Electrophotographic member and electrophotographic image forming apparatus

Abstract

To provide an electrophotographic member that contributes to stable formation of high-quality electrophotographic images even if it is used repeatedly.SOLUTION: An electrophotographic member having an endless shape, has a cylindrical film and a surface layer on an outer peripheral surface of the cylindrical film. A shrinkage ratio αp of the cylindrical film in a first direction that is a circumferential direction of the cylindrical film, and a shrinkage ratio αa of the cylindrical film in a second direction orthogonal to the circumferential direction, are both 2.0% or more. The electrophotographic member includes crystalline polyester as a binder, and further includes roughness forming particles dispersed in the binder. The surface layer has a projection caused by the roughness forming particle on an outer surface on the opposite side of a side facing the cylindrical film. The cylindrical film further includes amorphous polyester, and the amorphous polyester extends in the first direction and the second direction from at least the roughness forming particle as the center.SELECTED DRAWING: Figure 6

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to electrophotographic members and electrophotographic imaging apparatus including the same. [Background technology]

[0002] In an electrophotographic image forming apparatus, an electrophotographic belt made of a thermoplastic resin having an endless shape is used as a transport transfer belt for transporting a transfer material or an intermediate transfer belt. Such an electrophotographic belt has high strength and, for example, a surface resistance of 1×10 3 ~1×10 13 It is required to have a conductivity in the range of Ω / □.

[0003] Patent Document 1 discloses a conductive belt that is composed of a matrix containing a thermoplastic resin having ester bonds, an ionic liquid, and particles containing a silicone resin, and that can sufficiently suppress fluctuations in electrical resistance over time. Furthermore, Examples 1 to 7 of Patent Document 1 disclose a conductive belt that is produced by blow molding a preform made from a resin composition containing a thermoplastic polyester resin (polyethylene terephthalate) and silicone resin particles having an average particle diameter of 2 μm, and then cutting both ends of the blown bottle obtained by blow molding. Patent Document 2 discloses a tubular body formed by extruding a mixed resin containing a crystalline thermoplastic resin and an amorphous thermoplastic resin into a cylindrical shape. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-230456 A [Patent Document 2] JP 2014-149445 A Summary of the Invention [Problem to be solved by the invention]

[0005] At least one aspect of the present disclosure is directed to providing an electrophotographic member that contributes to stable formation of high-quality electrophotographic images even after repeated use. Also, at least one aspect of the present disclosure is directed to providing an electrophotographic image forming apparatus capable of forming high-quality electrophotographic images. [Means for solving the problem]

[0006] According to at least one aspect of the present disclosure, there is provided an electrophotographic member having an endless shape, comprising a cylindrical film and a surface layer on an outer peripheral surface of the cylindrical film, wherein the cylindrical film has a shrinkage rate αp in a first direction, which is its circumferential direction, and a shrinkage rate αa in a second direction perpendicular to the circumferential direction, both of which are 2.0% or more, the cylindrical film contains a crystalline polyester resin as a binder, and further contains roughness-forming particles dispersed in the binder, the surface layer has convex portions caused by the roughness-forming particles on an outer surface opposite to a side facing the cylindrical film, and the cylindrical film further contains an amorphous polyester, and the amorphous polyester extends in at least the first direction and the second direction with the roughness-forming particles as a center.

[0007] According to at least one aspect of the present disclosure, there is also provided an electrophotographic image forming apparatus comprising the above-described electrophotographic member as an intermediate transfer belt. Effect of the Invention

[0008] According to at least one aspect of the present disclosure, it is possible to obtain an electrophotographic member that contributes to the stable formation of high-quality electrophotographic images even when used repeatedly. Also, according to at least one aspect of the present disclosure, it is possible to obtain an electrophotographic image forming apparatus that can form high-quality electrophotographic images. [Brief description of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view showing an example of a full-color electrophotographic image forming apparatus utilizing an electrophotographic process. [Diagram 2] FIG. 2 is a schematic cross-sectional view of an injection molding device used in the examples. [Diagram 3] FIG. 2 is a schematic cross-sectional view of a primary blow molding device used in the examples. [Figure 4] FIG. 2 is a schematic cross-sectional view of a secondary blow molding device used in the examples. [Diagram 5] 1 is an explanatory diagram of a configuration example of an electrophotographic belt according to an embodiment of the present disclosure. [Figure 6] 2 is a schematic image of the vicinity of a roughness particle contained in an electrophotographic belt according to one embodiment of the present disclosure. [Figure 7] FIG. 1 is an explanatory diagram of a method for determining the extension of amorphous polyester around a roughness-imparting particle. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" expressing a numerical range means a numerical range including the lower limit and the upper limit, which are the endpoints, unless otherwise specified. In addition, when a numerical range is described in stages, the upper limit and the lower limit of each numerical range can be arbitrarily combined. In addition, in the present disclosure, for example, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. In the present disclosure, "Ω / □" is a unit of surface resistivity defined in Japanese Industrial Standards (JIS) K 6911:2006, and means "Ω / square".

[0011] The electrophotographic belt disclosed in Patent Document 1 is roughened by forming convex portions on the outer surface of the electrophotographic belt using particles containing a silicone resin with an average particle diameter of 2 μm, and can reduce sliding friction with a cleaning member such as a cleaning blade. In addition, an electrophotographic belt having an endless shape produced using a biaxially stretched bottle formed by stretching a test tube-shaped preform in two directions, the longitudinal direction and the radial direction, has a high elastic modulus and high strength because it is stretched (biaxially stretched) in the circumferential direction and the longitudinal direction perpendicular to the circumferential direction.

[0012] However, according to the study by the present inventors, when the conductive belt according to Patent Document 1 is used for repeatedly forming an electrophotographic image, there are cases where blank areas gradually occur in the electrophotographic image. When the positions of the outer surface of the electrophotographic belt corresponding to the blank areas in the electrophotographic image are observed, it is confirmed that the outer peripheral surface of the electrophotographic belt is partially peeled off and a minute step is generated. In addition, the cross section of the electrophotographic belt in the circumferential direction and the cross section of the electrophotographic belt in the longitudinal direction are observed with a scanning electron microscope (SEM). As a result, voids are observed around the silicone resin particles. In particular, there are voids extending in the circumferential direction and the longitudinal direction of the electrophotographic belt centered on the silicone resin particles. From these observation results, it is speculated that the partial peeling of the outer peripheral surface of the electrophotographic belt is caused by the presence of voids around the silicone resin particles, which reduces the adhesive force between the silicone resin particles and the binder around them. Specifically, it is believed that this is because the outer peripheral surface of the electrophotographic belt is repeatedly rubbed by a cleaning member or the like, causing the silicone resin particles, which have a weak adhesive strength, to selectively peel off from the voids around the particles.

[0013] In addition, the silicone resin particles contained in the electrophotographic belt are surrounded by the silicone resin particles. The reason why voids exist in the circumferential and longitudinal directions of the electrophotographic belt with the resin particles at the center is considered as follows. In the base layer, the crystalline thermoplastic polyester is crystallized with its molecules oriented. In such a crystal growth process, as the crystallization of the crystalline thermoplastic polyester progresses, the crystalline thermoplastic polyester hardens, and the crystalline thermoplastic polyester present around the roughness-forming particles such as silicone resin particles, which have a size (micron order) that can generate convex portions on the outer surface, cannot sufficiently follow the shape of the roughness-forming particles. In addition, as the crystallization of the crystalline thermoplastic polyester progresses, the adhesion with the roughness-forming particles also decreases. As a result, it is presumed that voids are formed in the circumferential and longitudinal directions of the electrophotographic belt with the roughness-forming particles at the center. This presumption is also considered to be correct because, when the outer surface of the electrophotographic member is viewed from above, the voids extend in the radial direction with the roughness-forming particles at the center, specifically, for example, the voids have a sombrero shape with the roughness-forming particles at the center.

[0014] Based on such consideration, the present inventors have repeatedly studied to obtain an electrophotographic member that has no voids around the roughness-forming particles while improving strength by orienting and crystallizing the molecules of crystalline polyester. As a result, they have found that by further blending amorphous polyester into a cylindrical film containing crystalline polyester, it is possible to obtain an electrophotographic member that has high strength, suppresses the formation of voids around the roughness-forming particles, and is less likely to peel off on the outer surface even after long-term use.

[0015] Specifically, an electrophotographic member according to one embodiment of the present disclosure has an endless shape and includes a cylindrical film and a surface layer on an outer circumferential surface of the cylindrical film. The cylindrical film has a shrinkage rate αp in a first direction, which is the circumferential direction, and a shrinkage rate αa in a second direction perpendicular to the circumferential direction, both of which are 2.0% or more, contains a crystalline polyester as a binder, and further contains roughness-imparting particles dispersed in the binder. The surface layer has convex portions caused by the roughness-imparting particles on the outer surface opposite to the side facing the cylindrical film. The cylindrical film further contains an amorphous polyester, which extends in at least the first direction and the second direction with the roughness-imparting particles as the center.

[0016] The present inventors speculate that the reason why the formation of voids around the roughness-imparting particles is suppressed in the cylindrical film having the above-mentioned configuration is as follows. In the process of crystal growth due to the regular alignment of the molecules of the crystalline polyester, other components such as the amorphous polyester contained in the cylindrical film are extruded from the crystalline portion. In addition, as the crystallization of the crystalline polyester progresses, voids are formed around the roughness-forming particles for the reasons described above. It is considered that the amorphous polyester extruded from the crystalline portion of the crystalline polyester is arranged so as to fill the voids around the roughness-forming particles. As a result, it is possible to obtain a configuration in which there are no or few voids around the roughness-forming particles. As a result, it is considered that peeling of the outer surface of the electrophotographic member can be effectively suppressed even by friction from a cleaning blade or the like when the electrophotographic member is used repeatedly.

[0017] Hereinafter, an electrophotographic member according to one embodiment of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiment.

[0018] <Electrophotographic materials> The electrophotographic member has a cylindrical film and a surface layer on the outer periphery of the cylindrical film. 5A shows a perspective view of an endless electrophotographic member (hereinafter, also referred to as an "electrophotographic belt") 500 according to at least one embodiment of the present disclosure. As an example of a layer structure, the cross section of the line AA' in FIG. 5A shows a base layer 50 made of a cylindrical film as shown in FIG. 5B. 1 and a surface layer 502 covering the outer peripheral surface of the base layer. In FIG. 5(a), an arrow 500p indicates the circumferential direction of the electrophotographic belt, and an arrow 500w indicates the longitudinal direction perpendicular to the circumferential direction of the electrophotographic belt. When an electrophotographic belt having such a configuration is used as an intermediate transfer belt, for example, an outer surface 500-1 of the surface layer 502 becomes a toner carrying surface. Also, the inner peripheral surface of the cylindrical film may constitute the inner peripheral surface of the electrophotographic member. The electrophotographic member may have layers other than the base layer and the surface layer.

[0019] <Cylindrical film> The cylindrical film includes a crystalline polyester as a binder, roughness-forming particles dispersed in the binder, and an amorphous polyester. The cylindrical film can be, for example, a molded product of a resin mixture including the crystalline polyester, the roughness-forming particles, and the amorphous polyester. The cylindrical film has a shrinkage rate αp in a first direction, which is the circumferential direction of the cylindrical film, and a shrinkage rate αa in a second direction perpendicular to the circumferential direction, both of which are 2.0% or more. Furthermore, the amorphous polyester extends in the first and second directions at least around the roughness-imparting particles, so that peeling can be suppressed even when the film is used repeatedly. In this manner, the electrophotographic member according to the present disclosure can reduce surface peeling even after repeated use, and therefore contributes to the stable formation of high-quality electrophotographic images.

[0020] The tensile modulus Ep in the circumferential direction (first direction) of the cylindrical film and the tensile modulus Ea in the direction perpendicular to the circumferential direction (second direction) are both preferably 1000 MPa or more. As described above, the electrophotographic belt is stretched by a plurality of rollers with a predetermined tension in the electrophotographic image forming apparatus. Here, by setting Ep to 1000 MPa or more, elongation and breakage can be prevented. Ep is more preferably 1100 MPa or more, and further preferably 1200 MPa. The upper limit of Ep is not particularly limited, but examples thereof include 2000 MPa or less, 1800 MPa or less, and 1600 MPa or less. That is, Ep is preferably 1000 to 2000 MPa, 1100 to 1800 MPa, and 1200 to 1600 MPa.

[0021] In addition, by applying a predetermined tension in the circumferential direction, a compressive force is applied in a direction perpendicular to the circumferential direction of the electrophotographic member. However, by setting Ea to 1000 MPa or more, it is possible to more reliably prevent the outer surface of the electrophotographic member from being wavy along the circumferential direction due to the compressive force, and the electrophotographic member can be driven stably. Ea ​​is more preferably 1100 MPa or more, and even more preferably 1200 MPa. The upper limit of Ea is not particularly limited, but examples thereof include 2000 MPa or less, 1800 MPa or less, and 1600 MPa or less. That is, Ea is preferably 1000 to 2000 MPa, 1100 to 1800 MPa, and 1200 to 1600 MPa.

[0022] The tensile modulus Ep and Ea can be controlled by the degree of orientation of the crystalline polyester in the circumferential direction of the cylindrical film and in the direction perpendicular to the circumferential direction. The degree of orientation of the crystalline polyester can be expressed by the shrinkage rate αp in the circumferential direction of the cylindrical film and the shrinkage rate αa in the direction perpendicular to the circumferential direction. As described above, αp and αa are both 2.0% or more. In a cylindrical film having αp and αa of 2.0% or more, the crystalline polyester is sufficiently oriented in the circumferential direction and in the direction perpendicular to the circumferential direction. Therefore, when the belt is stretched, the deformation of the belt can be suppressed by the action of shrinkage stress. And, the cylindrical film having such a shrinkage rate can have the above-mentioned tensile elastic modulus Ep and Ea of 1000 MPa or more. αp may be, for example, 2.00 to 6.50%, 2.00 to 6.00%, or 2.00 to 5.50%. αa may be, for example, 2.00 to 6.50%, 2.00 to 6.00%, or 2.00 It may be ~5.50%.

[0023] The thickness of the cylindrical film is not particularly limited, but since the film is arranged in a bent state inside an electrophotographic image forming apparatus, the thickness is preferably 40 μm to 500 μm, and more preferably 50 μm to 100 μm from the viewpoint of ensuring flexibility.

[0024] <Crystalline polyester> The crystalline polyester refers to, for example, a polyester that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement. The crystalline polyester can be obtained by polycondensation of dicarboxylic acid and diol, polycondensation of oxycarboxylic acid or lactone, or polycondensation using a plurality of these components. Other components may be used, for example, polyfunctional monomers may be used in combination. The crystalline polyester may be a homopolyester containing one type of ester bond, or a copolyester (copolymer) containing a plurality of ester bonds.

[0025] From the viewpoint of having high crystallinity and exhibiting excellent heat resistance, the crystalline polyester is preferably at least one selected from the group consisting of polyalkylene terephthalate, polyalkylene naphthalate, polyalkylene isophthalate, and copolymers containing these, and more preferably at least one selected from the group consisting of polyalkylene terephthalate, polyalkylene naphthalate, and copolymers containing these. Also, a copolymer of polyalkylene naphthalate and polyalkylene isophthalate can be suitably used.

[0026] The number of carbon atoms of the alkylene in the polyalkylene terephthalate, polyalkylene naphthalate, and polyalkylene isophthalate is preferably 2 to 16, more preferably 2 to 8, and even more preferably 2 to 4, in order to obtain a crystalline polyester having high crystallinity and high heat resistance. More specifically, the crystalline polyester may be at least one crystalline polyester selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyethylene isophthalate, as well as modified polyethylene terephthalate, modified polyethylene naphthalate, and modified polyethylene isophthalate, in which a part of the blocks of these polyesters are modified with other blocks. Here, the other blocks may be monomer units of at least one compound selected from the group consisting of 1,4-naphthalenedicarboxylic acid and 2,3-naphthalenedicarboxylic acid. These may be used alone or in combination of two or more. They may be blends or alloys, and other resins may be added.

[0027] The molecular weight of the crystalline polyester is not particularly limited, but in the case of PET, for example, the preferred weight average molecular weight is 50,000 to 80,000. In the case of PEN, the preferred weight average molecular weight is 20,000 to 80,000.

[0028] The content of the crystalline polyester in the cylindrical film is preferably 50.0% by mass or more, more preferably 60.0% by mass or more, based on the total mass of the cylindrical film. The upper limit is not particularly limited, but may be 95.0% by mass or less, or may be 90.0% by mass or less. For example, the preferred range is 50.0 to 95.0% by mass, or 60.0 to 90.0% by mass. By ensuring that the content ratio of crystalline polyester is within the above range, a sufficient amount of crystalline polyester can be oriented in the circumferential direction of the cylindrical film and in a direction perpendicular to the circumferential direction, thereby more reliably increasing the mechanical strength of the cylindrical film. The content of crystalline polyester in the cylindrical film can be determined, for example, by the following method. A sample taken from the cylindrical film (for example, 1 mm square × the entire thickness of the cylindrical film) is immersed in methyl ethyl ketone at a temperature of 23°C, and separated into a soluble portion (amorphous polyester) and an insoluble portion (crystalline polyester, roughness-forming particles, etc.). The insoluble portion is then immersed in hexafluoroisopropanol (HFIP) at a temperature of 25°C, and the crystalline polyester is dissolved in HFIP, and separated from the insoluble portion (roughness-forming particles). HFIP is removed from the HFIP solution of the crystalline polyester obtained, and the crystalline polyester as a residue is weighed.

[0029] The crystalline polyester obtained by the above method can be subjected to differential scanning calorimetry (DSC), pyrolysis GC / MS, IR, NMR and elemental analysis to determine its chemical structure, etc.

[0030] <Amorphous polyester> The amorphous polyester refers to, for example, a polyester that does not show a clear endothermic peak in differential scanning calorimetry (DSC) measurement. The amorphous polyester is not particularly limited. Examples of the amorphous polyester include a polyester having a structure corresponding to at least one phthalic acid selected from the group consisting of terephthalic acid, orthophthalic acid, and isophthalic acid, and a structure corresponding to at least two diols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, and cyclohexanedimethanol. Here, the "corresponding structure" refers to a structure derived from an acid and a structure derived from an alcohol as raw materials in the amorphous polyester. The same applies hereinafter in the present disclosure.

[0031] For example, a polycondensate of a copolymer having a structure corresponding to ethylene terephthalate and a structure corresponding to ethylene orthophthalate and the above diol, a polycondensate of a copolymer having a structure derived from ethylene terephthalate and a structure derived from ethylene isophthalate and the above diol. These copolymers may be block copolymers or random copolymers. In addition, the amorphous polyester may be used as a polymer alloy in which two or more amorphous polyesters are blended, or may be used as a polymer alloy in which two or more copolymers are blended. Suitable examples of amorphous polyesters include those having a structure corresponding to terephthalic acid and a structure corresponding to ethylene glycol and propylene glycol. Such amorphous polyesters are commercially available under the names of, for example, "Vylon GK640" and "Vylon GK880" (both trade names, manufactured by Toyobo Co., Ltd.).

[0032] The molecular weight of the amorphous polyester is not particularly limited, but the weight average molecular weight (Mw) is preferably 8,000 to 60,000, and more preferably 10,000 to 40,000, for example.

[0033] In the electrophotographic member, the content ratio of the amorphous polyester to the crystalline polyester is preferably 30.0% by mass or less, more preferably 20.0% by mass or less. The lower limit is not particularly limited, but is preferably, for example, 2.0 to 30.0% by mass, particularly 3.0 to 20.0% by mass. By setting the content ratio of the amorphous polyester to the crystalline polyester within the above range, a sufficient amount of the amorphous polyester can be extended in the cylindrical film to fill the voids around the particles.

[0034] The content of the amorphous polyester in the cylindrical film can be determined, for example, by the following method. A sample taken from the cylindrical film (for example, 1 mm square × the entire thickness of the cylindrical film) is immersed in methyl ethyl ketone (MEK) at a temperature of 23°C, and the soluble content (amorphous polyester) is measured. The resulting MEK solution of the amorphous polyester is then separated into a soluble fraction (crystalline polyester) and an insoluble fraction (crystalline polyester, roughness-forming particles, etc.). Next, MEK is removed from the resulting MEK solution of the amorphous polyester, and the residual amorphous polyester is weighed.

[0035] The chemical structure of the amorphous polyester resin can be identified by subjecting the amorphous polyester obtained by the above-mentioned method to pyrolysis GC / MS, IR, NMR, and elemental analysis.

[0036] An example of observing the state of the amorphous polyester resin in a cylindrical film is shown below. A sample piece of 5 mm in the circumferential direction and 5 mm in the longitudinal direction perpendicular to the circumferential direction (hereinafter, simply referred to as the "longitudinal direction") is cut out from any location of the electrophotographic member. A first cross section of the cut out sample piece in the circumferential direction of the cylindrical film and a second cross section in the longitudinal direction are polished using an ion beam. For example, a cross-section polisher can be used for polishing the cross section with an ion beam. Polishing the cross section with an ion beam can prevent the inclusion of an abrasive and can form a cross section with fewer polishing marks.

[0037] Next, the polished first and second cross sections of the sample piece are stained with ruthenium tetroxide, which can stain the amorphous polyester portion and make it possible to distinguish it from the crystalline polyester portion. The first and second cross sections of the stained sample piece are observed by a scanning electron microscope (SEM) or the like, and one of the roughness-forming particles exposed on each cross section is focused on, and a cross-sectional image of the focused roughness-forming particle and a 10 μm×10 μm region including the surrounding area is obtained. By staining in advance in this way, it is easier to obtain contrast in the observed image, and the state of the amorphous polyester can be evaluated more accurately.

[0038] An example of an SEM image obtained from the first cross section is shown in FIG. 6. As shown in FIG. 6, the amorphous polyester contained in the region 602 extends in the circumferential direction (first direction 603) of the cylindrical film and in the direction perpendicular to the circumferential direction (second direction) with the roughness-forming particle 601 as the center. It is preferable that the region (amorphous portion) 602 containing the amorphous polyester extends in the first direction 603 and the second direction from the central roughness-forming particle 601 and has a substantially triangular shape tapering from the roughness-forming particle 601 toward the first direction 603. More specifically, when the roughness-forming particle 601 on the outer surface of the electrophotographic member and its surroundings are viewed from the outer surface side of the electrophotographic member, it is preferable that the region 602 extends in the entire circumferential direction with the roughness-forming particle 601 as the center, forming a so-called "sombrero" shape. In this way, the amorphous polyester resin exists around the roughness-forming particle, and voids are unlikely to exist around the roughness-forming particle. It is believed that this makes it difficult for the adhesive strength between the roughness-imparting particles and the binder to decrease, and therefore peeling is unlikely to occur on the outer surface even when the electrophotographic member is used repeatedly. Such extension of the amorphous polyester can be achieved by producing a cylindrical film using the cylindrical film production method described below.

[0039] In the present disclosure, whether the amorphous polyester is present extending in the first direction and the second direction from the roughness-forming particle as the center can be confirmed, for example, by the following method. A test piece having a length of 5 mm along the circumferential direction of the electrophotographic belt, a length of 5 mm along the longitudinal direction perpendicular to the circumferential direction, and a thickness equal to the total thickness of the electrophotographic belt is cut out from an arbitrary position of the electrophotographic belt. A first cross section along the circumferential direction of the electrophotographic belt and a second cross section along the longitudinal direction of the obtained test piece are each polished using a cross-section polisher. The polished first and second cross sections of the test piece are stained with ruthenium tetroxide, which can stain amorphous parts. Next, the first and second cross sections are observed by scanning electron microscopy (SEM), focusing on one roughness-forming particle, and the roughness-forming particle and its surroundings are observed within 10 cm. An SEM image of an area of ​​μm×10 μm is obtained. At this time, the roughness-forming particles to be focused on are not particularly limited, but it is preferable to select roughness-forming particles whose maximum length of the cross section of the roughness-forming particles exposed on the cross section to be observed (first cross section, second cross section) is as close as possible to the diameter of the roughness-forming particles, and it is particularly preferable to select roughness-forming particles whose maximum length is equal to the diameter of the roughness-forming particles.

[0040] In the acquired SEM image, the dyed region is determined to be a region containing amorphous polyester. FIG. 7(a) shows an example of an SEM image of a 10 μm×10 μm region including the roughness-forming particle 601 and its surroundings, focusing on one roughness-forming particle 601 exposed in the first cross section. In this SEM image, the dyed region 602 is a region where amorphous polyester exists. Here, two points P11 and P12 at both ends of the region 602 extending in a first direction (see arrow 500p in FIG. 5) along the circumferential direction with the roughness-forming particle as the center are specified. Then, the angle (included angle) θ701 formed by the line segment 704 connecting the points P11 and P12 and the straight line 703 drawn parallel to the circumferential direction is measured. Then, if θ701 is 10° or less, the region 602 is determined to be extending in the first direction with the roughness-forming particle as the center. θ701 is preferably 5° or less, and particularly preferably 2° or less. There is no particular lower limit to θ701, but it is preferably 0°. The preferred range for θ701 is 0 to 10°, particularly preferably 0 to 5°, and further preferably 0 to 2°.

[0041] The extension of the amorphous polyester in the second direction is obtained from the second cross section in the same manner as described above. FIG. 7(b) shows an example of an SEM image of the roughness-forming particle 601 and a 10 μm×10 μm area including the surrounding area, focusing on one roughness-forming particle 601 exposed in the second cross section. In this SEM image, the dyed area 602 is the area where the amorphous polyester exists. Here, two points P21 and P22 at both ends of the area 602 extending in the longitudinal direction, i.e., in the second direction (see arrow 500w in FIG. 5) with the roughness-forming particle 601 as the center are specified. Then, the angle (included angle) θ702 between the line segment 706 connecting the points P21 and P22 and the straight line 705 drawn parallel to the longitudinal direction is measured. Then, if θ702 is 10° or less, the area 602 is deemed to be extending in the second direction with the roughness-forming particle as the center. θ702 is preferably 5° or less, and particularly preferably 2° or less. There is no particular lower limit to θ702, but it is preferably 0°. The preferred range for θ702 is 0 to 10°, particularly preferably 0 to 5°, and further preferably 0 to 2°.

[0042] A method for controlling θ701 and θ702 within the above ranges includes, for example, more accurate stretching in the longitudinal direction and in the radial expansion direction of a test tube-shaped preform when the preform is biaxially stretched. A specific method includes, for example, uniformly heating the preform during biaxial stretch molding.

[0043] <Roughness forming particles> The roughness-forming particles are particles that impart unevenness to the outer surface (toner image bearing surface) of the cylindrical film and have the effect of controlling the toner. By including the roughness-forming particles in the cylindrical film, it is possible to generate convex portions due to the roughness-forming particles on the outer surface opposite to the side facing the cylindrical film in the surface layer on the outer peripheral surface of the cylindrical film. The roughness-forming particles can be confirmed by observing the cross section of the cylindrical film using an SEM or the like. Roughness-forming particles have a wide variety of chemical structures, crystal structures, and crystallinity, and there are a wide variety of shapes and particle sizes depending on the polymerization method and pulverization method used.

[0044] As the roughness-imparting particles, known inorganic or organic fine particles can be used, for example, the following can be used: carbonates such as calcium carbonate, barium carbonate, and nickel carbonate; potassium titanate, barium titanate, strontium titanate, titanium Examples of the suitable particles include titanates such as lead zirconate; silica particles such as glass beads, metal oxides such as zeolite, alumina, ferrite, magnesium oxide, calcium oxide, zinc oxide, iron oxide, titanium oxide, and tin oxide; sulfates such as barium sulfate and calcium sulfate; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; metal sulfides such as molybdenum sulfide; mineral particles such as kaolin; silicone resin particles; fluoropolymer particles such as PTFE particles, PFPE particles, and PFA particles; aramid particles; and thermosetting resin particles. These may be used alone or in combination of two or more. Among the roughness-forming particles, silicone resin particles and silica particles are particularly preferred because they have excellent thermal stability, low surface energy, little aggregation between particles, and easy dispersion control. That is, it is particularly preferred that the roughness-forming particles include at least one particle selected from the group consisting of silicone resin particles and silica particles.

[0045] The shape and particle size of the roughness-imparting particles are not particularly limited, but it is preferable that the particle size is such that roughness can be formed on the surface, and that the particles are spherical. This is because spherical roughness-imparting particles are more likely to obtain isotropy in terms of the dispersion state and orientation state, and more likely to form roughness on the surface, compared with amorphous particles or fibrous materials. The particle size of the roughness-forming particles is not particularly limited as long as it can control the surface unevenness of the cylindrical film, but for example, the volume average particle size may be 0.4 μm or more, and preferably 1.0 μm or more. When it is within the above range, it becomes easy to control the surface unevenness of the cylindrical film. The upper limit of the volume average particle size is not particularly limited, and examples thereof include 0.4 to 5.0 μm and 1.0 to 5.0 μm.

[0046] In the cylindrical film, the content ratio of the roughness-imparting particles on a mass basis is not particularly limited, but is preferably 0.1 to 5.0 mass %, and more preferably 0.3 to 2.5 mass %.

[0047] <Additives> The cylindrical film may contain other components within a range that does not impair the effects of the present disclosure. Examples of other components include antioxidants, ultraviolet absorbers, organic pigments, inorganic pigments, pH adjusters, crosslinking agents, compatibilizers, release agents, coupling agents, lubricants, etc. These additives may be used alone or in combination of two or more types. The amount of additive used may be appropriately set and is not particularly limited.

[0048] The cylindrical film may also contain a conductive agent. Examples of the conductive agent include an electronic conductive agent such as carbon black, and an ionic conductive agent. Examples of the ionic conductive agent include, for example, an ionic liquid. An ionic liquid is a salt consisting of an anion and a cation, which has a melting point at a temperature of 100° C. or less. Specific examples of the ionic conductive agent include lithium bis(trifluoromethanesulfonyl)imide and lithium bis(fluorosulfonyl)imide, which are classified as ionic liquids. In the configuration according to the present disclosure, the ionic conductive agent is considered to be contained in large amounts in the region 602 containing the amorphous polyester in FIG. 7(a) and FIG. 7(b). This is because, in the process of crystallization of the crystalline polyester, the ionic conductive agent is extruded from the crystalline portion in the same manner as the amorphous polyester. As a result, it is considered to be present in large amounts in the region 602.

[0049] For example, when the cylindrical film contains an ion conductive agent, the content of the ion conductive agent based on the mass of the cylindrical film is not particularly limited, but is preferably, for example, 0.5 to 8.0 mass %.

[0050] Measured on the inner surface of an electrophotographic member in an environment of 23°C and 50% relative humidity. The surface resistivity A (Ω / □) of the electrophotographic material is 1.00×10 3 ~1.00×10 13 Ω / □ is preferable, and 1.00×10 5 ~1.10×10 12 Ω / □ is more preferable, and 1.00×10 7 ~1.10×10 11 It is more preferably Ω / □.

[0051] <Surface layer> The electrophotographic member has a surface layer on the outer peripheral surface of the cylindrical film. The surface layer has protrusions caused by the roughness-forming particles on the outer surface opposite to the side facing the cylindrical film. In this way, the electrophotographic member has a surface layer with protrusions, so that friction with the photosensitive drum and cleaning member can be reduced. The presence of protrusions can be confirmed by the method described below. The surface layer is not particularly limited, and may be, for example, a layer having excellent abrasion resistance, containing a cured product of an active energy ray curable resin. Such a surface layer may be provided, for example, by applying a composition containing an active energy ray curable resin, such as a photocurable resin, onto the outer peripheral surface of the cylindrical film, and curing the composition by irradiating the composition with ultraviolet light or the like. The thickness of the surface layer is not particularly limited, but is preferably, for example, 1 to 5 μm.

[0052] The photocurable resin is not particularly limited as long as it has a photocurable functional group in the molecule, and preferably includes, for example, a resin having a vinyl group, a propenyl group, an allyl group, a styryl group, an acryloyl group, a methacryloyl group, a maleimide group, etc. In addition, the photocurable resin is preferably a polyfunctional photocurable resin, and examples thereof include glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, diglycerin tri(meth)acrylate, sorbitan tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta- and hexa(meth)acrylate, and tetraglycerin penta(meth)acrylate. Among them, dipentaerythritol penta- and hexa(meth)acrylate are preferred, and dipentaerythritol penta- and hexaacrylate are more preferred.

[0053] The composition containing the active energy ray curable resin such as the photocurable resin preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, but may be a sulfonic acid compound, a diazomethane compound, a sulfonium salt compound, an iodonium salt compound, a disulfone compound, a benzophenone compound, an alkylphenone compound, etc. Among them, the alkylphenone compound is preferably an aminoalkylphenone compound, and specifically may be 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (e.g., Irgacure 907, manufactured by BASF).

[0054] The ten-point average roughness (Rzjis) of the electrophotographic member is preferably 0.110 or more, and more preferably 0.120 or more. There is no particular upper limit, but examples include 0.110 to 0.300, 0.120 to 0.250, and 0.120 to 0.200. When the ten-point average roughness Rzjis is measured at a total of eight points, four points in the circumferential direction of the electrophotographic member and two points in the direction perpendicular to the circumferential direction, the arithmetic average value of the ten-point average roughness Rzjis values ​​measured at the eight points is used. When the ten-point average roughness is within the above range, the contact area of ​​the cleaning blade tends to be small, and as a result, friction also tends to be small.

[0055] An example of the application of the electrophotographic member according to the present disclosure is an electrophotographic belt, and an example of the application of the electrophotographic belt is an intermediate transfer belt or a transport transfer belt. However, the present invention is not limited to this, and can also be applied to, for example, a conveyor belt that supports and conveys a recording medium such as paper. The electrophotographic member may have an endless shape.

[0056] <Cylindrical film manufacturing method> The cylindrical film can be produced, for example, through the following steps (i) to (iii). The cylindrical film is preferably a blow molded product. The cylindrical film is preferably a biaxially stretched cylindrical film. Step (i): A preform having a test tube shape is molded using a resin mixture containing a crystalline polyester, an amorphous polyester, and roughness-forming particles. Step (ii): The obtained preform is stretched in the axial direction of the preform using a stretching rod, and also, gas is introduced into the inside of the preform to stretch it in the circumferential direction, thereby stretch-molding in two axial and circumferential directions, to obtain a bottle-shaped molded product (hereinafter, also referred to as a "blow bottle") (biaxial stretch blow molding). Step (iii): Both ends of the resulting blown bottle are cut to obtain an endless cylindrical film.

[0057] The specific means for step (i) is not particularly limited, but examples thereof include the following means. First, pellets of a resin mixture containing crystalline polyester, amorphous polyester and roughness-forming particles are prepared. For example, pellets can be prepared by the following method: First, an amorphous polyester and roughness-forming particles are melt-kneaded to prepare an amorphous polyester mixture. Then, the obtained amorphous polyester mixture is mixed with a crystalline polyester, and further melt-kneaded to prepare pellets of the resin mixture. This makes it easier for the amorphous polyester to extend around the roughness-forming particles. As described above, in the cylindrical film according to the present disclosure, as the crystalline polyester crystallizes, the voids are filled with the amorphous polyester expelled from the crystalline portion. Therefore, by increasing the proportion of the amorphous polyester around the roughness-forming particles, the effect can be more easily achieved.

[0058] When the amorphous polyester mixture is melt-kneaded with the crystalline polyester, it is preferable to knead them at the following temperature: That is, it is preferable to knead them at a temperature equal to or higher than the highest melting point or softening point so that the polyester having the highest melting point or softening point among the crystalline polyester and the amorphous polyester to be contained in the resin mixture is well kneaded. The kneading method is not particularly limited, and a single screw extruder, a twin screw kneading extruder, a Banbury mixer, a roll, a Brabender, a Plastograph, a kneader, or the like can be used.

[0059] The resin mixture thus obtained is used to mold a preform having a test tube shape. The method for molding the preform is not particularly limited, and examples thereof include the following methods. As shown in FIG. 2, this method involves using an injection molding device 201 to inject the molten resin mixture into a preform molding die consisting of a cavity die 203 and a core die 207, and solidifying it within the preform molding die to form a preform 205. At this time, the temperature of the preform molding die into which the molten material is injected is preferably set to, for example, 40° C. or lower. The molten material injected into the die is cooled and solidified within the die, but by quickly cooling the molten material, the progress of crystallization of the crystalline polyester can be prevented. By suppressing the crystallization of the crystalline polyester in the preform, the crystal orientation in the biaxial directions of the crystalline polyester can be more accurately achieved in the biaxial stretch blow molding step (ii). Can be controlled.

[0060] Next, in step (ii), biaxial stretch blow molding is performed to stretch the test tube-shaped preform in the longitudinal and radial directions. First, as shown in Fig. 3(a), the preform 205 is placed in a heating device 301 and heated to a temperature at which it can be stretched. Examples of the temperature at which it can be stretched include 100 to 160°C. The heating time is preferably 5 minutes or less, more preferably 1 minute or less. By setting the heating time to 5 minutes or less, it is possible to prevent the crystallization of the crystalline polyester from progressing within the preform during heating. The heated preform is transported in the direction of the arrow 305. Next, a blow mold 303, which is formed by combining a left mold 303-1 and a right mold 303-2 to form a cylindrical cavity 303-3 therein, is lowered in the direction of the arrow 307 from directly above the heated preform 205. Then, as shown in Fig. 3(b), it is placed at the mouth of the blow mold 303.

[0061] In order to prevent the temperature of the heated preform from dropping before the start of the next biaxial stretching step, it is preferable to place the preform heated for a short period of time (e.g., within 20 seconds) at the mouth of the blow mold, which can prevent the progress of crystallization of the crystalline polyester in the preform due to slow cooling of the preform. The heating temperature of the preform in the heating device is not particularly limited as long as the preform can be stretched. For example, the heating temperature may be calculated in advance using a differential scanning calorimeter (DSC) for the resin mixture that is the constituent material of the preform, observing the endothermic peak or baseline shift during heating, or may be determined from the glass transition temperature (Tg).

[0062] Next, as shown in Fig. 3(c), the stretching rod 309 is driven in the direction of the arrow 311 to stretch the heated preform 205 placed in the blow mold 303 in the longitudinal direction of the preform 205. This stretching is called the first stretching. Also, gas is introduced into the preform from the mouth of the preform 205 (arrow 313) to expand the preform in its circumferential direction. This is called secondary stretching. Examples of gases to be blown include air, nitrogen, carbon dioxide, and argon. As a result, the preform 205 expands in each direction shown by the arrows 315 in FIG. 3(c), adheres to the inner wall of the cavity 303-3, and cools and solidifies in that state. The secondary stretching may be carried out following the primary stretching, but it is preferable to synchronize the drive of the stretching rod in the primary stretching step with the inflow of gas into the preform, so that the primary stretching and the secondary stretching are carried out approximately simultaneously. Next, the right mold 303-1 and the left mold 303-2 of the blow mold 303 are separated, and the blown bottle is taken out from the blow mold 303. By such step (ii), the amorphous polyester comes to extend in the first direction and the second direction with at least the roughness-forming particles as the center. In addition, in this biaxial stretch blow molding process, αp and αa can be adjusted within the above-mentioned ranges by adjusting the stretch ratios in the axial and circumferential directions of the preform.

[0063] Next, as shown in FIG. 3(d), the mouth side portion and the upper end portion opposite the mouth side of the obtained blown bottle 317 are cut to obtain a biaxially stretched cylindrical film 319 that will become the base layer. Before cutting the blown bottle 317, a heat treatment may be carried out as necessary to adjust the surface roughness of the outer circumferential surface of the blown bottle and to finely adjust the crystallinity of the crystalline polyester. Specifically, for example, as shown in FIG. 4, a blow bottle 317 is placed in a cylindrical mold 401, then an outer mold 405 is attached, and the blow bottle is filled with gas. To prevent gas from leaking out from inside the bottle, outer dies are attached to the top and bottom of the mold 401. This is placed on a rotating table 407, and the mold 401 is heated while rotating by a roller-shaped heater 403 that is in contact with the outer circumferential surface of the mold 401. The heating temperature is, for example, 130 to 190°C, and the heating time is, for example, such that the entire circumference of the blow bottle is heated uniformly for about 60 seconds.

[0064] <Electrophotographic image forming apparatus> An example of an electrophotographic image forming apparatus including an electrophotographic member according to at least one embodiment of the present disclosure as an intermediate transfer belt will be described below. The electrophotographic image forming apparatus has a so-called tandem configuration in which electrophotographic stations of multiple colors are arranged side by side in the rotation direction of the intermediate transfer belt (Figure 1). In the following explanation, the symbols for the components relating to the colors yellow, magenta, cyan, and black are suffixed with Y, M, C, and k, respectively, but the suffixes may be omitted for similar components.

[0065] In FIG. 1, around photosensitive drums (photoconductors, image carriers) 1Y, 1M, 1C, and 1k, charging devices 2Y, 2M, 2C, and 2k, exposure devices 3Y, 3M, 3C, and 3k, developing devices 4Y, 4M, 4C, and 4k, and an intermediate transfer belt (intermediate transfer body) 6 are arranged. The photosensitive drum 1 is rotated in the direction of the arrow F (counterclockwise) at a predetermined peripheral speed (process speed). The charging device 2 charges the peripheral surface of the photosensitive drum 1 to a predetermined polarity and potential (primary charging). The laser beam scanner as the exposure device 3 outputs a laser beam that is on / off modulated in response to image information input from an external device such as an image scanner or computer (not shown), and scans and exposes the charged surface of the photosensitive drum 1. This scanning and exposure forms an electrostatic latent image on the surface of the photosensitive drum 1 according to the target image information.

[0066] The developing devices 4Y, 4M, 4C, and 4k contain toner of each color component of yellow (Y), magenta (M), cyan (C), and black (k), respectively. Then, the developing device 4 to be used is selected based on image information, and developer (toner) is developed on the surface of the photosensitive drum 1, and the electrostatic latent image is visualized as a toner image. In this embodiment, a reversal development method is used in which toner is attached to the exposed portion of the electrostatic latent image to develop it. Furthermore, the charging device, exposure device, and developing device constitute an electrophotographic image forming means.

[0067] The intermediate transfer belt 6 is an electrophotographic belt having an endless shape. The intermediate transfer belt 6 is stretched by a plurality of rollers 20, 21, and 22 so that the outer circumferential surface of the intermediate transfer belt 6 comes into contact with the surface of the photosensitive drum 1. In this embodiment, the roller 20 is a tension roller that controls the tension of the intermediate transfer belt 6 to be constant, the roller 22 is a drive roller for the intermediate transfer belt 6, and the roller 21 is an opposing roller for secondary transfer. The intermediate transfer belt 6 is rotated in the direction of the arrow G by the drive of the roller 22. The primary transfer rollers 5Y, 5M, 5C, and 5k are disposed at primary transfer positions that face the photosensitive drum 1 across the intermediate transfer belt 6. That is, the electrophotographic image forming apparatus includes a plurality of rollers for stretching and rotating the electrophotographic belt, and the rollers are disposed in contact with the inner circumferential surface of the electrophotographic belt.

[0068] The unfixed toner images of each color formed on the photosensitive drum 1 are electrostatically primarily transferred in sequence onto the intermediate transfer belt 6 by applying a primary transfer bias of a polarity opposite to the charge polarity of the toner to the primary transfer roller 5 by a constant voltage source or a constant current source (not shown). A full-color image is then obtained on the intermediate transfer belt 6, in which the unfixed toner images of four colors are superimposed. The intermediate transfer belt 6 rotates while carrying the toner images thus transferred from the photosensitive drum 1. After each rotation of the photosensitive drum 1 after the primary transfer, the surface of the photosensitive drum 1 is cleaned of residual toner by a cleaning device 11, and the image forming process is repeated.

[0069] At the secondary transfer position of the intermediate transfer belt 6 facing the conveyance path of the recording material 7 as a transfer medium, a secondary transfer roller (transfer section) 9 is arranged in pressure contact with the toner image carrying surface of the intermediate transfer belt 6. At the rear side of the intermediate transfer belt 6 at the secondary transfer position, a counter roller 21 is arranged as a counter electrode of the secondary transfer roller 9 and to which a bias is applied. When the toner image on the intermediate transfer belt 6 is transferred to the recording material 7, a bias of the same polarity as the toner is applied to the counter roller 21 by a secondary transfer bias application means 28, for example, −1000 to −3000 V, and a current of −10 to −50 μA flows. The transfer voltage at this time is detected by a transfer voltage detection means 29. At the downstream side of the secondary transfer position, a cleaning device (blade cleaner) 12 is provided to remove the toner remaining on the intermediate transfer belt 6 after the secondary transfer.

[0070] The recording material 7 passes through a conveying guide 8 and is conveyed in the direction of arrow H, and is introduced to the secondary transfer position. The recording material 7 introduced to the secondary transfer position is clamped and conveyed at the secondary transfer position, at which time a constant voltage bias (transfer bias) controlled to a predetermined value is applied from a secondary transfer bias application means 28 to an opposing roller 21 of the secondary transfer roller 9. By applying a transfer bias of the same polarity as the toner to the opposing roller 21, the four full-color images (toner images) superimposed on the intermediate transfer belt 6 at the transfer site are transferred collectively to the recording material 7, and a full-color unfixed toner image is formed on the recording material. The recording material 7 to which the toner image has been transferred is introduced to a fixing device (not shown) and heated and fixed. EXAMPLES

[0071] EXAMPLES The present disclosure will be specifically described below with reference to examples and comparative examples, but the present disclosure is not limited thereto. The materials used in the manufacture of the electrophotographic members according to the examples and comparative examples are shown below. [Table 1] The physical properties of the materials in the table are as follows: ·TRN-8550FF: Weight average molecular weight 50000~80000 ·TN-8050SC: Weight average molecular weight 20000~80000 Vylon GK640: Has a structure corresponding to ethylene terephthalate and a structure corresponding to propylene terephthalate. Weight average molecular weight: 10,000 to 40,000 Vylon GK880: Has a structure corresponding to ethylene terephthalate and a structure corresponding to propylene terephthalate. Weight average molecular weight: 10,000 to 40,000 In addition, the particle size of the particles in the table indicates the volume average particle size. [Table 2]

[0072] (Methods for measuring and evaluating characteristic values) The methods for measuring and evaluating the characteristic values ​​of the electrophotographic belts according to the examples and comparative examples are as follows (1) to (5).

[0073] (Evaluation 1) Evaluation of shrinkage rate The shrinkage rate was measured as an index of the shrinkage stress of the cylindrical film of the electrophotographic belt by the following method. The shrinkage rate was measured using a thermomechanical analyzer (product name: TMA / SDTA841; manufactured by Mettler Toledo) under the following measurement conditions, and the change in the chuck distance was measured as the dimensional change of the sample. From the produced electrophotographic belt, a test piece A having a size of 5 mm in the circumferential direction × 20 mm in the direction perpendicular to the circumferential direction, and a test piece B having a size of 20 mm in the circumferential direction × 5 mm in the direction perpendicular to the circumferential direction were cut out and used. The thickness of each test piece was the total thickness of the electrophotographic belt. Note that, since the surface layer containing a (meth)acrylic resin does not substantially affect the value of the shrinkage rate, the test piece used in this evaluation was subjected to this evaluation with the surface layer still in the state.

[0074] Each test piece was held with a chuck distance of 10 mm and a load of 0.01 N, and was held at 25°C for 10 minutes. The temperature was then raised at 5°C / min to a temperature 10°C higher than the glass transition temperature of the test piece, held for 30 minutes, and then lowered again to 25°C at 5°C / min. The chuck distance before the temperature rise was taken as x1, and the chuck distance at the end of the temperature rise was taken as x2, and the shrinkage rate α (unit: %) was calculated using the following formula. α = (x1-x2) / x1×100 The arithmetic average value was calculated from the measurement results of five test pieces cut out from the same electrophotographic belt, and the average value of the measurement results obtained using test piece B was taken as the shrinkage rate αp in the circumferential direction of the electrophotographic belt, and the average value of the measurement results obtained using test piece A was taken as the shrinkage rate αa in the direction perpendicular to the circumferential direction of the electrophotographic belt. When expansion occurred, the value of the shrinkage rate was expressed as a negative value.

[0075] (Evaluation 2) Evaluation of tensile modulus The tensile modulus was measured in an environment of 23° C. and 50% relative humidity using a low-load universal material testing machine (product name: 34TM-5; manufactured by Instron Corporation) equipped with a 5 kN load cell. From the produced electrophotographic belt, a test piece 1 of 100 mm in the circumferential direction × 20 mm in the longitudinal direction and a test piece 2 of 20 mm in the circumferential direction × 100 mm in the longitudinal direction were cut out. The thickness of each test piece was the total thickness of the electrophotographic belt. The surface layer of the test piece was not removed because it did not affect the measurement value. Each test piece was then held in a pneumatic grip with a chuck distance of 50 mm. The held test piece was pulled at a constant speed of 5 mm / min, and the tensile modulus was calculated from the stress value at 0.25% strain using the obtained stress-strain curve and the thickness of the cylindrical film. The arithmetic average values ​​were calculated from the measurement results of five test pieces cut out from the same electrophotographic member, and the average value of the measurement results obtained using test piece 1 was defined as the tensile modulus of elasticity Ep in the circumferential direction of the cylindrical film, and the average value of the measurement results obtained using test piece 2 was defined as the tensile modulus of elasticity Ea in the direction perpendicular to the circumferential direction of the cylindrical film.

[0076] (Rating 3) Ten-point average roughness rating The ten-point average roughness (Rzjis) of the outer surface of the electrophotographic belt was evaluated by the following method. A surface roughness measuring instrument (product name: Surfcom 1500SD, manufactured by Tokyo Seimitsu Co., Ltd.) was used as the measuring device. Rzjis was measured in accordance with the Japanese Industrial Standards (JIS) B0601:1994 under the conditions of a cutoff wavelength of 0.25 mm, a measurement reference length of 0.25 mm, and a measurement length of 1.25 mm. Here, Rzjis was measured at a total of eight points, four points in the circumferential direction and two points in the direction perpendicular to the circumferential direction, for one electrophotographic member that was arbitrarily extracted by moving the stylus of the measuring instrument along the longitudinal direction of the electrophotographic belt relative to the outer surface. The arithmetic mean value of the ten-point average roughness Rzjis values ​​measured at the eight points was taken as the ten-point average roughness of the electrophotographic member. The measurement points were arbitrary positions in a central region 100 mm (200 mm wide) from the longitudinal center of the electrophotographic belt toward both ends in the longitudinal direction.

[0077] (Evaluation 4) Evaluation of surface resistivity The surface resistivity of the electrophotographic belt was measured in the following manner according to the method conforming to Japanese Industrial Standards (JIS) K6911:2006. The measurement device used was a high resistance meter (product name: Hiresta UP MCP-HT450, manufactured by Nitto Seiko Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.)). The probe used was a probe with a main electrode with an inner diameter of 50 mm, a guard ring electrode with an inner diameter of 53.2 mm, and an outer diameter of 57.2 mm (product name: UR-100, manufactured by Nitto Seiko Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.)). The surface resistivity is the surface area (1 cm 2 ) and is expressed in units of [Ω / □].

[0078] The electrophotographic belt thus produced was left for 24 hours in an environmental test room controlled at a temperature of 23°C and a relative humidity of 50%. Then, a voltage of 250V was applied to the inner surface of the electrophotographic belt for 10 seconds under an environment of a temperature of 23°C and a relative humidity of 50%, and the surface resistivity of the electrophotographic belt was measured at four points in the circumferential direction. The arithmetic average value of the obtained surface resistivities was taken as the surface resistivity A of the electrophotographic belt at normal temperature and normal humidity.

[0079] (Evaluation 5) Evaluation of peel resistance Using the electrophotographic image forming apparatus shown in FIG. 1, peel resistance was evaluated as follows. In an environment of a temperature of 25° C. and a relative humidity of 50%, the electrophotographic belt was stretched around a roller with the cleaning blade in contact with the outer surface of the electrophotographic belt. The electrophotographic belt was rotated at a driving speed of 150,000 revolutions, and the presence or absence of peeling of the electrophotographic belt was visually confirmed. If peeling was detected, the step height at the peeled portion was measured. A surface roughness measuring instrument (product name: Surfcom 1500SD, manufactured by Tokyo Seimitsu Co., Ltd.) was used to measure the step. The step D parameter was measured at a cutoff wavelength of 0.25 mm and an arbitrary measurement length longer than the peeled portion. From the measurement results, the locations where the step was larger than the thickness of the surface layer were counted as peeled portions. 1, a cleaning blade made of polyurethane elastomer with a durometer hardness of 77° measured by a method conforming to Japanese Industrial Standards (JIS) K6253-3 was used. The attachment position was set such that the set angle θ (the angle between the tangent to the tension roller 22 at the intersection between the electrophotographic member 6 and the cleaning blade 12 and the cleaning blade 12) was 24°, the penetration amount δ (the length in the thickness direction where the cleaning blade 12 overlaps with the tension roller 22) was 1.5 mm, and the contact pressure of the cleaning blade 11 was 0.6 N / cm. In addition, the electrophotographic member was moved to one end before the number of rotations reached 150,000, and the occurrence of driving failure due to buckling or the like was also evaluated.

[0080] (Evaluation 6) Measurement of the volume average particle size of roughness-forming particles The volume average particle diameter of the roughness-forming particles was measured by the following procedure. A sample with a length of 5 mm, a width of 5 mm, and a thickness equal to the entire thickness of the cylindrical film was taken from an arbitrary position of the electrophotographic belt. This sample was baked at a temperature of 400°C for 2 hours in a nitrogen atmosphere to incinerate the crystalline polyester and the amorphous polyester, thereby obtaining an ash product.

[0081] Next, 16 g of sucrose (Kishida Chemical) was added to 10 mL of ion-exchanged water and dissolved in a hot water bath to prepare a sucrose concentrate. 26 g of the sucrose concentrate and 1.0 g of the ash obtained above were added to a centrifuge tube (capacity 50 mL). Next, the centrifuge tube was shaken for 20 minutes at 300 strokes / minute (spm) using a universal shaker (product name: AS-1N; manufactured by AS ONE Co., Ltd.). After shaking, the solution in the centrifuge tube was transferred to a glass tube (50 mL) for a swing rotor and centrifuged at 3500 rpm for 30 minutes in a refrigerated high-speed centrifuge (product name: H-9R; manufactured by Kokusan Co., Ltd.). This allowed the roughness-forming particles to be separated from the ash. The separated roughness-forming particles were collected, filtered with a vacuum filter, and then dried in a dryer for 1 hour to obtain a sample for particle size measurement. This procedure was repeated multiple times to obtain the required amount.

[0082] The volume average particle diameter of the roughness-forming particles was measured using a particle size distribution analyzer (product name: FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.), which calculates the average particle diameter by dynamic light scattering. The measurement sample obtained by the above method was dispersed in isopropyl alcohol. The measurement conditions were a temperature of 23°C, a refractive index of 1.3749, and a viscosity of 1.77 mPa s, with the values ​​of isopropyl alcohol as the dispersion medium being referenced, and the analysis mode was the cumulant method, and the volume average particle diameter of the roughness-forming particles was measured.

[0083] (Evaluation 7) Confirmation of protrusions on the surface layer The surface layer was determined to have convexities caused by the roughness-forming particles on the outer surface opposite the side facing the cylindrical film when, in an SEM image, convexities caused by the roughness-forming particles are present on the outer surface of the cylindrical film and convexities are formed on the outer surface of the surface layer following the convexities, indicating that convexities caused by the roughness-forming particles are present on the outer surface of the surface layer.

[0084] (Evaluation 8) Confirmation of the state of amorphous polyester It was confirmed by the following procedure that the amorphous polyester extended at least in the first direction and the second direction with the roughness-imparting particle as the center. A test piece having a length of 5 mm along the circumferential direction of the electrophotographic belt, a length of 5 mm along the longitudinal direction perpendicular to the circumferential direction, and a thickness equal to the total thickness of the electrophotographic belt was cut out from an arbitrary position of the electrophotographic belt. A first cross section along the circumferential direction of the electrophotographic belt and a second cross section along the longitudinal direction of the obtained test piece were each polished using a cross-section polisher. The polished first and second cross sections of the test piece were stained with ruthenium tetroxide, which can stain the amorphous portion. Next, the first and second cross sections were observed by scanning electron microscopy (SEM), focusing on one roughness-forming particle, and an SEM image of a 10 μm×10 μm area including the roughness-forming particle and its surroundings was obtained. In this SEM image, the stained area was determined to be an area containing amorphous polyester. Then, for the SEM image obtained from the first cross section, two points on both ends of the circumferential direction with the roughness-forming particle as the center were identified in the stained area, and the angle (included angle) θ701 between the line segment connecting the two points and a straight line drawn parallel to the circumferential direction was measured.

[0085] Similarly, the SEM image obtained from the second cross section was examined to identify two points on both ends of the dyed region in the longitudinal direction with the roughness-forming particle at the center, and the angle (included angle) θ702 between the line segment connecting the two points and a line drawn parallel to the longitudinal direction was measured. The measurement results are shown in Table 2. When θ701 was 10° or less, it was determined that the amorphous polyester was extending in the first direction. When θ702 was 10° or less, it was determined that the amorphous polyester was extending in the second direction.

[0086] [Example 1] (Cylindrical film production) A preblend sample was prepared by mixing cPES1 and aPES1 ​​in Table 1 at the compounding ratio in Table 3. This preblend sample was melt-kneaded with Fi1, IC, and ES in Table 1 at the compounding ratio in Table 3 using a twin-screw extruder (product name: TEX30α, manufactured by Japan Steel Works, Ltd.) to prepare a resin mixture. The melt-kneading temperature was adjusted to be within the range of 270 to 320°C, and the hot melt-kneading time was 3 to 5 minutes. The resulting resin mixture was pelletized, and the resulting pellets were dried at a temperature of 140° C. for 10 hours. Next, the obtained pellets were put into an injection molding machine (product name: SE180D, manufactured by Sumitomo Heavy Industries, Ltd.). Then, with a cylinder set temperature of 270 to 320°C, the pellets were injection molded into a test tube-shaped mold whose temperature was adjusted to 30°C to form a preform. The obtained preform had a test tube shape with an outer diameter of 50 mm, an inner diameter of 46 mm, a length of 150 mm, and a thickness of 2 mm.

[0087] Next, the above preform was stretched in two axial and circumferential directions using a biaxial stretching molding device. First, as shown in FIG. 3A, preform 205 was placed in heating device 301 equipped with a non-contact heater (not shown) for heating preform 205, and heated by the heater so that the outer surface temperature of the preform became 120 to 160°C. Next, a blow mold 303, whose mold temperature was kept at 30° C., was lowered in the direction of arrow 307 onto the heated preform 205, and the heated preform 205 was placed at the mouth of the blow mold 303 (FIG. 3B). Next, as shown in Fig. 3C, the stretch bar 309 was driven in the direction of the arrow 311, and simultaneously with the start of driving the stretch bar, air adjusted to a temperature of 23°C was introduced into the interior of the preform 205 from its mouth portion as shown by the arrow 313 in Fig. 3C. In this way, the preform 205 was stretched in two axial directions and was brought into close contact with the inner wall of the blow mold. The driving speed of the stretch bar 309 was 2.0 m / sec, and the pressure of the air introduced into the blow bottle was 0.5 MPa. Next, the right side mold 303-1 and the left side mold 303-2 of the blow mold 303 were separated, and a bottle-shaped molded product (blow bottle) 317 was taken out from the blow mold 303.

[0088] Next, the obtained blow bottle 317 was set in a nickel cylindrical mold 401 produced by electroforming as shown in Fig. 4, and an outer mold 405 was attached. An air pressure of 0.1 MPa was applied to the inside of the blow bottle, and the outer peripheral surface of the blow bottle 317 was closely attached to the inner peripheral surface of the cylindrical mold by adjusting the pressure so that air would not leak to the outside. Furthermore, the entire circumference of the blow bottle was uniformly heat-treated at 130 to 190°C for 60 seconds using a heater 403 while rotating the nickel cylindrical mold 401 at a constant speed of 2 rotations / second.

[0089] Thereafter, air at a temperature of 25°C was blown onto this nickel cylindrical mold to cool it to room temperature (25°C), and the air pressure applied to the inside of blown bottle 317 was released to obtain blown bottle 317 whose dimensions had been improved by annealing. From the dimensions of preform 205 and blown bottle 317, the biaxial stretching ratios were: transverse stretching ratio (circumferential direction) Lp was 4.0 times, and longitudinal stretching ratio (direction perpendicular to the circumferential direction) La was 3.8 times. Next, as shown in FIG. 3D, the mouth side of the blown bottle 317 and the opposite side to the mouth side were cut to prepare a cylindrical film having a circumference of 628 mm, a width of 250 mm, and a thickness of 70 μm.

[0090] (Preparation of Coating Solution for Forming Surface Layer) The (meth)acrylic resin composition shown in Table 2 was weighed out in a ratio of AN / PTFE / GF / SL / IRG=66 / 20 / 1.0 / 12 / 1.0 (mass ratio in terms of solid content) to obtain a solution subjected to a rough dispersion treatment. The obtained solution was dispersed using a high-pressure emulsifying disperser (product name: Nanovater, manufactured by Yoshida Kikai Kogyo Co., Ltd.). This dispersion treatment was performed until the 50% average particle size of the contained PTFE became 200 nm. The obtained dispersion was used as a coating liquid for forming a surface layer (a mixture containing an active energy ray curable resin such as a photocurable resin).

[0091] (Example of surface layer formation) The cylindrical film thus produced was fitted to the outer circumference of a cylindrical mold (circumference 628 mm), the ends were sealed, and the mold was immersed in a container filled with the above-mentioned surface layer coating liquid, and the cylindrical film was raised so that the relative speed between the liquid level of the curable composition and the cylindrical film was constant. In this way, a coating film made of the coating liquid was formed on the cylindrical film surface.

[0092] In this embodiment, the lifting speed was adjusted to 10 to 50 mm / sec, and the film thickness of the surface layer was adjusted to 3 μm. The cylindrical film coated with the coating liquid was removed from the cylindrical mold and dried for 1 minute in an environment of 23°C under exhaust air. The drying temperature and drying time were appropriately adjusted according to the type of solvent, the solvent ratio, and the film thickness. After that, a UV irradiator (product name: UE06 / 81-3, manufactured by Eye Graphics Co., Ltd.) was used on the coating film, and the cumulative light amount was 600 mJ / cm 2 The coating was cured by irradiating it with ultraviolet light until the coating became cured. In this manner, the electrophotographic belt according to this example was produced.

[0093] The thickness of the surface layer was determined by a destructive test in which a cylindrical film separately produced under the same conditions was cut and the cross section was observed with an electron microscope (product name: XL30-SFEG, manufactured by FEI). Destructive testing revealed that the thickness of the surface layer was 2.8 μm. The obtained electrophotographic belt was subjected to the above-mentioned (Evaluation 1) to (Evaluation 8).

[0094] [Examples 2 and 3] The preform of Example 2 had a test tube shape with an outer diameter of 60 mm, an inner diameter of 56 mm, a length of 180 mm, and a thickness of 2.0 mm. The preform of Example 3 had a test tube shape with an outer diameter of 40 mm, an inner diameter of 36 mm, a length of 120 mm, and a thickness of 2.0 mm. The same as Example 1 was used except that the shape of the preform was changed and the materials were mixed in the amounts shown in Table 3. Similarly, an electrophotographic belt was produced and evaluated.

[0095] [Examples 4 to 7] An electrophotographic belt was produced in the same manner as in Example 1, except that the materials were mixed in the amounts shown in Table 3, and then evaluated. [Table 3]

[0096] [Comparative Examples 1 and 2] A pellet of a resin mixture was obtained in the same manner as in Example 1, except that a preblend sample mixed in the compounding ratio shown in Table 4 was used as a material. Then, a preform was produced in the same manner as in Example 1 using only the pellet of this resin mixture. Then, this preform was subjected to biaxial stretch molding in the same manner as in Example 1 to produce a cylindrical film. The electrophotographic member in Comparative Example 2 had a circumference of 628 mm, a width of 250 mm, and a thickness of 82 μm. The electrophotographic member in Comparative Example 3 had a circumference of 628 mm, a width of 250 mm, and a thickness of 63 μm. The obtained electrophotographic members were subjected to (Evaluation 1) to (Evaluation 8).

[0097] [Comparative Example 3] Using the preblend samples mixed in the compounding ratios shown in Table 4 as materials, a twin-screw kneading extruder (product name: PCM43, manufactured by Ikegai Corporation) was used to melt and mix under the following conditions to prepare a resin mixture. Output: 6kg / h Screw speed: 225 rpm Barrel control temperature: 270℃

[0098] The obtained resin mixture was melt-extruded under the following conditions using a single-screw extruder (manufactured by Plastics Engineering Research Institute Co., Ltd.) equipped with a spiral cylindrical die (inner diameter: 195 mm, slit width: 1.1 mm) at the tip to produce a cylindrical film of the following size. The cylindrical film thus obtained was used as the electrophotographic member according to Comparative Example 3. Output: 6kg / h Die temperature: 270℃ Size: Outer diameter 200mm, thickness 70μm The obtained electrophotographic members were subjected to (Evaluation 1) to (Evaluation 8). [Table 4]

[0099] The evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Tables 5 and 6. [Table 5] In the table, for example, 6.1E+10 is 6.1 x 10 10 Represents. [Table 6]

[0100] No amorphous polyester was included in Comparative Example 1. In other words, there were voids around the roughness-imparting particles included in the cylindrical film, and it is believed that peeling occurred starting from the voids as the electrophotographic member was repeatedly subjected to friction. In Comparative Example 2, no roughness-imparting particles are included. That is, no large irregularities are formed on the surface of the electrophotographic member, and the ten-point average roughness Rzjis value is small. Therefore, the contact area with the cleaning blade is large and the friction is large, which is considered to have caused a drive failure due to an abnormal motor torque during the test. In Comparative Example 3, the same raw material as in Example 1 is used, but it is not stretched. Therefore, the elastic modulus of the electrophotographic member in the circumferential direction and the direction perpendicular to the circumferential direction is extremely low, and the shrinkage rate in the circumferential direction and the direction perpendicular to the circumferential direction is also extremely low. Therefore, wrinkles were generated when stretched by a tension roller. When the test was started, the electrophotographic member was observed to be wavy, and the electrophotographic member was buckled toward one end of the tension roller.

[0101] The present disclosure relates to the following configurations. (Configuration 1) 1. An electrophotographic member having an endless shape, comprising: A cylindrical film and a surface layer on an outer circumferential surface of the cylindrical film, The cylindrical film is A shrinkage rate αp in a first direction, which is the circumferential direction, and a shrinkage rate αa in a second direction perpendicular to the circumferential direction are both 2.0% or more, The present invention relates to a coating composition comprising a crystalline polyester as a binder and further comprising roughness-forming particles dispersed in the binder; the surface layer has convex portions caused by the roughness-forming particles on an outer surface opposite to the side facing the cylindrical film, The cylindrical film further comprises an amorphous polyester, the amorphous polyester extending in at least the first direction and the second direction with the roughness-forming particle as a center. (Configuration 2) 2. The electrophotographic member according to claim 1, wherein the cylindrical film further comprises an ionic conductive agent, the ionic conductive agent being contained in the amorphous polyester. (Configuration 3) 3. The electrophotographic member according to configuration 1 or 2, wherein the crystalline polyester comprises at least one selected from the group consisting of polyalkylene terephthalate, polyalkylene naphthalate, polyalkylene isophthalate, and copolymers containing these. (Configuration 4) The amorphous polyester is A structure corresponding to at least one phthalic acid selected from the group consisting of terephthalic acid, orthophthalic acid, and isophthalic acid; and a structure corresponding to at least one diol selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, and cyclohexanedimethanol. (Configuration 5) 5. The electrophotographic member according to any one of configurations 1 to 4, wherein the content of the amorphous polyester relative to the crystalline polyester is 30.0% by mass or less. (Configuration 6) 6. The electrophotographic member according to any one of configurations 1 to 5, wherein the roughness-imparting particles include at least one of silicone resin particles and silica particles. (Configuration 7) 7. The electrophotographic member according to any one of Configurations 1 to 6, wherein the roughness-imparting particles have a volume average particle size of 0.4 μm or more. (Configuration 8) 8. The electrophotographic member according to any one of Configurations 1 to 7, wherein the ten-point height deviation of the electrophotographic member is 0.110 or more. (Configuration 9) 9. The electrophotographic member according to any one of configurations 1 to 8, wherein the cylindrical film is a biaxially stretched cylindrical film. (Configuration 10) 10. The electrophotographic member according to any one of configurations 1 to 9, wherein the electrophotographic member is an electrophotographic belt having an endless shape. (Configuration 11) 11. An electrophotographic image forming apparatus comprising the electrophotographic member according to any one of Configurations 1 to 10 as an intermediate transfer belt. [Explanation of symbols]

[0102] 1 photosensitive drum, 2 charging device, 3 exposure device, 4 developing device, 5 primary transfer roller, 6 Intermediate transfer belt, 7 recording material, 9 secondary transfer roller, 11 cleaning device (drum cleaner), 12 cleaning device (cleaning blade), 20 tension roller, 21 opposing roller, 22 driving roller, 28 transfer bias applying means, 29 transfer height Pressure detection means, 201 injection molding device, 203 cavity mold, 205 preform, 207 core mold, 301 heating device, 303 mold, 309 stretch rod, 317 blow bottle, 319 biaxially stretched cylindrical film, 401 cylindrical mold, 403 heater, 405 outer mold, 407 rotating table, 500 electrophotographic belt, 501 base layer, 502 surface layer, 601 Roughness forming particles, 602 amorphous polyester, 603 first direction

Claims

1. 1. An electrophotographic member having an endless shape, comprising: A cylindrical film and a surface layer on an outer circumferential surface of the cylindrical film, The cylindrical film is A shrinkage rate αp in a first direction, which is the circumferential direction, and a shrinkage rate αa in a second direction perpendicular to the circumferential direction are both 2.0% or more, The present invention relates to a coating composition comprising a crystalline polyester as a binder and further comprising roughness-forming particles dispersed in the binder; the surface layer has convex portions caused by the roughness-forming particles on an outer surface opposite to the side facing the cylindrical film, The cylindrical film further comprises an amorphous polyester, the amorphous polyester extending in at least the first direction and the second direction with the roughness-providing particle as a center.

2. 2. The electrophotographic member of claim 1, wherein said cylindrical film further comprises an ionic conductive agent, said ionic conductive agent being contained in said amorphous polyester.

3. 2. The electrophotographic member of claim 1, wherein the crystalline polyester comprises at least one selected from the group consisting of polyalkylene terephthalates, polyalkylene naphthalates, and polyalkylene isophthalates, and copolymers containing these.

4. The amorphous polyester is A structure corresponding to at least one phthalic acid selected from the group consisting of terephthalic acid, orthophthalic acid, and isophthalic acid; and a structure corresponding to at least one diol selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, and cyclohexanedimethanol.

5. 2. The electrophotographic member according to claim 1, wherein the content ratio of said amorphous polyester to said crystalline polyester is 30.0% by weight or less.

6. 2. The electrophotographic member of claim 1 wherein said roughness-forming particles comprise at least one of silicone resin particles and silica particles.

7. 2. The electrophotographic member of claim 1, wherein said roughness-imparting particles have a volume average particle size of 0.4 [mu]m or greater.

8. 2. The electrophotographic member according to claim 1, wherein the ten-point average roughness of said electrophotographic member is 0.110 or more.

9. 2. An electrophotographic member according to claim 1 wherein said cylindrical film is a biaxially oriented cylindrical film.

10. 2. The electrophotographic member of claim 1 wherein said electrophotographic member is an electrophotographic belt having an endless configuration.

11. 11. An electrophotographic image forming apparatus comprising the electrophotographic member according to claim 1 as an intermediate transfer belt.

Images