Electrophotographic member, electrophotographic process cartridge, electrophotographic image forming apparatus, and ion conducting agent

Abstract

To provide an electrophotographic member that can stably form high-quality electrophotographic images, even when it is subjected to formation of a large number of electrophotographic images over a long period in a low temperature environment.SOLUTION: An electrophotographic member has a conductive substrate, and a conductive layer on the substrate. The conductive layer includes a first resin and a second resin. The first resin is a resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring. The second resin includes a (meth)acrylic resin having a structure represented by the formula (1) and a specific structure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to an electrophotographic member incorporated in an apparatus employing an electrophotographic method. The present disclosure also relates to an electrophotographic process cartridge and an electrophotographic image forming apparatus using the electrophotographic member. The present disclosure also relates to an ionic conductive agent.

Background Art

[0002] In an electrophotographic image forming apparatus (also referred to as an "electrophotographic apparatus"), for example, an electrophotographic member having a conductive layer is used as a developing member, a charging member, a toner supply member, or a cleaning member. The conductive layer of the electrophotographic member has, for example, an electric resistance value controlled within a range of 1.0×10 5 ~1.0×10 9 Ω. Further, the conductivity needs to be uniform over the entire member and stable over time. As a conductive agent used to impart a predetermined conductivity to the conductive layer, there are conductive particles such as carbon black and ionic conductive agents such as salts of sulfonylimide anions and metal cations.

[0003] An electronically conductive roller containing conductive particles such as carbon black has an advantage that changes such as an increase in resistance due to uneven distribution of the conductive component are less likely to occur even during long-term energization. However, on the other hand, conductive particles such as carbon black are difficult to be uniformly dispersed, and locally high-resistance or low-resistance sites may occur. An ionically conductive roller containing an ionic conductive agent can reduce unevenness in electric resistance value caused by uneven dispersion of the conductive agent as compared with the electronically conductive roller, and locally high-resistance or low-resistance sites are less likely to occur. Therefore, in the developing roller, the developer can be uniformly developed on the photoreceptor, and in the charging roller, uniform charging of the photoreceptor surface becomes possible.

[0004] Patent Document 1 discloses a conductive roller formed using a polymer composition containing a salt having an anion having a fluoro group and a sulfonyl group and having a non-chlorine and non-bromine-based polymer as a main component.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, electrophotographic apparatuses have been required to maintain high image quality and high durability even in harsher environments. The inventors of the present invention mounted the conductive roller described in Patent Document 1 as a developing roller on an electrophotographic process cartridge, and using this process cartridge, output a large number of electrophotographic images in an environment at a temperature of 0°C. As a result, ghosting may occur in the electrophotographic images as the number of output sheets increases.

[0007] At least one aspect of the present disclosure is directed to providing an electrophotographic member that contributes to the stable formation of high-quality electrophotographic images in a low-temperature environment. Also, at least one aspect of the present disclosure is directed to providing an electrophotographic process cartridge that contributes to the stable formation of high-quality electrophotographic images. Also, at least one aspect of the present disclosure is directed to providing an electrophotographic image forming apparatus capable of stably forming high-quality electrophotographic images. Furthermore, at least one aspect of the present disclosure is directed to providing an ionic conductive agent that contributes to the effective dissociation of ions thereof.

Means for Solving the Problems

[0008] According to at least one aspect of the present disclosure, an electrophotographic member having a conductive substrate and a conductive layer on the substrate, wherein the conductive layer contains a first resin and a second resin, The first resin is a resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring. An electrophotographic member is provided, wherein the second resin includes a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2).

Chemical formula

Chemical formula

[0009] Further, according to at least one aspect of the present disclosure, an electrophotographic process cartridge configured to be detachable from the main body of an electrophotographic apparatus is provided, the electrophotographic process cartridge including the electrophotographic member of the present disclosure. Furthermore, according to at least one aspect of the present disclosure, an electrophotographic image forming apparatus including the electrophotographic member of the present disclosure as a developing member is provided.

[0010] In addition, according to at least one aspect of the present disclosure, an ion conductive agent including a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2) is provided. [Chemical formula] [Chemical formula] In formula (1), R 12 represents a hydrogen atom or a methyl group, R 13 represents an alkylene group having a straight chain or a branch with 1 to 7 carbon atoms, R 14 represents a fluorine atom or a perfluoroalkyl group having a straight chain or a branch with 1 to 4 carbon atoms, X + represents at least one selected from the group consisting of lithium ions, sodium ions, and potassium ions; In formula (2), R 21 represents a hydrogen atom or a methyl group, R 22 represents an alkyl group having a straight chain or a branch with 1 to 6 carbon atoms, or an alicyclic hydrocarbon group with 5 to 6 carbon atoms. [Advantages of the Invention]

[0011] According to at least one aspect of the present disclosure, an electrophotographic member that contributes to the stable formation of high-quality electrophotographic images in a low-temperature environment can be obtained. Also, according to at least one aspect of the present disclosure, an electrophotographic process cartridge that contributes to the stable formation of high-quality electrophotographic images can be obtained. Further, according to at least one aspect of the present disclosure, an electrophotographic image forming apparatus that can stably form high-quality electrophotographic images can be obtained. Moreover, according to at least one aspect of the present disclosure, an ionic conductive agent that contributes to the effective dissociation of ions can be obtained. [Brief Description of the Drawings]

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Embodiments for Carrying Out the Invention

[0013] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise specified. When numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined. Further, in the present disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any one of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. Note that when XX is a group, a plurality may be selected from XX, and the same applies to YY and ZZ. In the present disclosure, the (meth)acrylic resin includes at least one selected from the group consisting of acrylic resin and methacrylic resin. Further, the (meth)acrylate means at least one selected from the group consisting of methacrylate and acrylate.

[0014] ​The inventors of the present invention confirmed that, in the output test of electrophotographic images under a low-temperature environment using the conductive roller according to Patent Document 1 described above, the electrical resistance of the surface of the conductive roller immediately after the occurrence of ghosting increased. From this, it was speculated that the occurrence of ghosting was due to the accumulation of charges on the conductive roller as the number of output electrophotographic images increased. Based on such considerations, as a result of repeated studies by the inventors of the present invention, it has been found that the following electrophotographic member contributes to the solution of the above-described problems.

[0015] That is, an electrophotographic member according to one aspect of the present disclosure is an electrophotographic member having a conductive substrate and a conductive layer on the substrate, wherein the conductive layer contains a first resin and a second resin, the first resin is a resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring, and the second resin contains a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2), and relates to an electrophotographic member.

Chemical formula

Chemical formula

[0016] The inventors of the present invention speculate as follows on the reason why the electrophotographic member according to the above configuration is less likely to cause ghosting even when used for forming a large number of electrophotographic images in a low-temperature environment.

[0017] Generally, a compound containing a chemical species with strong Lewis acidity or Lewis basicity forms a crystal (ionic crystal) due to its strong electrostatic interaction. In this case, the above compound alone does not dissociate ions. In order to exhibit conductivity with such a compound, it is necessary to dissociate an anion and a cation. For this purpose, for example, adding water and solvating the cation to stabilize it is effective. Thus, in order to dissociate a compound showing strong electrostatic interaction, it is necessary to stabilize the dissociated chemical species.

[0018] A metal cation has a smaller ionic radius and higher mobility compared to an organic cation. Therefore, when a voltage is applied, even if it is polarized by energization, it is expected to quickly and uniformly diffuse when the voltage is removed. For this reason, it is less likely to cause an increase in resistance such as conduction degradation, which is preferable.

[0019] Patent Document 1 relates to a technique of coexisting a polyether-containing polymer or a polymer having a cyano group with a salt having an anion having a fluoro group and a sulfonyl group. In this document, the counter cation of the above anion is lithium. Lithium is an ionic species with strong Lewis acidity and shows strong ionic bonding, so it is difficult to dissociate and has low conductivity alone. For this reason, the idea of promoting dissociation and improving conductivity by stabilizing the cation generated by dissociation with a molecule having an electron-rich functional group is disclosed.

[0020] On the other hand, in the image output inspection conducted by the present inventors, when images were output until the end in a low-temperature environment such as 0°C, an increase in the resistance of the developing roller was observed. This is presumably due to the decrease in molecular mobility at low temperatures, which causes the structures for stabilizing cations to be spatially non-proximate. Also, even if they are spatially proximate, since not only cations but also the entire ionic molecule is attracted, as a result, it was considered that the dissociation of ions does not occur. To solve the above problems, a conductive agent that satisfies the following conditions (i) and (ii) is considered to be effective. (i) The structures for stabilizing cations are spatially proximate. (ii) When cations are attracted, anions remain in place.

[0021] The present inventors examined the molecular structures of compounds that satisfy conditions (i) and (ii). As a result, it was found that by including the following first resin and second resin in the conductive layer on the substrate, suitable functions can be obtained. (I) A resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring (first resin). (II) A resin containing a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2) (second resin).

Chemical formula

[0022] In formula (1), R 12 represents a hydrogen atom or a methyl group, R 13 represents an alkylene group having 1 to 7 carbon atoms (preferably 2 to 6, more preferably 3 to 5) and having a straight chain or a branch, R 14 represents a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms (preferably 1 to 2, more preferably 1) and having a straight chain or a branch, X +represents at least one selected from the group consisting of lithium ions, sodium ions, and potassium ions. [Chemical formula]

[0023] In formula (2), R 21 represents a hydrogen atom or a methyl group, R 22 represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 2 to 5, more preferably 2 to 4), or an alicyclic hydrocarbon group having 5 to 6 carbon atoms (preferably 6).

[0024] When the conductive layer contains a first resin and a second resin, a sulfonylimide anion and a metal cation, which are ionic components, and a structure expected to have a cation stabilizing effect are contained in the conductive layer. Structures expected to have a cation stabilizing effect include urethane bonds, ether bonds, and aromatic rings. The oxygen atom (urethane oxygen) in the urethane bond has an increased electron density due to the pushing-out effect of the non-bonding electron pair on nitrogen in the urethane bond. Therefore, stabilization of electron-poor cation species can be expected. Also, the oxygen atom in the ether bond is polarized based on the carbon-oxygen bond, and the electron density around the oxygen atom is increased. Therefore, it is expected to contribute to the stabilization of cation species. Furthermore, in the aromatic ring, the π electron cloud spreading over the aromatic ring is expected to contribute to the stabilization of cation species (cation-π stacking effect). Also, since the ionic component is immobilized at the tip of the structure of the second resin 502, when a structure (ether bond in FIG. 5) expected to have the above-described cation stabilizing effect contained in the first resin 501 attracts the cation, the anion is not attracted, and it is presumed that ionic dissociation is effectively performed (FIG. 5).

[0025] [[Ionic Conductive Agent]] The ionic conductive agent according to the present disclosure contains a (meth)acrylic resin having a structure represented by the above formula (1) and a structure represented by the above formula (2). The number average molecular weight (Mn) of the (meth)acrylic resin having a structure represented by the above formula (1) and a structure represented by the above formula (2) is preferably 1,000 to 100,000 (more preferably 10,000 to 50,000) from the viewpoint of the balance between bleed-out and compatibility.

[0026] In order to obtain the (meth)acrylic resin used in the ionic conductive agent according to the present disclosure, raw materials such as the following can be used. · Sulfonylimide-based ionic compound having an unsaturated reactive functional group · Aliphatic (meth)acrylate

[0027] [Sulfonylimide-based ionic compound] Examples of the compound capable of forming the structure represented by the formula (1) include a sulfonylimide-based ionic compound having an unsaturated reactive functional group represented by the following formula (1’).

Chemical formula

[0028] Specifically, for example, sulfonylimide-based ionic compounds having an unsaturated reactive functional group represented by the following formulas C-1 to C-8 can be mentioned.

Chemical formula

Chemical formula

[0029] [Aliphatic (meth)acrylate] Aliphatic (meth)acrylate can form the structure represented by the above formula (2). As the aliphatic (meth)acrylate, for example, at least one selected from the group consisting of (meth)acrylate having an alkyl group having 1 to 6 carbon atoms which is linear or branched, and (meth)acrylate having an alicyclic hydrocarbon group having 5 to 6 carbon atoms can be used. That is, an aliphatic (meth)acrylate represented by the following formula (2') can be used. [Chemical formula] In formula (2'), R 21 and R 22 represent the same as those in formula (2).

[0030] Specifically, (meth)acrylate having an alkyl group such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate; Examples include (meth)acrylate having an alicyclic hydrocarbon group such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate. Among them, at least one selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-hexyl (meth)acrylate, and cyclohexyl (meth)acrylate is preferable, and at least one selected from the group consisting of methyl methacrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-hexyl methacrylate, and cyclohexyl (meth)acrylate is more preferable. The aliphatic (meth)acrylate may be synthesized by a known method or a commercially available product may be used.

[0031] By reacting a sulfonylimide-based ionic compound having an unsaturated reactive functional group as described above with an aliphatic (meth)acrylate, a (meth)acrylic resin having the structure represented by the above formula (1) and the structure represented by the above formula (2) can be obtained. For example, the second resin is a copolymer of an aliphatic (meth)acrylate and a sulfonylimide-based ionic compound having an unsaturated reactive functional group. Further, a monomer having other unsaturated reactive functional groups may be used. The second resin is, for example, a resin different from the first resin.

[0032] In the (meth)acrylic resin having the structure represented by the above formula (1) and the structure represented by the above formula (2), the content of the structure represented by the formula (1) is preferably 25 to 75 parts by mass, more preferably 35 to 65 parts by mass, with respect to 100 parts by mass in total of the structure represented by the formula (2). When the mass ratio of the structure represented by the formula (1) is within this range, since there are also abundant structures expected to have a cation stabilizing effect while containing a sufficient amount of metal cations, dissociation between ions occurs preferably, and an improvement in ionic conductivity can be expected. These post-reaction states can be confirmed, for example, by analyzing by known means such as thermal decomposition GC / MS, FT-IR, NMR, etc.

[0033] <Cation> The cation X in the formula (1) + Examples of the cation X include at least one selected from the group consisting of lithium ions, sodium ions, and potassium ions. Among these cations, lithium ions are particularly preferred because they have a small ionic radius and high mobility.

[0034] <<Electrophotographic member>> The electrophotographic member according to one embodiment of the present disclosure includes a conductive substrate and a conductive layer on the substrate. It has. As an example of an electrophotographic member, a roller-shaped electrophotographic member (electrophotographic roller) is shown in FIGS. 1(a) to 1(c). The electrophotographic member 1 shown in FIG. 1(a) is composed of a conductive substrate 2 and a surface layer 3 formed of a conductive layer containing a first resin and a second resin provided on the outer periphery thereof. As shown in FIG. 1(b), an elastic layer 4 may be provided between the substrate 2 and the surface layer 3. Further, as shown in FIG. 1(c), the electrophotographic member 1 may have a three-layer structure in which an intermediate layer 5 is further disposed between the elastic layer 4 and the surface layer 3, or may have a multilayer structure in which a plurality of intermediate layers 5 are disposed. The conductive layer may be a resin layer made of a conductive resin.

[0035] Note that the layer structure of the electrophotographic member 1 is not limited to the structure shown in FIGS. 1(a) to 1(c). For example, the electrophotographic member 1 may have a structure in which another resin layer or a protective layer is laminated on the outer periphery of the conductive layer to form a surface layer, such as a structure in which a surface layer is further provided on the conductive layer provided on the outer periphery of the substrate 2. Further, it may have a configuration in which the conductive layer is used as the intermediate layer 5. Among these, in order to further enhance the effects of the present disclosure, the electrophotographic member of the present disclosure preferably has a configuration in which the conductive layer is the surface layer 3, as shown in FIGS. 1(a) to 1(c). That is, it is preferable that the conductive layer is present on the outermost surface layer of the electrophotographic member. Further, the electrophotographic member 1 preferably has an elastic layer 4.

[0036] The electrophotographic member according to one aspect of the present disclosure can be used, for example, as a developer carrier, a charging member, a developer supply / peeling member, a developer regulating member, and a cleaning blade. In particular, it can be suitably used as a developer carrier and a developer regulating member. Hereinafter, the configuration of the electrophotographic member according to one embodiment of the present disclosure will be described in detail.

[0037] <Conductive layer> As described above, the conductive layer includes the first resin and the second resin. Further, the conductive layer preferably includes a binder resin, and more preferably the binder resin includes the first resin. As described above, the first resin is a resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring. Among them, it is more preferable to have at least one selected from the group consisting of a urethane bond and an ether bond, and it is more preferable to have an ether bond. As a specific embodiment, for example, there is an embodiment in which the outermost conductive layer of the electrophotographic roller contains a binder resin. This is because, as described above, the binder resin exhibits the stabilizing action of metal cations. Further, from the viewpoints of the strength of the electrophotographic member and the rubbing against other members, the first resin is preferably at least one resin selected from the group consisting of polyurethane, polyether, and polyphenylene, more preferably polyurethane, and particularly preferably a crosslinked urethane resin.

[0038] The thickness of the conductive layer is not particularly limited, but is preferably 2.0 μm or more and 150.0 μm or less, and more preferably 5.0 μm or more and 100.0 μm or less. Within this range, the rubber hardness becomes suitable, and it becomes easier to suppress filming due to toner stress and set marks due to long-term contact with a regulating member.

[0039] [Crosslinked urethane resin] The crosslinked urethane resin is obtained by reacting a polyol having a hydroxyl group with an isocyanate compound to form a urethane group. The meaning of crosslinking here means that one or both selected from the group consisting of polyol and isocyanate compound, which are raw materials of the urethane resin, have three or more reactive functional groups, and thus have a three-dimensional network structure. Such a crosslinked urethane resin has excellent flexibility and high strength.

[0040] The urethane resin is obtained from a polyol, an isocyanate compound, and, if necessary, a chain extender. It is possible. Examples of the polyol which is a raw material of the urethane resin include polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, and mixtures thereof. Examples of the isocyanate compound which is a raw material of the urethane resin include the following. Tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (polymeric MDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), phenylene diisocyanate (PPDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), cyclohexane diisocyanate, and mixtures thereof. Among them, at least one selected from the group consisting of polymeric MDI and HDI is preferable.

[0041] Here, polymeric MDI is a mixture of monomeric MDI and a high molecular weight polyisocyanate, and is represented by the following formula (A). n in the formula (A) is preferably 0 or more and 4 or less. Commercially available polymeric MDI may be used, and examples include the Millionate MR series (manufactured by Tosoh Corporation) such as Millionate MR200 (trade name). [Chemical formula]

[0042] Examples of optional chain extenders include bifunctional low molecular weight diols such as ethylene glycol, 1,4-butanediol, and 3-methylpentanediol, trifunctional low molecular weight triols such as trimethylolpropane, and mixtures thereof. In addition, prepolymer-type isocyanate compounds having isocyanate groups at the terminals obtained by reacting the above-mentioned various isocyanate compounds with various polyols in advance in a state in which the isocyanate groups are in excess relative to the hydroxyl groups may be used. In addition, as these isocyanate compounds, materials in which the isocyanate groups are blocked with various blocking agents such as methyl ethyl ketone (MEK) oxime may be used.

[0043] Regardless of which material is used, a urethane resin can be obtained by reacting a polyol with an isocyanate compound by heating. When either or both of the polyol and the isocyanate compound have a branched structure and have three or more functional groups, the obtained urethane resin becomes a crosslinked urethane resin, which is preferable. From the viewpoint of stabilizing the above-mentioned metal cations, it is particularly preferable that either or both of the polyol and the isocyanate compound have an ethylene oxide structure or a propionoxide structure.

[0044] [IPN structure] The effect of the present disclosure is further enhanced by creating a spatial environment in which the first resin having a structure expected to stabilize cations and the second resin capable of acting as an ion conductive agent can mutually affect each other. It is preferable that the first region, which is up to 0.1 μm in the direction, contains a first resin and a second resin. When the first region contains the first resin and the second resin, the metal cations exhibiting electrical conductivity and the structure that stabilizes the cations are spatially close to each other. This makes it possible to more effectively increase the electrical conductivity on the outer surface of the conductive layer. Also, in the first region, it is particularly effective to form an Interpenetrating Polymer Network (IPN structure) with the first resin and the second resin. The IPN structure refers to a structure in which the network structures of two or more resins penetrate and intertwine with each other without being covalently bonded. When an IPN structure is formed, the improvement in conductivity described above is manifested on the outer surface of the developing member, so that unevenness in surface resistance can be preferably suppressed, and it becomes easier to suppress density unevenness in halftone and gradation abnormalities due to charge-up on the member surface accompanying image output. By performing an impregnation treatment on an electrophotographic member precursor containing the first resin using an impregnation treatment liquid containing a sulfonylimide-based ionic compound having an unsaturated reactive functional group represented by the above formula (1'), an aliphatic (meth)acrylate represented by the above formula (2'), and a polymerization initiator, an IPN structure can be formed in the first region.

[0045] The IPN structure in the conductive layer can be confirmed by the shift of the glass transition temperature (Tg) of the resin constituting the IPN structure by micro-sampling mass spectrometry. Specifically, it is confirmed by the following procedure.

[0046] It is considered that the peak top temperature in the thermochromatogram corresponding to the thermal decomposition temperature of the resin shifts to the high temperature side when the resin constitutes an IPN structure compared to the case where the resin exists alone. Therefore, by focusing on the first resin or the second resin in the conductive layer and comparing the peak top temperatures of the thermochromatograms of the other resin before and after decomposing and removing either resin, it can be confirmed that the first resin and the second resin constitute an IPN structure when the peak top temperature is lower after decomposition than before decomposition. Here, the thermochromatogram is a mass spectrum that can be obtained by micro-sampling thermogravimetric mass spectrometry.

[0047] The outline of micro-sampling mass spectrometry is shown below. First, prepare a sample by cutting a region to be measured of the electrophotographic member into thin slices with a microtome. As shown in FIG. 7, prepare samples from three regions called the first region 71, the second region 72, and the third region 73. The first region is a region from the outer surface of the conductive layer 74 to a depth of 0.1 μm, the second region is a region with a thickness of 0.1 μm from the inner surface of the conductive layer 74 (the surface facing the substrate 75) toward the outer surface, and the third region is a region with a depth in the depth direction of 1.0 μm or more and 1.1 μm or less from the outer surface. Then, the sample obtained from the first region is the first sample, the sample obtained from the second region is the second sample, and the sample obtained from the third region is the third sample. Prepare flakes with a size of 100 μm square and a thickness of 0.1 μm from each region of the conductive layer. For the measurement, use, for example, an ion trap type mass spectrometer installed in a gas chromatography mass spectrometer (trade name: Polaris Q, manufactured by Thermo Electron Corporation). Fix the sample to the filament located at the tip of the probe and insert it directly into the ionization chamber. Then, rapidly heat from room temperature to a temperature of 1000 °C at a constant heating rate. The sample decomposed and evaporated by heating is ionized by irradiation with an electron beam and detected by a mass spectrometer. At this time, under the condition that the heating rate is constant, a thermal chromatogram similar to the TG-MS (thermogravimetry-mass spectrometry) method with a mass spectrum called a total ion chromatogram (TIC) can be obtained. Also, since a thermal chromatogram for a fragment of a predetermined mass can be obtained, the peak temperature of the thermal chromatogram corresponding to the decomposition temperature of the desired molecular structure can be obtained. The peak temperature of the thermal chromatogram is correlated with the crosslinked structure in the resin structure, and as the crosslinking becomes denser, the peak temperature shifts to a higher temperature side. It will shift to the higher temperature side.

[0048] That the first resin and the second resin form an interpenetrating polymer network structure can be confirmed as follows. That is, by focusing on the first resin or the second resin, the difference in the peak temperature of the thermochromatogram of the fragments derived from the other resin before and after decomposing and removing either resin may be confirmed. For example, the difference in the peak temperature of the thermochromatogram of the fragments derived from the second resin before and after decomposing and removing the first resin may be confirmed.

[0049] Let the peak top temperature of the thermochromatogram corresponding to the second resin measured from the above first sample be A1 (°C). Also, let the peak top temperature of the thermochromatogram corresponding to the second resin measured from the second sample obtained by decomposing the first resin contained in the first sample be A2 (°C). When an interpenetrating polymer network structure is formed, A1 and A2 will satisfy the relationship represented by the following formula (X). A1 > A2 (X) As a method for decomposing the first resin, the pyridine decomposition method described later can be mentioned.

[0050] For the conductive layer, when the peak top temperature of the thermochromatogram corresponding to the first resin in the above first region is T1 (°C), and the peak top temperature of the thermochromatogram corresponding to the first resin contained in the second region having a thickness of 0.1 μm from the inner surface to the outer surface of the conductive layer is T2 (°C), it is preferable that T1 and T2 satisfy the relationship represented by the following formula (3). T1 > T2 (3) That the above formula (3) is satisfied can be confirmed by the above-described micro-sampling mass spectrometry method.

[0051] Also, it is preferable that the above T1 and T2 satisfy the following formula (4). (T1 - T2) > 1.0 (°C) (4) That the above formula (4) is satisfied can be confirmed by the above-described micro-sampling mass spectrometry method.

[0052] One of the functions performed by the conductive layer is to relieve the mechanical stress applied to the toner by the developer carrier. In order to fully exhibit such a function, the conductive layer is preferably flexible. For this purpose, in the second region having a thickness of 0.1 μm from the surface on the side facing the substrate of the conductive layer toward the outer surface, it is preferable that no IPN structure exists. Alternatively, even if an IPN structure exists, for example, it is preferably an IPN structure in which the degree of penetration of the second resin is weaker than that of the IPN structure in the first region. Therefore, it is preferable that the first region and the second region of the conductive layer satisfy the relationship represented by the above formula (3), and particularly preferably satisfy the relationship represented by the above formula (4). Here, T1 (°C) represents the peak top temperature of the thermochromatogram corresponding to the first resin, measured from a sample sampled from the first region. T2 (°C) represents the peak top temperature of the thermochromatogram corresponding to the first resin, measured from a sample sampled from the second region. The values of T1 and T2 can be adjusted by the concentration of the treatment liquid, the UV irradiation intensity, etc.

[0053] Also, when the peak top temperature of the thermochromatogram corresponding to the first resin in the third region having a depth of 1.0 μm or more and 1.1 μm or less from the outer surface of the conductive layer is T3 (°C) it is preferable that the above T1, the above T2, and T3 satisfy the relationship represented by the following formula (5) and the relationship represented by formula (6). T1>T3 (5) |T1-T3|>|T3-T2| (6) Satisfaction of the above formula (5) and formula (6) can be confirmed by the above-described microsampling mass spectrometry method.

[0054] ​In order to better exert the function of the conductive layer described above, when a region with a thickness of 0.1 μm from a depth of 1.0 μm or more and a depth of 1.1 μm or less from the outer surface of the conductive layer is defined as the third region, it is preferable that there is no IPN structure in the third region adjacent to the first region. Alternatively, even if there is an IPN structure, it is preferably an IPN structure in which the degree of penetration of the second resin is weaker than that of the IPN structure in the first region. Therefore, when the peak top temperature of the thermochromatogram corresponding to the first resin measured from the sample sampled from the third region is T3 (°C), it is preferable that T1, T2, and T3 satisfy the relationships represented by the above formula (5) and the above formula (6). The value of T3 can be adjusted according to the crosslinking density of the first resin or the like.

[0055] [Other components] In addition to the above, the conductive layer can contain a conductive substance, a crosslinking agent, a plasticizer, a filler, a bulking agent, a vulcanizing agent, a vulcanization aid, a crosslinking aid, an antioxidant, an anti-aging agent, a processing aid, a leveling agent, etc. within a range that does not inhibit the function of the conductive layer. Further, when surface roughness is required for the conductive layer, fine particles for imparting roughness can be contained in the conductive layer. Specifically, fine particles such as polyurethane resin, polyester resin, polyether resin, polyamide resin, (meth)acrylic resin, and polycarbonate resin can be used. The volume average particle diameter of the fine particles is preferably 1.0 μm or more and 30 μm or less, and the surface roughness (ten-point average roughness) Rzjis formed by the fine particles is preferably 0.1 μm or more and 20 μm or less. Note that Rzjis is a value measured based on JIS B0601 (1994).

[0056] <Substrate> The conductive substrate 2 functions as an electrode and a support member of the electrophotographic member 1. The substrate is composed of a conductive material such as a metal or alloy such as aluminum, copper alloy, or stainless steel; iron plated with chromium or nickel; or a conductive synthetic resin. Note that, in order to improve the adhesion between the substrate and the elastic layer described later, a primer may be applied to the surface of the substrate. As examples of the primer, a silane coupling agent-based primer, a urethane-based, acrylic-based, polyester-based, polyether-based or epoxy-based thermosetting resin, a thermoplastic resin, etc. can be used. Examples of commercially available primers include the following.

[0057] "DY39-051", "DY39-012", "DY39-115" (all are trade names, manufactured by Toray Dow Corning Co., Ltd.); "X-33-173", "PRIMER-NO.4", "PRIMER-NO.32", "PRIMER-NO.35" (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.); "XP81-405", "XP81-A6361", "XP81-B7015", "ME21", "ME151", "ME153", "XC9214" (all are trade names, manufactured by Momentive Performance Materials Japan LLC).

[0058] In order to improve the adhesion of the primer, known alkoxysilanes, titanates, etc. may be added. Specific examples of alkoxysilanes and titanates include tetramethoxysilane, tetraethoxysilane, tetra-n-butoxysilane, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, etc. It is preferable to add these in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the primer.

[0059] <Elastic layer> When the electrophotographic member is in the form of a roller, i.e., an electrophotographic roller, the elastic layer 4 has a function of imparting to the electrophotographic member 1 the elasticity necessary for forming a nip of a predetermined width at the contact portion between the electrophotographic member 1 and the photoreceptor. The elastic layer 4 is preferably a molded body of a rubber material. As the rubber material, various rubber materials conventionally used for conductive rubber rollers can be used. Specific examples of the rubber used for the rubber material include ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), fluororubber, silicone rubber, epichlorohydrin rubber, hydrogenated NBR, polysulfide rubber, urethane rubber, and the like. These may be used alone or in combination of two or more. Among these, silicone rubber is particularly preferred from the viewpoint of stability against deformation such as set performance. Examples of silicone rubber include polydimethylsiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polyphenylvinylsiloxane, and copolymers of these polysiloxanes.

[0060] Various additives such as a conductivity-imparting agent, a non-conductive filler, a crosslinking agent, and a catalyst may be appropriately blended in the elastic layer 4. As the conductivity-imparting agent, carbon black; conductive metals such as aluminum and copper; and fine particles of conductive metal oxides such as zinc oxide, tin oxide, and titanium oxide can be used. Among these, carbon black is preferred because good conductivity can be obtained with a relatively low addition amount.

[0061] As the carbon black, specifically, conductive carbon blacks such as Ketjen black (trade name, manufactured by Lion Corporation), acetylene black; carbon blacks for rubber such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, MT, etc., and in addition, carbon blacks for color ink subjected to oxidation treatment, pyrolytic carbon black can be used. These may be used alone or in combination of two or more. When using carbon black as the conductivity-imparting agent, it is more preferable to blend 10 to 80 parts by mass of carbon black with respect to 100 parts by mass of rubber in the rubber material.

[0062] In addition, examples of the non-conductive filler include silica, quartz powder, titanium oxide, zinc oxide, or calcium carbonate. Examples of the crosslinking agent include di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, or dicumyl peroxide. Examples of the catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and in particular, platinum-based catalysts are preferable. The elastic layer 4 may be formed of a plurality of layers. Also, an intermediate layer 5 may be provided between the base body 2 and the elastic layer 4, and between the elastic layer 4 and the surface layer 3. The thickness of the elastic layer 4 is preferably 0.25 to 8.00 mm, and more preferably 0.30 to 3.00 mm.

[0063] <<Electrophotographic apparatus>> The electrophotographic member according to the present disclosure can be suitably used as a developer carrier and a developer regulating member in an electrophotographic apparatus. The electrophotographic member can be applied to any of non-contact type developing devices and contact type developing devices using magnetic one-component toner or non-magnetic one-component toner, and developing devices using two-component toner. That is, the electrophotographic image forming apparatus of the present disclosure preferably includes the electrophotographic member of the present disclosure as a developing member. FIG. 2 is a schematic cross-sectional view showing an example of an electrophotographic apparatus in which the electrophotographic member according to the present disclosure is mounted as a developing roller of a contact type developing apparatus using a one-component toner. As shown in FIG. 2, a developing device 22 is detachably attached to the electrophotographic apparatus. The developing device 22 includes a toner container 20 that stores toner 15 as a one-component toner, a developing roller 16, a toner supply roller 19 that supplies toner to the developing roller 16, and a developing blade 21 that regulates the thickness of the toner layer on the developing roller 16. The developing roller 16 is located in an opening extending in the longitudinal direction of the toner container 20 and is disposed opposite to the photoreceptor 18. Further, a process cartridge 17 including a photoreceptor 18, a cleaning blade 26, a waste toner container 25, and a charging roller 24 is detachably attached to the electrophotographic apparatus. Note that the photoreceptor 18, the cleaning blade 26, the waste toner container 25, and the charging roller 24 may be provided in the electrophotographic apparatus main body.

[0064] The printing operation of the electrophotographic apparatus will be described below. FIG. 3 is a schematic cross-sectional view of an example of an electrophotographic apparatus according to an aspect of the present disclosure. The photoreceptor 18 rotates in the direction of the arrow and is uniformly charged by a charging roller 24 for charging the photoreceptor 18. Next, an electrostatic latent image is formed on the surface of the photoreceptor 18 by laser light 23 which is an exposure means. The electrostatic latent image is visualized as a toner image by applying toner 15 by a developing device 22 which is disposed in contact with the photoreceptor 18 (development). The development is so-called reversal development which forms a toner image in an exposure area. The toner image formed on the photoreceptor 18 is transferred onto a sheet 34 which is a recording medium by a transfer roller 29 which is a transfer member. The sheet 34 is fed into the apparatus via a paper feed roller 35 and a suction roller 36 and is conveyed between the photoreceptor 18 and the transfer roller 29 by an endless belt-shaped transfer conveyance belt 32. The transfer conveyance belt 32 is operated by a driven roller 33, a driving roller 28, and a tension roller 31. A voltage is applied from a bias power source 30 to the transfer roller 29 and the suction roller 36. The sheet 34 onto which the toner image has been transferred is subjected to a fixing process by a fixing device 27 and then discharged outside the apparatus, and the printing operation is completed. On the other hand, the transfer residual toner remaining on the photoreceptor 18 without being transferred is scraped off by a cleaning blade 26 which is a cleaning member for cleaning the photoreceptor surface and is stored in a waste toner storage container 25. The cleaned photoreceptor 18 repeats the above printing operation.

[0065] <<Electrophotographic process cartridge>> The electrophotographic member according to the present disclosure can be suitably used as a developing member such as a developer carrier, a developer supply / peeling member, and a developer regulating member in a process cartridge. That is, the electrophotographic process cartridge of the present disclosure is an electrophotographic process cartridge configured to be detachable from the main body of the electrophotographic apparatus and may include the electrophotographic member of the present disclosure. Further, it is preferable to include the electrophotographic member of the present disclosure as a developing member.

Example

[0066] The present disclosure will be described in detail below with specific examples, but the technical scope of the present disclosure is not limited thereto.

[0067] [[Raw material preparation]] [[Synthesis of polymerizable monomers: ionic compounds]] First, ionic compounds forming the structure represented by formula (1) (that is, sulfonylimide-based ionic compounds having an unsaturated reactive functional group represented by formula (1')) were synthesized. Synthesis examples of ionic compounds capable of forming the structure represented by formula (1) are shown.

[0068] [[Synthesis of ionic compound C-1]] 15.0 g (0.06 mol) of 3-sulfopropyl potassium methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in a mixture of 100 mL of tetrahydrofuran and 0.5 mL of N,N-dimethylformamide, and then 20 mL (0.28 mol) of thionyl chloride was added and stirred for 3 hours. This was concentrated under reduced pressure, and the residue was dissolved in dichloromethane. After washing with 50 mL of pure water and 50 mL of brine, it was concentrated under reduced pressure again to obtain a pale yellow liquid. The obtained pale yellow liquid was added to a solution prepared by dissolving 9.20 g (0.06 mol) of trifluoromethanesulfonylimide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 27.3 mL (0.20 mol) of triethylamine (manufactured by Kishida Chemical Co., Ltd.) in 50 mL of tetrahydrofuran, and the mixture was stirred for 2 hours. Thereafter, the reaction solution was concentrated under reduced pressure. The obtained residue was dissolved in dichloromethane, washed with 150 mL of pure water, and the organic layer was dried under reduced pressure to obtain a yellow liquid. The obtained yellow liquid was dissolved in 300 mL of tetrahydrofuran, and 1.43 g (0.18 mol) of lithium hydride (manufactured by Fujifilm Wako Pure Chemical Corporation) was added and stirred overnight. After filtering off the unreacted lithium hydride by celite filtration, the filtrate was dried under reduced pressure to obtain ionic compound C-1.

[0069] [[Synthesis of ionic compound C-2]] Ionic compound C-2 was obtained in the same manner as ionic compound C-1, except that the starting material was changed to 15.9 g (0.06 mol) of 3-Sulfopropyl Acrylate Potassium Salt (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0070] (Synthesis of ionic compound C-3) 7.78 g (0.07 mol) of Hydroxymethanesulfonate (manufactured by Atomax Chemicals Product) was dissolved in 50 mL of tetrahydrofuran, 5.17 g (0.06 mol) of methacrylic acid (manufactured by Kishida Chemical Co., Ltd.) and molecular sieve were added, and the mixture was stirred at 80 °C for 3 hours. After filtering through celite and drying the filtrate under reduced pressure, it was dissolved again in 50 mL of THF, 2.41 g (0.06 mol) of potassium hydride (manufactured by Merck) was added, and the mixture was stirred at room temperature for 2 hours. Using the white solid obtained after drying under reduced pressure as the starting material, ionic compound C-3 was obtained in the same manner as ionic compound C-1.

[0071] (Synthesis of ionic compound C-4) 12.9 g of 1-HEPTANESULFONYL CHLORIDE,7-HYDROXY (manufactured by Hong Kong Chemhere Product) and 6.07 g (0.06 mol) of triethylamine (manufactured by Kishida Chemical Co., Ltd.) were added to 80 mL of dichloromethane, and the mixture was stirred at room temperature. After washing with 100 mL of pure water, the organic phase was dried under reduced pressure to obtain an oily liquid. 5.64 g (0.06 mol) of sodium acrylate (manufactured by Merck) was dissolved in 50 mL of ethanol, the oily liquid obtained above and 0.022 g (0.20 mmol) of hydroquinone (manufactured by Kanto Chemical Co., Inc.) were added, and the mixture was stirred at 70 °C for 5 hours. Using the pale yellow solid obtained after drying under reduced pressure as the starting material, ionic compound C-4 was obtained in the same manner as ionic compound C-2.

[0072] (Synthesis of ionic compound C-5) Ionic compound C-5 was obtained in the same manner as ionic compound C-2, except that Trifluoromethanesulfonamide (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 5.94 g (0.06 mol) of sulfamoylfluoride (manufactured by Atomax Chemicals Product).

[0073] (Synthesis of ionic compound C-6) Ionic compound C-6 was obtained in the same manner as ionic compound C-1, except that Trifluoromethanesulfonamide (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 18.0 g (0.06 mol) of nonafluorobutane-1-sulfonamide (manufactured by Enamine).

[0074] (Synthesis of ionic compound C-7) Ionic compound C-7 was obtained in the same manner as ionic compound C-5, except that lithium hydride was changed to 4.32 g (0.18 mol) of Sodium Hydride (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0075] (Synthesis of ionic compound C-8) Ionic compound C-8 was obtained in the same manner as ionic compound C-6, except that lithium hydride was changed to 7.22 g (0.18 mol) of potassium hydride (manufactured by Merck). The chemical structures of the obtained reactive ionic compounds are shown in Formulas C-1 to C-8. [Chemical formula] [Chemical formula]

[0076] [Polymerizable monomer] As the raw material of the acrylic compound (i.e., aliphatic (meth)acrylate represented by Formula (2’)) that forms the structure represented by Formula (2), those shown in Table 1 below were used. [Table 1]

[0077] <Synthesis of (Meth)acrylic Sulfonyl Imide Conductive Agent (Second Resin)> ((Meth)acrylic Sulfonyl Imide Conductive Agent IP-9) Into a four-neck separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen inlet tube, 50.0 parts by mass of C-1 as a polymerizable monomer providing constitutional unit (1), 50.0 parts by mass of A-1 as a polymerizable monomer providing constitutional unit (2), 1.0 L of dry ethanol, and 1.0 part by mass of 2,2'-azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the system was stirred until homogeneous. While continuing stirring, the temperature in the reaction system was raised to 70 °C, and the reaction was carried out for 8 hours in a nitrogen-introduced reflux state. Then, by distilling off ethanol, the (meth)acrylic sulfonyl imide conductive agent IP-9, which is a copolymer, was obtained.

[0078] ((Meth)acrylic Sulfonyl Imide Conductive Agents IP-10 to IP-24) Except that the types and blending amounts of the polymerizable monomers were changed to the conditions shown in Table 2 below, (meth)acrylic sulfonyl imide conductive agents IP-9 to IP-24 were obtained in the same manner as the synthesis of IP-9.

Table 2

[0079] <Synthesis of Isocyanate Group-Terminated Prepolymer> An isocyanate compound for forming a urethane resin was synthesized. (Synthesis of Isocyanate Group-Terminated Prepolymer B-1) Under a nitrogen atmosphere, while maintaining the temperature in the reaction vessel at 65 °C, 100.0 parts by mass of a polypropylene glycol-based polyol (trade name: Excenol 230; manufactured by Asahi Glass Co., Ltd.) was gradually added dropwise to 33.8 parts by mass of polymeric MDI (trade name: Millionate MR; manufactured by Tosoh Corporation) in the reaction vessel. After the dropping was completed, the reaction was carried out at 65 °C for 2 hours, and 57.3 parts by mass of methyl ethyl ketone was added. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated urethane prepolymer B-1 having an isocyanate group content of 4.80% by weight.

[0080] (Synthesis of isocyanate group-terminated prepolymer B-2) Under a nitrogen atmosphere, 8.8 parts by mass of polymeric MDI (trade name: Millionate MT; manufactured by Tosoh Corporation) was dissolved in methyl ethyl ketone so that the final solid content became 50% by mass. Then, while maintaining the temperature in the reaction vessel at 65 °C, 100.0 parts by mass of an olefinic polyol (trade name: Poly bd R-45HT; manufactured by Idemitsu Kosan Co., Ltd.) was gradually added dropwise to the reaction vessel. After the dropping was completed, the reaction was carried out at 65 °C for 2 hours. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer B-2 having a solid content of 50% by mass and an isocyanate group content of 1.40% by weight.

[0081] (Synthesis of isocyanate group-terminated prepolymer B-3) Under a nitrogen atmosphere, 100.0 parts by mass of HDI (trade name, manufactured by Tosoh Corporation) was dissolved in methyl ethyl ketone so that the final solid content became 50% by mass. Then, while maintaining the temperature in the reaction vessel at 65 °C, 100.0 parts by mass of a polypropylene glycol-based polyol (trade name: Excenol 230; manufactured by Asahi Glass Co., Ltd.) was gradually added dropwise to the reaction vessel. After the dropping was completed, the reaction was carried out at 65 °C for 2 hours. The obtained reaction mixture was cooled to room temperature, and an isocyanate group-terminated prepolymer B-3 having a solid content of 50% by mass and an isocyanate group content of 3.20% by weight was obtained.

[0082] (Synthesis of isocyanate group-terminated prepolymer B-4) Under a nitrogen atmosphere, 100.0 parts by mass of HDI (trade name, manufactured by Tosoh Corporation) was dissolved in methyl ethyl ketone so that the final It was dissolved in methyl ethyl ketone so that the solid content became 50% by mass. Then, while maintaining the temperature in the reaction vessel at 65°C, 100.0 parts by mass of an olefinic polyol (trade name: Poly bd R-45HT; manufactured by Idemitsu Kosan Co., Ltd.) was gradually added dropwise to the reaction vessel. After completion of the dropwise addition, the reaction was carried out at a temperature of 65°C for 2 hours. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer B-4 having a solid content of 50% by mass and an isocyanate group content of 1.22% by weight. Table 3 shows the raw materials and physical properties of the above isocyanate group-terminated prepolymers B-1 to B-4.

Table 3

[0083] <<Preparation of Conductive Layer-Forming Paint>> (Preparation of Conductive Layer-Forming Paint E-9) As materials for the conductive layer, the materials shown in Table 4 below were stirred and mixed. Next, methyl ethyl ketone was added so that the total solid content ratio became 30% by mass, and then it was mixed with a sand mill. Then, it was further adjusted to a viscosity of 10 to 13 cps with methyl ethyl ketone to prepare a conductive layer-forming paint E-9.

Table 4

[0084] (Preparation of Conductive Layer-Forming Paint E’-1) As materials for the conductive layer, the materials shown in Table 5 below were stirred and mixed, and in the same manner as E-1, a conductive layer-forming paint E’-1 was obtained.

Table 5

[0085] (Preparation of Conductive Layer-Forming Paints E’-2 to E’-4) As materials for the conductive layer-forming paint, conductive layer-forming paints E’-2 to E’-4 were obtained in the same manner as E-1, except that the materials shown in Table 6 below were stirred and mixed.

Table 6

[0086] (Preparation of Coating for Forming Conductive Layer) Except for changing the types and blending amounts of the polyol and the curing agent and the type of the (meth)acryl sulfonylimide conductive agent as shown in Table 7 below, the coating for forming a conductive layer as shown in Table 7 was obtained by the same operations as the coating for forming a conductive layer E-9.

Table 7

[0087] <<Preparation of Impregnation Treatment Liquid>> As materials for the impregnation treatment liquid for impregnation treatment, the materials shown in Table 8 below were dissolved and mixed.

Table 8

[0088] <<Preparation of Conductive Roller>> <Preparation of Silicone Rubber Elastic Roller D’-1> As a conductive substrate, a core metal made of SUS304 with an outer diameter of 6 mm and a length of 264 mm was coated with a primer (trade name: DY35-051, manufactured by Toray Dow Corning Co., Ltd.) and heated at 150°C for 20 minutes. This conductive substrate was placed concentrically in a cylindrical mold with an inner diameter of 11.5 mm. As a material for the elastic layer, an addition-type silicone rubber composition obtained by mixing the materials shown in Table 9 below with Trimix (trade name: TX-15, manufactured by Inoue Manufacturing Co., Ltd.) was injected into a mold heated to 115°C. After injecting the material, it was heated and molded at 120°C for 10 minutes, cooled to room temperature, and then demolded from the mold to obtain an elastic roller D’-1 with an intermediate layer having a thickness of 2.71 mm formed on the outer periphery of the conductive substrate.

Table 9

[0089] <Production of NBR Rubber Elastic Roller D'-2> Each material of the type and amount shown in Table 10 below was mixed with a pressure kneader to obtain a kneaded rubber composition A.

Table 10

[0090] Furthermore, 166.0 parts by mass of the kneaded rubber composition A and each material of the type and amount shown in Table 11 below were mixed with an open roll to prepare an unvulcanized rubber composition.

Table 11

[0091] Next, a crosshead extruder having a supply mechanism for a conductive shaft core body and a discharge mechanism for an unvulcanized rubber roller was prepared. A die with an inner diameter of 16.5 mm was attached to the crosshead, and the crosshead extruder was adjusted to 80 °C and the conveying speed of the conductive shaft core body was adjusted to 60 mm / sec. Under these conditions, the unvulcanized rubber composition was supplied from the extruder, and the unvulcanized rubber composition was coated as an unvulcanized rubber layer on the circumferential surface of the conductive shaft core body prepared above in the crosshead to obtain an unvulcanized rubber roller. Next, the unvulcanized rubber roller was put into a hot air vulcanization furnace at 170 °C and heated for 60 minutes to obtain an unpolished conductive roller. Thereafter, the end portions of the NBR rubber elastic layer where the unvulcanized rubber layer was vulcanized were cut off and removed, and the surface of the NBR rubber elastic layer was polished with a rotary grinding wheel. Thereby, an elastic roller D'-2 having diameters of 8.4 mm at positions 90 mm from the center to both end portions and a center diameter of 8.5 mm was produced.

[0092] <Example 1-2> First, the previously produced elastic roller D'-1 was immersed in the coating material E'-1 for forming the conductive layer to form a coating film of the coating material on the surface of the elastic layer, and air-dried. Furthermore, by performing a heat treatment at a temperature of 150 °C for 1 hour, a conductive layer with a film thickness of about 15 μm was provided on the outer circumference of the elastic layer to produce a precursor of the conductive roller DG-1 (a precursor of an electrophotographic member). Subsequently, the precursor was immersed in the impregnation treatment liquid G-2 for 2 seconds to impregnate it with a (meth)acrylic component such as an ion conductive monomer. Thereafter, it was air-dried at room temperature for 30 minutes and dried at 90 °C for 1 hour to volatilize the solvent. While rotating the dried elastic roller, ultraviolet rays were irradiated so that the integrated light quantity became 15000 mJ / cm 2 2 and the (meth)acrylic component was cured. As the ultraviolet irradiation device, a high-pressure mercury lamp (trade name: Handy Type UV Curing Device, manufactured by Marionetwork Co., Ltd.) was used. Thereby, the developing roller DG-2 used in the example was obtained.

[0093] <Other Examples and Comparative Examples> Except that the coating material for forming the conductive layer used was the one shown in Table 12, in the same manner as in Example 1-2, a coating film was formed on the surface of the elastic layer of the elastic roller D'-1 or D'-2, and after drying, heat treatment was performed at a temperature of 150 °C for 1 hour, whereby the conductive rollers DG-2, DG-4, DG-6, DG-8 to DG-21 according to Examples 1-4, 1-6, 1-8 to 1-21 in Table 12 below, and the conductive roller DHG-1 according to Comparative Example 1-1 were obtained.

Table 12

[0094] <Example 2-9> The previously prepared elastic roller D'-1 was immersed in the coating material (E-9) for forming the conductive layer shown in Table 7 to form a coating film of the coating material on the surface of the elastic layer and air-dried. Further, heat treatment was performed at a temperature of 150 °C for 1 hour to provide a conductive layer with a film thickness of about 15 μm on the outer periphery of the elastic layer, whereby the conductive roller D-9 used in Example 2-9 was produced.

[0095] <Other Examples and Comparative Examples> Except that the coating material for forming the conductive layer to be used was shown in the table, in the same manner as in Examples 2-9, a coating film was formed on the surface of the elastic layer of the elastic roller D'-1 and dried, and then heat-treated at a temperature of 150°C for 1 hour, whereby the conductive rollers D-9 to D-24, D-27, D-28, D-31, D-32, D-35, D-36 according to Examples 2-9 to 2-24, 2-27, 2-28, 2-31, 2-32, 2-35, 2-36 shown in Table 12 and the conductive rollers DH-1 to DH-3, DH-5 according to Comparative Examples 2-1 to 2-3, 2-5 were obtained.

[0096] <Confirmation of the Structure of the Produced Article> Regarding the resin obtained in this synthesis example, using a thermal decomposition apparatus (trade name: Pyrofoil Sampler JPS-700, manufactured by Nippon Analytical Industry Co., Ltd.) and a GC / MS apparatus (trade name: FocusGC / ISQ, manufactured by Thermo Fisher Scientific Inc.), the thermal decomposition temperature was 590°C, helium was used as the carrier gas, and analysis was performed. As a result, from the obtained fragment peaks, it was confirmed that the resin had the structure represented by Formula (1) and the structure represented by Formula (2).

[0097] [Measurement of T1, T2, T3, A1, A2] By the above-described microsampling mass spectrometry method, a thermal chromatogram of a first region from the outer surface of the conductive layer (the surface opposite to the side facing the substrate) to a depth of 0.1 μm, a second region having a thickness of 0.1 μm from the inner surface of the conductive layer (the surface facing the substrate) toward the outer surface, and a third region from the outer surface in the depth direction of 1.0 μm or more and 1.1 μm or less was obtained. From the obtained thermal chromatogram, as the peak top temperature of the thermal chromatogram corresponding to polyurethane in each of the first region, the second region, and the third region, T1 (°C), T2 (°C), and T3 (°C) were determined, respectively. Also, the peak top temperature A1 of the thermal chromatogram corresponding to the second resin in the first region was obtained. Further, the polyurethane contained in the sample sampled from the first region was decomposed by the pyridine decomposition method described below to obtain a second sample. And the peak top temperature A2 of the thermal chromatogram corresponding to the second resin measured from the second sample was obtained.

[0098] In addition, samples from each region were collected using the micro-sampling method with FIB-SEM (product name: NVision40, manufactured by SII Nanotechnology Inc.). Specifically, first, using a razor blade, a cut was made from the outer surface of the conductive layer toward the substrate, and a rubber piece in a state where the cross-sections of the conductive layer and the intermediate layer were exposed was cut out. The rubber piece was placed on the SEM specimen stage so that the cross-section of the conductive layer was on the upper surface, and a sampling probe was fixed at a position corresponding to the outer surface of the conductive layer in the rubber piece. Further, a sample of the first region was collected by performing a cutting process with FIB at a position corresponding to 0.1 μm inside from the surface corresponding to the outer surface of the conductive layer. Regarding the second region, a cutting process with FIB was performed at a position 1.0 μm from the interface between the inner surface of the conductive layer and the intermediate layer toward the outer surface side. A sampling probe was fixed to the obtained cut surface, and a sample of the second region was collected by performing a cutting process with FIB at a position corresponding to 0.1 μm inside from the cut surface. Also, regarding the third region, by performing a cutting process with FIB at a position corresponding to 1.0 μm inside from the surface corresponding to the outer surface of the conductive layer in the same rubber piece as above, the third region was exposed. A sampling probe was fixed to the exposed surface, and a sample of the third region was collected by performing a cutting process with FIB at a position corresponding to 0.1 μm inside from the exposed surface. In any of the cutting processes, the acceleration voltage of FIB was 30 kV and the beam current was 27 mA.

[0099] [Pyridine decomposition method] The pyridine decomposition method is a method for selectively decomposing urethane bonds. That is, when the first resin is polyurethane, the presence or absence of an IPN structure can be confirmed by the pyridine decomposition method. In a sample having an IPN structure between the second resin and polyurethane, by performing the pyridine decomposition method, the second resin can be obtained after removing the structure derived from polyurethane. From the obtained second resin, the change in the peak temperature of the thermochromatogram due to the presence or absence of the IPN structure can be captured. The pyridine decomposition method is specifically performed by the following method. Using a microtome, a sample was cut out from the outer surface of the conductive layer with a thickness of 0.1 μm, and 500 mg was collected. For the obtained sample, 0.5 mL of a mixed solution of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and water mixed at a mass ratio of 3:1 was added, and decomposition was carried out by heating at 130 °C for 15 hours in a sealed container made of fluororesin (Teflon (registered trademark)) with a stainless steel jacket. The obtained decomposition product was subjected to a reduced pressure treatment to remove pyridine. Using the sample thus obtained, the above-described microsampling mass spectrometry was performed to obtain the value of A2. From the obtained values of A1 and A2 and formula (X), the presence or absence of the IPN structure was determined. The results are shown in Table 13. When the first resin is not polyurethane, the presence or absence of the IPN structure can be specified as follows. That is, only the raw material of the second resin is cured to obtain the second resin. Using the obtained second resin as a measurement sample, the above-described microsampling mass spectrometry is performed. Since the peak top temperature of the obtained thermochromatogram is the peak top temperature when the second resin exists as a single substance, the peak top temperature corresponds to the peak top temperature A2 of the thermochromatogram.

[0100] <<Evaluation of Conductive Roller>> Regarding the obtained conductive rollers according to the examples and comparative examples, evaluations were performed on the following items. The results are shown in Table 13 below.

Table 13

[0101] <Evaluation of Roller Resistance Value Variation> The roller resistance value was measured using a conductive roller left in an environment of 0 °C for 6 hours or more. [Measurement of Initial Roller Resistance] Fig. 4 shows a schematic configuration diagram of a roller resistance value fluctuation evaluation jig according to the present disclosure. In Fig. 4(a), in an environment of 0°C, while pressing both ends of a conductive shaft core body 42 via a conductive bearing 38 with a load of 4.9 N each, a cylindrical metal 37 with a diameter of 24 mm was rotated at a surface speed of 50 mm / sec to drive a conductive roller 41. Next, in Fig. 4(b), a voltage of 50 V was applied by a high-voltage power supply 39, and the potential difference between both ends of a resistor having a known electrical resistance (having an electrical resistance two or more digits lower than the electrical resistance of the conductive roller) disposed between the cylindrical metal 37 and the ground was measured. For the measurement of the potential difference, a voltmeter 40 (FLUKE 189 TRUE RMS MULTIMETER) was used. From the measured potential difference and the electrical resistance of the resistor, the current flowing through the cylindrical metal via the conductive roller 41 was obtained by calculation. The electrical resistance value of the conductive roller 41 was obtained by dividing the applied voltage of 50 V by the obtained current. Here, for the measurement of the potential difference, sampling was performed for 3 seconds starting from 2 seconds after voltage application, and the value calculated from the average value was used as the initial roller resistance value.

[0102] [Measurement of Roller Resistance after Evaluation] After performing the ghost evaluation described later, the roller was immediately taken out, and the roller resistance after energization was measured in the 0°C environment as it was.

[0103] [Energization Degradation] The value obtained by dividing the roller resistance value after evaluation by the initial roller resistance value (roller resistance value after evaluation / initial roller resistance value) was used as an index of energization degradation.

[0104] <Ghost Evaluation> Next, after leaving the conductive roller for which the initial roller resistance was measured as described above in an environment of 0°C for 6 hours or more, the following evaluation was performed. A laser printer (product name, LBP7700C; manufactured by Canon) having a configuration as shown in Fig. 3 was installed in an environment of 0°C, and the conductive roller as the electrophotographic member of this example was loaded as a developing roller, and the evaluation of ghost images was performed. That is, using a black toner, a solid black image with a 15 mm square at the tip and then a halftone image covering the entire surface were printed as an image pattern on one sheet. Next, the density unevenness of the period of the developing roller as a toner carrier appearing in the halftone portion was visually evaluated, and ghost evaluation was performed according to the following criteria. [Ghost evaluation in an environment of 0°C] A: No ghost is observed at all. B: Very slight ghost is observed. C: Obvious ghost is observed.

[0105] [Horizontal streak image evaluation] Next, regarding the electrophotographic members according to Examples 1 - 21 and Comparative Examples 2 - 5 obtained, the above-described roller resistance value fluctuation evaluation was performed, and using these as charging rollers, evaluation was performed on the following items. Due to the change in conductivity (increase in electrical resistance) caused by energizing the charging roller, fine streak-like density unevenness (horizontal streaks) may occur in the halftone image. This is called a horizontal streak image. This horizontal streak image tends to occur more as the conductivity of the charging roller changes, and tends to become more noticeable with long-term use of the electrophotographic apparatus. The electrophotographic member of the present disclosure was incorporated into an electrophotographic apparatus as a charging roller, and the following evaluation was performed.

[0106] As a charging roller of an electrophotographic laser printer (product name: HP Color Laserjet Enterprise CP4515dn, manufactured by HP), the conductive rollers obtained in Examples 1 - 21 and Comparative Examples 2 - 5 were mounted. And A durability test was performed to continuously output an image with a printing density of 4% (an image depicting horizontal lines with a width of 2 dots and an interval of 50 dots in a direction perpendicular to the rotation direction of the photoreceptor). Also, after continuously outputting 24,000 images, a halftone image (an image depicting horizontal lines with a width of 1 dot and an interval of 2 dots in a direction perpendicular to the rotation direction of the photoreceptor) was output for image checking. The obtained images were visually observed, and fine streak-like density unevenness (horizontal streaks) was evaluated. The evaluation results are shown in Table 14. A: The level at which no horizontal streaks occur at all. B: The level at which horizontal streaks occur slightly only at the image edges. C: Horizontal streaks occur in approximately half of the image area and are prominent.

Table 14

[0107] <Consideration of Evaluation Results> The electrophotographic member produced in Example 3-1 contains the first resin and the second resin according to the present disclosure in the conductive layer, and the second resin contains a (meth)acrylic resin having a predetermined structure. Therefore, the resistance increase after image output in a 0°C environment is small, and the image quality is also maintained well. On the other hand, Comparative Example 3-1 that does not contain at least one of the first resin and the second resin according to the present disclosure has a large resistance increase before and after image output in the above environment, and significant adverse effects also occur in image evaluation.

[0108] The present disclosure includes the following configurations. [Configuration 1] An electrophotographic member having a conductive substrate and a conductive layer on the substrate, wherein the conductive layer contains a first resin and a second resin, the first resin is a resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring, the second resin is An electrophotographic member characterized by including a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2): TIFF2025110363000030.tif43170TIFF2025110363000031.tif33170In formula (1), R 12 represents a hydrogen atom or a methyl group, R 13 represents an alkylene group having a straight chain or a branch with 1 to 7 carbon atoms, R 14 represents a fluorine atom or a perfluoroalkyl group having a straight chain or a branch with 1 to 4 carbon atoms, X +represents at least one selected from the group consisting of lithium ion, sodium ion and potassium ion; In formula (2), R 21 represents a hydrogen atom or a methyl group, R 22 represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 5 to 6 carbon atoms. [Configuration 2] The conductive layer contains a binder resin, The electrophotographic member according to Configuration 1, wherein the binder resin contains the first resin. [Configuration 3] The electrophotographic member according to Configuration 1 or 2, wherein the first resin is at least one resin selected from the group consisting of polyurethane, polyether, and polyphenylene. [Configuration 4] The electrophotographic member according to any one of Configurations 1 to 3, wherein the conductive layer contains the first resin and the second resin in a first region having a depth of up to 0.1 μm from the outer surface of the conductive layer. [Configuration 5] The electrophotographic member according to Configuration 4, wherein in the first region, the first resin and the second resin form an interpenetrating polymer network structure. [Configuration 6] The electrophotographic member according to Configuration 5, wherein the first resin is polyurethane. [Configuration 7] In the first region, when the peak top temperature of the thermochromatogram corresponding to the first resin is T1 (°C), When the peak top temperature of the thermochromatogram corresponding to the first resin contained in a second region having a thickness of 0.1 μm from the inner surface of the conductive layer toward the outer surface is T2 (°C), the electrophotographic member according to Configuration 5 or 6, wherein T1 and T2 satisfy the relationship represented by the following formula (3): T1>T2 (3). [Configuration 8] The electrophotographic member according to Configuration 7, wherein T1 and T2 satisfy the following formula (4): (T1 - T2)>1.0 (°C) (4). [Configuration 9] The electrophotographic member according to any one of Configurations 1 to 8, wherein the thickness of the conductive layer is 2.0 μm or more and 150.0 μm or less. [Configuration 10] When the peak top temperature of the thermochromatogram corresponding to the first resin in the first region is T1 (°C), When the peak top temperature of the thermochromatogram corresponding to the first resin contained in the second region having a thickness of 0.1 μm from the inner surface of the conductive layer toward the outer surface is T2 (°C), When the peak top temperature of the thermochromatogram corresponding to the first resin in the third region having a depth of 1.0 μm or more and 1.1 μm or less in the depth direction from the outer surface of the conductive layer is T3 (°C), the electrophotographic member according to any one of Configurations 5 to 9, wherein T1, T2, and T3 satisfy the relationship represented by the following formula (5) and the relationship represented by formula (6): T1>T3 (5); |T1-T3|>|T3-T2| (6). [Configuration 11] An electrophotographic process cartridge configured to be detachable from the main body of an electrophotographic apparatus, comprising the electrophotographic member according to any one of Configurations 1 to 10. [Configuration 12] The electrophotographic process cartridge according to Configuration 11, comprising the electrophotographic member as a developing member. [Configuration 13] An electrophotographic image forming apparatus comprising the electrophotographic member according to any one of Configurations 1 to 10 as a developing member. [Configuration 14] An ionic conductive agent containing a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2): TIFF2025110363000032.tif43170TIFF2025110363000033.tif33170In formula (1), R 12 represents a hydrogen atom or a methyl group, R 13represents an alkylene group having a straight chain or a branch with 1 to 7 carbon atoms, R 14 represents a fluorine atom or a perfluoroalkyl group having a straight chain or a branch with 1 to 4 carbon atoms, X + represents at least one selected from the group consisting of lithium ion, sodium ion and potassium ion; In formula (2), R 21 represents a hydrogen atom or a methyl group, R 22 represents an alkyl group having a straight chain or a branch with 1 to 6 carbon atoms, or an alicyclic hydrocarbon group with 5 to 6 carbon atoms.

Explanation of symbols

[0109] 1: Electro-photographic member, 2: Substrate, 3: Surface layer, 4: Elastic layer, 5: Intermediate layer

Claims

1. An electrophotographic member having a conductive substrate and a conductive layer on the substrate, wherein the conductive layer contains a first resin and a second resin, the first resin is a resin having at least one selected from the group consisting of a urethane bond, an ether bond, and an aromatic ring, the second resin contains a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2): An electrophotographic member characterized by: In formula (1), R １２ represents a hydrogen atom or a methyl group, R １３ represents an alkylene group having 1 to 7 carbon atoms and being linear or branched, R １４ represents a fluorine atom or a perfluoroalkyl group having a linear or branched chain with 1 to 4 carbon atoms, X ＋ represents at least one selected from the group consisting of lithium ion, sodium ion and potassium ion; In formula (2), R ２１ represents a hydrogen atom or a methyl group, R ２２ represents an alkyl group having 1 to 6 carbon atoms and being linear or branched, or an alicyclic hydrocarbon group having 5 to 6 carbon atoms.

2. the conductive layer contains a binder resin, the electrophotographic member according to claim 1, wherein the binder resin contains the first resin.

3. The electrophotographic member according to claim 1, wherein the first resin is at least one resin selected from the group consisting of polyurethane, polyether, and polyphenylene.

4. The electrophotographic member according to claim 1, wherein in a first region from the outer surface of the conductive layer to a depth of 0.1 μm in the depth direction, the first resin and the second resin are included.

5. The electrophotographic member according to claim 4, wherein in the first region, the first resin and the second resin form an interpenetrating polymer network structure.

6. The electrophotographic member according to claim 5, wherein the first resin is polyurethane.

7. Let the peak top temperature of the thermochromatogram corresponding to the first resin in the first region be T1 (°C), Let the peak top temperature of the thermochromatogram corresponding to the first resin contained in a second region having a thickness of 0.1 μm from the inner surface of the conductive layer toward the outer surface be T2 (°C). The electrophotographic member according to claim 5, wherein T1 and T2 satisfy the relationship represented by the following formula (3): T1 > T2 (3).

8. The electrophotographic member according to claim 7, wherein T1 and T2 satisfy the following formula (4): (T1 - T2) > 1.0 (°C) (4).

9. The electrophotographic member according to claim 1, wherein the thickness of the conductive layer is 2.0 μm or more and 150.0 μm or less.

10. Let the peak top temperature of the thermochromatogram corresponding to the first resin in the first region be T1 (°C), Let the peak top temperature of the thermochromatogram corresponding to the first resin contained in a second region having a thickness of 0.1 μm from the inner surface of the conductive layer toward the outer surface be T2 (°C), When the peak top temperature of the thermochromatogram corresponding to the first resin in the third region with a depth of 1.0 μm or more and 1.1 μm or less in the depth direction from the outer surface of the conductive layer is T3 (°C), the electrophotographic member according to claim 5, wherein T1, T2, and T3 satisfy the relationship represented by the following formula (5) and the relationship represented by formula (6): T1 > T3 (5); |T1 - T3| > |T3 - T2| (6).

11. An electrophotographic process cartridge configured to be detachable from the main body of an electrophotographic apparatus, comprising the electrophotographic member according to any one of claims 1 to 10. An electrophotographic process cartridge characterized by this.

12. The electrophotographic process cartridge according to claim 11, comprising the electrophotographic member as a developing member.

13. An electrophotographic image forming apparatus, characterized by comprising the electrophotographic member according to any one of claims 1 to 10 as a developing member.

14. An ion conductive agent containing a (meth)acrylic resin having a structure represented by the following formula (1) and a structure represented by the following formula (2): In formula (1), R １２ represents a hydrogen atom or a methyl group, R １３ represents an alkylene group having 1 to 7 carbon atoms and being linear or branched, R １４ represents a fluorine atom or a perfluoroalkyl group having a straight-chain or branched chain with 1 to 4 carbon atoms, X ＋ represents at least one selected from the group consisting of lithium ion, sodium ion and potassium ion; In formula (2), R ２１ represents a hydrogen atom or a methyl group, R ２２ represents an alkyl group having 1 to 6 carbon atoms and being linear or branched, or an alicyclic hydrocarbon group having 5 to 6 carbon atoms.

Images