Electrophotographic member, process cartridge, and electrophotographic image forming apparatus

Abstract

To provide an electrophotographic member that is quickly restored from deformation despite inclusion of urethane elastomer with low hardness, has good wear resistance, and can prevent a streak-like image defect.SOLUTION: An electrophotographic member is provided, and the electrophotographic member has an elastic layer having conductivity. The elastic layer includes urethane elastomer and conductive filler. The urethane elastomer has a matrix and a plurality of domains dispersed in the matrix. A parameter A indicating the viscoelasticity term of the domain and a parameter B indicating the viscoelasticity term of the matrix, which are measured in a predetermined viscoelasticity image of a cross section of the elastic layer from which the domains and the matrix are exposed, have a relationship of A<B. The elastic layer has a micro rubber hardness of 20 to 50 degrees at a temperature of 23°C. Distortion of the elastic member five seconds after removal of load measured at a temperature of 23°C by a predetermined method is 1.00 μm or less.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present disclosure is directed to an electrophotographic member used in an electrophotographic image forming apparatus (hereinafter also simply referred to as an "image forming apparatus") such as an electrophotographic copying machine, a printer, etc. The present disclosure is also directed to a process cartridge and an electrophotographic image forming apparatus. [Background technology]

[0002] An image forming apparatus that employs electrophotography (such as a copier, facsimile, or printer that uses electrophotography) mainly consists of an electrophotographic photoconductor (hereinafter also referred to as a "photoconductor"), a charging device, an exposure device, a developing device, a transfer device, and a fixing device. In an image forming apparatus, a photoconductor is first charged by a charging member (hereinafter also referred to as a "charging roller") and then exposed to light, forming an electrostatic latent image on the photoconductor. The toner in a toner container is applied onto a toner carrier (hereinafter also referred to as a "developing roller") by a toner regulating member, and is transported to a developing area by the developing roller. The toner transported to the developing area develops the electrostatic latent image on the photoconductor at the contact point between the photoconductor and the developing roller. The toner on the photoconductor is then transferred to a recording paper by a transfer means, and fixed by heat and pressure. Any toner remaining on the photoconductor is removed by a cleaning member.

[0003] Conventionally, the elastic layer of such a developing roller or charging roller is required to have high recovery from deformation, i.e., small compression set and small micro rubber hardness, and therefore, vulcanized rubbers with high electrical resistance, such as silicone rubber, acrylonitrile butadiene rubber, and epichlorohydrin rubber, have been used as the material for the elastic layer. On the other hand, the elastic layer is also required to be conductive. Since the vulcanized rubber has high electrical resistance, a conductive filler such as carbon black may be contained in the elastic layer to make it conductive. However, the conductive filler may increase the micro rubber hardness of the elastic layer and increase the compression set. An increase in the micro rubber hardness of the elastic layer, for example, increases the stress that the developing roller exerts on the toner. An increase in the compression set of the elastic layer may cause a phenomenon in which, for example, when a stationary developing roller abuts against a toner regulating member for a long time, the deformation of the contact portion of the developing roller with the toner regulating member does not easily recover. The partial deformation of the developing roller causes uneven development. An increase in the compression set of the elastic layer may cause a phenomenon in which, for example, when a stationary charging roller abuts against a photosensitive drum for a long time, the deformation of the contact portion of the charging roller with the photosensitive drum does not easily recover. The partial deformation of the charging roller causes uneven charging of the photosensitive drum.

[0004] Patent Document 1 discloses a conductive member for electrophotographic devices, which includes an elastic layer, and is composed of a conductive first polymer phase containing one or more polymers, a non-conductive second polymer phase containing one or more polymers and existing separately from the first polymer phase, and an interfacial phase existing between the first polymer phase and the second polymer phase, containing a compatibilizer made of a polymer containing either one or both of the polymer components contained in the first polymer phase and the polymer components contained in the second polymer phase. Patent Document 1 describes that the conductive member for electrophotographic devices exhibits low hardness and low sag that cannot be obtained by the conductive phase alone due to the presence of the non-conductive phase in the conductive elastic layer, and that the uniform fine dispersion of both phases enables charge control at the toner size level, suppresses resistance unevenness, and exhibits excellent chargeability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-116685 A [Non-patent literature]

[0006] [Non-Patent Document 1] IEEE Transactions on SYSTEMS, MAN, AND CYBERNETICS, Vol. SMC-9, No. 1, January 1979, pp. 62-66 Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors have studied the conductive member for electrophotographic equipment according to Patent Document 1. As a result, they have found that the conductive member for electrophotographic equipment according to Patent Document 1 still has room for improvement in terms of recovery from deformation.

[0008] At least one aspect of the present disclosure is directed to providing an electrophotographic member having high electrical conductivity, low hardness, and excellent recovery from deformation. At least one aspect of the present disclosure is directed to providing a process cartridge that contributes to the stable formation of high-quality electrophotographic images. Furthermore, at least one aspect of the present disclosure is directed to providing an electrophotographic image forming apparatus that can stably form high-quality electrophotographic images. [Means for solving the problem]

[0009] According to at least one aspect of the present disclosure, An electrophotographic member, the electrophotographic member having an elastic layer having electrical conductivity, the elastic layer includes a urethane elastomer and a conductive filler; The urethane elastomer has a matrix and a plurality of domains dispersed in the matrix, A relationship between a parameter A indicating the viscoelastic term of the domain and a parameter B indicating the viscoelastic term of the matrix, which is measured in a viscoelastic image of a cross section of the elastic layer where the domain and the matrix are exposed, by a scanning probe microscope, is A <Bであり、 The micro rubber hardness of the elastic layer at a temperature of 23°C is 20 to 50 degrees, An electrophotographic member is provided in which, at a temperature of 23°C, a Vickers indenter is brought into contact with the matrix on the outer surface of the elastic layer, the Vickers indenter is pressed into the elastic layer at a load rate of 10 mN / 30 seconds, the load of 10 mN is maintained for 60 seconds, and then the load is released, and the distortion 5 seconds after the load is released is 1.00 μm or less.

[0010] According to at least one aspect of the present disclosure, there is provided a process cartridge configured to be detachably mountable to an image forming apparatus, the process cartridge including the electrophotographic member of the present disclosure.

[0011] Further, in accordance with at least one aspect of the present disclosure, there is provided an electrophotographic imaging apparatus comprising an electrophotographic member of the present disclosure. Effect of the Invention

[0012] According to at least one aspect of the present disclosure, an electrophotographic member having high conductivity, low hardness, and excellent recovery from deformation can be obtained. According to at least one aspect of the present disclosure, a process cartridge contributing to the formation of high-quality electrophotographic images can be obtained. Furthermore, according to at least one aspect of the present disclosure, an electrophotographic image forming apparatus capable of forming high-quality electrophotographic images can be obtained. [Brief description of the drawings]

[0013] [Figure 1] 1 is a schematic cross-sectional view illustrating an example of an electrophotographic member according to one embodiment of the present disclosure. [Diagram 2] 2 is a schematic cross-sectional view of one embodiment of an elastic layer of an electrophotographic member according to one aspect of the present disclosure. [Diagram 3] 5A to 5C are diagrams illustrating deformation of an elastic layer according to the present disclosure. [Figure 4] FIG. 4 is a diagram for explaining the position and direction of cutting out a cross section. [Diagram 5] 1A to 1C are schematic diagrams illustrating a method for manufacturing an electrophotographic member according to one embodiment of the present disclosure. [Figure 6] 1 is a schematic cross-sectional view of an example of an image forming apparatus according to an embodiment of the present disclosure. [Figure 7] FIG. 2 is a schematic cross-sectional view of an example of a process cartridge according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In the present disclosure, the expressions "XX to YY" and "XX to YY" expressing a numerical range mean a numerical range including the lower and upper limits, unless otherwise specified. In addition, when a numerical range is described in stages, any combination of the upper and lower limits of each numerical range is disclosed.

[0015] The present inventors have speculated as follows why the conductive member for electrophotographic devices according to Patent Document 1 has insufficient deformation recovery. That is, the characteristics of low hardness and low settling of the conductive member for electrophotographic devices according to Patent Document 1 are achieved by separating the components of the conductive elastic layer into a conductive phase and a flexible phase (paragraph

[0030] of Patent Document 1, etc.). Here, the conductive phase and the flexible phase are formed by phase separation of two types of polymers that are incompatible with each other. Therefore, there is no chemical bond between the conductive phase and the flexible phase. Therefore, it is considered that the recovery behavior from deformation of the conductive elastic layer when a load is applied to the conductive elastic layer and then the load is removed occurs independently in the conductive phase and the flexible phase. It has been speculated that this is one of the causes of insufficient recovery from deformation of the conductive elastic layer. Based on such consideration, the present inventors have further studied and found that a urethane elastomer having a specific structure can achieve both flexibility and recovery from deformation at an extremely high level even when a conductive filler is contained therein. Hereinafter, preferred embodiments of the electrophotographic member and the like according to the present disclosure will be described in detail.

[0016] <Electrophotographic materials> 1(a) and 1(b) are schematic circumferential cross-sectional views of two embodiments of electrophotographic members having a roller shape according to the present disclosure (hereinafter also referred to as "electrophotographic rollers"). An electrophotographic roller 1A shown in Fig. 1(a) has a conductive mandrel 2 and a conductive elastic layer (hereinafter also simply referred to as "elastic layer") 3 that covers the surface (outer circumferential surface) of the mandrel 2. An electrophotographic roller 1B shown in Fig. 1(b) further has a surface layer 4 on the surface (hereinafter also referred to as "outer surface") of the elastic layer 3 on the side opposite to the side facing the mandrel 2. Note that the electrophotographic roller according to the present disclosure is not limited to these configurations, and may have, for example, an adhesive layer (not shown) between each layer.

[0017] (Core body) The mandrel 2 is preferably conductive in order to supply power to the surface of the electrophotographic member through the mandrel. The mandrel preferably has an electrical resistance value lower than that of the elastic layer, and the mandrel has a volume resistivity of 10 3 It is preferable that the resistivity is Ω·cm or less. The conductive mandrel can be appropriately selected from those known in the field of electrophotographic members, and is preferably made of metal such as aluminum, aluminum alloy, stainless steel, iron, etc. In order to improve corrosion resistance and abrasion resistance, these metals may be plated with chromium, nickel, etc. The shape of the mandrel may be any shape selected from hollow (cylindrical) and solid (columnar). For example, a columnar mandrel may be used in which the surface of a carbon steel alloy is plated with nickel to a thickness of about 5 μm. The outer diameter of the cylindrical or columnar mandrel may be appropriately selected depending on the image forming device to be mounted.

[0018] (Elastic layer) The elastic layer 3 satisfies the following requirements (1-1) to (1-4). Requirement (1-1): The elastic layer includes a urethane elastomer and a conductive filler, and the urethane elastomer has a matrix and a plurality of domains dispersed in the matrix. Requirement (1-2): The relationship between parameter A, which indicates the viscoelasticity term of the domain, and parameter B, which indicates the viscoelasticity term of the matrix, measured in a viscoelastic image by a scanning probe microscope of a cross section of the elastic layer in which the domain and the matrix are exposed, is A. <Bである。 That is, a matrix domain structure of the urethane elastomer is observed in the cross section of the elastic layer in the thickness direction, and the elastic modulus of the matrix of the urethane elastomer observed in the cross section of the elastic layer in the thickness direction is greater than the elastic modulus of the domain.

[0019] Requirement (1-3): The micro rubber hardness of the elastic layer at a temperature of 23° C. is 20 to 50. Requirement (1-4): At a temperature of 23°C, a Vickers indenter is abutted against the matrix on the outer surface of the elastic layer, the Vickers indenter is pressed into the elastic layer at a loading rate of 10 mN / 30 seconds, the load of 10 mN is maintained for 60 seconds, and then the load is removed. The distortion 5 seconds after removal of the load is 1.00 μm or less. In the urethane elastomer, the matrix mainly plays a role in allowing the urethane elastomer to exhibit high recovery from deformation, and the domain mainly plays a role in allowing the urethane elastomer to have low hardness. Furthermore, as described later, in the urethane elastomer according to the present disclosure, it is considered that the domain and the matrix are chemically bonded by urethane bonds at the boundary between the domain and the matrix. Therefore, it is considered that the recovery of the domain from deformation when the load applied to the urethane elastomer is removed proceeds in conjunction with the recovery of the matrix from deformation. It is considered that this makes the elastic layer according to the present disclosure extremely recoverable from deformation. By adopting such an elastic layer, the elastic layer exhibits the softness specified in the above requirement (1-3) and the extremely high recovery from deformation specified in the above requirement (1-4). In addition, general urethane elastomers also have a difference in elastic modulus between the so-called hard segment and soft segment. However, in general urethane elastomers, the soft segment constitutes the matrix and the hard segment constitutes the domain, and while it has the flexibility related to the above requirement (1-3), it is thought that it does not show the fast recovery speed from deformation related to the provision of requirement (1-4).

[0020] Fig. 2(a) is a partial cross-sectional view in the circumferential direction of an electrophotographic roller 1A according to one embodiment of the present disclosure, and Fig. 2(b) is a partial cross-sectional view in the longitudinal direction of a mandrel 2 of the electrophotographic roller 1A. 2(a) and 2(b) show schematic diagrams of a matrix 31 of a urethane elastomer, a plurality of domains 32 dispersed in the matrix 31, and a conductive filler 33 contained in the elastic layer, as observed in a cross section through the thickness direction of the elastic layer 3. As described above, the urethane elastomer has a matrix 31 and a plurality of domains 32 dispersed in the matrix. The matrix exhibits higher elasticity than the domains. In addition, it is preferable that at least a part of the outer surface of the elastic layer is made of a matrix. In the electrophotographic roller shown in Figures 2(a) and 2(b), an example is shown in which the entire outer surface of the elastic layer 3 is made of a matrix.

[0021] 3(a) and 3(b) are diagrams illustrating the recovery from deformation of the elastic layer 3 according to the present disclosure. As shown in FIG. Since the domains 32 have lower elasticity than the matrix 31, when the elastic layer 3 is compressed in the direction of the arrow F as shown in FIG. 3(b), the domains 32 deform preferentially. Therefore, even if the matrix 31 has high elasticity, the micro rubber hardness of the elastic layer can be reduced. Furthermore, when the elastic layer is released from compression, the elasticity of the matrix 31, which is the continuous phase, allows the thickness of the elastic layer to quickly return to the thickness before compression. In other words, the matrix 31 exhibits high recovery from deformation.

[0022] (Micro rubber hardness of elastic layer) The micro rubber hardness of the elastic layer at a temperature of 23°C is 20 to 50 degrees. By setting the micro rubber hardness to 50 degrees or less, the nip width between the developing roller and the toner regulating member and the nip width between the charging roller and the photoconductor are increased, and the contact pressure is not excessively increased. This makes it difficult for the toner on the developing roller to fuse to the developing roller, and for the toner that has slipped through the cleaning member and adhered to the charging roller to fuse to the charging roller. In addition, by setting the micro rubber hardness to 20 degrees or more, the mechanical strength is increased, and the end of the elastic layer is less likely to be scraped off even when used in an image forming apparatus with a long life. The micro rubber hardness is preferably 20 to 40 degrees, and more preferably 22 to 38 degrees. The micro rubber hardness can be adjusted by, for example, the elastic modulus of the matrix, the amount of conductive filler contained in the matrix, the ratio of the matrix to the domain, etc. Specifically, for example, increasing the elastic modulus of the matrix, increasing the ratio of the conductive filler contained in the matrix, and decreasing the ratio (volume) of the domain to the matrix act in the direction of increasing the micro rubber hardness. The micro rubber hardness can be obtained, for example, as follows. The locations for measuring the micro rubber hardness are the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, for a total of three locations, where the length of the elastic layer in the longitudinal direction is L. At each measurement location, the surface is measured for micro rubber hardness at a temperature of 23°C using a micro rubber hardness meter (product name: MD-1capa; manufactured by Kobunshi Keiki Co., Ltd., indenter: Type A (indenter shape: cylindrical, diameter 0.16 mm, height 0.5 mm, pressure leg dimensions: outer diameter 4 mm, inner diameter 1.5 mm), measurement mode: peak hold mode).

[0023] (Parameter indicating viscoelasticity) The matrix 31 and the domain 32 have a relationship between a parameter A indicating the viscoelastic term of the domain and a parameter B indicating the viscoelastic term of the matrix, which is measured in a viscoelastic image by a scanning probe microscope. <Bである。 The parameters A and B can be obtained by preparing a slice from the elastic layer and measuring the slice with a scanning probe microscope (SPM / AFM). As the scanning probe microscope, for example, "S-Image" (product name) manufactured by Hitachi High-Tech Science Corporation can be used. Furthermore, examples of means for sectioning include a sharp razor, a microtome, and a focused ion beam method (FIB), but in this disclosure a microtome is used. The slices are prepared at three locations in total, namely, the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where L is the longitudinal length of the elastic layer. Then, as shown in Fig. 4, a total of three slices are prepared from cross sections 41 to 43 in the thickness direction of the elastic layer. As a result, the obtained slices have a cross section in which the domain and matrix are exposed. In addition, the region that deforms when the electrophotographic member comes into contact with another member is mainly a thickness region from the outer surface of the elastic layer to a depth of 100 μm. Therefore, the observation region is a thickness region from the surface of the elastic layer to a depth of 100 μm. Specifically, for the observation region of cross sections 41 to 43, a square observation region with one side of 50 μm is selected within the thickness region from the outer surface of each slice to a depth of 100 μm, and viscoelastic images are observed in a total of three observation regions.

[0024] The measurement mode for viscoelastic images using SPM was the micro viscoelastic dynamic force mode ( The VE-DFM is used in Viscoelastic Dynamic Force Mode (VE-DFM). The cantilever used is a silicon microcantilever for DFM (SI-DF3 (product name), Hitachi High-Tech Science, spring constant = 1.9 N / m). The scanning frequency is 0.5 Hz. VE-DFM is one of the measurement modes of SPM (scanning probe microscope). In VE-DFM, a surface topography image can be obtained by controlling the distance between the probe and the measurement sample so that the vibration and amplitude of the cantilever is constant while the cantilever is resonating. In addition, VF-DFM can image the viscoelasticity distribution from the deflection amplitude of the cantilever when a periodic force is applied by micro-vibrating the sample in the Z direction. If the sample is hard, the cantilever amplitude will be large because the sample deformation is small, and if the sample is soft, the sample deformation vibration is induced and the cantilever amplitude will be small. The obtained amplitude is converted into mV as a displacement, which becomes a parameter indicating the viscoelasticity term. Therefore, parameters A and B are indicators showing the relationship between the hardness of the domain and the hardness of the matrix present in one observation sample. In VF-DFM, the magnitude of the cantilever amplitude is output in voltage, so the units of parameters A and B are mV. Also, the larger the value, the higher the elasticity.

[0025] After acquiring the viscoelastic image, the parameters indicating the viscoelastic term in each observation region are obtained for 10 points each for the matrix and domain, and their arithmetic mean values ​​are taken as parameter A indicating the viscoelastic term of the domain and parameter B indicating the viscoelastic term of the matrix. The measurement procedure will be described later.

[0026] The ratio (A / B) of parameter A (mV) to parameter B (mV) is preferably 0.65 or less, more preferably 0.60 or less, and more preferably 0.50 or less. The smaller A / B is, the greater the difference in viscoelasticity between the matrix and the domain, making it easier to achieve both hardness and recovery from deformation. The lower limit of A / B is not particularly limited, but the smaller the ratio, the more preferable. Specifically, it is, for example, 0.10. The preferred range of A / B is, for example, 0.10 or more and 0.65 or less, 0.10 or more and 0.60 or less, 0.10 or more and 0.50 or less, particularly 0.10 or more and 0.40 or less, and further 0.10 or more and 0.30 or less. The parameters A and B can be adjusted, for example, by the modulus of elasticity of the domain and the matrix. The modulus of elasticity of the matrix can be increased, for example, by using a trimer compound or a polymer compound of polyisocyanate as a raw material for forming the matrix to increase the crosslink density of the matrix. The modulus of elasticity of the domain can be reduced by increasing the molecular weight of the polyether polyol as a raw material for forming the domain, for example, to decrease the crosslink density of the domain and decrease the modulus of elasticity.

[0027] (Recovery from deformation) When a Vickers indenter is abutted against the matrix on the outer surface of the elastic layer at a temperature of 23°C, the Vickers indenter is pressed into the elastic layer at a loading rate of 10 mN / 30 seconds, the load of 10 mN is maintained for 60 seconds, and then the load is removed, the distortion 5 seconds after removal of the load is 1.00 μm or less. By setting the strain 5 seconds after unloading to 1.00 μm or less when measured under the above conditions, it is possible to suppress streaky image defects when applied as a developing roller for a high-speed printer. This is because the deformation of the developing roller can be restored to the size of one normal toner particle or less during the short time between the operation of the high-speed printer and the development of the electrostatic latent image. In addition, even when applied to a charging roller, since the recovery from deformation is fast, uneven discharge to the photoconductor is unlikely to occur, and the occurrence of streaky image defects due to uneven charging of the photoconductor can be prevented. As described above, in the elastic layer according to the present disclosure, it is considered that the domain and the matrix are chemically bonded by urethane bonds at the boundary between the domain and the matrix. Therefore, it is considered that the recovery from deformation of the domain when the load applied to the urethane elastomer is removed is linked to the recovery from deformation of the matrix. As a result, the elastic layer according to the present disclosure It is believed that the elastic layer has extremely high recovery from deformation, and the strain 5 seconds after unloading can be kept within the above range. The strain 5 seconds after unloading can be adjusted, for example, by the elastic modulus of the matrix, assuming that the matrix and the domain are chemically bonded. Specifically, for example, the elastic modulus of the matrix can be increased by increasing the crosslink density of the urethane elastomer matrix using a polyisocyanate trimer compound or polymer compound as at least one of the raw materials of the urethane elastomer. The strain 5 seconds after unloading is preferably 0.90 μm or less, more preferably 0.80 μm or less. The lower limit of the strain 5 seconds after unloading is not particularly limited, but is usually 0.00 μm, may be 0.05 μm, or may be 0.10 μm. For example, the preferable range is 0.00 to 1.00 μm, 0.00 to 0.90 μm, or 0.00 to 0.80 μm. The value of the strain 5 seconds after unloading is the value obtained by an indentation test using a microhardness tester (nanoindenter). The measurement temperature is 23°C. The indenter used for the measurement is a Vickers indenter in the shape of a square pyramid with an opposing angle of 136°. The measurement method is to bring the Vickers indenter into contact with the matrix portion of the surface of the elastic layer, press the Vickers indenter into the elastic layer at a speed of 10 mN / 30 seconds, and maintain the load of 10 mN for 60 seconds. Next, the load is removed (unloaded) at an unloading speed of 10 mN / 1 second, and the strain of the elastic layer 5 seconds after unloading is measured. Furthermore, the measurement positions are three in total, namely, the center of the elastic layer in the longitudinal direction, and two positions at L / 4 from both ends of the elastic layer toward the center, where L is the longitudinal length of the elastic layer.

[0028] (Matrix elastic modulus) The elastic modulus of the matrix 31 present in the observation area at a temperature of 23°C is preferably 1 to 13 MPa. By setting the elastic modulus of the matrix to 1 MPa or more, the spring effect of the matrix is ​​increased, and the deformation recovery can be made faster. In addition, by setting the elastic modulus of the matrix to 13 MPa or less, the hardness of the matrix is ​​reduced, and the micro-rubber hardness of the elastic layer can be kept lower. Furthermore, by setting the elastic modulus of the matrix 31 to 2 MPa or more, the effect of the matrix as a spring is further increased, and the deformation recovery can be made faster, which is more preferable. In addition, by setting the elastic modulus of the matrix to 8 MPa or less, the hardness of the matrix is ​​further reduced, and the micro-rubber hardness of the elastic layer can be kept low, which is more preferable. As a result, it becomes easier to prevent image defects and edge scraping caused by toner fusion. That is, the elastic modulus of the matrix is ​​more preferably 2 to 8 MPa, and even more preferably 5 to 8 MPa. The elastic modulus of the matrix can be adjusted by, for example, increasing the crosslink density using a trimer compound or polymer compound of polyisocyanate. Normally, increasing the elastic modulus also increases the micro rubber hardness of the elastic layer, but in the present disclosure, multiple low-elasticity domains are dispersed in the matrix, so excessive hardness can be suppressed.

[0029] The elastic modulus of the matrix can be calculated by preparing a slice of the elastic layer and measuring the slice with a scanning probe microscope (SPM / AFM). As the scanning probe microscope, for example, "MFP-3D-Origin" (product name) manufactured by Oxford Instruments Co., Ltd. can be used. Examples of the means for sectioning include a sharp razor, a microtome, and a focused ion beam (FIB) method. The slices are prepared at three locations in total, namely, the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where L is the longitudinal length of the elastic layer. Then, as shown in Fig. 4, a total of three slices are prepared from cross sections 41 to 43 in the thickness direction of the elastic layer. As a result, the obtained slices have a cross section in which the domain and matrix are exposed. For the same reason as in the measurement of the parameters indicating the viscoelastic term, the observation areas of the cross sections 41 to 43 were selected from arbitrary areas within the area corresponding to the thickness area from the outer surface of each section to a depth of 100 μm. Observation areas of 50 μm square are selected, and phase images are observed in a total of three observation areas. The measurement mode of the phase image by the SPM is AM-AFM. The cantilever is a silicon cantilever for dynamic mode, for example, "OMCL-AC-160TS" (product name, manufactured by Olympus Corporation, spring constant = 47.08 N / m). The scanning frequency is 0.5 Hz. After acquiring the phase image, a force curve is measured using SPM to measure the elastic modulus of the matrix. The force curve measurement mode is contact mode, and Force The distance is 500 nm, and the trigger point is 0.01 V. As in the above, the cantilever is a silicon cantilever for dynamic mode, for example, "OMCL-AC-160TS" (product name, manufactured by Olympus Corporation, spring constant = 47.08 N / m). The scanning frequency is 1 Hz. The elastic modulus of the matrix was calculated at 10 points in each of the three observation areas, for a total of 30 points, and the arithmetic mean value of each was taken as the elastic modulus of the matrix.

[0030] (Conductive filler contained in the matrix) The elastic layer contains a conductive filler. The conductive filler is preferably unevenly distributed in the matrix. That is, the matrix preferably contains the conductive filler. Electrophotographic members require that the elastic layer have low electrical resistance. If the electrical resistance is not sufficiently low, image defects such as low density will occur in solid images. In the elastic layer, the matrix contains a conductive filler, which makes it easier to realize an elastic layer with low electrical resistance. Furthermore, the conductive filler is unevenly distributed in the matrix, which makes it easier to exert the function of suppressing the increase in micro rubber hardness of the domain.

[0031] The conductive filler can be used without any particular limitation as long as it exhibits conductivity. For example, solid carbon materials such as carbon black, graphite, carbon nanotubes, fullerenes, graphene, and carbon nanowalls; metal powders such as silver, copper, aluminum, nickel, and iron; conductive metal oxides such as conductive tin oxide and conductive titanium oxide; and inorganic ionic substances such as lithium perchlorate, sodium perchlorate, and calcium perchlorate. These can be used alone or in combination of two or more. Among these, solid carbon materials such as carbon black, graphite, carbon nanotubes, fullerenes, graphene, and carbon nanowalls are preferred from the viewpoint that electrical conductivity can be imparted by adding a small amount. More preferably, conductive carbon black such as furnace black, thermal black, acetylene black, ketjen black, PAN (polyacrylonitrile)-based carbon, and pitch-based carbon is preferred, since it is easy to adjust the resistance range to a desired range by appropriately selecting the particle size, structure, etc. Also, carbon nanotubes are preferred, since they can impart conductivity with the addition of an extremely small amount.

[0032] Preferred examples of conductive carbon black include Denka Black manufactured by Denka Corporation, Ketjen Black series manufactured by Lion Corporation, and NIPex160IQ manufactured by Orion Engineered Carbons, Inc. Examples of the Ketjen Black series include Ketjen Black EC600JD, Ketjen Black EC300J, Carbon ECP, and Carbon ECP600JD.

[0033] The mechanism by which carbon black exhibits electrical conductivity is explained by percolation theory, which states that when the filling rate of carbon black is low, electrical conductivity does not change; however, when the filling rate exceeds a certain critical rate, the carbon black forms conductive paths arranged at intervals or less, resulting in a rapid increase in electrical conductivity (a decrease in volume resistivity), which then tends to reach a constant value.

[0034] In addition to the conductive filler, an ionic conductive agent may be used in the elastic layer to adjust the electrical resistance. As the ionic conductive agent, the ionic conductive agent that can be used in the surface layer described later may be used.

[0035] (Proportion of conductive filler in matrix) The ratio of the conductive filler 33 contained in the matrix observed in a cross section in the thickness direction of the elastic layer will be described below. The ratio of the conductive filler contained in the matrix means the ratio of the area of ​​the conductive filler contained in the matrix to the total area of ​​the conductive filler present in an observation region described later. The proportion of the conductive filler contained in the matrix can be calculated by preparing a slice of the elastic layer and measuring the slice with a scanning electron microscope. As the scanning electron microscope, for example, "Helios" (product name) manufactured by Thermo Fisher Scientific can be used. In addition, the measurement can also be performed with a transmission electron microscope (TEM) or a scanning probe microscope (SPM / AFM). Examples of devices for sectioning include a sharp razor, a microtome, a focused ion beam (FIB), etc. Among the above devices, an ultramicrotome capable of preparing ultrathin sections is particularly suitable. The locations where the slices are prepared are three in total, the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where the longitudinal length of the elastic layer is L. Then, as shown in Fig. 4, a total of three slices are prepared from cross sections 41 to 43 in the thickness direction of the elastic layer. As a result, the slices obtained have a cross section in which the domain and matrix are exposed. For the same reason as in the measurement of the parameters indicating the viscoelasticity term, the observation regions of the cross sections 41 to 43 are each placed in a thickness region from the outer surface to a depth of 100 μm, with a square observation region of 50 μm on each side, and the ratio of the conductive filler contained in the matrix is ​​calculated for a total of three observation regions. A detailed calculation method will be described later.

[0036] That is, when the longitudinal length of the elastic layer is L, for each of three cross sections exposing the domain and matrix in the thickness direction of the elastic layer at the longitudinal center of the elastic layer and two locations at L / 4 from both ends of the elastic layer toward the center, when a square observation area with one side measuring 50 μm is placed in the thickness region from the outer surface of the elastic layer to a depth of 100 μm, it is preferable that each of the observation areas satisfies requirement (3). Requirement (3): The ratio of the area of ​​the conductive filler contained in the matrix present in the observation region to the total area of ​​the conductive filler present in the observation region is 95% or more.

[0037] The area ratio of the conductive filler contained in the matrix may be 85% or more, or may be 90% or more. The upper limit of the area ratio of the conductive filler contained in the matrix is ​​not particularly limited, but may be 100% or may be 99%. For example, it is preferably 85 to 100%, 90 to 100%, or 95 to 100%. By ensuring that the proportion of the conductive filler contained in the matrix is ​​within the above range, an increase in the hardness of the domains can be prevented, and both low micro rubber hardness and high recovery from deformation can be achieved. The proportion of conductive filler contained in the matrix can be increased by preparing a dispersion in step (ii) described below, since the interface between the matrix and the domain is strongly phase-separated by the urethane reactive emulsifier, and even if a conductive filler is added after step (ii), a large amount of conductive filler can be prevented from entering the domain, and the proportion of conductive filler contained in the matrix can be increased. In addition, the proportion of conductive filler contained in the matrix can be increased by improving the dispersibility between the conductive filler and the matrix material used. In addition, the proportion of conductive filler contained in the matrix can be decreased by improving the dispersibility between the conductive filler and the domain material used. Specifically, the amount of hydrophilic functional groups on the surface of the conductive filler can be reduced, thereby reducing the amount of conductive filler contained in the matrix. In addition, by increasing the amount of hydrophilic functional groups on the surface of the conductive filler, the ratio of the conductive filler contained in the matrix can be reduced.

[0038] The content of the conductive filler in the elastic layer is preferably 0.02 to 5.0% by mass based on the mass of the elastic layer. When the content of the conductive filler is 0.02% by mass or more, the conductivity of the elastic layer is better. When the content of the conductive filler is 5.0% by mass or less, it is easy to achieve both conductivity, low hardness, and low compression set. The content of the conductive filler is more preferably 0.05 to 4.5 mass %, and further preferably 0.1 to 4.0 mass %. Specifically, if the specific surface area is 500m 2 In the case of carbon black having a specific surface area of ​​less than 500 m / g (for example, Denka Black manufactured by Denka Corporation), the content is preferably 1.0 to 4.5 mass%, and more preferably 1.5 to 4.0 mass%. 2 In the case of carbon black having a specific surface area of ​​500 m / g or more (for example, Ketjen Black series manufactured by Lion Corporation), the content is preferably 0.2 to 4.0 mass%, more preferably 0.5 to 3.5 mass%. 2In the case of tube-shaped carbon fibers (carbon nanotubes) or needle-shaped carbon fibers (carbon nanofibers) (for example, single-walled carbon nanotubes (TUBALL (registered trademark)) manufactured by Oxyal Corp.) with a carbon content of 0.05 to 3.0 mass % or more, the carbon content is preferably 0.1 to 2.5 mass %. When the conductive filler is a solid carbon material, the content thereof can be calculated using a thermogravimetric differential thermal analyzer (TG-DTA).

[0039] Specifically, the measurement is carried out in the following manner. Using TG-DTA, a sample placed in a specified container is heated to 600°C at a heating rate of 10°C / min in a nitrogen atmosphere, held for 10 minutes, then cooled to 400°C at a cooling rate of 10°C / min, and the weight loss W1 (%) from the start of measurement is measured. Next, the sample is heated again to 800°C at a heating rate of 10°C / min in an air atmosphere, and the weight loss W2 (%) from the start of measurement is measured. The conductive filler (solid carbon material) content can be calculated as the difference between W2 and W1 (W2-W1 (%)).

[0040] (Cross-sectional area and number of domains) The cross-sectional area and number of domains 32 of the urethane elastomer observed in a cross section of the elastic layer in the thickness direction will be described. When the longitudinal length of the elastic layer is L, for each of three cross sections in which the domain and matrix are exposed in the thickness direction of the elastic layer, namely, at the longitudinal center of the elastic layer and two locations at L / 4 from both ends of the elastic layer toward the center, when a square observation area with one side measuring 50 μm is placed in the thickness region from the outer surface of the elastic layer to a depth of 100 μm, it is preferable that each of the observation areas satisfies the following requirements (2-1) and (2-2). Requirement (2-1): The total cross-sectional area of ​​the domains present in the observation region is 15 to 45% of the area of ​​the observation region. Requirement (2-2): Among the domains present in the observation region, the proportion of domains having a cross-sectional area of ​​0.1 to 13.0 area % of the area of ​​the observation region is 70% or more by number.

[0041] Regarding requirement (2-1), by making the ratio of the total cross-sectional area of ​​the domains present in the observation region 15% or more by area, the micro rubber hardness of the elastic layer can be kept low. Also, by making the ratio of the total cross-sectional area of ​​the domains 45% or less by area, the elastic layer can recover from deformation more quickly. Moreover, the proportion of the total cross-sectional area of ​​the domains present in the observation region is more preferably 20 to 40 area %, and further preferably 25 to 35 area %. The ratio of the total cross-sectional area of ​​the domains is, for example, When the matrix contains a carbonate structure and the domain contains a polyether structure represented by formula (2), the content ratio can be adjusted by changing the content ratio of the polycarbonate structure represented by formula (1) contained in the matrix and the polyether structure represented by formula (2) contained in the domain. For example, increasing the content ratio of the polyether structure represented by formula (2) increases the ratio of the total cross-sectional area of ​​the domain. In addition, by keeping the content ratio of the polyether structure represented by formula (2) within the above range, inversion of the matrix and the domain is unlikely to occur, and the polyether structure represented by formula (2) is unlikely to become the main component of the matrix. The cross-sectional area of ​​the domain can be increased, for example, by increasing the number average molecular weight of the polyether polyol that forms the polyether structure represented by formula (2).

[0042] Regarding requirement (2-2), by setting the ratio of the number of domains having a cross-sectional area of ​​0.1 to 13.0% of the area of ​​the observation region to 70% or more of the total number of domains in the observation region, the number of domains large enough to be deformed sufficiently when the elastic layer is pressed against the observation region is ensured. Therefore, the micro rubber hardness of the elastic layer can be lowered. In addition, since the number of large domains that deform excessively when a load is applied to the elastic layer is small, the micro rubber hardness of the elastic layer can be prevented from becoming too low. Furthermore, the proportion of domains having a cross-sectional area of ​​0.1 to 13.0 area % relative to the area of ​​the observation region is preferably 70 to 100% by number, more preferably 80 to 100% by number, and even more preferably 90 to 100% by number. The ratio of the number of domains having a cross-sectional area of ​​0.1 to 13.0% of the area of ​​the observation region can be adjusted by the size of the cross-sectional area of ​​the domain. The ratio of the number of domains meeting the above requirement increases as the cross-sectional area of ​​the domain is moved closer to the center of the range of the above requirement. As described above, the cross-sectional area of ​​the domain can be adjusted by the number average molecular weight of the polyether polyol forming the polyether structure represented by formula (2), and increases as the number average molecular weight of the polyether polyol increases. In addition, the cross-sectional area of ​​the domain decreases when the isocyanate index in the step of obtaining the first polyether described later or the shear force when mixing the materials is increased. The ratio of the total cross-sectional area of ​​the domains present in the observation region and the ratio of the number of domains having a cross-sectional area of ​​0.1 to 13.0 area % relative to the area of ​​the observation region can be measured following the method for the ratio of the conductive filler contained in the matrix in the previous section, and details will be described later.

[0043] The average cross-sectional area of ​​the domains present in the observation region is preferably 0.08 to 16.00 area % relative to the area of ​​the observation region, more preferably 0.10 to 15.00 area %, and even more preferably 0.10 to 13.00 area %. By being in the above range, it becomes easy to adjust the ratio of the number of domains having a cross-sectional area of ​​0.10 to 13.00 area % relative to the area of ​​the observation region. As described above, the average cross-sectional area of ​​the domains can be adjusted by the number average molecular weight of the polyether polyol forming the polyether structure represented by formula (2), and increases as the number average molecular weight of the polyether polyol increases. In addition, the average cross-sectional area of ​​the domains decreases when the isocyanate index in the step of obtaining the first polyether described below is increased or when the shear force when mixing the materials is increased.

[0044] (Domain circularity) In the cross section of the elastic layer in the thickness direction, where the domains and the matrix are exposed, the percentage of the number of domains having a circularity of 0.60 to 0.95 in the observed region is preferably 70% by number or more, more preferably 80% by number or more, and even more preferably 90% by number or more. The upper limit may be 100% by number or less, or 98% by number or less. For example, the percentage is preferably 70 to 98% by number, 80 to 100% by number, or 90 to 100% by number. In domains having a circularity within the above range, when the domain recovers from deformation, anisotropy is unlikely to occur in the direction in which the domain shape recovers. Furthermore, a large number (proportion) of domains having a circularity within the above range makes it less likely that anisotropy will occur in the recovery from deformation of the elastic layer. In other words, an elastic layer can be made to recover from deformation in a more isotropic manner. As a result, wrinkles, etc. due to anisotropy in the recovery from deformation are unlikely to occur in the elastic layer after recovery from deformation. Note that when wrinkles, etc. occur, circumferential stripe-like image defects may occur randomly in the longitudinal direction along the position of the wrinkles. The circularity of the domains and the ratio of the number of the domains can be measured by the method described later. The ratio of the number of domains with a circularity of 0.60 to 0.95 can be adjusted, for example, by changing the speed at which the material is injected into the mold. By slowing down the injection speed, the shear force applied to the material is also reduced, allowing the material to be heat-cured while maintaining a high circularity.

[0045] When the longitudinal length of the elastic layer is L, and a square observation area 50 μm on a side is placed in a thickness region from the outer surface of the elastic layer to a depth of 100 μm in each of three cross sections in which the domains and matrix are exposed in the thickness direction of the elastic layer at a total of three locations, namely, the longitudinal center of the elastic layer and two locations at L / 4 from both ends of the elastic layer toward the center, the average circularity of the domains present in the observation area is preferably 0.55 to 1.00, more preferably 0.60 to 0.98, and even more preferably 0.60 to 0.95. By being in the above range, it becomes easy to adjust the ratio of the number of domains having a circularity of 0.60 to 0.95 to be in the above range. The average circularity of the domains can be adjusted, for example, by changing the speed at which the material is injected into the mold. Slowing the injection speed reduces the shear force applied to the material, allowing it to be cured by heat while maintaining a high degree of circularity.

[0046] (Elastic layer material) The urethane elastomer will now be described. As described above, the elastic layer includes a urethane elastomer and a conductive filler, and the urethane elastomer has a matrix 31 and a plurality of domains 32 dispersed in the matrix. That is, the urethane elastomer has a matrix domain structure. In this case, it is preferable that the matrix 31 has a structure capable of enhancing recovery from deformation, and the domain 32 has a structure that contributes to suppressing an increase in micro rubber hardness. The fact that the elastic layer contains a urethane elastomer can be determined by analysis using, for example, a spectroscopic analyzer such as a microscopic infrared spectroscopic analyzer, or a mass spectrometer.

[0047] The matrix 31 preferably contains a polycarbonate structure represented by the following formula (1). Polyurethane obtained by reacting a polyol having a polycarbonate structure (polycarbonate polyol) with a polyisocyanate exhibits high elasticity due to the strong intermolecular force between carbonate groups. Therefore, it is preferable as a structure contained in the matrix. The matrix has at least one polycarbonate structure represented by formula (1), and preferably has a plurality of polycarbonate structures. When the matrix has a plurality of polycarbonate structures represented by formula (1), the polycarbonate structure can be a repeating structural unit. [ka] (In formula (1), R 1 represents an alkylene group having 3 to 9 carbon atoms (preferably 3 to 6).

[0048] R in formula (1) 1 The alkylene group having 3 to 9 carbon atoms represented by the following formula may have a linear structure or a branched structure, but more preferably has a branched structure. R 1 By being an alkylene group having 3 to 9 carbon atoms, incompatibility with the domain containing the polyether structure represented by the following formula (2) described later is ensured, and the matrix and the domain can be clearly phase-separated. This makes it possible to more reliably exhibit the two functions of the urethane elastomer, namely, softness and fast recovery from deformation. Also, R 1 By being an alkylene group having a branched structure with 3 to 9 carbon atoms (preferably 4 to 9), the intermolecular force between the carbonate groups can be appropriately suppressed, and the matrix can be prevented from becoming excessively high in elasticity. R 1 For example, -(CH2) m -(m=3 to 9, preferably 3 to 6), -CH2C(CH3)2CH2-, -CH2CH(CH3)CH2-, -(CH2)2CH(CH3)(CH2)2-, etc. These can be used alone or in combination of two or more. The matrix contains a polycarbonate structure represented by formula (1) and R1 That is an alkylene group having 3 to 9 carbon atoms can be determined by analysis using, for example, a spectroscopic analyzer such as a microscopic infrared spectroscopic analyzer, or a mass spectrometer.

[0049] The domain 32 preferably contains a polyether structure represented by the following formula (2). Polyether exhibits a low elastic modulus due to weak intermolecular forces between ether groups. Therefore, it is preferable as a structure to be contained in the domain. The domain has at least one polyether structure represented by formula (2), and preferably has a plurality of polyether structures represented by formula (2). When the domain has a plurality of polyether structures represented by formula (2), the polyether structures can be repeating structural units. [ka] (In formula (2), R 2 represents an alkylene group having 3 to 5 carbon atoms (preferably 4 to 5).

[0050] R in Equation (2) 2 The alkylene group having 3 to 5 carbon atoms represented by the following formula may have a linear structure or a branched structure, but preferably has a branched structure. R 2 By being an alkylene group having 3 to 5 carbon atoms, incompatibility with the matrix containing the polycarbonate structure represented by formula (1) is ensured, and the matrix and the domain can be clearly phase-separated. This makes it possible to more reliably exhibit the two functions of the urethane elastomer, namely softness and fast recovery from deformation. Also, R 2 By being an alkylene group having a branched structure and having 3 to 5 carbon atoms (preferably 4 to 5), crystallization of the domain can be suppressed, and the hardness of the domain can be more easily reduced, resulting in the domain having a low elastic modulus. R 2 For example, -(CH2) m-(m=3 to 5, preferably 4 to 5), -CH2CH(CH3)-, -CH2C(CH3)2CH2-, -CH2CH(CH3)CH2-, -(CH2)2CH(CH3)CH2-, etc. These can be used alone or in combination of two or more kinds. The domain contains a polyether structure represented by formula (2) and R 2 That is an alkylene group having 3 to 5 carbon atoms can be determined by analysis using, for example, a spectroscopic analyzer such as a microscopic infrared spectroscopic analyzer, or a mass spectrometer.

[0051] (Method of manufacturing urethane elastomer) An example of a method for producing the above-mentioned urethane elastomer includes the following steps (i) to (iii) ) is an example of a method. Step (i): A step of reacting a first polyether having at least two isocyanate groups with a first polycarbonate polyol having at least two hydroxyl groups to obtain a urethane reactive emulsifier having at least two hydroxyl groups. Step (ii): A step of mixing a urethane reactive emulsifier and a second polycarbonate polyol to obtain a dispersion in which droplets containing at least a portion of the urethane reactive emulsifier are dispersed in the second polycarbonate polyol. Step (iii): A step of preparing a mixture for forming an elastic layer containing the dispersion obtained in step (ii) and a polyisocyanate having at least two isocyanate groups, and then reacting the urethane reactive emulsifier, the second polycarbonate polyol, and the polyisocyanate having at least two isocyanate groups in the mixture for forming an elastic layer.

[0052] Each step of the above manufacturing method will be described with reference to FIG. 5 (conductive filler not shown). In step (i), a first polyether 51 having at least two isocyanate groups is mixed with a first polycarbonate polyol 52 having at least two hydroxyl groups. In the presence of a catalyst, the isocyanate groups and hydroxyl groups in the mixture are reacted to link them via a urethane bond, thereby obtaining a urethane reactive emulsifier 53 having at least two hydroxyl groups. The urethane reactive emulsifier is a reactive emulsifier having a urethane bond.

[0053] In step (ii), the urethane reactive emulsifier 53 obtained in step (i) is dispersed in the second polycarbonate polyol 55. Here, the urethane reactive emulsifier can be mixed with the second polycarbonate polyol newly added in this step. Also, the excess unreacted material of the first polycarbonate polyol in step (i) can be used as the second polycarbonate polyol. The first polyether 51 contained in the urethane reactive emulsifier 53 is incompatible with the second polycarbonate polyol 55 and forms droplets 54 . On the other hand, the first polycarbonate polyol 52 contained in the urethane reactive emulsifier 53 is compatible with the second polycarbonate polyol 55. Therefore, the droplets 54 containing the first polyether constituting a part of the urethane reactive emulsifier are uniformly and stably dispersed in the second polycarbonate polyol 55 via the first polycarbonate polyol 52. As a result, a dispersion is obtained in which the droplets 54 containing the first polyether 51 of the urethane reactive emulsifier 53 are dispersed in the second polycarbonate polyol 55. For the sake of explanation, the steps (i) and (ii) are described separately, but these steps may be a continuous series of steps.

[0054] In order to incorporate the conductive filler into the matrix, it is preferable to add and disperse the conductive filler after step (ii). That is, the method for producing a urethane elastomer preferably includes a step of adding and dispersing the conductive filler in the dispersion obtained in step (ii). Also, the conductive filler may be added and dispersed in step (ii). If the conductive filler is added to the second polycarbonate polyol in advance, the viscosity of the polycarbonate polyol increases due to its high intermolecular force, which may reduce the workability in step (ii). On the other hand, if it is added after step (ii), the viscosity does not increase excessively even if the conductive filler is added, because the first polyether, which has low intermolecular force and low viscosity, is present. Also, in step (ii), the interface between the matrix and the domain is firmly phase-separated by the urethane reactive emulsifier, so even if the conductive filler is added and stirred after step (ii), a large amount of the conductive filler does not enter the domain.

[0055] In step (ii), the second polycarbonate polyol 55 in which the droplets 54 are dispersed can be the unreacted product of the first polycarbonate polyol used in step (i) with the first polyether. By using an excess amount of the first polycarbonate polyol with respect to the first polycarbonate polyol, it is possible to obtain a dispersion in which the urethane reactive emulsifier 53 is dispersed in the excess first polycarbonate polyol (i.e., the second polycarbonate polyol 55) as described in step (ii). Even when an excess amount of the first polycarbonate polyol is used, it is also possible to add additional polycarbonate polyol (second polycarbonate polyol) as a dispersion medium for the urethane reactive emulsifier. In this case, the added polycarbonate polyol may have the same chemical composition as the first polycarbonate polyol used in step (i) or may have a different chemical composition.

[0056] On the other hand, in step (i), the first polycarbonate polyol and the first polyether are reacted in equivalent amounts, and when the first polycarbonate polyol is completely consumed, a new polycarbonate polyol is used as the second polycarbonate polyol to prepare a dispersion in step (ii). Even in this case, the polycarbonate polyol used as the second polycarbonate polyol may have the same chemical composition as the first polycarbonate polyol or may have a different chemical composition.

[0057] Finally, in step (iii), a mixture for forming an elastic layer is prepared, which contains the dispersion prepared in step (ii) and a polyisocyanate 56 having at least two isocyanate groups. Next, the hydroxyl group of the urethane reactive emulsifier 53 or the hydroxyl group of the second polycarbonate polyol 55 in the mixture for forming an elastic layer is reacted with the isocyanate group of the polyisocyanate 56. In this way, a network structure is formed via urethane bonds, and the mixture for forming an elastic layer is cured to obtain a urethane elastomer. The urethane elastomer 500 thus obtained has a matrix domain structure in which the domain 32 containing the polyether structure of the first polyether 51 is dispersed in the matrix 31 containing the polycarbonate structure of the first polycarbonate polyol 52 and the second polycarbonate polyol 55, which are unreacted substances. In addition, the domain 32 is mainly composed of a polyether structure, and the inside of the domain can be made substantially free of a crosslinked structure. In other words, the domains 32 may be present in a matrix in a substantially liquid state, which may allow the domains to have a low modulus of elasticity in the urethane elastomer.

[0058] Furthermore, it is believed that the domains are not simply confined in the matrix, but that the domains and the matrix are chemically bonded by urethane bonds at the boundary between the domains and the matrix. Therefore, when the load applied to the urethane elastomer is removed, the recovery of the domains from deformation can be linked to the recovery of the matrix from deformation. This is believed to give the elastic layer according to the present disclosure an extremely high recovery from deformation. In addition, because the recovery of the domains from deformation is linked to the recovery of the matrix from deformation, the elastic layer can stably recover better from deformation even when the load is repeatedly applied and removed. Here, as described above, the domain can be made substantially liquid with substantially no crosslinked structure inside. This can further soften the urethane elastomer. At this time, the substantially liquid domain deformed by the application of a load to the urethane elastomer has a low elastic modulus, so it is considered difficult for it to spontaneously recover from the deformation. However, in the urethane elastomer according to the present disclosure, as described above, it is considered that the domain and the matrix are chemically bonded at the boundary with the matrix. Due to the presence of this chemical bond, even the substantially liquid domain can recover well from the deformation together with the deformation recovery of the matrix. Therefore, the urethane elastomer according to the present disclosure having a substantially liquid domain can achieve a higher level of flexibility and recovery from deformation.

[0059] In addition, the above steps (i) and (ii) are carried out in order to stably and uniformly disperse the components that are originally low in compatibility. This is a process for stably dispersing a polyether, which is difficult to disperse, in a polycarbonate polyol. That is, a first polyether 51 is reacted with a first polycarbonate polyol 52 to form a urethane reactive emulsifier 53. This is a process for obtaining a dispersion in which polyether segments corresponding to the first polyether 51 are stably and uniformly dispersed in a second polycarbonate polyol. This makes it easy to prepare a urethane elastomer in which domains 32 having a high circularity and a relatively uniform size distribution, which are small on the order of micrometers, are dispersed in a matrix 31.

[0060] As another method for mixing materials with low compatibility, for example, there is a method of mixing and dispersing them with high shear force. However, in this method, as a result of applying high shear force to the polyether, the shape of the domain becomes distorted, the circularity decreases, and the size of the domains may become uneven. In addition, the dispersion state is unstable, and the aggregation of the domains progresses in a relatively short time. In addition, the incompatibility between the polyether and the polycarbonate polyol is not guaranteed, and the phase separation between the matrix and the domains of the obtained urethane elastomer becomes unclear. Therefore, it is difficult to obtain a urethane elastomer that gives an elastic body that is flexible and has excellent recovery from deformation, as disclosed in the present disclosure.

[0061] The first polyether has at least two isocyanate groups. The first polyether is preferably a polyether containing a polyether structure represented by formula (2). The first polyether can be obtained, for example, by a process of reacting a polyether polyol having at least two hydroxyl groups and containing the polyether structure represented by formula (2) with a polyisocyanate having at least two isocyanate groups. Examples of polyether polyols include polyether polyols containing an alkylene structure, such as polypropylene glycol, polytetramethylene glycol, a copolymer of tetrahydrofuran and neopentyl glycol, and a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran, and random or block copolymers of these polyalkylene glycols. These may be used alone or in combination of two or more.

[0062] Among the polyether polyols, amorphous polyether polyols are preferred from the viewpoints of incompatibility with the second polycarbonate polyol and of enabling low hardness to be achieved. More preferably, the liquid composition contains at least one selected from the group consisting of polypropylene glycol, a copolymer of tetrahydrofuran and neopentyl glycol, and a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran.

[0063] The number average molecular weight of the polyether polyol is preferably 1000 to 50000. More preferably, it is 1200 to 30000. When the number average molecular weight is 1000 or more, the incompatibility with the polycarbonate polyol is ensured, and the phase separation between the matrix and the domain of the obtained urethane elastomer becomes clear, which is preferable. In addition, when the number average molecular weight is 50000 or less, the domain is easily formed, and the phase separation form is stabilized, which is preferable.

[0064] The number average molecular weight of the polyether polyol can be calculated by the following formula (3) using the hydroxyl value (mgKOH / g) and the valence of the polyether polyol. For example, the number average molecular weight of a polyether polyol having a hydroxyl value of 56.1 mgKOH / g and a valence of 2 can be calculated to be 2000. Number average molecular weight = 56.1 × 1000 × valence ÷ hydroxyl value (3)

[0065] Examples of the polyisocyanate to be reacted with the polyether polyol include pentamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, or trimer compounds (isocyanurates) or polymer compounds of these polyisocyanates, allophanate type polyisocyanates, biuret type polyisocyanates, water-dispersible polyisocyanates, etc. These polyisocyanates can be used alone or in combination of two or more kinds. Among polyisocyanates, a bifunctional isocyanate (diisocyanate) having two isocyanate groups is preferred because of its high compatibility with the first polyether and the ease of adjusting physical properties such as viscosity. More preferably, the polyisocyanate contains at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. Xylylene diisocyanate is even more preferred.

[0066] In the step of reacting the polyether polyol with the polyisocyanate, the isocyanate index is preferably 1.2 to 5.0. By having the isocyanate index in this range, the components derived from the first polyether remaining without being network structured can be reduced, and the exudation of liquid substances from the urethane elastomer can be suppressed. The isocyanate index indicates the ratio ([NCO] / [OH]) of the number of moles of isocyanate groups in the isocyanate compound to the number of moles of hydroxyl groups in the polyol compound. The first polyether obtained by the reaction of polyether polyol with polyisocyanate has a structure in which hydroxyl groups and isocyanate groups are linked via urethane bonds formed by the reaction of the hydroxyl groups and isocyanate groups. The number average molecular weight of the first polyether is preferably 1,000 to 50,000. More preferably, the number average molecular weight is 1,200 to 30,000. The number average molecular weight of the first polyether can be calculated using the standard polystyrene molecular weight conversion or the hydroxyl value (mgKOH / g) and the valence. The number average molecular weight converted into polystyrene molecular weight conversion can be measured using high performance liquid chromatography. For example, a high-speed GPC apparatus (product name: HLC-8220GPC, manufactured by Tosoh Corporation) is equipped with a column: Shodex GPCLF-804 (exclusion limit molecular weight: 2×10 6 , Separation range: 3×10 2 ~2×10 6 ) in series. When using the hydroxyl value and valence, the number average molecular weight can be calculated using the following formula. For example, the number average molecular weight of a polyol with a hydroxyl value of 56.1 mg KOH / g and a valence of 2 can be calculated to be 2000. Number average molecular weight = 56.1 x 1000 x valence ÷ hydroxyl value The number average molecular weight of the first polyether can be adjusted by changing the number average molecular weight of the polyether polyol or polyisocyanate used, or by changing the reaction temperature, reaction time, etc. in the step of reacting the polyether polyol with the polyisocyanate.

[0067] The first polycarbonate polyol has at least two hydroxyl groups. The first polycarbonate polyol is preferably a polycarbonate polyol containing a polycarbonate structure represented by formula (1). Examples of the first polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene, and a ring-opening polymer of a cyclic carbonate ester (such as an alkylene carbonate).

[0068] Examples of polyhydric alcohols include propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, and glyceryl. Examples of suitable ethanolamines include ethanol, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), and sugar alcohols (such as xylitol and sorbitol).

[0069] Examples of the alkylene carbonate include trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0070] The number average molecular weight of the first polycarbonate polyol is preferably 500 to 10,000. More preferably, it is 700 to 8,000. When the number average molecular weight is 500 or more, in the case where the domain contains a polyether structure represented by formula (2), incompatibility with the domain is ensured, and phase separation between the matrix and the domain can be made clearer. In addition, by setting the number average molecular weight to 10,000 or less, an excessive increase in viscosity of the first polycarbonate polyol can be prevented. The number average molecular weight of the first polycarbonate polyol can be calculated in the same manner as the method for calculating the number average molecular weight of the polyether polyol described above.

[0071] The second polycarbonate polyol used in step (ii) can be any of the polycarbonate polyols listed in the first polycarbonate polyol. As described above, the first polycarbonate polyol and the second polycarbonate polyol may have the same chemical composition, or may be different from each other.

[0072] The amounts of the first polyether and the first polycarbonate polyol used are not particularly limited as long as they are sufficient to form clear domains by dispersing the droplets 54 in the second polycarbonate polyol 55. For example, the ratio of the first polyether:first polycarbonate polyol is preferably 10:90 to 50:50, and more preferably 15:85 to 45:55, on a mass basis.

[0073] The polyisocyanate 56 having at least two isocyanate groups used in step (iii) may be the same as the polyisocyanate exemplified above as the raw material of the first polyether to be reacted with the polyether polyol. These polyisocyanates may be used alone or in combination of two or more kinds. From the viewpoint of increasing the elastic modulus of the matrix, it is preferable that the polyisocyanate 56 includes a polyisocyanate having at least three isocyanate groups, such as a polyisocyanate trimer compound (isocyanurate) or polymer compound, an allophanate type polyisocyanate, or a biuret type polyisocyanate, among the polyisocyanates exemplified above. More preferably, the compound contains at least one selected from the group consisting of a trimer compound (isocyanurate) of pentamethylene diisocyanate, a trimer compound (isocyanurate) of hexamethylene diisocyanate, a polymeric compound of diphenylmethane diisocyanate, and polymeric MDI.

[0074] Among the above, polymeric MDI is preferred. Polymeric MDI is a mixture of monomeric MDI and high molecular weight polyisocyanate, and is represented by the following formula (A). n in formula (A) is preferably 0 or more and 4 or less. As the polymeric MDI, commercially available products may be used, and examples thereof include Millionate MR series (manufactured by Tosoh Corporation), such as Millionate MR200 (product name). [ka]

[0075] As the polyisocyanate 56 having at least two isocyanate groups, it is preferable to use a polyisocyanate having at least three isocyanate groups such as polymeric MDI in combination with a bifunctional isocyanate having two isocyanate groups. The combination of these is preferable from the viewpoint of achieving both low hardness and low compression set, since the crosslink density of the matrix can be adjusted by using these in combination.

[0076] The amount of the polyisocyanate having at least three isocyanate groups and the bifunctional isocyanate having two isocyanate groups is not particularly limited. The amount of the bifunctional isocyanate:polyisocyanate having at least three isocyanate groups when mixed with the dispersion in step (iii) is preferably 3:1 to 1:10, more preferably 1:1 to 1:6. The amount of the polyisocyanate relative to 100 parts by mass of the dispersion in step (iii) is also not particularly limited, and may be, for example, 1 to 10 parts by mass, or 3 to 8 parts by mass.

[0077] As the catalyst, a known urethanization catalyst or an isocyanurate catalyst (isocyanate trimerization catalyst) can be used. These may be used alone or in combination. Examples of the urethane catalyst include tin-based urethane catalysts such as dibutyltin dilaurate and stannous octoate, and amine-based urethane catalysts such as triethylenediamine, tetramethylguanidine, pentamethyldiethylenetriamine, diethylimidazole, tetramethylpropanediamine, N,N,N'-trimethylaminoethylethanolamine, and 1,4-diazabicyclo[2.2.2]octane-2-methanol. These may be used alone or in combination. Among these urethane catalysts, triethylenediamine and 1,4-diazabicyclo[2.2.2]octane-2-methanol are preferred in terms of particularly promoting the urethane reaction.

[0078] Examples of isocyanurate catalysts include metal oxides such as Li2O and (Bu3Sn)2O; hydride compounds such as NaBH4; alkoxide compounds such as NaOCH3, KO-(t-Bu), and borates; amine compounds such as N(C2H5)3, N(CH3)2CH2C2H5, and 1,4-ethylenepiperazine (DABCO); alkaline carboxylate salt compounds such as HCOONa, Na2CO3, PhCOONa / DMF, CH3COOK, (CH3COO)2Ca, alkali soap, and naphthenates; alkaline formate compounds; and quaternary ammonium salt compounds such as ((R)3-NR'OH)-OCOR". In this example, Bu represents a butyl group, Ph represents a phenyl group, and R, R', and R" represent any alkyl group. In addition, examples of the combined catalyst (cocatalyst) used as the isocyanurate catalyst include amine / epoxide, amine / carboxylic acid, amine / alkyleneimide, etc. These isocyanurate catalysts and combined catalysts may be used alone or in combination.

[0079] As a catalyst for urethane synthesis, N,N,N'-trimethylaminoethylethanolamine (hereinafter referred to as ETA), which acts alone as a urethanization catalyst and also acts as an isocyanurate catalyst, may be used.

[0080] In the method for producing a urethane elastomer, a chain extender (a polyfunctional low molecular weight polyol) may be used as necessary. Examples of the chain extender include glycols having a number average molecular weight of 1000 or less. Examples of the glycol include ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG), 1,4-butanediol (1,4-BD), 1,6-hexanediol (1,6-HD), 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (terephthalyl alcohol), and triethylene glycol. Examples of chain extenders other than glycols include polyhydric alcohols having a valence of three or more. Examples of polyhydric alcohols having a valence of three or more include trimethylolpropane, glycerin, pentaerythritol, and sorbitol. These may be used alone or in combination. If necessary, additives such as pigments, plasticizers, waterproofing agents, antioxidants, conductive agents, ultraviolet absorbing agents, and light stabilizers may also be used in combination.

[0081] (Method of manufacturing elastic layer) The elastic layer can be formed, for example, by carrying out the reaction step in step (iii) in the above-mentioned method for producing a urethane elastomer on the circumferential surface of the mandrel. Other conditions can be the same as those in the method for producing a urethane elastomer. Specifically, for example, a method of preparing a mixture containing the dispersion prepared in step (ii) and a polyisocyanate having at least two isocyanate groups, and curing the mixture on the circumferential surface of the mandrel can be mentioned. That is, the method of producing the elastic layer can be, for example, a method including the following steps (2-i) to (2-iv). Step (2-i): A step of reacting a first polyether having at least two isocyanate groups with a first polycarbonate polyol having at least two hydroxyl groups to obtain a urethane reactive emulsifier having at least two hydroxyl groups. Step (2-ii): A step of mixing a urethane reactive emulsifier and a second polycarbonate polyol to obtain a dispersion in which droplets containing at least a portion of the urethane reactive emulsifier are dispersed in the second polycarbonate polyol. Step (2-iii): A step of mixing the dispersion obtained in step (2-ii) with a polyisocyanate having at least two isocyanate groups to obtain a mixture for forming an elastic layer. Step (2-iv): A step of reacting the urethane reactive emulsifier, the second polycarbonate polyol, and the polyisocyanate having at least two isocyanate groups in the mixture for forming the elastic layer on the peripheral surface of the mandrel.

[0082] As a method for hardening the elastic layer-forming mixture on the circumferential surface of the mandrel, for example, a method of injecting the material for the elastic layer containing the mixture for forming the elastic layer into a mold in which a cylindrical pipe, a piece for holding the mandrel, and the mandrel are arranged, and then heating and hardening (cast molding method) can be used. In addition, a method of applying the material for the elastic layer containing the mixture for forming the elastic layer onto the circumferential surface of the mandrel to form a coating film, and then heating and hardening the coating film can also be used. In addition, after the elastic layer-forming mixture is cured on the peripheral surface of the mandrel, it is preferable to further carry out aging.

[0083] (Surface layer) A surface layer may be provided on the surface of the elastic layer as required. Materials for forming the surface layer include resin, natural rubber, and synthetic rubber. Resins include thermosetting resins. A fluororesin, polyamide resin, acrylic resin, polyurethane resin, silicone resin, or butyral resin can be used as the resin, since the viscosity of the coating material can be easily controlled. These resins can be used alone or in combination of two or more kinds. They may also be copolymers. A conductive agent can be blended into the surface layer in order to adjust the electrical resistance of the electrophotographic roller, and the volume resistivity of the surface layer can be adjusted by an ionic conductive agent or an electronic conductive agent.

[0084] Examples of ionic conductive agents include the following: inorganic ionic substances such as lithium perchlorate, sodium perchlorate, and calcium perchlorate; cationic surfactants such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, trioctyl propyl ammonium bromide, and modified aliphatic dimethyl ethyl ammonium ethosulfate; zwitterionic surfactants such as lauryl betaine, stearyl betaine, and dimethyl alkyl lauryl betaine; quaternary ammonium salts such as tetraethyl ammonium perchlorate, tetrabutyl ammonium perchlorate, and trimethyl octadecyl ammonium perchlorate; and organic acid lithium salts such as lithium trifluoromethanesulfonate. These may be used alone or in combination of two or more.

[0085] Examples of electronic conductive agents include: Metallic fine particles and fibers, such as aluminum, palladium, iron, copper, and silver; Conductive metal oxides, such as titanium oxide, tin oxide, and zinc oxide; Composite particles in which the surfaces of the metallic fine particles, fibers, and metal oxides mentioned above are treated by electrolytic treatment, spray coating, or mixed shaking; Carbon powders, such as furnace black, thermal black, acetylene black, ketjen black, PAN (polyacrylonitrile)-based carbon, and pitch-based carbon.

[0086] The surface layer may contain other particles. Examples of the other particles include insulating particles. Examples of the insulating particles include the following: polyamide resin, silicone resin, fluororesin, (meth)acrylic resin, styrene resin, phenol resin, polyester resin, melamine resin, urethane resin, olefin resin, epoxy resin, copolymers, modified products, and derivatives thereof. Rubbers such as ethylene-propylene-diene copolymer (EPDM), styrene-butadiene copolymer rubber (SBR), silicone rubber, urethane rubber, isoprene rubber (IR), butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR), and epichlorohydrin rubber, polyolefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, fluororubber-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, ethylene-vinyl acetate-based thermoplastic elastomers, polyvinyl chloride-based thermoplastic elastomers, and chlorinated polyethylene-based thermoplastic elastomers. Among these, (meth)acrylic resins, styrene resins, urethane resins, fluorine resins, and silicone resins are particularly preferred.

[0087] The materials constituting the surface layer can be dispersed using a known dispersing device that uses beads such as a sand mill, a paint shaker, a dyno mill, or a pearl mill. The method for applying the resulting dispersion is not particularly limited, but a dipping method is preferred because of its simple operation.

[0088] <Electrophotographic image forming apparatus> FIG. 6 shows a schematic configuration of one example of an electrophotographic image forming apparatus equipped with an electrophotographic member according to one embodiment of the present disclosure. In FIG. 6, the image forming apparatus includes a photoconductor 61, a charging device, a latent image forming device, a developing device, a transfer device, The image forming apparatus includes a fixing device, a cleaning device, and a fixing device. The photoconductor 61 is a rotating drum having a photosensitive layer on a conductive substrate, and is rotated in the direction of the arrow at a predetermined peripheral speed (process speed). The charging device has a function of charging the photoconductor 61, and has a contact-type charging roller 62 that is placed in contact with the photoconductor 61 by abutting against it with a predetermined pressing force. The charging roller 62 rotates in the direction of the arrow in accordance with the rotation of the photoconductor 61. The charging roller 62 applies a predetermined DC voltage from a charging power source 63 to the charging roller 62, thereby charging the photoconductor 61 to a predetermined potential. A latent image forming device (not shown) performs exposure to light and forms an electrostatic latent image on the photoconductor 61. An exposure device such as a laser beam scanner is used as the latent image forming device. The latent image forming device forms an electrostatic latent image by irradiating the uniformly charged photoconductor 61 with exposure light 64 corresponding to image information. The developing device has a function of developing a toner image, and includes a developing roller 65 disposed adjacent to or in contact with the photoconductor 61. The developing roller 65 develops the electrostatic latent image by reversal development using toner that has been electrostatically treated to have the same polarity as the charged polarity of the photoconductor 61, thereby forming a toner image on the photoconductor 61. The transfer device has a function of transferring the developed toner image onto recording material P, and has a contact-type transfer roller 66. The transfer roller 66 rotates in the direction of the arrow in accordance with the rotation of the photoreceptor 61, and transfers the toner image from the photoreceptor 61 onto recording material P, such as plain paper. The recording material P is transported in the direction of the arrow by a paper feed system (not shown) having a transport member. The cleaning device has a function of collecting residual toner remaining on the photoconductor 61, and includes a blade-type cleaning member 68 and a collection container 69. After the toner image is transferred to the recording material P, the cleaning device mechanically scrapes off and collects the residual toner remaining on the photoconductor 61. Here, by adopting a simultaneous development and cleaning method in which the developing device collects the transfer residual toner, it is possible to omit the cleaning device. The fixing device has the function of fixing the toner image and is composed of a fixing belt 67 having a heated roll. By rotating in the direction of the arrow, the toner image transferred onto the recording material P is fixed and the recording material P is discharged outside the machine. In the image forming apparatus, the electrophotographic member described above can be suitably used as the charging roller 62 or the developing roller 65. That is, the electrophotographic image forming apparatus can be equipped with the electrophotographic member of the present disclosure.

[0089] <Process cartridge> A schematic configuration of one embodiment of a process cartridge according to one embodiment of the present disclosure is shown in Fig. 7. The process cartridge integrates a photoconductor 71, a charging roller 72, a developing roller 73, and a cleaning member 74, and is configured to be detachably attachable to the main body of an electrophotographic image forming apparatus. The process cartridge is equipped with the electrophotographic member according to one embodiment of the present disclosure described above, and such electrophotographic member can be suitably used in particular as the charging roller 72 and the developing roller 73. That is, the process cartridge is a process cartridge configured to be detachably mountable to the main body of an electrophotographic image forming apparatus, and may be a process cartridge equipped with the electrophotographic member of the present disclosure. EXAMPLES

[0090] An embodiment of the present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to the following examples.

[0091] <Example 1> (Preparation of mixture for forming elastic layer) 20.1 parts by mass of polypropylene glycol (product name: PREMINOL S 4013F, manufactured by AGC Corporation), 20.1 parts by mass of polypropylene glycol (product name: Uniol D-400 A first polyether having two isocyanate groups was synthesized by adding 19.2 parts by mass of isocyanate diisocyanate (XDI) (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 parts by mass of xylylene diisocyanate (XDI) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 500 ppm of 1,4-diazabicyclo[2.2.2]octane-2-methanol (product name: RZETA, manufactured by Tosoh Corporation) as a curing catalyst to a closed mixer and stirring for 4 hours in a closed mixer adjusted to 100°C. Incidentally, in the following examples and comparative examples, the amount of the curing catalyst is expressed in ppm by mass based on the mass of the elastic layer-forming mixture excluding the curing catalyst. This was mixed with 50.4 parts by mass of polycarbonate diol (product name: Duranol G3452, manufactured by Asahi Kasei Corporation).Then, the mixture was further stirred for 2 hours in a closed mixer adjusted to 100°C to synthesize a urethane reactive emulsifier having two hydroxyl groups (step (2-i)), and a dispersion in which droplets containing at least a portion of the urethane reactive emulsifier were dispersed in the polycarbonate diol was obtained (step (2-ii)). To this dispersion, 2.0 parts by mass of carbon black (product name: Denka Black powder, manufactured by Denka Co., Ltd.) was added and stirred for 3 minutes in a self-revolving vacuum degassing mixer at a rotation speed of 800 rpm and a revolution speed of 1600 rpm to obtain a dispersion in which the carbon black was dispersed. Next, 1.0 part by mass of xylylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter, sometimes referred to as "XDI") and 5.0 parts by mass of polyisocyanate (product name: Millionate MR-200, manufactured by Tosoh Corporation; hereinafter, sometimes referred to as "MR-200") were added to the dispersion in which the carbon black was dispersed, and the mixture was stirred for 2 minutes under conditions of a rotation speed of 800 rpm and a revolution speed of 1600 rpm in a self-revolving vacuum degassing mixer to obtain a mixture for forming an elastic layer (step (2-iii)).

[0092] (Manufacture of electrophotographic roller) A primer (product name: Metalock N-33, manufactured by Toyo Kagaku Kenkyusho Co., Ltd.) was applied to a SUS304 mandrel having a diameter of 6 mm and a length of 250 mm, and the mandrel was baked for 30 minutes at 130° C. Next, this mandrel was placed concentrically in a cylindrical mold having an inner diameter of 11.5 mm, and the mixture for forming the elastic layer was injected into the cylindrical mold preheated to 130° C. over 10 seconds. The cylindrical mold was heated at 130°C for 1 hour, and then demolded, and aged at 80°C for 2 days to obtain an elastic layer (step 2-iv). The ends of the elastic layer were then removed to obtain an electrophotographic roller with a length of 225 mm and an elastic layer thickness of 2.0 mm. The obtained electrophotographic roller was evaluated as follows.

[0093] <Evaluation method for electrophotographic rollers> (Evaluation 1: Review and analysis of the matrix and domain) Using a freeze cutting system (product name: EM FC6, manufactured by Leica Microsystems) and an ultramicrotome (product name: EM UC6, manufactured by Leica Microsystems), ultrathin slices (500 μm × 500 μm × 5 μm) were prepared from the elastic layer of the electrophotographic roller. The slices were prepared at three locations in total: the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where the length of the elastic layer in the longitudinal direction is L. The slices were prepared in which the cross section in the thickness direction of the elastic layer, in which the domain and matrix were exposed, was exposed. Mapping measurements were performed on the prepared sections using an infrared microscope and imaging system (product names: Spectrum 400 (analyzer) and Spotlight 400 (scanner), manufactured by PerkinElmer) to create mapping images. The measurements were performed using an ATR imaging accessory with a pixel size of 1.56 μm and a resolution of 16 cm. -1 Mapping measurements were performed under the conditions of a field of view of 300 μm×300 μm and a scan speed of 1.0 cm / s. The above mapping image is an image of the magnitude of the integrated value of the infrared absorption spectrum for each pixel. From the obtained mapping image, the presence of a matrix and domains was confirmed. Furthermore, from the infrared absorption spectrum of the matrix in the mapping image, it was confirmed that the matrix contained a structure corresponding to polycarbonate diol. From the infrared absorption spectrum of the domains in the mapping image, it was confirmed that the domains contained a structure corresponding to polypropylene glycol, that is, the matrix contained a carbonate structure represented by formula (1), and the domains contained an ether structure represented by formula (2).

[0094] (Evaluation 2: Measurement of micro rubber hardness) The micro rubber hardness of the elastic layer was measured using a micro rubber hardness tester (product name: MD-1capa, manufactured by Kobunshi Keiki Co., Ltd.). For the measurement, the electrophotographic roller was left in an environment at a temperature of 23°C for 24 hours or more, and the measurement was performed using a measuring device placed in the same environment. The indenter used was a type A indenter (indenter shape: height 0.50 mm, diameter 0.16 mm, cylindrical, pressure leg dimensions: outer diameter 4 mm, inner diameter 1.5 mm), and the measurement mode was peak hold mode. The locations for measuring the micro rubber hardness were three in total: the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where L is the longitudinal length of the elastic layer. The micro rubber hardness was measured once at each measurement location at a temperature of 23°C.

[0095] (Evaluation 3: Measurement of parameters indicating viscoelasticity) In the same manner as in Evaluation 1, ultrathin slices having cross sections exposing the domain and matrix were prepared from three locations: the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center. Within the thickness region from the outer surface to a depth of 100 μm on each section, an arbitrary square observation region with one side of 50 μm was selected, and viscoelasticity images were measured in a total of three observation regions using a scanning probe microscope (product name: S-Image, manufactured by SII Nano Technology Inc.). The measurement mode for the viscoelasticity images was VE-DFM. The cantilever used was "SI-DF3" (product name, manufactured by Hitachi High-Tech Science Corporation, spring constant = 1.9 N / m). The scanning frequency was 0.5 Hz. From the obtained viscoelastic images, parameters indicating the viscoelastic term in each observation region were calculated for 10 points each for the matrix and domain, and parameter A (mV) indicating the viscoelastic term of the domain and parameter B (mV) indicating the viscoelastic term of the matrix were obtained from the arithmetic mean values. It was confirmed by SPM viscoelasticity images that the domains and the matrix were exposed in the cross section.

[0096] (Evaluation 4: Measurement of recovery from deformation of the elastic layer) The recovery from deformation of the elastic layer was evaluated by an indentation test using a nanoindenter (product name: HM2000, manufactured by Fisher Instruments, Inc.) at a temperature of 23° C. For the measurement, the electrophotographic roller was left in an environment at a temperature of 23° C. for 24 hours or more, and the measurement was performed using a measuring device placed in the same environment. The measurement locations were three in total: the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where L is the longitudinal length of the elastic layer. In the indentation test, a Vickers indenter was placed in contact with the matrix on the outer surface of the elastic layer, and the Vickers indenter (square pyramid type, facing angle 136°) was pressed into the elastic layer at a loading rate of 10 mN / 30 seconds, and the load of 10 mN was maintained for 60 seconds. After that, the load was removed at a loading rate of 10 mN / second, and the strain was measured once at each measurement location 5 seconds after the completion of the unloading.

[0097] (Evaluation 5: Measurement of matrix elastic modulus) In the same manner as in Evaluation 1, ultrathin slices were prepared from three locations: the longitudinal center of the elastic layer, and two locations at L / 4 from both ends of the elastic layer toward the center, exposing the cross section of the domain and matrix. A square observation area with a side length of 50 μm was placed at an arbitrary position within the area corresponding to the thickness region from the outer surface of the elastic layer of each slice to a depth of 100 μm. Then, a scanning probe microscope (product name: MFP-3D-Origin, Oxford University) was used to observe the three observation areas in total. The phase image was observed using an AFM (manufactured by Olympus Instruments Co., Ltd.). The phase image measurement mode was AM-AFM. The cantilever used was an "OMCL-AC-160TS" (product name, manufactured by Olympus Corporation, spring constant = 47.08 N / m). The scanning frequency was 0.5 Hz. From the obtained phase image, the elastic modulus of the matrix was obtained by measuring a force curve using the above-mentioned scanning probe microscope. The force curve measurement mode was contact mode, the force distance was 500 nm, and the trigger point was 0.01 V. In addition, the cantilever used was "OMCL-AC-160TS" (product name, manufactured by Olympus Corporation, spring constant = 47.08 N / m). In addition, the scanning frequency was 1 Hz. For each observation area, the elastic modulus of the matrix was calculated at 10 points, and the arithmetic mean value was calculated. Incidentally, it was confirmed by SPM phase images that the domains and the matrix were exposed in the cross section.

[0098] (Evaluation 6: Evaluation of the area ratio of conductive fillers present in the matrix and domains) Sections (500 μm × 500 μm × 100 nm) were prepared from the electrophotographic roller using a freeze cutting system (product name: EM FC6, manufactured by Leica Microsystems) and an ultramicrotome (product name: EM UC6, manufactured by Leica Microsystems). The sections were prepared at three locations in total, the center of the elastic layer in the longitudinal direction, and two locations at L / 4 from both ends of the elastic layer toward the center, where the length of the elastic layer in the longitudinal direction is L, and sections were prepared in which the cross section in the thickness direction of the elastic layer, in which the domain and matrix were exposed, were exposed. A square observation area with a side length of 50 μm was placed at an arbitrary position within the region corresponding to the thickness region from the outer surface of the elastic layer to a depth of 100 μm in each section. Then, a high-resolution electron energy loss spectroscopy microscope (product name: H-7100FA, manufactured by Hitachi High-Technologies Corporation) combining a transmission electron microscope (TEM) and an electron energy loss spectroscopy (EELS) was used for a total of three observation regions to obtain TEM images and oxygen atom mapping images (hereinafter also simply referred to as "mapping images") of the observation regions under conditions of an acceleration voltage of 100 kV, an observation magnification of 3,000 times, and a beam diameter of 2 nm.

[0099] The TEM image confirmed the presence of a matrix and a domain in the observed region. In addition, the mapping image showed that the region not containing oxygen atoms, i.e., the carbon black (conductive filler) portion, could be distinguished from the urethane elastomer region. The TEM image and mapping image also identified the carbon black present in the matrix and the carbon black present in the domain. Next, the mapping image was binarized using image processing software (product name: ImageProPlus, manufactured by Media Cybernetics) to binarize the carbon black portion and the urethane elastomer portion to obtain a binarized image for analysis. The threshold value for binarization was determined based on the luminance distribution of the mapping image, based on the Otsu's algorithm described in Non-Patent Document 1. Next, the total area of ​​carbon black (conductive filler) present in the matrix in the observation region and the total area of ​​carbon black (conductive filler) present in the domain in the observation region were calculated from the obtained binary image using the counting function of the image processing software. Then, the ratio (area ratio) of the total area of ​​carbon black present in the matrix to the total area of ​​carbon black present in the observation region was calculated.

[0100] (Evaluation 7: Measurement of domain cross-sectional area and number) Each of the three viscoelastic images obtained in Evaluation 3 was processed using image processing software (product name: ImageProPlus, manufactured by Media Cybernetics) in 256 gradations. The monochrome image was converted to a grayscale image and then binarized to obtain a binary image for analysis. The threshold for binarization was determined based on the luminance distribution of the monochrome image, based on the Otsu algorithm described in Non-Patent Document 1. Furthermore, the cross-sectional area of ​​the domains, the number of domains, and the average cross-sectional area of ​​the domains were calculated from the obtained binary image using the counting function of the image processing software. However, among the domains determined to be domains by the counting function, domains with a cross-sectional area of ​​less than 0.05% by area of ​​the 50 μm square observation area were regarded as noise and removed from the data. Then, the ratio (area %) of the total cross-sectional area of ​​the domains in each observation area to the area of ​​the observation area was calculated. In addition, the number of domains in each observation region whose cross-sectional area was 0.1 to 13.0 area% of the observation region was determined, and the ratio (area %) of the number of domains having a cross-sectional area of ​​0.1 to 13.0 area% relative to the observation region was calculated.

[0101] (Evaluation 8: Measurement of circularity and number of domains) From the binarized images obtained in Evaluation 7, the circularity and average circularity of the domains were calculated using the counting function of the image processing software. However, noise was removed from the data in the same manner as in Evaluation 7. Then, the number of domains with a circularity of 0.60 to 0.95 among the domains in each observation region was counted, and the ratio (number %) of the number of domains with a circularity of 0.60 to 0.95 to the total number of domains in each observation region was calculated.

[0102] (Evaluation 9: Evaluation of streaky image defects) A color laser printer (product name: LBP7700C, manufactured by Canon Inc.) and a process cartridge incorporating an electrophotographic roller as a developing roller were acclimatized to an environment of temperature 23° C. / humidity 50% RH for 24 hours, and then image evaluation was performed. Specifically, a process cartridge incorporating an electrophotographic roller as a developing roller was installed in the above-mentioned color laser printer, and 10 halftone images (images depicting horizontal lines with a width of 1 dot and an interval of 2 dots in the direction perpendicular to the rotation direction of the photoreceptor) were output continuously, and the images obtained were visually observed, and streak-like image defects were judged according to the following two criteria. <Evaluation of streaky image defects 9-1> Rank A: No streaky image defects were observed from the first sheet. Rank B: Streaky image defects are observed only on the first sheet. Rank C: Streaky image defects are observed on the second and subsequent sheets. <Evaluation of streaky image defects 9-2> Rank A: No streak-like image defects are observed over the entire length of the electrophotographic roller. Rank B: Streaky image defects are observed in a portion of the longitudinal direction of the electrophotographic roller. Rank C: Streaky image defects are observed over a wide range in the longitudinal direction of the electrophotographic roller and are noticeable.

[0103] (Evaluation 10: Evaluation of edge scraping, toner fusion, and image defects caused by toner fusion) The above color laser printer and a process cartridge incorporating the electrophotographic roller as a developing roller were allowed to acclimate to an environment of temperature 23° C. / humidity 50% RH for 24 hours. Thereafter, the electrophotographic roller was attached as a developing roller to the above-mentioned color laser printer, and an image of horizontal lines with a width of 2 dots and an interval of 50 dots was continuously output on 10,000 sheets. During the continuous output of 10,000 sheets, the developing roller was taken out every 1,000 sheets and visually observed, and the abrasion of the end portion of the developing roller and the fusion of toner were judged according to the following criteria. <Evaluation 10-1: Evaluation of edge wear> The number of sheets output when scraping of the end portion of the developing roller was observed was counted as the number of sheets generated. <Evaluation 10-2: Evaluation of toner fusion> The number of sheets output when fusion of toner to the developing roller was observed was counted as the number of sheets generated.

[0104] <Evaluation 10-3: Evaluation of image defects caused by toner fusion> During the continuous output of 10,000 sheets, the images output every 10th sheet were checked. If there was an image defect such as toner being transferred to the paper at intervals of one revolution of the electrophotographic roller in areas other than the horizontal lines, the output was temporarily stopped and the electrophotographic roller was removed from the process cartridge. If the location where the image defect occurred matched the location and size of the fused toner part of the electrophotographic roller, the number of sheets output at the time of the temporary stop was counted as the number of sheets with image defects caused by fused toner.

[0105] (Evaluation 11: Solid image density evaluation) A color laser printer (product name: LBP7700C, manufactured by Canon Inc.) and a process cartridge incorporating an electrophotographic roller as a developing roller were acclimatized to an environment of 15°C temperature and 10% RH for 24 hours, after which a full solid image was printed in the same environment and the density was evaluated. The density evaluation was measured using a spectrodensitometer: X-Rite504 (product name, S-DG Corporation). The image density was the average value when 15 random points were measured for one full solid image. Images that met the following criteria were rated "OK", and those that did not were rated "NG". If the full solid image met the following criteria, it could be judged that the image density was sufficient. Criteria: For a single solid full-surface image, the average value when measuring 15 random points is 1.3 or more.

[0106] <Examples 2 to 7, 9 to 12, 14, 15, and 18> Except for preparing an elastic layer-forming mixture using the materials shown in Table 4 in the blending amounts shown in Table 4, an elastic layer was formed in the same manner as in Example 1, and an electrophotographic roller according to each Example was produced. The obtained electrophotographic roller was evaluated in the same manner as in Example 1. Details of the materials in Table 4 are shown in Tables 1, 2 and 3. The same applies to the following examples.

[0107] <Example 8> Except for preparing an elastic layer-forming mixture using the materials shown in Table 4 in the blending amounts shown in Table 4 and injecting the elastic layer-forming mixture into the cylindrical mold for 5 seconds, an elastic layer was formed in the same manner as in Example 1 to produce an electrophotographic roller according to Example 8. The obtained electrophotographic roller was evaluated in the same manner as in Example 1.

[0108] <Examples 13, 16, and 17> Except for preparing an elastic layer-forming mixture using the materials shown in Table 4 in the amounts shown in Table 4 and injecting the elastic layer-forming mixture into the cylindrical tubular mold for 3 seconds, an elastic layer was formed in the same manner as in Example 1 to produce an electrophotographic roller according to each Example. The obtained electrophotographic roller was evaluated in the same manner as in Example 1. [Table 1]

[0109] In the table, tetrahydrofuran-neopentyl glycol copolymer is a polyether glycol represented by HO-(CH2CH2CH2CH2O)m-(CH2C(CH3)2CH2O)n-OH. In other words, the description of 4 (straight chain) + 5 (branched) for the number of carbon atoms in tetrahydrofuran-neopentyl glycol copolymer is R 2 This indicates that the compound contains a linear structure having four carbon atoms and a branched structure having five carbon atoms. [Table 2]

[0110] In the table, Kuraray Polyol C-2090 (manufactured by Kuraray Co., Ltd.) is a polycarbonate polyol having a number average molecular weight of 2000, a hydroxyl value of 56.3 mgKOH / g, and a structure corresponding to 1,6-hexanediol and a structure corresponding to 3-methyl-1,5-pentanediol. 1indicates that it contains a linear structure having 6 carbon atoms and a branched structure having 6 carbon atoms. Kuraray Polyol P-2050 is a polyester polyol having a structure corresponding to adipic acid and a structure corresponding to 3-methyl-1,5-pentanediol. [Table 3] [Table 4]

[0111] <Comparative Example 1> (Preparation of mixture for forming elastic layer) 24.9 parts by mass of polypropylene glycol (product name: PREMINOL S 4013F, manufactured by AGC Inc.), 24.0 parts by mass of polypropylene glycol (product name: Uniol D-4000, manufactured by NOF Corporation), 3.1 parts by mass of xylylene diisocyanate (XDI) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 500 ppm of 1,4-diazabicyclo[2.2.2]octane-2-methanol (product name: RZETA, manufactured by Tosoh Corporation) as a curing catalyst were added to a closed mixer and stirred for 4 hours in a closed mixer adjusted to 100°C to synthesize a polyether having two isocyanate groups. This was mixed with 41.5 parts by mass of polycarbonate diol (product name: Duranol G3452, manufactured by Asahi Kasei Corporation).Then, the mixture was further stirred for 2 hours in a closed mixer adjusted to 100°C to synthesize a urethane reactive emulsifier having two hydroxyl groups, and a dispersion was obtained in which droplets containing at least a portion of the urethane reactive emulsifier were dispersed in the polycarbonate diol. To this dispersion, 2.0 parts by mass of carbon black (product name: Denka Black powder, manufactured by Denka Co., Ltd.) was added and stirred for 3 minutes in a self-revolving vacuum degassing mixer at a rotation speed of 800 rpm and a revolution speed of 1600 rpm to obtain a dispersion in which the carbon black was dispersed. Next, 0.1 parts by mass of xylylene diisocyanate (XDI) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.6 parts by mass of polyisocyanate (product name: Millionate MR-200, manufactured by Tosoh Corporation) were added to the dispersion in which the carbon black was dispersed, and the mixture was stirred for 2 minutes under conditions of a rotation speed of 800 rpm and a revolution speed of 1600 rpm in a self-revolving vacuum degassing mixer to form an elastic layer. A mixture was obtained. Except for using the thus obtained elastic layer-forming mixture, an electrophotographic roller according to Comparative Example 1 was obtained in the same manner as in Example 1. The obtained electrophotographic roller was evaluated in the same manner as in Example 1.

[0112] Regarding the result of evaluation 1, the matrix and the domain were clearly phase-separated. It was also confirmed that the matrix contained a structure corresponding to polypropylene glycol, and the domain contained a structure corresponding to polycarbonate diol. In other words, the relationship between the domain and the matrix was reversed from that of the urethane elastomer of Example 1.

[0113] <Comparative Example 2> (Preparation of mixture for forming elastic layer) 20.1 parts by mass of polypropylene glycol (product name: PREMINOL S 4013F, manufactured by AGC Inc.), 19.2 parts by mass of polypropylene glycol (product name: Uniol D-4000, manufactured by NOF Corporation), and 500 ppm of 1,4-diazabicyclo[2.2.2]octane-2-methanol (product name: RZETA, manufactured by Tosoh Corporation) as a curing catalyst were added to a closed mixer and stirred for 2 hours in a closed mixer adjusted to 100°C. This was mixed with 50.4 parts by mass of polycarbonate diol (product name: Duranol G3452, manufactured by Asahi Kasei Corporation), and then stirred for an additional 2 hours in a closed mixer adjusted to 100°C. Further, 2.0 parts by mass of carbon black (product name: Denka Black powder, manufactured by Denka Co., Ltd.) was added, and the mixture was stirred for 3 minutes with a rotary vacuum degassing mixer at a rotation speed of 800 rpm and a revolution speed of 1600 rpm. To this was added 3.5 parts by mass of xylylene diisocyanate (XDI) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.0 parts by mass of polyisocyanate (product name: Millionate MR-200, manufactured by Tosoh Corporation). The resulting mixture was stirred for 2 minutes in a self-revolving vacuum degassing mixer at a rotation speed of 800 rpm and a revolution speed of 1600 rpm to obtain a mixture for forming an elastic layer. An elastic layer was formed in the same manner as in Example 1, except that this mixture for forming an elastic layer was used, and an electrophotographic roller according to Comparative Example 2 was produced. The obtained electrophotographic roller was evaluated in the same manner as in Example 1. In this comparative example, the same raw materials as in Example 1 were used. However, no urethane reactive emulsifier was synthesized, and therefore no dispersion in which droplets containing at least a part of the urethane reactive emulsifier were dispersed in polycarbonate diol was formed. Regarding the results of evaluation 1 of the electrophotographic roller obtained by this comparative example, although a matrix and a domain were observed, the boundary between the matrix and the domain was extremely unclear. Although the reason is unclear, the elastic layer according to this comparative example was produced without going through a process of forming a dispersion in which droplets containing at least a part of the urethane reactive emulsifier were dispersed in polycarbonate diol. Therefore, in the process of forming the elastic layer, although polycarbonate diol and polypropylene glycol are phase-separated due to the difference in compatibility between polycarbonate glycol and polycarbonate diol, a region in which polycarbonate diol and polypropylene glycol are mixed is formed around the droplet containing polycarbonate diol, so that the boundary between the matrix and the domain is considered to be unclear. Also, in the elastic layer according to this comparative example, it is considered that almost no urethane bond is formed at the interface between the domain and the matrix. As a result, it is considered that the result of evaluation 4 is large at 3.00 μm.

[0114] <Comparative Example 3> (Preparation of mixture for forming elastic layer) 46.6 parts by mass of polycarbonate diol (product name: Kuraray Polyol C-2090, manufactured by Kuraray Co., Ltd.), 44.8 parts by mass of silicone particles (product name: KMP-598, manufactured by Shin-Etsu Chemical Co., Ltd.) which are soft resin particles, and 1,4-diazabicyclo[4.1.2]cyclopentadiene as a curing catalyst. [2.2.2] 500 ppm of octane-2-methanol (product name: RZETA, manufactured by Tosoh Corporation) was added to a closed mixer and stirred for 4 hours in a closed vacuum mixer adjusted to 100°C. Further, 2.0 parts by mass of carbon black (product name: Denka Black, manufactured by Denka Co., Ltd.) was added, and the mixture was stirred for 3 minutes using a rotary vacuum degassing mixer at a rotation speed of 800 rpm and a revolution speed of 1600 rpm. To this was added 2.6 parts by mass of xylylene diisocyanate (XDI) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.2 parts by mass of polyisocyanate (product name: Millionate MR-200, manufactured by Tosoh Corporation). The resulting mixture was stirred for 2 minutes in a self-revolving vacuum degassing mixer at a rotation speed of 800 rpm and a revolution speed of 1600 rpm to obtain a mixture for forming an elastic layer. Except for using this elastic layer-forming mixture, an elastic layer was formed in the same manner as in Example 1 to produce an electrophotographic roller according to Comparative Example 3. The obtained electrophotographic roller was evaluated in the same manner as in Example 1. In the evaluation of the electrophotographic roller according to this Comparative Example, the silicone particles were regarded as domains.

[0115] <Comparative Example 4> (Preparation of mixture for forming elastic layer) 100.0 parts by mass of NBR (trade name: N230SV, manufactured by JSR Corporation), 50.0 parts by mass of carbon black (trade name: Toka Black #7360, manufactured by Tokai Carbon Co., Ltd.), 70.0 parts by mass of calcium carbonate (trade name: Nanox #30, manufactured by Maruo Calcium Co., Ltd.), 7.0 parts by mass of zinc oxide (trade name: zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.), and 2.8 parts by mass of zinc stearate (trade name: SZ-2000, manufactured by Sakai Chemical Industry Co., Ltd.) were mixed in a pressure kneader for 16 minutes under conditions of a filling rate of 70 vol% and a blade rotation speed of 30 rpm, to obtain an unvulcanized rubber for forming a matrix. Next, 100.0 parts by mass of SBR (trade name: Tufden 2003, manufactured by Asahi Kasei Corporation), 5.0 parts by mass of zinc oxide (trade name: zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.), and 2.0 parts by mass of zinc stearate (trade name: SZ-2000, manufactured by Sakai Chemical Industry Co., Ltd.) were mixed in a pressure kneader for 16 minutes under conditions of a filling rate of 70 vol% and a blade rotation speed of 30 rpm to obtain an unvulcanized rubber for domain formation.

[0116] Further, 65.0 parts by mass of unvulcanized rubber for forming a matrix and 35.0 parts by mass of unvulcanized rubber for forming a domain were mixed in a pressure kneader at a filling rate of 70 vol% and a blade rotation speed of 30 rpm for 16 minutes to obtain an unvulcanized rubber mixture. 100.0 parts by mass of the obtained unvulcanized rubber mixture, 3.0 parts by mass of sulfur (product name: Sulfac PMC, manufactured by Tsurumi Chemical Industry Co., Ltd.), and 2.0 parts by mass of tetrabenzyl thiuram disulfide (product name: TBZTD, manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed on an open roll with a front roll rotation speed of 10 rpm, a rear roll rotation speed of 8 rpm, and a roll gap of 2 mm, and turned left and right a total of 20 times, and then thinly passed 10 times with a roll gap of 0.5 mm to obtain a mixture for forming an elastic layer.

[0117] (Manufacture of electrophotographic roller) A primer (product name: Metalock N-33, manufactured by Toyo Kagaku Kenkyusho Co., Ltd.) was applied to a SUS304 mandrel having a diameter of 6 mm and a length of 250 mm, and baked at 130° C. for 30 minutes. Next, a die with an inner diameter of 14.0 mm was attached to the tip of a crosshead extruder having a mandrel supply mechanism and an unvulcanized rubber roller discharge mechanism, and the crosshead extruder was preheated to 80° C. The conveying speed of the mandrel was adjusted to 60 mm / sec, and the elastic layer forming mixture was supplied from the extruder to cover the outer periphery of the mandrel with the elastic layer forming mixture in the crosshead, thereby obtaining an unvulcanized rubber roller. The obtained unvulcanized rubber roller was heated in a hot air vulcanizing oven at 170°C for 60 minutes to obtain a roller having an elastic layer formed on the outer periphery of the mandrel. After that, the end of the elastic layer was removed, and the surface of the elastic layer was rotated. By grinding with a rolling grindstone, an electrophotographic roller having a length of 225 mm and an elastic layer thickness of 2.0 mm was obtained. The obtained electrophotographic roller was evaluated in the same manner as in Example 1.

[0118] The evaluation results of Examples 1 to 18 and Comparative Examples 1 to 3 are shown in Tables 5-1 to 5-4 and 6. [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4] In Tables 5-1 to 5-4, M represents a matrix, D represents a domain, A and B represent parameters A and B indicating the viscoelastic term, respectively, and PPG represents polypropylene glycol. [Table 6]

[0119] In the electrophotographic rollers according to Examples 1 to 18, the micro rubber hardness of the elastic layer was low, and a plurality of domains were dispersed in the matrix containing the urethane elastomer. In addition, the parameter B indicating the viscoelasticity term of the matrix was larger than the parameter A indicating the viscoelasticity term of the domain, and the circularity of the domain was high, and the elastic modulus of the matrix was also high, so that good results were obtained in the evaluation of streak-like image defects. In addition, although toner fusion was observed in some electrophotographic rollers, no image defects due to toner fusion occurred.

[0120] On the other hand, in the electrophotographic roller according to Comparative Example 1, parameter A indicating the viscoelasticity term of the domain was larger than parameter B indicating the viscoelasticity term of the matrix. As a result, since A>B was not satisfied, an excessive decrease in micro rubber hardness occurred, and edge chipping occurred. In the electrophotographic roller according to Comparative Example 2, polyether was synthesized, and the matrix domain structure was formed by mechanical phase separation without going through the process of synthesizing a urethane reactive emulsifier. Therefore, the phase separation was unclear, and the circularity of the domain was also reduced. As a result, the micro rubber hardness was less than 20 degrees, the distortion was 3 μm, and edge scraping and streak images occurred.

[0121] The electrophotographic roller according to Comparative Example 3 used soft particles as the domain, but in order to maintain the shape of the particles, the parameter A indicating the viscoelasticity term was much larger than that of the domain according to the present disclosure, and the parameter B indicating the viscoelasticity term of the matrix also had to be made large, resulting in a micro rubber hardness of 60. And, toner fusion occurred. In the image evaluation, image defects due to toner fusion occurred on 8,410 sheets. In the electrophotographic roller according to Comparative Example 4, vulcanized rubber was used as the material for the elastic layer, and therefore the abrasion resistance was low, and scraping occurred at the ends.

[0122] The present disclosure relates to the following configurations. (Configuration 1) An electrophotographic member, the electrophotographic member having an elastic layer having electrical conductivity, the elastic layer includes a urethane elastomer and a conductive filler; The urethane elastomer has a matrix and a plurality of domains dispersed in the matrix, A relationship between a parameter A indicating the viscoelastic term of the domain and a parameter B indicating the viscoelastic term of the matrix, which is measured in a viscoelastic image of a cross section of the elastic layer where the domain and the matrix are exposed, by a scanning probe microscope, is A <Bであり、 The micro rubber hardness of the elastic layer at a temperature of 23°C is 20 to 50 degrees, an electrophotographic member characterized in that when a Vickers indenter is brought into contact with the matrix on the outer surface of the elastic layer at a temperature of 23°C, the Vickers indenter is pressed into the elastic layer at a loading rate of 10 mN / 30 seconds, the load of 10 mN is maintained for 60 seconds, and then the load is removed, the distortion 5 seconds after removal of the load is 1.00 μm or less. (Configuration 2) 2. The electrophotographic member of embodiment 1, wherein the conductive filler is conductive carbon black. (Configuration 3) 3. The electrophotographic member according to configuration 1 or 2, wherein, when a length in the longitudinal direction of the elastic layer is L, a square observation area having a side length of 50 μm is placed in a thickness region from an outer surface of the elastic layer to a depth of 100 μm in each of three cross sections in which the domain and the matrix are exposed in the thickness direction of the elastic layer, the cross sections being at a total of three locations, namely, the center of the elastic layer in the longitudinal direction and two locations each having a length of L / 4 from each end of the elastic layer toward the center, each of the observation areas satisfies requirement (1) and requirement (2). Requirement (1): The total cross-sectional area of ​​the domains present in the observation region accounts for 15 to 45% of the area of ​​the observation region. Requirement (2): Among the domains present in the observation region, the proportion of domains having a cross-sectional area of ​​0.1 to 13.0 area % relative to the area of ​​the observation region is 70% or more by number. (Configuration 4) 4. The electrophotographic member according to any one of Configurations 1 to 3, wherein the proportion of the domains having a circularity of 0.60 to 0.95 in the observation region is 70% by number or more. (Configuration 5) The matrix comprises a polycarbonate structure represented by formula (1), and 5. The electrophotographic member according to any one of configurations 1 to 4, wherein the domain contains a polyether structure represented by formula (2). TIFF2024062624000014.tif26170 (in formula (1), R 1 represents an alkylene group having 3 to 9 carbon atoms. TIFF2024062624000015.tif16170 (in formula (2), R 2represents an alkylene group having 3 to 5 carbon atoms. (Configuration 6) R 1 6. The electrophotographic member according to configuration 5, wherein is an alkylene group having a branched structure and having 3 to 9 carbon atoms. (Configuration 7) R 2 is an alkylene group having a branched structure and having 3 to 5 carbon atoms. (Configuration 8) The electrophotographic member according to any one of Configurations 1 to 7, wherein, when a length in the longitudinal direction of the elastic layer is L, a square observation area having a side length of 50 μm is placed in a thickness region from an outer surface of the elastic layer to a depth of 100 μm in each of three cross sections in which the domain and the matrix in the thickness direction of the elastic layer are exposed at a total of three locations, namely, a center of the elastic layer in the longitudinal direction and two locations each having a length of L / 4 from each end of the elastic layer toward the center, each of the observation areas satisfies requirement (3). Requirement (3): The ratio of the area of ​​the conductive filler contained in the matrix present in the observation region to the total area of ​​the conductive filler present in the observation region is 95% or more. (Configuration 9) 9. The electrophotographic member according to any one of configurations 1 to 8, wherein the ratio of the parameter A to the parameter B (A / B) is 0.65 or less. (Configuration 10) 10. A process cartridge configured to be detachably mountable to a main body of an electrophotographic image forming apparatus, the process cartridge comprising the electrophotographic member according to any one of Configurations 1 to 9. (Configuration 11) An electrophotographic image forming apparatus comprising the electrophotographic member according to any one of Configurations 1 to 9.

Claims

1. An electrophotographic member, the electrophotographic member having an elastic layer having electrical conductivity, the elastic layer includes a urethane elastomer and a conductive filler; The urethane elastomer has a matrix and a plurality of domains dispersed in the matrix, a parameter A indicating a viscoelastic term of the domain and a parameter B indicating a viscoelastic term of the matrix, the parameter A being measured in a viscoelastic image of a cross section of the elastic layer, in which the domain and the matrix are exposed, by a scanning probe microscope, the relationship between A and B being A<B; The micro rubber hardness of the elastic layer at a temperature of 23°C is 20 to 50 degrees, an electrophotographic member characterized in that, at a temperature of 23°C, a Vickers indenter is brought into contact with the matrix on the outer surface of the elastic layer, the Vickers indenter is pressed into the elastic layer at a loading rate of 10 mN / 30 seconds, the load of 10 mN is maintained for 60 seconds, and then the load is released, and a distortion 5 seconds after the load is released is 1.00 μm or less.

2. 2. The electrophotographic member of claim 1 wherein said conductive filler is conductive carbon black.

3. 2. The electrophotographic member according to claim 1, wherein, when a length of the elastic layer in the longitudinal direction is L, a square observation area having a side length of 50 μm is placed in a thickness region from an outer surface of the elastic layer to a depth of 100 μm for each of three cross sections in which the domain and the matrix are exposed in the thickness direction of the elastic layer, the cross sections being at a center in the longitudinal direction of the elastic layer and two locations at a distance of L / 4 from both ends of the elastic layer toward the center, and each of the observation areas satisfies requirement (1) and requirement (2). Requirement (1): The ratio of the total cross-sectional area of ​​the domains present in the observation region is 15 to 45 area % of the area of ​​the observation region. Requirement (2): The proportion of domains present in the observation region that have a cross-sectional area of ​​0.1 to 13.0% of the area of ​​the observation region is 70% or more by number.

4. 4. The electrophotographic member according to claim 3, wherein the proportion of the number of domains having a circularity of 0.60 to 0.95 in the observation region is 70% or more by number.

5. The matrix comprises a polycarbonate structure represented by formula (1), and 2. The electrophotographic member of claim 1, wherein said domain comprises a polyether structure represented by formula (2). (In formula (1), R １ represents an alkylene group having 3 to 9 carbon atoms. (In formula (2), R ２ represents an alkylene group having 3 to 5 carbon atoms.

6. The R １ 6. The electrophotographic member according to claim 5, wherein is an alkylene group having a branched structure and having 3 to 9 carbon atoms.

7. The R ２ 6. The electrophotographic member according to claim 5, wherein is an alkylene group having a branched structure and having 3 to 5 carbon atoms.

8. 2. The electrophotographic member according to claim 1, wherein, when a length of the elastic layer in the longitudinal direction is L, a square observation area having a side length of 50 μm is placed in a thickness region from an outer surface of the elastic layer to a depth of 100 μm for each of three cross sections in which the domains and the matrix in the thickness direction of the elastic layer are exposed, the cross sections being at a center of the elastic layer in the longitudinal direction and two locations at a distance of L / 4 from both ends of the elastic layer toward the center, and each of the observation areas satisfies requirement (3). Requirement (3): The ratio of the area of ​​the conductive filler contained in the matrix present in the observation region to the total area of ​​the conductive filler present in the observation region is 95% or more.

9. 2. The electrophotographic member according to claim 1, wherein the ratio of said parameter A to said parameter B (A / B) is 0.65 or less.

10. 10. A process cartridge configured to be detachably mountable to a main body of an electrophotographic image forming apparatus, the process cartridge comprising the electrophotographic member according to any one of claims 1 to 9.

11. An electrophotographic image forming apparatus comprising the electrophotographic member according to any one of claims 1 to 9.

Images