intermediate transfer member can be suppressed, and the secondary transfer property is improved. The microhardness of the surface of the intermediate transfer member is more preferably 80 MPa or more, and more preferably 100 MPa or more.
On the other hand, the microhardness of the surface of the intermediate transfer member measured by an ultra microhardness meter is preferably 400 MPa or less, and more preferably 380 MPa or less.
When the intermediate transfer member has a base layer and a surface layer, the microhardness of the surface of the intermediate transfer member can be controlled by components used when forming the surface layer. When the surface layer has a matrix-domain structure, it should be controlled by the type and amount of binder resin contained in the matrix, the material contained in the domain (for example, PFPE), solvent and dispersant, and combinations thereof. Can do.

[Matrix-domain structure]
PFPE has a very small surface free energy. Therefore, it is a material that can reduce the adhesion of the toner to the surface of the surface layer by being contained in the surface layer of the intermediate transfer member.
PFPE tends to move to the interface with air, that is, to the surface side of the surface layer, because of its very small surface free energy. That is, PFPE tends to be unevenly distributed on the surface side of the surface layer.
When the PFPE having such characteristics is used for the surface layer of the intermediate transfer member, the present inventors distribute the PFPE in the thickness direction of the surface layer by making the PFPE exist as a domain in the matrix constituting the surface layer. It has been found that it is preferable.

This matrix-domain structure indicates that PFPE is present not only on the surface side of the surface layer of the intermediate transfer member but also on the entire surface layer, and that a large amount of PFPE is present on the surface layer. Show. As a result, even if the image output is repeated and the surface layer of the intermediate transfer member is chemically and / or physically deteriorated and the PFPE on the surface disappears, the domain of the PFPE existing in the surface layer remains. By exposing to the surface of the surface layer, PFPE can always be present on the surface of the surface layer. By doing so, the transferability of the intermediate transfer member can be maintained well.
This indicates that the intermediate transfer member having the matrix-domain structure has the same peak as that in the initial state as a result of surface analysis by X-ray photoelectron spectroscopy (XPS) even after being subjected to output of a large number of images. This is also supported by the result that it is detected at a value of the degree.

Further, as described above, since the surface layer of the intermediate transfer member which is a preferred embodiment of the present invention has a matrix-domain structure in the thickness direction, the domain containing PFPE is in the thickness direction of the surface layer, that is, It is distributed from the base layer side to the surface side of the surface layer.
In the surface layer having such a configuration, a part of the domain located on the surface side of the surface layer is exposed on the surface or exposed at an early stage of image formation. As a result, a state where domains containing PFPE are scattered in the matrix is also formed on the surface of the surface layer. In this way, the toner is less likely to adhere to the surface having regions with different adhesion to the toner, and this is a preferable form in order to maintain good transferability.

  Furthermore, the components used when forming the surface layer of the intermediate transfer member, for example, the types and combinations of binder resin, PFPE, solvent, and dispersant contained in the matrix, make it possible to expose PFPE exposed on the surface of the surface layer. There may be a structure in which voids exist in a part of the domain. In the form in which the concave portions are scattered like islands on the surface due to the presence of such voids, the surface is easily scraped by a physical action by rubbing of a cleaning blade or paper. As a result, the supply of PFPE from the PFPE domain in the recess is promoted and the surface is easily scraped, so that the PFPE domain existing in the thickness direction is likely to appear on the surface. Thereby, the action of PFPE is effectively expressed. Further, since the contact area between the surface and the toner is reduced due to the concave portion, the adhesion force of the toner to the surface of the intermediate transfer member is reduced. With such an action, a structure in which voids exist in a part of the PFPE domain exposed on the surface of the intermediate transfer member can be said to be a preferable form as a structure for maintaining good transferability. The effect of the recess can also be manifested by controlling the surface shape by physical surface processing such as nanoimprinting or lapping.

  The surface layer of the intermediate transfer member in which the matrix-domain structure is observed in the cross section in the thickness direction easily forms a state where regions containing PFPE are scattered in an island shape on the surface. For this reason, when the surface of the intermediate transfer member is observed with an SEM, a state in which regions containing PFPE are scattered in an island shape is often observed. In such a case, it is preferable that the size of the interspersed domains observed on the surface and the ratio of the domains occupying the surface are the same as the respective numerical ranges observed in the cross-sectional observation with the SEM. Specifically, the average major axis of the domain is preferably 30 nm or more and 3000 nm or less, and more preferably 100 nm or more and 1000 nm or less. Moreover, it is preferable that the ratio of the area of a domain is 1 area% or more and 50 area% or less with respect to the area of a matrix.

The structure of the intermediate transfer member will be described by taking as an example a belt-shaped intermediate transfer member (intermediate transfer belt) having a base layer and a surface layer, and the surface layer having a matrix-domain structure.
[Base layer]
The base layer of the intermediate transfer member preferably contains a resin and a conductive agent, and is preferably a semiconductive layer (film).
Examples of the resin for the base layer include polyimide, polyamideimide, polyetheretherketone, polyphenylene sulfide, and polyester. Among these, polyimide, polyamideimide, and polyetheretherketone are preferable from the viewpoint of strength. Only 1 type may be used for resin and 2 or more types may be used for it.
As the conductive agent for the base layer, for example,
Electron conductive materials such as carbon black, antimony-doped tin oxide, titanium oxide, conductive polymers,
Examples thereof include sodium perchlorate, lithium, cationic or anionic ionic surfactants, nonionic surfactants, and ion conductive materials such as oligomers or polymers having oxyalkylene repeating units.

The volume resistivity of the base layer is preferably 1.0 × 10 ⁷ Ω · cm or more and 1.0 × 10 ¹² Ω · cm or less. The surface resistivity of the base layer is preferably 1.0 × 10 ⁸ Ω / □ or more and 1.0 × 10 ¹⁴ Ω / □ or less. By setting the volume resistivity of the base layer to 1.0 × 10 ⁷ Ω · cm or more and 1.0 × 10 ¹² Ω · cm or less, image defects due to charge-up during continuous driving or insufficient transfer bias can be suppressed. . By setting the surface resistivity of the base layer to 1.0 × 10 ⁸ Ω / □ or more and 1.0 × 10 ¹⁴ Ω / □ or less, image defects due to peeling discharge or toner scattering when the transfer material is separated from the intermediate transfer belt are prevented. Can be suppressed.
Further, the volume resistivity and the surface resistivity of the intermediate transfer member formed by forming the surface layer on the base layer are preferably the same values as those of the base layer. For this reason, the surface layer of the intermediate transfer member is also preferably a semiconductive layer.
That is, the volume resistivity of the intermediate transfer member is preferably 1.0 × 10 ⁷ Ω · cm or more and 1.0 × 10 ¹² Ω · cm or less. The surface resistivity of the intermediate transfer member is preferably 1.0 × 10 ⁸ Ω / □ or more and 1.0 × 10 ¹⁴ Ω / □ or less.
In order to adjust the volume resistivity and surface resistivity of the intermediate transfer member, the surface layer preferably contains a conductive agent.
As the conductive agent contained in the surface layer, for example,
Electron conductive materials such as carbon black, antimony-doped tin oxide, titanium oxide, conductive polymers,
Examples thereof include sodium perchlorate, lithium, cationic or anionic ionic surfactants, nonionic surfactants, and ion conductive materials such as oligomers or polymers having oxyalkylene repeating units.

[matrix]
Examples of the binder resin contained in the matrix of the surface layer include styrene resin, acrylic resin, methacrylic resin, epoxy resin, polyester resin, polyether resin, silicone resin, and polyvinyl butyral resin. Only 1 type may be used for binder resin and 2 or more types may be used for it.
The binder resin is used to disperse domains such as PFPE, ensure adhesion with the base layer, and ensure mechanical strength characteristics.
Among the binder resins, methacrylic resins or acrylic resins (methacrylic resins and acrylic resins are collectively referred to as “(meth) acrylic resins” hereinafter) favorably disperse domains (particularly PFPE domains). This is preferable.
The surface layer in which the matrix contains (meth) acrylic resin as the binder resin and the domain contains PFPE can be formed, for example, by the following method. First, a polymerizable monomer, a solvent, PFPE, and a dispersant for forming a (meth) acrylic resin are dispersed in a wet dispersion apparatus, and the obtained dispersion is applied to the base layer by a coating method such as bar coating or spray coating. Apply to form a coating film. The obtained coating film is dried to remove the solvent, and polymerized by a curing method (curing polymerization method) such as thermosetting, electron beam curing or UV curing to form a surface layer.

For polymerization, for example, a polymerization initiator such as Irgacure (trade name) manufactured by Ciba Geigy may be used. In addition, additives such as the conductive agent, the antioxidant, the leveling agent, the crosslinking agent, and the flame retardant described above may be used. Further, a solid filler may be used for reinforcement.
The content of the binder resin in the surface layer is preferably 20.0% by mass to 95.0% by mass with respect to the total mass of the surface layer, and is preferably 30.0% by mass to 90.0% by mass. The following is more preferable.
The film thickness of the surface layer is preferably 1 μm or more from the viewpoint of durability, and preferably 20 μm or less, more preferably 10 μm or less from the viewpoint of bending resistance when the belt is stretched. preferable.

Below, the example of the polymerizable monomer for forming a (meth) acrylic resin is given.
(I) pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, alkyl acrylate, benzyl acrylate, phenyl acrylate, ethylene glycol diacrylate, bisphenol A diacrylate (ii) pentaerythritol triacrylate Methacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, alkyl methacrylate, benzyl methacrylate, phenyl methacrylate, ethylene glycol dimethacrylate, bisphenol A dimethacrylate (meth) acrylic resin It is preferably a polymer having obtained unit by polymerizing relations.
From the viewpoint of reducing the adhesive force, the binder resin is preferably hard. For this reason, when using a (meth) acrylic resin, it is preferable to use bifunctional or more crosslinkable monomer (bifunctional or more (meth) acrylate) and to make it high hardness. Specifically, the average number of (meth) acrylic functional groups of the polymerizable monomer is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Such a highly crosslinkable and high hardness resin is likely to be thermosetting, and from this point of view, a (meth) acrylic resin or other thermosetting resin including the other is preferably used for the surface layer of the intermediate transfer member.

[Physical properties of binder resin in matrix]
The binder resin contained in the matrix is preferably a solid. Specifically, it is preferable that the glass transition temperature of the binder resin is equal to or higher than the operating temperature range. More specifically, the glass transition temperature of the binder resin is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher.
The microhardness of the binder resin is preferably 250 MPa or more. The plastic deformation hardness of the binder resin is preferably 40 kg / mm ² or more. The maximum indentation deformation amount of the binder resin is preferably 0.3 μm or less. The Young's modulus of the binder resin is preferably 5.0 GPa or more. The measurement conditions of the physical property value with the ultra-micro hardness meter will be described later.
The surface layer of the intermediate transfer member preferably has a mass loss of 4.0 mg or less by a Taber abrasion test (JIS-K-7204, load: 4.9 N, rotation speed: 100 rpm). It is preferable that the same mass reduction | decrease of the binder resin contained in a matrix is 4.5 mg or less.

[domain]
In the present invention, PFPE constituting a domain is an oligomer or polymer having a perfluoroalkylene ether as a unit.
Examples of the unit of perfluoroalkylene ether include units of perfluoromethylene ether, perfluoroethylene ether, and perfluoropropylene ether. Examples of commercially available perfluoroalkylene ethers include demnum (trade name) from Daikin Industries, Ltd., Krytox (trade name) from DuPont, and fomblin (trade name) from Solvay Solexis.
Among PFPEs, PFPE having unit 1 represented by the following formula (a) and / or unit 2 represented by the following formula (b) is preferable.

Further, among PFPE, those having a reactive functional group capable of forming a bonded state or a state close to bonding with the binder resin on the surface layer of the intermediate transfer member are preferable. This is because the movement of the PFPE contained in the surface layer to the surface is suppressed by the interaction with the binder resin, and as a result, the domain having PFPE is more easily formed in the surface layer of the intermediate transfer member. .
Examples of the reactive functional group include an acryl group, a methacryl group, and an oxiranyl group.
As PFPE having such a reactive functional group, for example, Fluorolink MD500, MD700, 5101X, 5113X, AD1700 (above, trade name) of Solvay Solexis, Daikin Industries, Ltd. Optool DAC, Fluorolink S10 (trade name), which is a silane coupling agent, and the like. Among them, PFPE having a structure represented by the following formula (1) or a structure represented by the following formula (2) is preferable.

(In the formula (1), A is a portion formed from the unit 1 and / or the unit 2, and the repetition number p of the unit 1 and the repetition number q of the unit 2 are independently 0 ≦ p ≦ 50, When 0 ≦ q ≦ 50, p + q ≧ 1, and A has both unit 1 and unit 2, unit 1 and unit 2 may form a block copolymer structure or randomly A copolymer structure may be formed.)

(In the formula (2), B is a portion formed from the unit 1 and / or the unit 2, and the repeating number r of the unit 1 and the repeating number s of the unit 2 are independently 0 ≦ r ≦ 50, When 0 ≦ s ≦ 50, r + s ≧ 1, and B has both unit 1 and unit 2, unit 1 and unit 2 may form a block copolymer structure or randomly A copolymer structure may be formed.)

The number average molecular weight of PFPE is preferably from 100 to 20,000, more preferably from 380 to 20,000.
The PFPE in the surface layer of the intermediate transfer member may be fixed, may not be fixed, or both the fixed PFPE and the non-fixed PFPE coexist. Good. A suitable PFPE content in the coexisting system is sufficient to reduce the surface free energy of the surface of the intermediate transfer member and to retain the PFPE domain inside the surface layer of the intermediate transfer member. Is considered to be combined with a sufficient amount of PFPE. Further, the domain of PFPE at this time is such that, even when the surface layer is chemically and / or physically deteriorated due to repeated image output, the PFPE continues to exist in the surface layer and exhibits good transferability. It is preferable that a sufficient amount of PFPE to continue to be exhibited is contained in the surface layer. As a result of investigations by the present inventors, the content of PFPE in the surface layer is 5. 5% of the total mass of the surface layer from the viewpoint of exhibiting the effect of suppressing the adhesion of toner to the surface of the intermediate transfer member over a long period of time. It is preferably 0% by mass or more and 70.0% by mass or less, more preferably 10.0% by mass or more and 60.0% by mass or less, and more preferably 20.0% by mass or more and 50.0% by mass or less. Is more preferable.

Further, a dispersing agent may be contained in the surface layer in order to allow PFPE to exist stably as a domain in the surface layer of the intermediate transfer member. Examples of the dispersant include a surfactant, an amphiphilic block, which is a compound having an affinity with a perfluoroalkyl chain and a hydrocarbon, that is, a compound having amphiphilic properties of fluorinated and anhydrofluoric. Examples thereof include copolymers and amphiphilic graft copolymers. Among them,
(I) a block copolymer obtained by copolymerizing a vinyl monomer having a fluoroalkyl group and acrylate or methacrylate;
(Ii) A comb-type graft copolymer obtained by copolymerizing an acrylate or methacrylate having a fluoroalkyl group and a methacrylate macromonomer having polymethyl methacrylate in the side chain is preferred.

Examples of the block copolymer (i) include “Modiper F200”, “Modiper F210”, “Modiper F2020”, “Modiper F600”, and “Modiper FT-600” (or more) manufactured by Nippon Oil & Fats Co., Ltd. , Product name). Examples of the above-mentioned comb graft copolymer (ii) include “Aron GF-150”, “Aron GF-300”, and “Aron GF-400” manufactured by Toa Gosei Co., Ltd. ).
1.0 mass% or more and 70.0 mass% or less are preferable with respect to the total mass of a surface layer, and, as for content of a dispersing agent, it is more preferable that they are 5.0 mass% or more and 60.0 mass% or less.

In the example of the production method described later, the precursor state domain is obtained when the polymerizable monomer, solvent, PFPE and, if necessary, the dispersing agent for dispersing the dispersing resin with a wet dispersing device for forming a binder resin such as (meth) acrylic resin. Is formed. The dispersion is applied onto the base layer by a coating method such as bar coating, spray coating, or ring coating, and the resulting coating film is dried to remove the solvent. Then, the surface layer which has a matrix-domain structure can be formed on a base layer by making it superpose | polymerize with hardening methods (curing polymerization method), such as thermosetting, electron beam hardening, or UV hardening.
Further, an ultra-micro hardness meter for measuring the micro hardness of the surface of the intermediate transfer member can also measure the plastic deformation hardness, the maximum indentation amount, and the Young's modulus. The plastic deformation hardness of the intermediate transfer member is 1
It is preferably 5 kg / mm ² or more. The maximum indentation deformation amount of the intermediate transfer member is preferably 0.4 μm or less. The Young's modulus of the intermediate transfer member is preferably 2.0 GPa or more. These measurements are preferably made with a deformation of several to 20% of the film thickness of the layer.

[Method for producing intermediate transfer member]
[Method for producing base layer]
The base layer of the intermediate transfer member can be produced, for example, by the following method.
When a thermosetting resin such as polyimide is used for the base layer, a conductive agent (for example, carbon black) is dispersed as a varnish together with a precursor of a thermosetting resin or a soluble thermosetting resin and a solvent. A semiconductive film can be formed by applying it to a mold and performing a baking step of baking the applied material. The thickness of the semiconductive film serving as the base layer is preferably 30 μm or more and 150 μm or less.

When a thermoplastic resin is used for the base layer, a conductive agent (for example, carbon black), a thermoplastic resin, and additives as necessary are mixed, and melt-kneaded with a biaxial kneader or the like to produce a semiconductive resin composition. Make it. Next, a semiconductive film can be obtained by a method in which the resin composition is melted and extruded into the shape of a sheet, film or seamless belt. As a method for producing a seamless belt, a method of extruding from a cylindrical die to form a seamless belt may be used, or a method of joining sheets formed by extrusion to make them seamless. In addition to this molding method, molding can also be performed using hot pressing or injection molding. The thickness of the semiconductive film serving as the base layer is preferably 30 μm or more and 150 μm or less.
Further, it is preferable to perform a crystallization treatment for the purpose of improving the mechanical strength and durability of the intermediate transfer member. Examples of the crystallization treatment include annealing treatment at a temperature equal to or higher than the glass transition temperature (Tg) of the resin used. By the annealing treatment, crystallization of the used resin can be promoted. The intermediate transfer member thus obtained is not only excellent in mechanical strength and durability but also excellent in terms of wear resistance, chemical resistance, slidability, toughness and flame retardancy. Can be produced.

  In addition, it can confirm that the intermediate transfer body used for this invention has the outstanding mechanical strength by performing the tension test by JISK7113. The tensile elastic modulus of the intermediate transfer member is preferably 1.5 GPa or more, more preferably 2.0 GPa or more, and more preferably 2.5 GPa or more. The tensile elongation at break of the intermediate transfer member is preferably 10% or more, and more preferably 20% or more. As a bending fatigue test, JIS P 8115 is known, and even in this case, excellent characteristics can be confirmed.

[Method for forming surface layer]
The surface layer of the intermediate transfer member can be formed by the following method.
The surface layer is
(1) A mixing step of obtaining a mixture by mixing PFPE, a polymerizable monomer for forming a binder resin, and, if necessary, a dispersant and a polymerization initiator,
(2) A coating process for coating the mixture on the base layer, and (3) a polymerization process for polymerizing the polymerizable monomer in the mixture,
It can be formed through.

First, in the mixing step (1), PFPE, a polymerizable monomer for forming a binder resin, and, if necessary, a dispersant and a polymerization initiator are mixed with a stirring homogenizer and an ultrasonic homogenizer to obtain a mixture. At this time, a solvent, a curing agent (for example, a UV curing agent), a conductive agent, and an additive may be added to the mixture.
Examples of the solvent include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethylene glycol, and the like.
Examples of the curing agent include a photopolymerization initiator and a thermal polymerization initiator.
Examples of the additive include a conductive agent, filler particles, a colorant, and a leveling agent.
Next, in the coating step (2), the mixture obtained in the mixing step (1) is coated on the base layer by a coating method such as a bar coating method, a spray coating method, or a ring coating method. After coating, the obtained coating film is dried at a temperature of 60 ° C. or higher and 90 ° C. or lower to remove the solvent.
Next, in the polymerization step (3), the polymerizable monomer in the coating film is cured and polymerized. Examples of the curing polymerization method include methods such as thermal curing, electron beam curing, and ultraviolet curing. Preferably, the method is a method in which the polymerizable monomer in the mixture is cured and polymerized by irradiating the mixture applied on the base layer with ultraviolet rays.
The intermediate transfer body according to the present invention can be obtained through such steps.

[Measurement method of micro hardness]
In the present invention, the micro hardness of the surface of the intermediate transfer member was measured using an ultra micro hardness meter (trade name: ENT-1100, manufactured by Elionix Co., Ltd.). As the ultra-micro hardness meter, a diamond triangular indenter with a ridge angle of 115 ° was used, and the micro hardness was measured with a load of 50 mg.

[Measurement of wear amount]
The amount of abrasion on the surface of the intermediate transfer member was measured by a Taber abrasion test based on JIS-K-7204. As a measuring device, the amount of decrease in mass caused by scraping when the wear wheel CS-17 is used with a rotary abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a load of 4.9 N and a rotational speed of 60 rpm is used as the amount of wear. It was measured.

[Measuring method of average major axis of domain]
Regarding the average major axis of the domain, the cross section of the surface layer of the intermediate transfer member was observed using SEM (trade name: S-4800, manufactured by Hitachi High-Technologies Corporation).
First, a sample obtained by cutting out the surface layer of the intermediate transfer member with a microtome (trade name: EM UC7, manufactured by Leica Microsystems) was used as a sample. At this time, a cross-sectional SEM image in which at least one domain could be confirmed in a unit area of 15 μm ² when the cross-section was magnified 20000 times was used. When the number of domains was 10 or less, the major axis of all domains in the field of view was measured. When the number of domains was 10 or more, 10 domains were selected at random and the major axis of the domain was measured. The same operation was repeated 10 times with the SEM observation of the cross section with the changed field of view, and the average value of the major axis of each domain measured in the SEM images of the ten cross sections was defined as the average major axis of the domain in the present invention. .

[Measurement method of domain area]
Regarding the area of the domain, the same sample as that used for measuring the average major axis of the domain was used, and the cross section of the surface layer of the intermediate transfer member was measured with SEM (trade name: S-4800, Hitachi High Co., Ltd.). Technology). At this time, the ratio of the area of the domain in a unit area of 15 μm ² when the cross section was enlarged 20000 times was measured. The same operation was repeated 10 times with the SEM observation of the cross-section with the changed field of view, and the average value of the ratio of the area of each domain measured in 10 SEM images of the cross-section was calculated as the area of the domain in the present invention. It was a ratio.

[Measuring Method of Contact Angle θ (A) with Water on Surface of Photoreceptor and Contact Angle θ (B) with Water on Surface of Intermediate Transfer Member]
An image processing contact angle measuring device CA-X (trade name) manufactured by Kyowa Interface Science Co., Ltd. was used.
The measurement method is as follows.
A surface section was cut from the surface of the photoreceptor or the surface of the intermediate transfer member with a cutter, and fixed on the sample stage. Pure water was supplied from the droplet supply needle tip to form pure water droplets on the sample surface. The coordinates of the left end, right end, and apex angle of the water droplet were determined by image processing, and the contact angle was determined from the calculated water droplet diameter (2r) and height (h) by the following formula.
ω = 2 tan ⁻¹ (h / r)

In the present invention, θ (A) is preferably 70 ° or more and 100 ° or less, and more preferably 80 ° or more and 95 ° or less.
The performance required for the photoreceptor is high durability against mechanical external force. The hardness of the film is higher as the amount of deformation with respect to external stress is smaller.
In the photoreceptor, a hardness test is performed using a Vickers square pyramid diamond indenter, and a universal hardness value (HU) when pressed at a maximum load of 6 mN satisfies a condition of 150 N / mm ² or more and 220 N / mm ² or less. The strength of the surface of the photoreceptor is greatly improved.

The universal hardness value (HU) of the surface of the photoreceptor is preferably 150 N / mm ² or more and 220 N / mm ² or less, and more preferably 170 N / mm ² or more and 200 N / mm ² or less. If the HU exceeds 220 N / mm ² , the paper powder or toner sandwiched between the charging rollers or the like tends to apply a large pressure locally and cause deep scratches. On the other hand, when the HU is less than 150 N / mm ² , there is a tendency that the paper powder and toner sandwiched between the charging rollers are rubbed to cause scraping or fine scratches.
When radiation curing is used when forming the surface layer of the photoreceptor, the HU on the surface of the photoreceptor can be controlled by the irradiation condition of the radiation.

The photoreceptor according to the present invention preferably has a protective layer.
The protective layer preferably contains a compound (cured product) cured by polymerizing and / or crosslinking a hole transporting compound having one or more chain polymerizable functional groups in the same molecule. The hole transporting compound having a chain polymerizable functional group refers to a compound in which a chain polymerizable functional group is chemically bonded to a part of the hole transporting compound. Details are described in JP-A-2000-66424. More preferably, there are two or more chain polymerizable functional groups in the same molecule. As the chain polymerizable functional group, an acryloyloxy group (CH ₂ ═CHCOO—) and a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—) are preferable.

In the present invention, the universal hardness value (HU) and elastic deformation rate of the surface of the photosensitive member are measured using a microhardness measuring device (trade name: Fisherscope H100V, manufactured by Fisher) in an environment of 25 ° C./50% RH. Measured value. This Fischer scope H100V is an apparatus in which continuous hardness is required by abutting an indenter against a measurement object (the surface of the photoconductor), continuously applying a load to the indenter, and directly reading the indentation depth under the load. It is.
In the present invention, a Vickers square pyramid diamond indenter having a facing angle of 136 ° is used as the indenter, and the final load (final load) continuously applied to the indenter is 6 mN when the object to be measured is a photoconductor. The time for holding the final load of 6 mN (holding time) was 0.1 second. The measurement points were 273 points.
An outline of the output chart of the microhardness measuring apparatus is shown in FIG.
In FIG. 4, the vertical axis represents the load F (mN) applied to the indenter, and the horizontal axis represents the indentation depth h (μm). FIG. 4 shows the results when the load applied to the indenter is increased stepwise to maximize the load (A → B) and then decreased gradually (B → C). FIG. 4 shows the results when the load applied to the indenter is increased stepwise to finally make the load 6 mN, and then the load is decreased stepwise.
The universal hardness value (HU) can be obtained by the following formula from the indentation depth of the indenter when a final load of 6 mN is applied to the indenter.

（上記式中、ＨＵ（Ｎ／ｍｍ^２）は、ユニバーサル硬さ値を意味し、Ｆｆ（Ｎ）は、最終荷重を意味し、Ｓｒ（ｍｍ^２）は、最終荷重をかけたときの圧子の押し込まれた部分の表面積を意味し、ｈｆ（μｍ）は、最終荷重をかけたときの圧子の押し込み深さを意味する。）

(In the above formula, HU (N / mm ² ) means the universal hardness value, Ff (N) means the final load, and Sr (mm ² ) is the indenter when the final load is applied. (The surface area of the pushed-in portion means hf (μm) means the indentation depth when the final load is applied.)

  The elastic deformation rate is obtained from the amount of work (energy) performed by the indenter with respect to the measurement target (the surface of the photoconductor), that is, the change in energy due to the increase or decrease of the load with respect to the measurement target (the surface of the photoconductor). be able to. Specifically, a value (We / Wt) obtained by dividing the elastic deformation work We by the total work Wt is the elastic deformation rate. Note that the total work Wt is the area of the region surrounded by A-B-D-A in FIG. 4, and the elastic deformation work We is the area of C-B-D-C of 4 It is an area.

When using a photoreceptor having a high surface hardness as described above as the photoreceptor according to the present invention, the wear resistance is improved, but the cleaning property may be lowered, so that the surface of the photoreceptor is roughened. It is preferred that the surface be a surface. Specifically, the surface roughness Rz (10-point average surface roughness) of the photoreceptor is preferably 0.2 μm or more and 3.0 μm or less. Further, the average interval Sm of the irregularities on the surface of the photoreceptor is preferably 10 μm or more and 100 μm or less. Further, the sharpness RKu of the surface of the photoreceptor is preferably more than 3 and less than 20.
When Rz is smaller than 0.2 μm, the contact area between the cleaning blade and the surface of the photosensitive member is increased, and chattering of the cleaning blade and wear or chipping of the cleaning blade are likely to occur. As a result, as the number of image output sheets increases, it may become difficult to maintain good cleaning properties. Even when Sm is larger than 100 μm, the adhesion between the cleaning blade and the surface of the photoreceptor increases, and as the number of image output sheets increases, it may be difficult to maintain good cleaning properties. On the other hand, when Rz is larger than 3 μm or Sm is smaller than 10 μm, the cleaning blade cannot sufficiently contact the surface of the photosensitive member, and the effect of blocking the transfer residual toner is reduced, so that the toner slips easily. There is.

In the present invention, the surface roughness of the surface of the photoreceptor was measured as follows using a contact-type surface roughness measuring machine (trade name: Surfcorder SE3500, manufactured by Kosaka Laboratory Ltd.).
Detector: Diamond needle with R of 2 μm and 0.7 mN Filter: 2CR
Cut-off value: 0.8mm
Measurement length: 2.5mm
Feeding speed: 0.1mm / s
Under the above conditions, 10-point average surface roughness Rz data defined in JIS B 0601 was processed. Further, the average interval Sm of the irregularities on the surface of the photoreceptor was also measured under the same conditions as Rz, and the arithmetic average value obtained from the following formula was defined as Sm.

（上記式中、Ｓｍｉは、凹凸の間隔を意味し、ｎは、基準長さ内で凹凸の間隔の個数を意味する。）

(In the above formula, Smi means the unevenness interval, and n means the number of unevenness intervals within the reference length.)

As a support for the photoreceptor, any support having conductivity (conductive support) may be used, and examples thereof include a support made of metal or alloy such as aluminum, copper, chromium, nickel, zinc, and stainless steel. It is done. Further, examples of the shape of the support include a drum shape and a belt shape.
An undercoat layer having a barrier function or an adhesive function may be provided on the support.
The undercoat layer is used to improve the adhesion of the photosensitive layer, improve coating properties, protect the support, cover defects on the support, improve charge injection from the support, and protect against electrical breakdown of the photosensitive layer. Formed.
Examples of the material for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, and copolymer nylon. And gelatin.
The undercoat layer can be formed by applying an undercoat layer coating solution prepared by dissolving the above materials in a solvent on a support.
The thickness of the undercoat layer is preferably from 0.1 μm to 2 μm.

The photosensitive layer of the photoreceptor may be a so-called single-layer type photosensitive layer containing a charge generation material and a charge transport material in the same layer, or a charge generation layer containing a charge generation material and a charge transport material containing a charge transport material. A so-called function-separated type (laminated type) photosensitive layer that is functionally separated into layers may be used. In the present invention, a function separation type (laminated type) photosensitive layer is preferable.
Examples of the charge generation material used for the photosensitive layer (charge generation layer) include selenium-tellurium, pyrylium, thiapyrylium dyes, and the like. Also, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments (trisazo pigments) having various central metals and crystal types (for example, crystal types such as α, β, γ, ε, or X type) , Disazo pigments, monoazo pigments), indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanine, amorphous silicon and the like.

When the photosensitive layer is a function separation type (laminated type) photosensitive layer, the charge generation layer can be formed as follows. That is, a charge generation material and a binder resin in an amount of 0.3 to 4 times the charge generation material are dispersed together with a solvent to prepare a charge generation layer coating solution, and the charge generation layer coating solution is applied. It can be formed by forming a coating film and drying the coating film. Examples of the dispersion treatment method include a method using a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill and the like. Further, a vapor-deposited film of a charge generation material can be used as the charge generation layer.
The thickness of the charge generation layer is preferably 3 μm or less, and more preferably 0.1 μm or more and 2 μm or less.

Examples of the binder resin for the charge generation layer include polymers or copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene, polyvinyl Examples include alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.
Examples of the charge transport material used in the photosensitive layer (charge transport layer) include, for example, poly-N-vinylcarbazole, polystyryl anthracene, and other high molecular compounds having a heterocyclic ring or condensed polycyclic aromatics, pyrazoline, imidazole, and oxazole. , Triazole, carbazole, etc., low molecular weight compounds such as triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, hydrazone derivatives Etc.
When the photosensitive layer is a function separation type (laminated type) photosensitive layer, the charge transport layer can be formed as follows. That is, a charge transport material and, if necessary, a binder resin are dissolved in a solvent to prepare a charge transport layer coating solution, the charge transport layer coating solution is applied to form a coating film, and the coating film is dried. Can be formed. The ratio of the charge transport material to the binder resin is preferably 20 parts by mass or more and 100 parts by mass or less, and 30 parts by mass or more and 100 parts by mass, when the total mass of both is 100 parts by mass. The following is more preferable. If the amount of the charge transporting material is too small, the charge transporting ability may be lowered, and the sensitivity may be lowered and the residual potential may be increased.
Examples of the binder resin for the charge transport layer include polymers or copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene, polyvinyl Examples include alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

When the photosensitive layer is a single-layer type photosensitive layer, the single-layer type photosensitive layer is prepared by dispersing and / or dissolving the charge generation substance and the charge transport substance in the binder resin to prepare a photosensitive layer coating solution, It can form by apply | coating the coating liquid for photosensitive layers, forming a coating film, and drying a coating film.
A protective layer may be provided on the photosensitive layer.
When the protective layer contains a compound cured by polymerizing and / or crosslinking a hole transporting compound having a chain polymerizable functional group, the protective layer can be formed as follows. That is, after coating a protective layer coating liquid containing a hole transporting compound having a chain polymerizable functional group to form a coating film, the hole transporting compound having a chain polymerizable functional group is polymerized and / or It can be formed by crosslinking.
Examples of the method for applying the coating solution for each layer include a dip coating method, a spray coating method, a curtain coating method, and a spin coating method. Among these, the dip coating method is preferable from the viewpoints of efficiency and productivity. Further, the layer can be formed by vapor deposition, a film forming method using plasma, or the like.

The hole transporting compound having a chain polymerizable functional group can be polymerized and / or crosslinked by heat, light such as visible light and ultraviolet light, or radiation such as an electron beam. Therefore, the hole transporting compound is contained in the coating liquid and, if necessary, a polymerization initiator, and the coating film of the coating liquid is irradiated with heat, light and / or radiation to thereby form the hole transporting compound. It can be polymerized and / or crosslinked.
In the present invention, it is preferable to polymerize and / or crosslink (cure) a hole transporting compound having a chain polymerizable functional group by radiation. The universal hardness value (HU) and elastic deformation rate of the surface of the photoreceptor can be controlled by the irradiation condition of the radiation. An advantage of polymerization by radiation is that a polymerization initiator is not necessarily required. By not using a polymerization initiator, a very high-purity three-dimensional matrix protective layer is formed, and good electrophotographic characteristics can be obtained. The radiation used is preferably an electron beam or γ-ray, more preferably an electron beam. In the case of electron beam irradiation, examples of the accelerator include a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type. When irradiating an electron beam, it is preferable to control the irradiation conditions of the electron beam in consideration of electrophotographic characteristics and durability.
In the case of irradiation with an electron beam, the acceleration voltage is preferably 250 kV or less, and more preferably 150 kV or less. The irradiation dose is preferably 0.1 Mrad or more and 100 Mrad or less, and more preferably 0.5 Mrad or more and 20 Mrad or less. When the acceleration voltage is too large, the electrophotographic characteristics of the photoreceptor are liable to be deteriorated by the electron beam irradiation. Further, if the irradiation dose is too small, the curing tends to be insufficient, and if the irradiation dose is too large, the electrophotographic characteristics of the photoreceptor are likely to deteriorate.
In order to perform curing more sufficiently, it is preferable to apply heat during the polymerization reaction by electron beam irradiation. The timing of applying heat may be any before, during, or after electron beam irradiation, as long as the photoconductor is at a certain temperature while radicals generated by electron beam irradiation exist. The latter is preferred. The heating is preferably performed so that the temperature of the photoreceptor is in the range of room temperature (25 ° C.) to 250 ° C., and more preferably in the range of 50 ° C. to 150 ° C. If the temperature is too high, the material used for the photoreceptor tends to deteriorate and the electrophotographic characteristics tend to deteriorate. The heating time is preferably about several seconds to several tens of minutes. The atmosphere during electron beam irradiation or heating is preferably in the air, in an inert gas such as nitrogen or helium, or in a vacuum. From the viewpoint of suppressing radical deactivation due to oxygen, it is more preferably in an inert gas or in a vacuum.
The thickness of the protective layer is preferably 3 μm or more and 10 μm or less.

  The toner used in the image forming method of the present invention has a surface contact angle with water of 60 ° or more and 80 ° or less when the toner is formed into a pellet. Preferably, it is 65 degrees or more and 75 degrees or less. When the contact angle of water on the surface of the toner pellet molding with water exceeds 80 °, the adhesion between the toners is too small, and the lump of toner particles is destroyed during transfer to form a uniform toner layer. Becomes difficult. Further, when the contact angle of water on the surface of the molded toner pellet is less than 60 °, problems such as fogging due to excessive toner aggregation are likely to occur. When the developing means has a developing roller, it tends to cause a coating failure on the surface of the developing roller.

The toner particles according to the present invention contain a binder resin.
The toner particles are further
Wax and
It is preferable to contain a polymer having a structure obtained by reacting a vinyl resin component and a hydrocarbon compound (preferably polyolefin).
The present inventors include a polymer having a structure in which a vinyl-based resin component and a hydrocarbon compound react with each other in toner particles, and subject the toner particles to a heat treatment (hot air treatment), whereby a photoreceptor is obtained. It was found that the primary transfer from the toner to the intermediate transfer member is good. As a result, it has been found that an image with high in-plane uniformity and high density stability can be output over a long period of time. Although the mechanism is not clear, the present inventors speculate as follows.
Wax and a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted are contained in toner particles, and the toner is subjected to a heat treatment, whereby the wax is directed toward the surface of the toner particles. The moving speed can be controlled, and the wax can be unevenly distributed on the surface of the toner particles. By forming this surface structure, it becomes easy to control the contact angle of water on the surface of the molded toner pellet to 60 ° or more and 80 ° or less. As a result, the toner aggregates due to the pressure applied during transfer from the photosensitive member to the intermediate transfer member, and a uniform toner layer can be formed on the surface of the intermediate transfer member.
Further, when the toner is primarily transferred to the intermediate transfer member, the toner is pressed against the intermediate transfer member with a high pressure, so that the compacted state is obtained. Thereafter, when the intermediate transfer member is secondarily transferred to the transfer material, the adhesion force between the particles of the compacted toner is high and the adhesion force between the intermediate transfer member and the toner particles is low. Therefore, the toner remains on the surface of the intermediate transfer member, and thus the amount of toner remaining on the surface of the intermediate transfer member is reduced.

  In other words, the contact angle of water on the surface of the molded toner pellet is made by adding toner and a polymer having a structure in which a vinyl resin component and a hydrocarbon compound react with each other and performing heat treatment. Can be controlled to 60 ° or more and 80 ° or less. Further, the contact angle of water on the surface of the toner pellet molding can be controlled by adjusting the wax content or the temperature of the heat treatment (hot air treatment). A uniform toner layer can be formed from the photosensitive member to the intermediate transfer member by using a toner whose contact angle with water on the surface of the toner pellet molding is controlled. In addition, uniform transferability can be maintained by increasing the adhesion between toner particles and suppressing internal collapse. Further, the present inventors consider that the effect can be manifested regardless of the smoothness of the transfer material, and that the effect is remarkably manifested in combination with an intermediate transfer member having low adhesion to the toner.

[resin]
As the binder resin used for the toner particles according to the present invention, for example,
Homopolymers of styrene or substituted styrenes such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene;
Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid Acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer, etc. Styrenic copolymer;
Polyvinyl chloride, phenol resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl Butyral, terpene resin, coumarone-indene resin, petroleum resin;
Etc.
Among these, a polyester resin is preferable from the viewpoint of control of low-temperature fixability and chargeability.

Here, the polyester resin means a resin having a “polyester unit” in the resin chain. As a component constituting the polyester unit, for example,
A dihydric or higher alcohol monomer component;
And divalent or higher acid monomer components such as divalent or higher carboxylic acid, divalent or higher carboxylic acid anhydride, and divalent or higher carboxylic acid ester.
Examples of the bivalent or higher alcohol monomer component include:
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenedio 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanete Trol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1 2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.
Among these, as the alcohol monomer component, an aromatic diol is preferable. In the unit derived from the alcohol monomer component constituting the polyester resin, the unit derived from the aromatic diol is preferably contained in a proportion of 80 mol% or more.

Examples of divalent or higher acid monomer components include:
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof;
Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof;
Succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydride thereof;
Unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
Etc.
Among these, the acid monomer component is preferably a polyvalent carboxylic acid such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, or an anhydride thereof.
The acid value of the polyester resin is preferably 1 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of the stability of the triboelectric charge amount.
In addition, the acid value of resin can be adjusted by adjusting the kind and compounding quantity of the monomer used for manufacture of resin. Taking a polyester resin as an example, the acid value can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and / or molecular weight during resin production. Moreover, an acid value can also be adjusted by making terminal alcohol react with a polyvalent acid monomer (for example, trimellitic acid) after ester condensation polymerization.

As the polymer having a structure obtained by reacting the vinyl resin component with a hydrocarbon compound, a polymer in which the hydrocarbon compound is a polyolefin is preferable. Furthermore, a graft polymer having a structure in which a polyolefin resin is grafted to a vinyl resin component or a graft polymer having a vinyl resin component in which a vinyl monomer is graft polymerized to a polyolefin is more preferable.
The polymer having a structure in which the vinyl resin component and the hydrocarbon compound react with each other functions as a surfactant for the binder resin and wax melted in the kneading step and the surface smoothing step during toner production. To do. Therefore, the polymer can control the primary average dispersed particle diameter of the wax in the toner particles and the transfer rate of the wax to the surface of the toner particles when heat treatment (surface treatment with hot air) is performed.
Regarding the graft polymer having a structure in which a polyolefin is grafted to the vinyl resin component or the graft polymer having a vinyl resin component in which a vinyl monomer is graft polymerized to the polyolefin, the polyolefin is an unsaturated hydrocarbon having one double bond. It is not particularly limited as long as it is a polymer or copolymer of a monomer, and various polyolefins can be used. In particular, polyethylene and polypropylene are preferably used.

Examples of vinyl monomers include:
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 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 Styrene monomers such as styrene and derivatives thereof;
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate;
Vinyl monomers containing nitrogen atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide;
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid;
Unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride;
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, fumarate Half esters of unsaturated dibasic acids such as acid methyl half esters and mesaconic acid methyl half esters;
Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid;
Α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid;
Α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, anhydrides of α, β-unsaturated acids and lower fatty acids;
Vinyl monomers containing a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their anhydrides, and monoesters thereof;

Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) Hexyl) vinyl monomers containing hydroxyl groups such as styrene;
Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- Acrylic esters such as chloroethyl and acrylic esters such as phenyl acrylate;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl Methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acrylate and diethylaminoethyl methacrylate;
Etc.

A polymer having a structure in which a vinyl-based resin component and a hydrocarbon compound are reacted can be obtained by a method such as a reaction between the above-described monomers or a reaction between a monomer of one polymer and the other polymer. it can.
As a unit of vinyl resin component, it is preferable to contain a unit derived from styrene, and it is more preferable to further contain a unit derived from acrylonitrile and / or methacrylonitrile.
The mass ratio between the hydrocarbon compound and the vinyl resin component (hydrocarbon compound / vinyl resin component) in the polymer is preferably 1/99 or more and 75/25 or less. By using the hydrocarbon compound and vinyl resin component in the above range, it is easy to disperse the wax in the toner particles, and the wax moves to the surface of the toner particles when performing heat treatment (surface treatment with hot air) as necessary. Easy to control speed.
The content of the polymer having a structure obtained by reacting the vinyl resin component and the hydrocarbon compound in the toner particles is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. Preferably there is. Moreover, it is preferable that the weight average molecular weight (Mw) of the said polymer is 6000 or more and 8000 or less, and it is preferable that a number average molecular weight (Mn) is 1500 or more and 5000 or less.
Use of the polymer in the above range facilitates dispersion of the wax in the toner particles, and facilitates control of the transfer rate of the wax to the surface of the toner particles during heat treatment (surface treatment with hot air).

[wax]
The toner particles according to the present invention may contain a wax.
As a wax, for example,
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax;
Oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; Waxes based on fatty acid esters such as carnauba wax;
Deoxidized part or all of fatty acid esters such as deoxidized carnauba wax;
Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid;
Unsaturated fatty acids such as brassic acid, eleostearic acid, parinaric acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol;
Polyhydric alcohols such as sorbitol;
Esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, and melyl alcohol;
Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide;
Saturated fatty acid bisamides such as methylene bis-stearic acid amide, ethylene bis-capric acid amide, ethylene bis-lauric acid amide, hexamethylene bis-stearic acid amide;
Unsaturated fatty acid amides such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl sebacic acid amide;
aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide;
Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (commonly referred to as metal soap);
Waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid;
Partial esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride;
Examples include methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of improving low-temperature fixability and fixing wrapping resistance (suppression of wrapping of a transfer material during fixing).
The content of the wax in the toner particles is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
A differential scanning calorimeter (D) from the viewpoint of both toner storage stability and high-temperature offset resistance
In the endothermic curve at the time of temperature rise measured by SC), the peak temperature of the maximum endothermic peak existing in the temperature range of 30 ° C. or higher and 200 ° C. or lower is preferably 50 ° C. or higher and 110 ° C. or lower.

[Colorant]
The toner particles according to the present invention may contain a colorant. As the colorant, a pigment or a dye may be used alone, but it is preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
Examples of the colorant include the following.
Examples of black colorants include:
Carbon black;
Examples thereof include a yellow colorant, a magenta colorant, and a cyan colorant that are adjusted to black.
Among the magenta colorants, as the pigment, for example,
C. 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: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282;
C. I. Pigment violet 19;
C. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35
Etc.
Among the magenta colorants, examples of the dye include
C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121;
C. I. Disperse thread 9;
C. I. Solvent violet 8, 13, 14, 21, 27;
C. I. Disper Violet 1
Oil-soluble dyes such as
C. 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;
C. I. Basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28
And basic dyes such as

Among the cyan colorants, as the pigment, for example,
C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17;
C. I. Bat Blue 6;
C. I. Acid Blue 45;
Examples thereof include copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.
Among the cyan colorants, examples of the dye include C.I. I. Solvent Blue 70 etc. are mentioned.
Among the yellow colorants, as the pigment, for example,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185;
C. I. Bat Yellow 1, 3, 20
Etc.
Among the yellow colorants, examples of the dye include C.I. I. Solvent yellow 162 etc. are mentioned.
The content of the colorant in the toner particles is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Charge control agent]
The toner particles according to the present invention may contain a charge control agent (CA agent). The charge control agent contained in the toner particles is preferably an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount.
As a negative charge control agent, for example,
A polymeric compound having a side chain of a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a sulfonic acid or a carboxylic acid;
A polymer compound having a sulfonate or a sulfonated ester in the side chain;
A polymer compound having a carboxylate or a carboxylic acid ester in the side chain;
Boron compounds;
Urea compounds;
Silicon compounds;
Examples include calix arene.
The charge control agent may be added internally or externally to the toner particles.
The content of the charge control agent in the toner particles is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

[External additive]
The toner according to the present invention may further include an external additive in addition to the toner particles in order to improve fluidity and adjust the triboelectric charge amount.
Examples of the external additive include inorganic fine particles such as silicon oxide (silica), titanium oxide, aluminum oxide, and strontium titanate.
The inorganic fine particles used for the external additive are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
The specific surface area of the external additive is preferably 10 m ² / g or more and 50 m ² / g or less from the viewpoint of suppressing embedding of the external additive.
The content of the external additive in the toner is preferably 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.
For mixing the toner particles and the external additive, for example, a mixer such as a Henschel mixer can be used.

The toner according to the present invention is preferably mixed with a magnetic carrier and used as a two-component developer from the viewpoint of obtaining a stable image over a long period of time.
Examples of magnetic carriers include:
Iron powder with oxidized surface,
Unoxidized iron powder,
Metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earth, and alloy particles thereof
Magnetic materials such as oxide particles and ferrite,
Magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state
Etc.

[Production method]
Various manufacturing methods can be employed for the toner manufacturing method according to the present invention.
Hereinafter, a toner manufacturing method using a pulverization method will be described as an example.
In the raw material mixing step, as a material constituting the toner particles, for example, a binder resin and, if necessary, components such as a wax, a colorant, and a charge control agent are weighed and mixed in a predetermined amount. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauter mixer, and a mechano-hybrid (manufactured by Nihon Coke Industries Co., Ltd.).
Next, the mixed material is melt-kneaded to disperse components such as wax in the binder resin.
Examples of the kneader used in the melt-kneading process include batch kneaders such as a pressure kneader and a Banbury mixer, and continuous kneaders. From the viewpoint of continuous production, a single or twin screw extruder is preferred.
Examples of the kneader include a KTK type twin screw extruder (manufactured by Kobe Steel), a TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikekai Co., Ltd.), 2 Examples thereof include a shaft extruder (manufactured by Kay C.K.), co-kneader (manufactured by Buss), and kneedex (manufactured by Nippon Coke Industries, Ltd.).
The resin composition obtained by melt kneading may be rolled with two rolls or cooled with water or the like.

Next, the cooled resin composition is pulverized to a desired particle size. In this pulverization step, for example, after coarse pulverization with a pulverizer, it can be further finely pulverized with a fine pulverizer. Examples of the pulverizer include a crusher, a hammer mill, and a feather mill. Examples of the pulverizer include a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nissin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industry), an air jet system, and the like.
Then, if necessary, toner particles can be obtained by classification using a classifier or a sieving machine. Examples of classifiers and sieving machines include inertial class elbow jets (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classifier turboplex (manufactured by Hosokawa Micron Corporation), and TSP separator (manufactured by Hosokawa Micron Corporation). , Faculty (manufactured by Hosokawa Micron Corporation) and the like.

In the present invention, the obtained toner particles (before the heat treatment) are preferably subjected to a heat treatment and subjected to a spheroidization treatment. By subjecting the toner particles to heat treatment for spheroidization, the toner particles can be efficiently spheroidized.
Examples of the heat treatment (spheroidization treatment by heat) method include a method of performing a surface treatment by heat using the surface treatment apparatus shown in FIG.
In FIG. 1, a mixture (such as toner particles to be heat-treated) that is quantitatively supplied by the raw material supply means 101 is introduced into a feed pipe installed on the vertical line of the raw material supply means by the compressed gas adjusted by the compressed gas adjustment means 102. 103. The mixture that has passed through the introduction pipe is uniformly dispersed by a conical protrusion 104 provided at the center of the raw material supply means, and is guided to a radially extending eight-direction supply pipe 105 to perform heat treatment. 106.
At this time, the flow of the mixture supplied to the processing chamber is regulated by the regulating means 109 for regulating the flow of the mixture provided in the processing chamber. Therefore, the mixture supplied to the processing chamber is heat-treated while swirling in the processing chamber and then cooled.

Heat for heat-treating the supplied mixture is supplied from the hot air supply means 107, distributed by the distribution member 112, and introduced into the processing chamber by turning the hot air in a spiral manner by the turning member 113 for turning the hot air. Is done. As the structure, the turning member 113 for turning hot air has a plurality of blades, and the turning of hot air can be controlled by the number and angle of the blades. The temperature of the hot air supplied into the processing chamber is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 130 ° C. or higher and 170 ° C. or lower, at the outlet of the hot air supply means 107. If the temperature of the hot air is too low, the surface roughness of the toner particles may vary. On the other hand, if the temperature of the hot air is too high, the melting state proceeds too much, so that the coalescence of the toner particles proceeds, and the toner particles may be coarsened or fused. If the temperature at the outlet of the hot air supply means is within the above range, the toner particles can be uniformly spheroidized while suppressing the fusion and coalescence of the toner particles due to excessive heating of the mixture. Hot air is supplied from the hot air supply means outlet 111.
The heat-treated toner particles (heat-treated toner particles) are cooled by the cold air supplied from the cold air supply means 108. The temperature supplied from the cold air supply means 108 is preferably -20 ° C or higher and 30 ° C or lower. If the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the fusion and coalescence of the heat-treated toner particles are suppressed without hindering uniform spheroidization of the mixture. be able to. The absolute moisture content of the cold air is preferably 0.5 g / m ³ or more and 15.0 g / m ³ or less.

The cooled heat-treated toner particles are recovered by the recovery means 110 at the lower end of the processing chamber. A blower (not shown) is provided at the tip of the collecting means, and is thereby configured to be sucked and conveyed.
The powder particle supply port 114 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same direction, and the recovery means 110 of the surface treatment device determines the swirling direction of the swirled toner particles. It is provided on the outer periphery of the processing chamber so as to maintain. The cool air supplied from the cool air supply means 108 is configured to be supplied from the outer periphery of the apparatus to the peripheral surface of the processing chamber from the horizontal and tangential directions. The swirling direction of the pre-heat treatment toner particles supplied from the powder supply port, the swirling direction of the cool air supplied from the cold air supplying means, and the swirling direction of the hot air supplied from the hot air supplying means are all the same direction. Therefore, the turbulent flow is less likely to occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner particles before the heat treatment, and the dispersibility of the toner particles before the heat treatment is improved. A small amount of heat-treated toner particles having a uniform shape can be obtained.

Thereafter, if necessary, external additives such as inorganic fine particles and resin particles are added and mixed (externally added) to give fluidity or to improve charging stability, thereby obtaining a toner. be able to.
As the mixing device, for example, a mixing device having a rotating body having a stirring member and a main casing provided with a gap between the stirring member and the stirring member can be used.
As a mixing device, for example,
Henschel mixer (Mitsui Mine Co., Ltd.);
Super mixer (manufactured by Kawata Corporation);
Ribocorn (Okawara Manufacturing Co., Ltd.);
Nauter mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron Corporation);
Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.);
Ladige mixer (manufactured by Matsubo);
Nobilta (manufactured by Hosokawa Micron Corporation)
Etc. In particular, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is preferably used in order to uniformly mix and loosen the aggregates of external additives (such as silica).
At the time of mixing, in order to obtain the desired toner performance, for example, the processing amount, the number of rotation of the stirring shaft, the stirring time, the shape of the stirring blade, the temperature in the tank, and the like can be controlled.
Further, when a coarse aggregate of additives is present in the obtained toner in a free state, a sieving machine or the like may be used as necessary.

The toner according to the present invention is a toner having toner particles and an external additive, wherein the toner particles contain a binder resin (preferably a polyester resin) and a wax (preferably a hydrocarbon wax),
In the FT-IR spectrum obtained by measurement using the ATR method, using Ge as the ATR crystal and setting the infrared light incident angle to 45 °, the maximum absorption peak in the range of 2843 cm ^{−1 to} 2853 cm ^−1. The intensity is Pa, and the maximum absorption peak intensity in the range from 1713 cm ^{−1 to} 1723 cm ⁻¹ is Pb,
Using ATR method using a KRS5 as ATR crystal, the measured and FT-IR spectra obtained at the conditions was 45 ° infrared light incident angle, the maximum absorption peak of 2843cm ^-1 or 2853cm ^-1 the range When the intensity is Pc and the maximum absorption peak intensity in the range from 1713 cm ^{−1 to} 1723 cm ⁻¹ is Pd,
A toner satisfying the relationship of the following formula (2) is preferable.
1.05 ≦ P1 / P2 ≦ 2.00 (2)
[In Formula (2), P1 = Pa / Pb and P2 = Pc / Pd. ]
Note that the maximum absorption peak intensity Pa is a value obtained by subtracting the mean value of the absorption peak intensity of 3050 cm ^-1 and 2600 cm ^-1 from the maximum value of the absorption peak intensity of 2843cm ^-1 or 2853cm ^-1 or less.
Further, the maximum absorption peak intensity Pb is a value obtained by subtracting the mean value of the absorption peak intensity of 1763cm ^-1 and 1630 cm ^-1 from the maximum value of the absorption peak intensity of 1713 cm ^-1 or 1723 cm ^-1 or less.
Further, the maximum absorption peak intensity Pc is a value obtained by subtracting the mean value of the absorption peak intensity of 3050 cm ^-1 and 2600 cm ^-1 from the maximum value of the absorption peak intensity of 2843cm ^-1 or 2853cm ^-1 or less.
Further, the maximum absorption peak intensity Pd is a value obtained by subtracting the mean value of the absorption peak intensity of 1763cm ^-1 and 1630 cm ^-1 from the maximum value of the absorption peak intensity of 1713 cm ^-1 or 1723 cm ^-1 or less.

P1 is an index related to the abundance ratio of the wax to the binder resin at about 0.3 μm from the surface of the toner particle in the depth direction of the toner particle from the surface of the toner particle toward the center of the toner particle. P2 is an index relating to the abundance ratio of the wax to the binder resin at about 1.0 μm from the surface of the toner particles.
In the present invention, the index (P1) relating to the abundance ratio of the wax to the binder resin at about 0.3 μm from the surface of the toner particle is related to the abundance ratio of the wax to the binder resin at about 1.0 μm from the surface of the toner particle. It is preferable to make it larger than the index (P2). That is, it is preferable to control the index ratio [P1 / P2] (that is, the degree of uneven distribution of wax in the depth direction of the toner particles from the surface of the toner particles toward the center of the toner particles) related to the existence ratio.

By controlling [P1 / P2] within the above range, a toner layer can be uniformly formed on the surface of the photosensitive member or the surface of the intermediate transfer member during transfer.
[P1 / P2] is preferably 1.10 or more and 1.70 or less, and more preferably 1.15 or more and 1.65 or less.

[P1 / P2] of conventional pulverized toner (toner manufactured by a pulverization method) that has not been spheroidized using heat, or polymerized toner (toner manufactured by a polymerization method) is less than 1.00 In order to improve the fixing separation property, it was necessary to add a large amount of wax. As a result, the change in the triboelectric charge amount due to embedding or desorption of the external additive becomes large, and there may be a case where density fluctuation or white background fogging occurs.
In addition, in the conventional toner spheroidized using heat, the value of [P1 / P2] varies depending on the degree of spheroidization. However, in the conventional toner spheroidized using heat, the wax immediately comes out on the surface of the toner particles with a small amount of heat, and the value of [P1 / P2] is increased before the toner particles are sufficiently spheroidized. It was over 2.00.

In the FT-IR spectrum, the absorption peak in the range of 1713 cm ⁻¹ or more and 1723 cm ⁻¹ or less is a peak mainly caused by — (C═O) — stretching vibration derived from the binder resin.
As peaks derived from the binder resin, various peaks other than the above, such as out-of-plane vibration of CH of the aromatic ring, may be detected. However, many peaks exist in the range of 1500 cm ⁻¹ or less, and it is difficult to separate only the binder resin peak, and an accurate numerical value cannot be calculated. For this reason, an absorption peak in the range of 1713 cm ⁻¹ or more and 1723 cm ⁻¹ or less that can be easily separated from other peaks is used as the peak derived from the binder resin.

In the FT-IR spectrum, the absorption peak in the range of 2843 cm ⁻¹ or more and 2853 cm ⁻¹ or less is a peak mainly caused by the stretching vibration (symmetric) of —CH ₂ — derived from wax.
The peak of the wax, there is a peak of the in-plane bending vibration of CH ₂ in the 1500 cm ^-1 or less 1450 cm ^-1 or even other than the above are detected. However, it also overlaps with the peak derived from the binder resin, and it is difficult to separate the wax peak. For this reason, an absorption peak in the range of 2843 cm ⁻¹ or more and 2853 cm ⁻¹ or less that can be easily separated from other peaks is used as the peak derived from the wax.

Upon obtaining the Pa and Pc, why subtracting the mean value of the absorption peak intensity of 3050 cm ^-1 and 2600 cm ^-1 from the maximum value of the absorption peak intensity of 2843cm ^-1 or 2853cm ^-1 the range eliminates the influence of baseline This is because the true peak intensity is calculated. Usually, since there is no absorption peak in the vicinity of 3050 cm ⁻¹ and 2600 cm ⁻¹ , the baseline intensity can be calculated by calculating the average value of these two points. Further, in obtaining the Pb and Pd, why subtracting the mean value of the absorption peak intensity of 1763cm ^-1 and 1630 cm ^-1 from the maximum value of the absorption peak intensity of 1713 cm ^-1 or 1723 cm ^-1 The following ranges are also the same.
The maximum absorption peak intensity derived from the binder resin (Pb and Pd) and the maximum absorption peak intensity derived from the wax (Pa and Pc) correlate with the abundance of the binder resin and the wax. Therefore, in the present invention, the ratio of wax to the binder resin is calculated by dividing (dividing) the maximum absorption peak intensity derived from the wax by the maximum absorption peak intensity derived from the binder resin.

As a result of the study by the present inventors, it has been found that P1 has a correlation with the glossiness of the image and the anti-fixing wrapping property. This is considered to be due to the following reasons.
By adjusting P1 to an appropriate range, the abundance ratio of the wax to the binder resin in the depth direction from the surface of the toner particle to about 0.3 μm is appropriately increased, and the wax is melted, whereby the toner particle The exudation of wax existing in the vicinity of the center of the glass is promoted. As a result, even in an image forming apparatus that forms an image at a high speed, the wax melts quickly in the fixing process and a sufficient amount of the liquid exudes, thereby exhibiting a mold release effect and good releasability between the fixing member and the toner layer. become.
Specifically, P1 is preferably 0.10 or more and 0.70 or less, and more preferably 0.12 or more and 0.66 or less.

  P1 can be controlled by changing the heat treatment conditions or by controlling the type and / or content of the wax contained in the toner particles before the heat treatment. For example, in order to increase P1, there are methods of increasing the heat treatment temperature and increasing the wax content in the toner particles. On the other hand, in order to reduce P1, there are methods of lowering the heat treatment temperature or reducing the wax content in the toner particles. However, when P1 is controlled by these methods, the rate of change of P1 is too fast and control is difficult. Therefore, in addition to the above method, it is preferable to control the dispersion state of the wax in the toner particles. Thereby, the changing speed of P1 is controlled. For example, the dispersibility of the wax in the toner particles can be controlled by incorporating hydrophobic silica particles into the toner particles as an internal additive.

In order to improve the glossiness of the image and the anti-fixing wrapping property, it is preferable to control P1 within the above range. However, the wax is soft because its molecular weight is smaller than that of the binder resin. For this reason, even when P1 is controlled within the above range, the change in the triboelectric charge amount may increase due to long-term use, and density fluctuations and white background fogging may occur.
Therefore, by further controlling the abundance ratio of the wax to the binder resin (P2) at about 1.0 μm in the depth direction from the surface of the toner particles, a charge imparting member for imparting charge to the toner and the toner, It is preferable to improve the stability of the triboelectric charge amount.
Here, in the present invention, in order to develop the stability of the triboelectric charge amount between the toner and the charging member, it is preferable to suppress embedding of the external additive used in the toner. Specifically, since there was a correlation between the wax abundance ratio at about 1.0 μm and the embedding suppression of the external additive, in the present invention, the wax abundance ratio at about 1.0 μm was adopted as P2.
Regarding the mechanism, the present inventors infer as follows.

In order to suppress the change in the triboelectric charge amount between the toner and the charge imparting member over time, it is preferable to suppress the change in the surface of the toner particles through long-term use. Specifically, it is preferable to suppress detachment and embedding of the external additive due to stress in the developing device.
The embedding of the external additive is considered to involve not only the hardness of the surface of the toner particles but also the hardness of the lower layer. For example, even if the amount of wax on the outermost surface layer of toner particles is large, if the lower layer is composed of a hard resin layer, it is considered that the external additive is not embedded so as to lose its function. Therefore, it is preferable to control the abundance ratio (P2) of the wax to the binder resin at about 1.0 μm in the depth direction from the surface of the toner particles. By controlling P2 within a specific range, it is considered that embedding of the external additive can be controlled and a change in the triboelectric charge amount can be suppressed.
Specifically, P2 is preferably 0.05 or more and 0.35 or less, and more preferably 0.06 or more and 0.33 or less.
P2 can be controlled by changing the type and / or content of the wax, the dispersion diameter of the wax in the toner particles, and the heat treatment conditions. Regarding the dispersion diameter of the wax in the toner particles, for example, the dispersion diameter of the wax in the toner particles can be controlled by incorporating hydrophobic silica particles into the toner particles as an internal additive.

A method for measuring various physical properties of the toner and raw materials in the present invention will be described below.
[Measurement method of peak molecular weight (Mp), number average molecular weight (Mn) and weight average molecular weight (Mw) of resin]
The peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) as follows.
First, the sample (resin) was dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Then, the obtained solution was filtered through a solvent-resistant membrane filter “Maeshori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. In addition, the sample solution was adjusted so that the density | concentration of the component soluble in THF might be about 0.8 mass%. Using this sample solution, measurement was performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (specifically, trade name: TSK standard polystyrene F-850, F-450, F-288, F-128, F
-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, manufactured by Tosoh Corporation). The molecular weight calibration curve created using this was used.

[Measurement method of softening point of resin]
The softening point of the resin was measured using a constant load extrusion type capillary rheometer (trade name: 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 molten 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 apparatus is defined as the softening point. In addition, 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). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.
As a measurement sample, about 1.0 g of resin is compressed for about 60 seconds at about 10 MPa using a tablet molding compressor (trade name: NT-100H, manufactured by NP System Co., Ltd.) in an environment of 25 ° C. It was molded into a cylindrical shape having a diameter of about 8 mm.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method Starting temperature: 40 ° 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

[Measurement of maximum endothermic peak of wax]
The peak temperature of the maximum endothermic peak of the wax was measured according to ASTM D3418-82 using a differential scanning calorimeter (trade name: Q1000, manufactured by TA Instruments). For the temperature correction of the detection part of the apparatus, the melting points of indium and zinc were used, and for the heat amount correction, the heat of fusion of indium was used.
Specifically, about 10 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature is raised between a measurement temperature range of 30 ° C. and 200 ° C. Measurements were made at a rate of 10 ° C / min. In the measurement, the temperature was once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature was raised again. The temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 ° C. or more and 200 ° C. or less in the second temperature raising process was defined as the peak temperature of the maximum endothermic peak of the wax.

[Measurement method of contact angle of toner on surface of pellet molded product with water]
An image processing contact angle measuring device CA-X (trade name) manufactured by Kyowa Interface Science Co., Ltd. was used.
The measurement method is as follows.
The toner was pressed by a tablet molding machine at a pressure of 300 kN / cm ² to obtain a sample having a diameter of 27 mm.
This sample was fixed on the sample stage, and pure water was supplied from the tip of the droplet supply needle to form pure water droplets (water droplets) on the surface of the sample. The coordinates of the left end, right end, and apex angle of the water droplet were determined by image processing, and the contact angle was determined from the calculated water droplet diameter (2r) and height (h) by the following formula.
ω = 2 tan ⁻¹ (h / r)
The measurement was performed 20 times per sample, and the average value of 18 measured values excluding the maximum value and the minimum value was defined as the contact angle.

[Calculation method of P1 and P2]
The FT-IR spectrum was measured by the ATR method using a Fourier transform infrared spectroscopic analyzer (trade name: Spectrum One, manufactured by PerkinElmer) equipped with a universal ATR measuring accessory (Universal ATR Sampling Accessory). A specific measurement procedure and a calculation method of [P1 / P2] obtained by dividing P1 and P2 and P1 by P2 are as follows.
The incident angle of infrared light (λ = 5 μm) was set to 45 °. As the ATR crystal, an ATR crystal of Ge (refractive index = 4.0) and an ATR crystal of KRS5 (refractive index = 2.4) were used. Other conditions are as follows.
Range
Start: 4000 cm ⁻¹
End: 600 cm ⁻¹ (Ge ATR crystal)
400 cm ⁻¹ (ATR crystal of KRS5)
Duration
Scan number: 16
Resolution: 4.00 cm ⁻¹
Advanced: With CO ₂ / H ₂ O correction

[Calculation method of P1]
(1) A Ge ATR crystal (refractive index = 4.0) was mounted on the apparatus.
(2) Scan type was set to Background, Units was set to EGY, and the background was measured.
(3) Scan type was set to Sample, and Units was set to A.
(4) 0.01 g of the toner was precisely weighed on the ATR crystal.
(5) The sample was pressurized with a pressure arm (Force Gauge is 90).
(6) A sample was measured.
(7) Baseline correction was performed on the obtained FT-IR spectrum by using Automatic Correction.
(8) The maximum value of the absorption peak intensity in the range of 2843 cm ⁻¹ or more and 2853 cm ⁻¹ or less was calculated (Pa1).
(9) The average value of absorption peak intensities at 3050 cm ⁻¹ and 2600 cm ⁻¹ was calculated (Pa2).
(10) Pa1-Pa2 = Pa. Pa was defined as the maximum absorption peak intensity of 2843cm ^-1 or 2853cm ^-1 or less.
(11) The maximum value of the absorption peak intensity in the range from 1713 cm ^{−1 to} 1723 cm ⁻¹ was calculated (Pb1).
(12) The average value of the absorption peak intensities at 1763 cm ⁻¹ and 1630 cm ⁻¹ was calculated (Pb2).
(13) Pb1-Pb2 = Pb. Pb was defined as the maximum absorption peak intensity of 1713 cm ^-1 or 1723 cm ^-1 or less.
(14) Pa / Pb = P1.

[Calculation method of P2]
(1) A KRS5 ATR crystal (refractive index = 2.4) was mounted on the apparatus.
(2) 0.01 g of the toner was precisely weighed on the ATR crystal.
(3) The sample was pressurized with a pressure arm (Force Gauge is 90).
(4) A sample was measured.
(5) Baseline correction was performed on the obtained FT-IR spectrum by using Automatic Correction.
(6) The maximum value of the absorption peak intensity in the range of 2843 cm ^{−1 to} 2853 cm ⁻¹ was calculated (Pc1).
(7) The average value of the absorption peak intensities at 3050 cm ⁻¹ and 2600 cm ⁻¹ was calculated (Pc2).
(8) Pc1-Pc2 = Pc. Pc was defined as the maximum absorption peak intensity of 2843cm ^-1 or 2853cm ^-1 or less.
(9) The maximum value of the absorption peak intensity in the range from 1713 cm ^{−1 to} 1723 cm ⁻¹ was calculated (Pd1).
(10) The average value of the absorption peak intensities at 1763 cm ⁻¹ and 1630 cm ⁻¹ was calculated (Pd2).
(11) Pd1-Pd2 = Pd. Pd was defined as the maximum absorption peak intensity of 1713 cm ^-1 or 1723 cm ^-1 or less.
(12) Pc / Pd = P2.
[Calculation method of P1 / P2]
P1 / P2 was calculated using P1 and P2 obtained as described above.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to these.

[Production Example of Intermediate Transfer Member 1]
A polyimide intermediate transfer belt mounted on an electrophotographic apparatus (electrophotographic image forming apparatus, trade name: iRC2620, manufactured by Canon Inc.) was used as a base layer. And the surface layer was formed in the surface of this base layer by the method shown below, and the intermediate transfer body concerning an Example and a comparative example was produced.
The physical properties (volume resistivity, surface resistivity, microhardness, wear amount, average major axis of domain, and domain area) of the intermediate transfer belt 1 used in Example 1 below are shown in Table 1. Table 2 shows the results of the image evaluation.
Further, in the intermediate transfer belt 1 of Example 1, the cross section in the thickness direction of the surface layer shows a matrix-domain structure, the matrix contains a binder resin, and the domain contains PFPE. I was able to confirm.

Dipentaerythritol hexaacrylate 8.0 parts by mass Pentaerythritol tetraacrylate 17.0 parts by mass Pentaerythritol triacrylate 5.0 parts by mass Methyl ethyl ketone 43.0 parts by mass Ethylene glycol 15.0 parts by mass Antimony-doped oxidation Tin fine particles (trade name: SN-100P, manufactured by Ishihara Sangyo Co., Ltd.) 4.0 parts by mass Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy) 2.0 parts by mass Dispersant (trade name: product name: GF-300 (solid content concentration: 25%), manufactured by Toagosei Co., Ltd. 20.0 parts by mass-PFPE having a structure represented by the above formula (1) (trade name: MD500 (number average molecular weight: 1700), 7.0 parts by mass The above materials are stirred by a homogenizer (manufactured by As One Co., Ltd.) In mixing, followed by dispersing, further subjected to dispersion by a dispersion device Nanomizer (manufactured by Yoshida Kikai Co., Ltd.), to obtain a mixed dispersion of the above materials. By applying this mixed dispersion on the surface of the intermediate transfer belt made of polyimide to form a coating film, and drying the coating film at 70 ° C. for 3 minutes, irradiation with 500 mJ / cm ² of ultraviolet rays, An intermediate transfer belt 1 having a surface layer thickness of 4 μm was obtained. The physical properties of the obtained intermediate transfer belt 1 are shown in Table 1.

[Example of production of intermediate transfer member 2]
In the production example of the intermediate transfer body 1, dipentaerythritol hexaacrylate was not used, the amount of pentaerythritol tetraacrylate used was changed to 20.0 parts by mass, and the amount of pentaerythritol triacrylate was changed to 10.0 parts by mass. did. Except for these, the intermediate transfer belt 2 was obtained in the same manner as the intermediate transfer body 1. The physical properties of the obtained intermediate transfer belt 2 are shown in Table 1.

[Production Example of Intermediate Transfer Member 3]
In the production example of the intermediate transfer member 2, the amount of dispersant used was changed to 64.0 parts by mass, and the amount of PFPE used was changed to 21.0 parts by mass. Except for these, the intermediate transfer belt 3 was obtained in the same manner as the intermediate transfer body 1. The physical properties of the obtained intermediate transfer belt 3 are shown in Table 1.

[Example of production of intermediate transfer member 4]
In the production example of the intermediate transfer body 3, pentaerythritol triacrylate was not used, 20.0 parts by mass of 2-ethylhexyl acrylate was used, and 10.0 parts by mass of butyl acrylate was used. Otherwise, the intermediate transfer belt 4 was obtained by the same method as that for the intermediate transfer member 3. Table 1 shows the physical properties of the intermediate transfer belt 4 thus obtained.

[Example of production of intermediate transfer member 5]
In the production example of the intermediate transfer member 1, the amount of PFPE used was changed to 30.0 parts by mass without using a dispersant. Except for these, the intermediate transfer belt 5 was obtained in the same manner as in the production example of the intermediate transfer member 1. The physical properties of the obtained intermediate transfer belt 5 are shown in Table 1.
When the cross section in the thickness direction of the intermediate transfer belt 5 was observed with an SEM, the matrix-domain structure could not be confirmed unlike the intermediate transfer belt of the example. Therefore, in the intermediate transfer belt 5, the average major axis of the domain and the area of the domain could not be measured.

[Example of production of intermediate transfer member 6]
In the production example of the intermediate transfer member 5, the amount of PFPE used was changed to 0.3 parts by mass. Otherwise, the intermediate transfer belt 6 was obtained in the same manner as in the production example of the intermediate transfer member 5. The physical properties of the obtained intermediate transfer belt 6 are shown in Table 1.
When the cross section in the thickness direction of the intermediate transfer belt 6 was observed with an SEM, the matrix-domain structure could not be confirmed unlike the intermediate transfer belt of the example. Therefore, in the intermediate transfer belt 6, the average major axis of the domain and the area of the domain could not be measured.

[Production Example of Intermediate Transfer Member 7]
In the production example of the intermediate transfer member 3, PFPE (MD500) was changed to PFPE (trade name: 5113X (number average molecular weight: 1000), manufactured by Solvay Solexis Co., Ltd.), and the amount used was changed to 32.5 parts by mass. did. Except for these, the intermediate transfer belt 7 was obtained in the same manner as in the production example of the intermediate transfer member 3. The physical properties of the obtained intermediate transfer belt 7 are shown in Table 1.
When the cross section in the thickness direction of the intermediate transfer belt 7 was observed with an SEM, the matrix-domain structure could not be confirmed unlike the intermediate transfer belt of the example. Therefore, the intermediate transfer belt 7 cannot measure the average major axis of the domain and the area of the domain.

[Example of production of intermediate transfer member 8]
In the production example of the intermediate transfer member 1, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate and pentaerythritol triacrylate were not used. Moreover, 30.0 mass parts of butyl acrylate was used, and the usage-amount of PFPE was changed into 15.0 mass parts. Otherwise, the intermediate transfer belt 8 was obtained by the same method as that for the intermediate transfer body 1. The physical properties of the obtained intermediate transfer belt 8 are shown in Table 1.
A Taber abrasion test was performed using the intermediate transfer belt 8, but the amount of wear could not be measured because the surface layer of the intermediate transfer belt 8 was all removed.

[Production Example of Photosensitive Member 1]
An aluminum cylinder having a diameter of 30 mm was prepared for a hardness test and an actual machine test. An aluminum cylinder was subjected to honing treatment and subjected to ultrasonic water washing to obtain a support (conductive support).
Next, 160 parts of methoxyethanol, 64 parts (0.06 mol) of an 85% butanol solution of zirconium tetra-n-butoxide (manufactured by Kanto Chemical Co., Ltd.) and 22 parts of titanium tetra-n butoxide (manufactured by Kishida Chemical Co., Ltd.) 0.14 mol) was added dropwise, and a mixed solution of methoxyethanol / water = 160 parts / 11 parts was further added. Next, a solution obtained by adding 20 parts of acetylacetone to 200 parts of methanol was further added dropwise, and then mixed with 55 parts of a 10% by mass methanol solution of hydroxypropylcellulose (manufactured by Tokyo Chemical Industry Co., Ltd.), thereby applying an undercoat layer. A liquid was prepared.
This undercoat layer coating solution was dip-coated on a support, and the resulting coating film was dried at 120 ° C. for 15 minutes to form an undercoat layer having a thickness of 0.3 μm.

Next, 3 parts of an oxytitanium phthalocyanine crystal having a strong peak at 9.0 °, 14.2, 23.9, and 27.1 ° in the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα Then, 3 parts of polyvinyl butyral (trade name S-REC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 35 parts of cyclohexanone were placed in a sand mill using glass beads having a diameter of 1 mm. Then, a dispersion treatment was carried out for 2 hours, and then 60 parts of ethyl acetate was added to prepare a charge generation layer coating solution.
The charge generation layer coating solution was dip coated on the undercoat layer, and the resulting coating film was dried at 50 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.
Next, 10 parts of a styryl compound represented by the following structural formula (1), and

下記構造式（２）で示される構造単位（ユニット）を有するポリカーボネート樹脂１０部

10 parts of polycarbonate resin having a structural unit represented by the following structural formula (2)

Was dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating solution for charge transport layer.
This charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 10 μm.
Next, 60 parts of a hole transporting compound represented by the following structural formula (3)

Was dissolved in a mixed solvent of 50 parts of monochlorobenzene / 50 parts of dichloromethane, and 10 parts of polytetrafluoroethylene (PTFE) particles were further added. And the coating liquid for protective layers was prepared by carrying out the dispersion process with a high voltage | pressure disperser (microfluidizer, Microfluidics company make).
This protective layer coating solution was dip coated on the charge transport layer to form a coating film. This coating film was irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 4 Mrad in an atmosphere having an oxygen concentration of 10 ppm. Then, the protective layer with a film thickness of 5 micrometers was formed by heat-processing for 10 minutes on the conditions which the temperature of a coating film becomes 100 degreeC in the same atmosphere.
Thus, a photoreceptor 1 having a subbing layer, a charge generation layer, a charge transport layer, and a protective layer in this order on the support, and the protective layer being a surface layer, was produced. Table 2 shows the physical properties of the photoreceptor 1 thus obtained.

[Production Example of Photosensitive Member 2]
In the same manner as the photoreceptor 1, an undercoat layer and a charge generation layer were formed on the support.

Next, 60 parts of the hole transporting compound having the structure represented by the above formula (4) was dissolved in a mixed solvent of 30 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a charge transport layer coating solution.
This coating solution for charge transport layer was dip coated on the charge generation layer to form a coating film. This coating film was irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 12 Mrad in an atmosphere having an oxygen concentration of 10 ppm. Then, the charge transport layer having a film thickness of 15 μm was formed by performing heat treatment for 10 minutes under the same atmosphere under the condition that the temperature of the coating film was 100 ° C.
In this manner, a photoreceptor 2 having a subbing layer, a charge generation layer, and a charge transport layer in this order on the support, and the charge transport layer being a surface layer was produced. Table 2 shows the physical properties of the resulting photoreceptor 2.

[Production Example of Photoreceptor 3]
The hole transporting compound used in the protective layer is changed from the hole transporting compound represented by the above structural formula (3) to the hole transporting compound represented by the following structural formula (5).

Changed to Other than that, Photoreceptor 3 was produced in the same manner as Photoreceptor 1. Table 2 shows the physical properties of the photoreceptor 3 obtained.

[Production Example of Photoreceptor 4]
In the production example of the photoreceptor 1, after forming the charge transport layer, a protective layer coating solution was prepared by the following procedure.
Antimony-containing tin oxide fine particles having an average particle diameter of 0.02 μm (trade name: T-1, manufactured by Mitsubishi Materials Corporation), (3,3,3-trifluoropropyl) trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) A solution obtained by mixing 30 parts and 300 parts of a 95% ethanol-5% aqueous solution was put in a milling apparatus. The solution dispersed for 1 hour was filtered, washed with ethanol, dried, and heated at 120 ° C. for 1 hour to treat the surface of the tin oxide fine particles.
Next, 25 parts of a curable acrylic monomer represented by the following structural formula (6) as a photopolymerizable monomer,

5 parts of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator, 50 parts of the surface-treated antimony-containing tin oxide particles and 300 parts of ethanol were mixed and placed in a sand mill apparatus. Then, 20 parts of polytetrafluoroethylene particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) are mixed into the dispersion obtained by the dispersion treatment for 96 hours, and 10 parts of the polytetrafluoroethylene particles are further mixed. Part was added. Then, the coating liquid for protective layers was prepared by carrying out a dispersion process with a high-pressure disperser (microfluidizer, manufactured by Microfluidics).
The protective layer coating solution is applied onto the charge transport layer by dip coating, and the resulting coating film is dried, and then irradiated with ultraviolet rays at a light intensity of 1000 mW / cm ² for 30 seconds with a metal halide lamp, whereby the film thickness is reduced. A 3 μm protective layer was formed.
In this way, the photoreceptor 4 was produced. Table 2 shows the physical properties of the photoreceptor 4 thus obtained.

[Production Example of Photoreceptor 5]
In the same manner as the photoreceptor 1, an undercoat layer and a charge generation layer were formed on the support.
Next, 9 parts of a compound represented by the following structural formula (7) as a charge transport material,

下記構造式（８）で示される化合物１部、

1 part of a compound represented by the following structural formula (8),

下記式（９）で示される構造単位（ユニット）を有するポリアリレート樹脂（重量平均分子量：１０００００）１２．５部、及び、

12.5 parts of a polyarylate resin (weight average molecular weight: 100,000) having a structural unit (unit) represented by the following formula (9), and

下記式（１０）で示されるシリコーン変性樹脂（重量平均分子量：５０００）０．０２５部

0.025 parts of a silicone-modified resin (weight average molecular weight: 5000) represented by the following formula (10)

Was dissolved in a mixed solvent of 40 parts of dimethoxymethane / 60 parts of monochlorobenzene to prepare a coating solution for a charge transport layer.
The charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 28 μm.
In this way, the photoreceptor 5 was produced. Table 2 shows the physical properties of the resulting photoreceptor 5.

[Production Example of Photosensitive Member 6]
In the photoreceptor 4, the amount of polytetrafluoroethylene particles used was changed to 5.0 parts. Otherwise, the photoreceptor 6 was produced in the same manner as in the production example of the photoreceptor 4. Table 2 shows the physical properties of the obtained photoreceptor 6.

[Production Example of Photoreceptor 7]
In the photoreceptor 1, the amount of polytetrafluoroethylene particles used was changed to 20 parts. Other than that, Photoreceptor 7 was produced in the same manner as in Production Example of Photoreceptor 1. Table 2 shows the physical properties of the photoreceptor 7 obtained.

[Production Example of Photoreceptor 8]
In the photoreceptor 3, the amount of polytetrafluoroethylene particles used was changed to 20 parts. Otherwise, the photoreceptor 8 was produced in the same manner as in the production example of the photoreceptor 3. Table 2 shows the physical properties of the obtained photoreceptor 8.

[Example of toner production]
[Production Example of Binder Resin 1]
76.9 parts by mass (0.167 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane,
24.1 parts by mass (0.145 mol) of terephthalic acid, and
0.5 parts by mass of titanium tetrabutoxide was placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (First Reaction Step) Then, 2.0 parts by mass (0.010 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step) to obtain a binder resin 1.
The binder resin 1 had an acid value of 10 mgKOH / g and a hydroxyl value of 65 mgKOH / g. Moreover, the molecular weight by GPC was a weight average molecular weight (Mw) 8,000, a number average molecular weight (Mn) 3,500, a peak molecular weight (Mp) 5,700, and the softening point was 90 degreeC.

[Example of production of binder resin 2]
71.3 parts by mass (0.155 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane,
24.1 parts by mass (0.145 mol) of terephthalic acid, and
0.6 parts by mass of titanium tetrabutoxide was placed in a 4-liter four-necked flask made of glass, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 5.8 parts by mass (0.030 mol%) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step), whereby a binder resin 2 was obtained.
The binder resin 2 had an acid value of 15 mgKOH / g and a hydroxyl value of 7 mgKOH / g. Moreover, the molecular weight by GPC was the weight average molecular weight (Mw) 200,000, the number average molecular weight (Mn) 5,000, the peak molecular weight (Mp) 10,000, and the softening point was 130 degreeC.

[Production Example of Polymer A]
・ Low density polyethylene (Mw 1400, Mn 850, DSC has a maximum endothermic peak of 100 ° C.) 18 parts by mass ・ Styrene 66 parts by mass ・ N-butyl acrylate 13.5 parts by mass ・ Acrylonitrile 2.5 parts by mass are charged into an autoclave After N ₂ substitution, the temperature was maintained at 180 ° C. with stirring. A polymer in which 50 parts by mass of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped into the system for 5 hours, the solvent was separated and removed after cooling, and the vinyl resin component reacted with the low-density polyethylene. A was obtained. When the molecular weight of the polymer A was measured, it was weight average molecular weight (Mw) 7100 and number average molecular weight (Mn) 3000. Furthermore, the transmittance at a wavelength of 600 nm measured at a temperature of 25 ° C. in a dispersion dispersed in a 45 volume% methanol aqueous solution was 69%.

[Production Example of Polymer B]
-Low density polyethylene (weight average molecular weight (Mw) is 1300, number average molecular weight (Mn) is 800, maximum endothermic peak by DSC is 95 ° C) 20 parts by mass-o-methylstyrene 65 parts by mass-n-butyl acrylate 11 parts by mass Part: Methacrylonitrile 4.0 parts by mass The above materials were charged into an autoclave, the system was replaced with N ₂ , and then maintained at 170 ° C. while stirring at elevated temperature. A polymer in which 50 parts by mass of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped into the system for 5 hours, the solvent was separated and removed after cooling, and the vinyl resin component reacted with the low-density polyethylene. B was obtained. When the molecular weight of the polymer B was measured, it was weight average molecular weight (Mw) 6900 and number average molecular weight (Mn) 2900. Furthermore, the transmittance at a wavelength of 600 nm measured at a temperature of 25 ° C. in a dispersion dispersed in a 45 volume% methanol aqueous solution was 63%.

[Production Example of Silica Fine Particle 1]
For the production of the silica fine particles, the combustion furnace used a hydrocarbon-oxygen mixed burner having a double tube structure capable of forming an inner flame and an outer flame. A two-fluid nozzle for slurry injection was grounded at the center of the burner, and a silicon compound as a raw material was introduced. A hydrocarbon-oxygen flammable gas was jetted from around the two-fluid nozzle to form an inner flame and an outer flame as a reducing atmosphere. By controlling the amount and flow rate of combustible gas and oxygen, the atmosphere, temperature, flame length, etc. were adjusted. Silica fine particles were formed from the silicon compound in the flame, and further fused to a predetermined particle size. Then, after cooling, it was obtained by collecting with a bag filter or the like.
Silica fine particles were produced using hexamethylcyclotrisiloxane as a raw material silicon compound, and the resulting silica fine particles 99.6% by mass were surface treated with 0.4% by mass of hexamethyldisilazane.

[Production Example of Toner 1]
-Binder 1 50.0 parts by mass-Binder 2 20.0 parts by mass-Fischer-Tropsch wax (peak temperature of maximum endothermic peak is 76 ° C)
6.0 parts by mass I. Pigment Blue 15: 3 5.0 parts by mass-Aluminum 5-, 5-di-t-butylsalicylate compound 0.5 parts by mass-Polymer A 5.0 parts by mass Henschel mixer (FM-75 type, Mitsui Mine) Using a biaxial kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set to 125 ° C. after mixing under the conditions of a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes. did. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (trade name: T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, a rotary classifier (trade name: 200
Classification was performed using TSP (manufactured by Hosokawa Micron Corporation) to obtain toner particles. As the operating condition of the rotary classifier (trade name: 200TSP, manufactured by Hosokawa Micron Corporation), the speed of the classifying rotor was set to 50.0 s- ¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.7 μm. 4.5 parts by mass of silica fine particles 1 are added to 100 parts by mass of the obtained toner particles, and a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) is used for a rotation speed of 30 s ^-1 and a rotation time of 10 minutes. The mixture was mixed under conditions, and heat treatment was performed by the surface treatment apparatus shown in FIG. The operating conditions were a feed rate of 5 kg / hour. Also, the hot air temperature C is 220 ° C., the hot air flow rate is 6 m ³ / min, the cold air temperature E is 5 ° C., the cold air flow rate is 4 m ³ / min, the cold air absolute water content is 3 g / m ³ , the blower air flow is 20 m ³ / min, The injection air flow rate was 1 m ³ / min. The obtained treated toner particles had an average circularity of 0.963 and a weight average particle diameter (D4) of 6.2 μm. To 100 parts by mass of the obtained treated toner particles, 0.8 parts by mass of hydrophobic silica fine particles having a number average particle diameter of 10 nm of primary particles surface-treated with 20% by mass of hexamethyldisilazane, and 16 parts by mass of isobutyltrimethoxysilane. % Of the primary particles surface-treated with 0.2% by weight of titanium oxide fine particles having a number average particle diameter of 30 nm was added, and the rotation speed was 30 s ⁻¹ with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.). And mixing under conditions of a rotation time of 10 minutes to obtain toner 1. Table 3 shows the physical properties of the obtained toner.

[Production Examples of Toner 2 to 11, Toner 13 to 15, and Toner 17]
As shown in Table 3, the amounts of WAX and polymer used (added amounts) were changed, and the hot air temperature was changed. Except these, Toner 1 to 11, Toner 13 to 15, and Toner 17 were obtained in the same manner as in Toner 1 Production Example. Table 3 shows the physical properties of the obtained toner.

[Production Example of Toner 12]
-Binder 1 50.0 parts by mass-Binder 2 20.0 parts by mass-Fischer-Tropsch wax (peak temperature of maximum endothermic peak is 76 ° C)
3.0 parts by mass C.I. I. Pigment Blue 15: 3 5.0 parts by mass-3,5-di-t-butylsalicylic acid aluminum compound 0.5 parts by mass Using the above material with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.), After mixing under conditions of a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, the mixture was kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at 125 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (trade name: T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, classification was performed using a rotary classifier (trade name: 200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. As an operating condition of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation), the classification rotor rotation speed was set to 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.7 μm. To 100 parts by mass of the obtained treated toner particles, 0.8 parts by mass of hydrophobic silica fine particles having a number average particle diameter of 10 nm of primary particles surface-treated with 20% by mass of hexamethyldisilazane, and 16 parts by mass of isobutyltrimethoxysilane. % Of the primary particles surface-treated with 0.2% by weight of titanium oxide fine particles having a number average particle diameter of 30 nm was added, and the rotation speed was 30 s ⁻¹ with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.). And the toner 12 was obtained by mixing under conditions of a rotation time of 10 minutes. Table 3 shows the physical properties of the obtained toner.

[Production Example of Toner 16]
As shown in Table 3, the amounts of WAX and polymer used (added amounts) were changed. Except for these, Toner 16 was obtained in the same manner as in Toner 12 Production Example. Table 3 shows the physical properties of the obtained toner.

[Example of manufacturing magnetic carrier 1]
Water was added to 100 parts by mass of Fe ₂ O ₃ and pulverized with a ball mill for 15 minutes to produce a magnetic core having an average particle size of 55 μm.
Next, a mixed solution of 1 part by mass of a straight silicone resin (trade name: KR271, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 part by mass of γ-aminopropyltriethoxysilane, and 98.5 parts by mass of toluene was added to the above-mentioned magnetic material. It added to 100 mass parts of cores. Further, the solvent was removed by drying under reduced pressure at 70 ° C. for 5 hours while stirring and mixing with a solution vacuum kneader. Then, the magnetic carrier 1 was obtained by performing the baking process for 2 hours at 140 degreeC, and sieving with a sieve shaker (300MM-2 type | mold, Tsutsui physics and chemistry machine: 75 micrometers opening).

[Example 1]
The toner 1 and the magnetic carrier 1 are mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the toner concentration is 9% by mass, with a rotation speed of 0.5 s ⁻¹ and a rotation time of 5 minutes. The two-component developer 1 was obtained by mixing under conditions. The following evaluations were performed for combinations of toner, carrier, intermediate transfer member, and photoreceptor shown in Table 4. Table 4 shows values obtained by subtracting the contact angle θ (B) of the surface of the intermediate transfer member with respect to water from the contact angle θ (A) of the surface of the photoreceptor with respect to water. The evaluation results are shown in Table 5.

(Evaluation 1) Evaluation Method of Line Reproducibility A modified machine of a full color copying machine (trade name: imageRUNNER ADVANCE C5255) manufactured by Canon Inc. was used as an image forming apparatus.
The image evaluation was performed by outputting 50000 original images with a printing ratio of 5% in each environment of high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (15 ° C., 10% RH). An image was output for evaluation.
Thin line images having line widths of 60 μm, 120 μm and 180 μm were output, and the presence or absence of toner loss was confirmed visually and with a magnifying glass. The evaluation criteria are as follows.
(Evaluation criteria for line reproducibility)
A: There is no toner omission and each line image is clear.
B: Some toner missing is recognized by loupe confirmation.
C: Some toner missing portions are confirmed in the line image by visual inspection.

(Evaluation 2) Transferability Evaluation Method A modified machine of a full color copying machine (trade name: imageRUNNER ADVANCE C5255) manufactured by Canon Inc. was used as an image forming apparatus. Solid image output after 70000 image output durability test (image with 10% printing rate) in high temperature and high humidity environment (30 ° C, 80% RH) and low temperature and low humidity environment (15 ° C, 10% RH) did. The transfer residual toner on the photoreceptor (photosensitive drum) at the time of solid image formation was removed by taping with a transparent polyester adhesive tape. The peeled adhesive tape was affixed on paper, and the density was measured with a spectral densitometer (500 series, X-Rite). Moreover, only the adhesive tape was affixed on paper and the density | concentration in that case was also measured. A density difference obtained by subtracting the latter density value from the former density was calculated, and this density difference was evaluated based on the evaluation criteria shown below.
During continuous image output of 70000 sheets, image output was performed under the same development conditions and transfer conditions (no calibration) as the first sheet. In the 70000 image output durability test, copy plain paper CS-680 (A4 paper, basis weight: 68 g / m ² , sold by Canon Marketing Japan Inc.) was used as the transfer material for evaluation. For the solid image after the output test, copy paper Multi-Purpose Paper: commonly called voice paper (A4 paper, basis weight: 75 g / m ² , sold by Canon USA) was used.
(Evaluation criteria for transferability)
A: Density difference less than 0.05 B: Density difference from 0.05 to less than 0.10 C: Density difference from 0.10 to less than 0.20

(Evaluation 3) Image unevenness evaluation method A modified machine of a full color copier manufactured by Canon Inc. (trade name: imageRUNNER ADVANCE C5255) was used as an image forming apparatus. Image evaluation was performed by outputting a blue solid image on the entire surface of the evaluation paper.
Image evaluation was performed in a high-temperature and high-humidity environment (30 ° C./80% RH) immediately after starting image output, after outputting 5000 images and after outputting 50000 images, images formed on the transfer material were Visual evaluation was made based on the criteria. As the transfer material for evaluation, copy paper Multi-Purpose Paper: commonly called voice paper (A4 paper, basis weight: 75 g / m ² , sold by Canon USA) was used.
(Evaluation criteria for image unevenness)
A: There is no unevenness in the image.
B: There is almost no unevenness in the image.
C: Some unevenness is seen in the image.

(Evaluation 4) Method for evaluating fog on non-image area (white background) In a high temperature and high humidity environment (30 ° C./80% RH), the fog on the white background before and after the durability test was measured.
The average reflectance Dr (%) of the evaluation paper before image output was measured by a reflectometer (trade name: REFECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku).
Outputs 50,000 images (image with a printing rate of 10%) in a high-temperature and high-humidity environment (30 ° C./80% RH), and after the durability test (50000th image), 00H image area; white background reflectance Ds (%) Was measured. Copy plain paper CS-680 (A4 paper, basis weight: 68 g / m ² , sold by Canon Marketing Japan Inc.) was used as the transfer material for evaluation. From the obtained Dr and Ds (before image output and after the durability test), fog (%) was calculated using the following formula. The obtained fog was evaluated according to the following evaluation criteria.
Fog (%) = Dr (%) − Ds (%)
(Fog evaluation criteria)
A: Less than 0.5% B: 0.5% or more and less than 1.0% C: 1.0% or more and less than 2.0%

(Evaluation 5) Evaluation method for cleaning After an image output durability test of 50000 sheets in a high-temperature and high-humidity environment (30 ° C./80% RH) (image with a printing rate of 10%), an image with an image area ratio of 10% is further obtained. 1000 sheets were output. Copy plain paper CS-680 (A4 paper, basis weight: 68 g / m ² , sold by Canon Marketing Japan Inc.) was used as the transfer material for evaluation. In the image after 1000 sheets were output, the degree of generation of a vertical streak image due to the residual toner that was not cleaned was observed and evaluated based on the following evaluation criteria.
(Evaluation criteria for cleaning properties)
A: There is no image defect.
B: Two to three thin vertical stripes are generated.
C: Slight vertical stripes (4 or more) are generated.

[Examples 2 to 21, Comparative Examples 1 to 6]
Evaluations were made in the same manner as in Example 1 with combinations of toner, carrier, intermediate transfer member, and photoreceptor shown in Table 4. Table 4 shows the values obtained by subtracting the contact angle θ (B) of the surface of the intermediate transfer member with respect to water from the contact angle θ (A) with respect to the surface of the photoreceptor, and Table 5 shows the evaluation results.

101: Raw material quantitative supply means, 102: Compressed gas adjusting means, 103: Introducing pipe, 104: Protruding member, 105: Supply pipe, 106: Processing chamber, 107: Hot air supply means, 108: Cold air supply means, 109: Regulation Means: 110: recovery means, 111: hot air supply means outlet, 112: distribution member, 113: swivel member, 114: powder particle supply port,
1Y, 1M, 1C, 1K: photosensitive drum, 2Y, 2M, 2C, 2K: charging roller, 3Y, 3M, 3C, 3K: laser beam scanner, 4Y, 4M, 4C, 4K: developing means, 5Y, 5M, 5C 5K: primary transfer roller, 7: intermediate transfer belt, 8: secondary transfer roller, 9: fixing device, 10: electrophotographic apparatus, 11: cleaning blade, 12: cassette, 13: pickup roller, 14: transport roller 15: registration roller pair, 16: transport roller pair, 17: discharge roller pair, 71: drive roller, 72: tension roller, 73: driven roller, 91: fixing roller, 92: pressure roller, S: transfer material 200: Intermediate transfer member, 201: Base layer, 203: Surface layer, 203-1: Matrix, 203-3: Domain

Claims (6)

A charging step for charging the surface of the photoreceptor;
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the charged photoreceptor;
Developing the electrostatic latent image with toner to form a toner image;
A primary transfer step of transferring the toner image to the surface of the intermediate transfer member;
A cleaning step of removing residual toner remaining on the surface of the photoreceptor after the primary transfer step;
A secondary transfer step of transferring the toner image transferred to the surface of the intermediate transfer member onto a transfer material;
A fixing step of fixing the toner image transferred to the transfer material to the transfer material;
An image forming method comprising:
When the contact angle of water on the surface of the photoreceptor is θ (A) and the contact angle of water on the surface of the intermediate transfer member is θ (B), θ (B) is 100 ° or more and 150 ° or less. The θ (A) and the θ (B) satisfy the relationship of the following formula (1),
−70 ° ≦ θ (A) −θ (B) <0 ° (1)
The toner has toner particles containing a binder resin;
An image forming method, wherein the contact angle of water on the surface of a molded pellet obtained by pressing the toner at a pressure of 300 kN / cm ² is 60 ° or more and 80 ° or less. ^2. The image forming method according to claim 1, wherein a universal hardness value (HU) when pressed at a maximum load of 6 mN on the surface of the photoreceptor is 150 N / mm ² or more and 220 N / mm ² or less. The intermediate transfer body is an intermediate transfer body having a base layer and a surface layer,
The surface layer has a matrix-domain structure having a matrix and a domain in its thickness direction;
The matrix contains a binder resin;
The domain contains a perfluoropolyether;
3. The image forming method according to claim 1, wherein the surface of the intermediate transfer body has a micro hardness of 50 MPa or more as measured by an ultra micro hardness meter. The toner particles further
Wax and
The image forming method according to any one of claims 1 to 3, further comprising a polymer having a structure formed by a reaction between a vinyl resin component and a hydrocarbon compound. The toner particles further contain a wax;
The toner further has an external additive;
The toner is
In the FT-IR spectrum obtained by measurement using the ATR method, using Ge as the ATR crystal and setting the infrared light incident angle to 45 °, the maximum absorption peak in the range of 2843 cm ^{−1 to} 2853 cm ^−1. The intensity is Pa, and the maximum absorption peak intensity in the range from 1713 cm ^{−1 to} 1723 cm ⁻¹ is Pb,
Using ATR method using a KRS5 as ATR crystal, the measured and FT-IR spectra obtained at the conditions was 45 ° infrared light incident angle, the maximum absorption peak of 2843cm ^-1 or 2853cm ^-1 the range When the intensity is Pc and the maximum absorption peak intensity in the range from 1713 cm ^{−1 to} 1723 cm ⁻¹ is Pd,
The image forming method according to any one of claims 1 to 4, which satisfies a relationship represented by the following formula (2).
1.05 ≦ P1 / P2 ≦ 2.00 (2)
[In Formula (2), P1 = Pa / Pb and P2 = Pc / Pd. ] The θ (A) and the θ (B) satisfy the relationship of the following formula (1) ′.
The image forming method according to claim 1.
−60 ° ≦ θ (A) −θ (B) <− 10 ° (1) ′

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