Electrophotographic components, developing apparatus, electrophotographic process cartridge, and electrophotographic image forming apparatus

Abstract

To provide an electrophotographic component that can stably form high-quality electrophotographic images even when subjected to the formation of a large number of electrophotographic images over a long period of time in a low-temperature environment. [Solution] An electrophotographic component characterized in that the first resin is a crosslinked urethane resin having at least one selected from the group consisting of a cationic structure represented by formula (C-1) and a cationic structure represented by formula (C-2), as well as polymer chains in the molecule, and the second resin is a crosslinked acrylic resin having at least one selected from the group consisting of a substructure represented by formula (C-3), a substructure represented by formula (C-4), and a substructure represented by formula (C-5), as well as polymer chains in the molecule, and when the region from the outer surface of the conductive layer to a depth of 0.1 μm is defined as the first region, the first resin and the second resin constitute an interpenetrating polymer network structure in the first region.

Description

[Technical Field]

[0001] This disclosure relates to an electrophotographic component and a developing device incorporated into an apparatus employing an electrophotographic method. Furthermore, the present invention relates to an electrophotographic process cartridge having the developing device and an electrophotographic image forming apparatus. [Background technology]

[0002] In an electrophotographic image forming apparatus (also called an "electrophotographic apparatus"), electrophotographic components equipped with a conductive layer are used, for example, as developing components, charging components, toner supply components, and cleaning components. The conductive layer of the electrophotographic component has, for example, an electrical resistance value of 1.0 × 10⁻⁶. 5 ~1.0×10 9 It is controlled within the range of Ω.

[0003] Furthermore, the conductivity must be uniform throughout the entire component and stable over time. Conductive agents used to impart the desired conductivity to the conductive layer include conductive particles such as carbon black, and ionic conductive agents such as salt compounds of sulfonylimid anions and metal cations.

[0004] Electronically conductive rollers, which are made by adding conductive particles such as carbon black, have the advantage that even with prolonged current flow, changes such as increased resistance due to uneven distribution of conductive components are less likely to occur. However, on the other hand, conductive particles such as carbon black are difficult to disperse uniformly, and areas of high or low resistance may occur locally.

[0005] Ion-conductive rollers, which have an ionic conductive agent added, can reduce the unevenness in electrical resistance caused by uneven dispersion of the conductive agent compared to electronically conductive rollers, and are less likely to produce areas with localized high or low resistance. Therefore, in developing rollers, the developer can be uniformly developed onto the photoreceptor, and in charging rollers, uniform charging of the photoreceptor surface becomes possible.

[0006] Further, in order to exhibit high conductivity throughout the service life, it is necessary to reduce the transfer of substances from the contact member to the surface of the electrophotographic member. The transferred substances may increase the resistance of the surface of the electrophotographic member and degrade image quality, and this phenomenon is remarkable in high-temperature and high-humidity environments. Countermeasures against such member contamination by increasing the hardness of the outermost surface and reducing the tackiness of the polymer resin have been disclosed.

[0007] Patent Document 1 discloses that, for a crosslinked urethane resin containing an anion and having a specific cationic structure in the molecule, in a first region from the outer surface to a depth of 0.1 µm, at least one of a crosslinked acrylic resin having an ether bond and a crosslinked epoxy resin having an ether bond forms an interpenetrating polymer network structure. A technique relating to an electrophotographic member capable of achieving uniform conductivity of the member itself and good chargeability of a developer while suppressing transfer of substances from other members is disclosed. [Prior Art Literature] [Patent Literature]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2021-176003 [Summary of the Invention] [Problem to be Solved by the Invention]

[0009] In recent years, electrophotographic apparatuses are required to maintain high image quality and high durability even under more severe environments and in higher-speed electrophotographic processes. The inventors of the present invention mounted the conductive roller described in Patent Document 1 on an electrophotographic process cartridge as a developing roller, and output a large number of electrophotographic images in an environment at a temperature of 0°C using this process cartridge. As a result, as the number of output sheets increased, ghosting was sometimes observed in the electrophotographic images.

[0010] At least one aspect of the present disclosure is directed to providing an electrophotographic member that contributes to stable formation of high-quality electrophotographic images under low-temperature environments. Furthermore, 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. [Means for Solving the Problems]

[0011] In order to solve the above problems, the present disclosure provides: An electrophotographic member comprising a substrate and a conductive layer on the substrate, wherein the conductive layer has a thickness of 0.1 µm or more, the conductive layer contains a first resin, a second resin, and a bis(fluorosulfonyl)imide anion, the first resin is a crosslinked urethane resin having, in a molecule thereof, at least one selected from the group consisting of a cationic structure represented by the following formula (C-1) and a cationic structure represented by the following formula (C-2), and a polymer chain, the second resin is a crosslinked acrylic resin having, in a molecule thereof, at least one selected from the group consisting of a partial structure represented by the following formula (C-3), a partial structure represented by the following formula (C-4), and a partial structure represented by the following formula (C-5), and a polymer chain, when a region extending from the outer surface of the conductive layer to a depth of 0.1 µm in the depth direction is defined as a first region, the first resin and the second resin form an interpenetrating polymer network structure in the first region, An electrophotographic member characterized by the above. [Chemical Formula] (In formula (C-1), R 11 to R 15 are each independently any one selected from the group consisting of the following (a) to (c), and any two of R 11 to R 15 are (c). (a) a hydrogen atom (b) a saturated hydrocarbon group having 1 to 6 carbon atoms (c) a structure comprising a moiety bonded to the polymer chain of the crosslinked urethane resin) [Chemical Formula] (In formula (C-2), R 21 to R 26 are each independently any one selected from the group consisting of the above (a) to above (c), and R 21 to R 26 include any two of which that are the above (c).) ## Chemical Formula (In formula (C-3), R 1 represents a structure composed of carbon, hydrogen and oxygen having 2 to 8 carbon atoms, and * represents a structure including a moiety bonded to a polymer chain of the crosslinked acrylic resin.) ## Chemical Formula (In formula (C-4), R 2 represents a structure composed of carbon, hydrogen and oxygen having 3 to 8 carbon atoms, and * represents a structure including a moiety bonded to a polymer chain of the crosslinked acrylic resin.) ## Chemical Formula (In formula (C-5), R 3 represents a structure composed of carbon, hydrogen and oxygen having 3 to 8 carbon atoms, and * represents a structure including a moiety bonded to a polymer chain of the crosslinked acrylic resin.) Effects of the Invention

[0012] According to at least one aspect of the present disclosure, an electrophotographic member that contributes to stable formation of high-quality electrophotographic images under low-temperature environments can be obtained. Further, according to at least one aspect of the present disclosure, an electrophotographic process cartridge that contributes to 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. Brief Description of Drawings

[0013] [Figure 1]This is a schematic cross-sectional view of an example of an electrophotographic roller according to one aspect of this disclosure. [Figure 2] This is a schematic diagram of an example of a process cartridge according to one aspect of this disclosure. [Figure 3] This is a schematic cross-sectional view of an example of an electrophotographic apparatus according to one aspect of this disclosure. [Figure 4] This is a schematic diagram of a jig for evaluating the resistance value of a developing roller. [Figure 5] This is a schematic cross-sectional view of an example of a blade member according to one aspect of the present disclosure. [Figure 6] This is an explanatory diagram of microsampling mass spectrometry. [Modes for carrying out the invention]

[0014] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be combined in any way.

[0015] Furthermore, in this disclosure, any statement such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of the following: 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.

[0016] [One Embodiment] One embodiment relates to an electrophotographic component. The electrophotographic components disclosed herein are An electrophotographic component comprising a substrate and a conductive layer on the substrate, The thickness of the conductive layer is 0.1 μm or more. The conductive layer contains a first resin, a second resin, and a bis(fluorosulfonyl)imide anion. The first resin is a crosslinked urethane resin having at least one selected from the group consisting of a cationic structure represented by the following formula (C-1) and a cationic structure represented by the following formula (C-2), as well as a polymer chain within its molecule. The second resin is a crosslinked acrylic resin having at least one selected from the group consisting of a substructure represented by the following formula (C-3), a substructure represented by the following formula (C-4), and a substructure represented by the following formula (C-5), as well as a polymer chain within its molecule. When the region from the outer surface of the conductive layer to a depth of 0.1 μm is defined as the first region, the first resin and the second resin in the first region constitute an interpenetrating polymer network structure. It is characterized by the following: [ka] (In formula (C-1), R 11 ~R 15 Each is independently selected from the group consisting of (a) to (c) below, and R 11 ~R 15 Any two of these are (c). (a) Hydrogen atom (b) saturated hydrocarbon groups having 1 to 6 carbon atoms (c) A structure including a portion that is bonded to the polymer chain of the crosslinked urethane resin. [ka] (In formula (C-2), R 21 ~R 26 Each of these is independently selected from the group consisting of (a) to (c), and R 21 ~R 26 Two of these are (c) above. [ka] (In formula (C-3), R 1 (* represents a structure consisting of carbon atoms with 2 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) [ka] (In formula (C-4), R 2 (* represents a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) [ka] (In formula (C-5), R 3 (* represents a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.)

[0017] The inventors confirmed that the electrical resistance of the conductive roller surface increased immediately after the occurrence of ghosting in an electrophotographic image output test in a low-temperature environment using a conductive roller according to Patent Document 1. From this, they inferred that the occurrence of ghosting is caused by the accumulation of charge on the conductive roller as the number of electrophotographic images output increases, especially in severe low-temperature environments.

[0018] <<Improvement Mechanism>> The inventors of the present invention surmise the following reason why the electrophotographic component according to the present invention is less likely to produce ghosting even when used to form a large number of electrophotographic images in a low-temperature environment.

[0019] In environments above room temperature, molecules can move freely due to thermal stress. However, in low-temperature environments, thermal mobility is restricted, and molecular mobility decreases. In this case, ionic species with large ionic radii suffer from spatial bulkiness, which exacerbates the decrease in molecular mobility.

[0020] Patent Document 1 further describes a crosslinked urethane resin having a specific structure within its molecule, wherein in a first region from the outer surface to a depth of 0.1 μm, at least one of a crosslinked acrylic resin having ether bonds and a crosslinked epoxy resin having ether bonds constitutes an interpenetrating polymer network structure.

[0021] This interpenetrating polymer network structure effectively suppresses the mobility of crosslinked urethane resins and inhibits the migration of free cations to the outermost surface, thereby suppressing the triboto reduction of the developer in environments above room temperature. On the other hand, in low-temperature environments, such an interpenetrating polymer network structure can act in a way that hinders the molecular mobility of anions.

[0022] Furthermore, the crosslinked acrylic resin or crosslinked epoxy resin described in Patent Document 1 has ether bonds within its molecule. Due to their high electron density, ether bonds can cause electrostatic repulsion with anions. Because this interpenetrating structure is formed on the outermost surface, it is considered that the difficulty in anions migrating to the outermost surface, both spatially and electrically, leads to charge accumulation on the conductive roller and ultimately to the generation of ghosting.

[0023] The inventors of this invention believe that a configuration satisfying the following conditions is effective in solving these problems. (i) Select an anion with a sufficiently small ionic radius. (ii) Sufficiently reduce the proportion of electron-rich oxygen functional groups. The inventors investigated the configuration of an electrophotographic component that satisfies conditions (i) and (ii). As a result, they arrived at the configuration of the present invention.

[0024] The fluorosulfonylimide included in the present invention has a smaller ionic radius than the trifluorosulfonylimide shown in Patent Document 1. Therefore, it is less susceptible to the limitations of thermal mobility imposed by the IPN structure. Furthermore, by using an impregnation agent having the structure represented by formulas (C-3) to (C-5), electrostatic repulsion is effectively limited. For this reason, it is believed that the electrophotographic component of the present invention suppresses migration from other components, significantly improves the conductivity of the outermost surface, and enables the acquisition of output images with uniform density free from ghosting.

[0025] <<Conductive layer>> The electrophotographic component relating to this disclosure has a conductive layer thickness of 0.1 μm or more, and the conductive layer contains a first resin, a second resin, and a bis(fluorosulfonyl)imide anion. In this disclosure, the thickness of the conductive layer can be confirmed by scanning electron microscopy (SEM) observation of the cross-section.

[0026] <Anion> The anionic component of this disclosure preferably contains a bis(fluorosulfonyl)imide anion (also called an FSI anion) because it exhibits high ion mobility in the first and second resins, and when the anion is localized by current, it moves easily using the concentration gradient as a driving force. Furthermore, in this disclosure, it is preferable that 80% by mass or more of the anionic component contained in the conductive layer is a bis(fluorosulfonyl)imide anion.

[0027] In this disclosure, it is preferable that the amount of anionic component contained in the conductive layer is 0.01 parts by mass or more and 0.2 parts by mass or less, relative to a total of 100 parts by mass of the first resin and the second resin contained in the conductive layer. By doing so, it is possible to provide an electrophotographic component that contributes to the more stable formation of higher quality electrophotographic images in low-temperature environments.

[0028] <First resin> The electrophotographic component of this disclosure is a crosslinked urethane resin in which the first resin has at least one selected from the group consisting of a cationic structure represented by the following formula (C-1) and a cationic structure represented by the following formula (C-2), as well as polymer chains within the molecule. [ka] (In formula (C-1), R 11 ~R 15 Each is independently selected from the group consisting of (a) to (c) below, and R 11 ~R 15 Any two of these are (c). (a) Hydrogen atom (b) saturated hydrocarbon groups having 1 to 6 carbon atoms (c) A structure including a portion that is bonded to the polymer chain of the crosslinked urethane resin. [ka] (In formula (C-2), R 21 ~R 26 Each of these is independently selected from the group consisting of (a) to (c), and R 21 ~R 26 Two of these are (c) above. In this disclosure, the structure and quantity of the resin can be confirmed, for example, by nuclear magnetic resonance (NMR) and matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS).

[0029] Examples of the saturated hydrocarbon groups having 1 to 6 carbon atoms in (b) above include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups; branched alkyl groups such as isopropyl, isobutyl, s-butyl, t-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl groups; and cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl.

[0030] (c) The structure including a portion of the resin bonded to the polymer chain via a urethane bond includes the structure after a reaction between a structure having a hydroxyl group such as a hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group, or triethylene glycol ether group and an isocyanate group.

[0031] <Second resin> The electrophotographic component of this disclosure is a crosslinked acrylic resin having a polymer chain within its molecule, at least one selected from the group consisting of a substructure represented by the following formula (C-3), a substructure represented by the following formula (C-4), and a substructure represented by the following formula (C-5). [ka] (In formula (C-3), R 1 (* represents a structure consisting of carbon atoms with 2 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) [ka] (In formula (C-4), R 2 (* represents a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) [ka] (In formula (C-5), R 3 (* represents a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.)

[0032] In this disclosure, it is preferable that the monomer forming the second resin is a monomer with three or more functionalities. By doing so, it is possible to provide an electrophotographic component that contributes to the more stable formation of higher-quality electrophotographic images in low-temperature environments.

[0033] <<Method for manufacturing a resin layer>> A conductive layer can be formed, for example, by forming a coating film of a paint for forming a conductive layer, which contains the raw materials of the resin that make up the conductive layer, on an elastic layer described later, and then reacting the raw materials of the resin in the coating film with each other.

[0034] The paint contains the following (i) to (iii) as raw materials for the resin. (i) Ionic conductive agent for introducing a cationic substructure represented by at least one of formulas (C-1) and (C-2) into a resin. (ii) Polyisocyanate that forms a urethane resin when reacted with the ionic conductive agent. (iii)(ii) Polyols that form urethane resin by reacting with the polyisocyanate described in (iii)(ii)

[0035] <(i) Ionic conductive agents> Ionic conductive agents are compounds having two hydroxyl groups and possessing both cations and anions. The structure of the cation corresponds to the compound represented by formula (C-1) or formula (C-2) above.

[0036] In terms of the relatively high conductivity of the resulting conductive layer, imidazolium cations and pyridinium cations are preferred, with imidazolium cations being particularly preferred. This is because the positive charge of the imidazolium cation is delocalized on the imidazolium ring, which can relatively suppress the effect of toner charge being removed by the cationic organic group.

[0037] The anions in ionic conductive agents are as described above. The amount of ionic conductive agent is preferably 0.01 parts by mass or more and 20 parts by mass or less relative to the conductive layer. If the amount is 0.01 parts by mass or more, a conductive layer with high conductivity can be obtained. If the amount is 20 parts by mass or less, a conductive layer with minimal leaching of the ionic conductive agent can be obtained.

[0038] The ionic conductive agent according to the present invention can be obtained by synthesizing a precursor using one or more known nucleophilic substitution reactions, such as the Menschtkin reaction, and then carrying out a known ion exchange reaction.

[0039] Therefore, compounds containing a nucleophilic nitrogen atom, such as imidazole compounds and pyridine compounds, can be used as nucleophiles. Furthermore, electrophiles can include, for example, alkyl halides with substituted hydroxyl groups.

[0040] Furthermore, the alkali metal salt used in the ion exchange reaction can be an alkali metal salt containing the anion according to the present invention, such as lithium alkylsulfonate salt or potassium alkylsulfonylimide salt.

[0041] By changing the nucleophile and electrophile used in the nucleophilic substitution reaction and the alkali metal salt used in the ion exchange reaction to a desired combination, the target ionic conductive agent can be synthesized by a combination of known methods.

[0042] <(ii) Polyisocyanates> Examples of isocyanate compounds include aliphatic polyisocyanates such as ethylene diisocyanate and 1,6-hexamethylene diisocyanate (HDI), alicyclic polyisocyanates such as isophorone diisocyanate (IPDI), cyclohexane 1,3-diisocyanate and cyclohexane 1,4-diisocyanate, aromatic polyisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate, xylylene diisocyanate and naphthalene diisocyanate, and copolymers thereof, as well as isocyanurates, TMP adducts, biuret compounds, and their block compounds.

[0043] Among these, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate are preferred. These compounds have high reactivity with the hydroxyl groups of cations, reducing the proportion of cations not bonded to the resin. As a result, a conductive layer with minimal leaching of the ionic conductive agent can be obtained.

[0044] Furthermore, it is preferable to use a polyether polyol or polyester polyol, described later, as the polyisocyanate, as an isocyanate-terminated prepolymer obtained by reacting it with an isocyanate such as 2,4-tolylene diisocyanate (TDI), 1,4-diphenylmethane diisocyanate (MDI), or isophorone diisocyanate (IPDI).

[0045] In this way, polyether polyols or polyester polyols can be dispersed in the resin along with ionic conductive agents or amino compounds. As a result, a conductive layer with excellent flexibility can be obtained.

[0046] The amount of polyisocyanate blended is preferably such that the ratio of isocyanate groups to the total number of hydroxyl groups in the ionic conductive agent and the amino compound (1.0) is between 1.0 and 2.0. A ratio of 1.0 or more yields a conductive layer with excellent charge imparting properties. A ratio of 2.0 or less yields a conductive layer with excellent flexibility. Note that the above total number includes the number of hydroxyl groups in the polyol when a polyol is used.

[0047] (iii) Polyols The paint for forming the conductive layer may further contain polyols other than the above-mentioned ionic conductive agent and amino compounds (hereinafter also referred to as "other polyols"). The other polyols have multiple hydroxyl groups in their molecules, and these hydroxyl groups react with the polyisocyanate. The other polyols are not particularly limited, and examples include polyether polyols and polyester polyols.

[0048] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of polyester polyols include polyester polyols obtained by the condensation reaction of diol components such as 1,4-butanediol, 3-methyl-1,4-pentanediol, and neopentyl glycol, or triol components such as trimethylolpropane, with dicarboxylic acids such as adipic acid, phthalic anhydride, terephthalic acid, and hexahydroxyphthalic acid.

[0049] The conductive layer may contain, if necessary, general resins other than the resin according to the present invention, rubber materials, compounding agents, conductivity imparters, non-conductive fillers, crosslinking agents, and catalysts, to the extent that the effects of the present invention are not impaired.

[0050] Examples of rubber materials include ethylene-propylene-diene copolymer rubber, acrylonitrile-butadiene rubber, chloroprene rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, silicone rubber, epichlorohydrin rubber, and urethane rubber.

[0051] Examples of compounding agents include fillers, softeners, processing aids, tackifiers, anti-tackifiers, and foaming agents commonly used with resins. Examples of conductivity imparters include carbon black; conductive metals such as aluminum and copper; and fine particles of conductive metal oxides such as conductive zinc oxide, conductive tin oxide, and conductive titanium oxide.

[0052] Examples of non-conductive fillers include silica, quartz powder, titanium dioxide, or calcium carbonate. Examples of crosslinking agents include tetraethoxysilane, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, or dicumyl peroxide.

[0053] If surface roughness is required for the conductive layer of the developing element, fine particles for roughness control may be added to the conductive layer. In particular, when the developing element of the present invention is applied to a developing roller, it is preferable that the fine particles used for roughness control in the conductive layer have a volume-average particle size of 3 to 20 μm, as this will result in a developing roller with excellent toner transport capabilities.

[0054] Furthermore, the amount of fine particles added to the conductive layer is preferably 1 to 50 parts by mass per 100 parts by mass of the resin solids content of the conductive layer, in order to avoid impairing the effects of the present invention. Fine particles of polyurethane resin, polyester resin, polyether resin, polyamide resin, acrylic resin, and phenolic resin can be used for roughness control.

[0055] The method for forming the conductive layer is not particularly limited, but examples include spraying, dipping, or roll coating with paint. The developing member of the present invention can be applied to electrophotographic components such as developing rollers and developing blades.

[0056] When the developing member of the present invention is applied to a developing roller in a developing apparatus, the developing agent may be magnetic or non-magnetic, and may be one-component or two-component. The developing apparatus may be non-contact or contact type.

[0057] <<Interpenetration Network (IPN) Structure>> In the electrophotographic component of this disclosure, when the region from the outer surface of the conductive layer to a depth of 0.1 μm is defined as the first region, the first resin and the second resin constitute an interpenetrating polymer network structure in the first region.

[0058] To further enhance the effects of this disclosure, it is preferable to create a spatial environment in which the first resin, which has a structure expected to stabilize cations, and the second resin, which can act as an ionic conductive agent, mutually influence each other. Specifically, it is preferable to include the first resin and the second resin in a first region extending from the outer surface of the conductive layer (the surface opposite to the side facing the substrate) to a depth of 0.1 μm.

[0059] In the first region, if the material contains both a first resin and a second resin, the conductive metal cation and the structure that stabilizes the cation are in spatial proximity. This allows for better conductivity on the outer surface of the conductive layer. Furthermore, in this disclosure, it is preferable that 80% by mass or more of the resin contained in the first region of the conductive layer consists of both the first resin and the second resin.

[0060] Furthermore, in the first region, it is particularly effective to have the first resin and the second resin form an interpenetrating polymer network (IPN) structure. An IPN structure is a structure in which the network structures of two or more resins intertwine and interlock with each other without being bonded together by covalent bonds.

[0061] When an IPN structure is formed, the above-mentioned improvement in conductivity manifests on the outer surface of the developing material, so uneven resistance on the surface can be effectively suppressed, making it easier to suppress density unevenness in halftones and gradation abnormalities caused by charge-up on the material surface associated with image output.

[0062] The peak-top temperature in the thermal chromatogram, which corresponds to the thermal decomposition temperature of the resin, is thought to be shifted to a higher temperature when the resin is present in an IPN structure compared to when it is present alone.

[0063] Therefore, by focusing on either the first or second resin in the conductive layer, and comparing the peak top temperature of the thermal chromatogram of the other resin before and after decomposition and removal of one of the resins, it can be confirmed that the first and second resins constitute an IPN structure if the peak top temperature is lower after decomposition than before decomposition. Here, a thermal chromatogram is a mass spectrum obtained by microsampling pyrolysis mass spectrometry.

[0064] The following is an overview of microsampling mass spectrometry. First, the area to be measured from the electrophotographic component is cut into thin sections using a microtome to prepare the sample. As shown in Figure 6, the sample is prepared from three areas, referred to as the first area 71, the second area 72, and the third area 73.

[0065] The first region is the area from the outer surface of the conductive layer 74 to a depth of 0.1 μm, the second region is the area from the inner surface of the conductive layer 74 (the surface facing the substrate 75) toward the outer surface with a thickness of 0.1 μm, and the third region is the area from the outer surface toward a depth of 1.0 μm or more and 1.1 μm or less. The sample obtained from the first region is designated as the first sample, the sample obtained from the second region as the second sample, and the sample obtained from the third region as the third sample.

[0066] From each region of the conductive layer, a 100 μm square, 0.1 μm thick flake is prepared. For measurement, an ion trap type mass spectrometer, such as the one mounted on a gas chromatography-mass spectrometer ("Polaris Q" (product name, Thermo Electron), is used. The sample is fixed to a filament located at the tip of the probe and inserted directly into the ionization chamber.

[0067] Subsequently, the sample is rapidly heated from room temperature to 1000°C at a constant heating rate. The sample, which has decomposed and evaporated due to heating, is ionized by electron beam irradiation and detected by a mass spectrometer. Under conditions of a constant heating rate, a thermal chromatogram similar to that obtained by TG-MS (thermogravimetric-mass simultaneous analysis) is obtained, which has a mass spectrum called a total ion chromatogram (TIC).

[0068] Furthermore, since a thermal chromatogram can be obtained for a fragment of a predetermined mass, 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 crosslinking structure in the resin structure; the denser the crosslinking, the higher the peak temperature shifts.

[0069] The fact that the first resin and the second resin constitute an interpenetrating polymer network structure can be confirmed as follows: Focusing on either the first or second resin, check the difference in peak temperature of the thermal chromatogram of fragments derived from the other resin before and after decomposing and removing one of the resins. For example, check the difference in peak temperature of the thermal chromatogram of fragments derived from the second resin before and after decomposing and removing the first resin.

[0070] When the peak top temperature of the thermal chromatogram derived from the second resin, measured from the first sample sampled from the first region, is denoted as A1 (°C), and the peak top temperature of the thermal chromatogram derived from the second resin, measured from the second sample obtained by decomposing the first resin contained in the first sample, is denoted as A2 (°C), it is preferable that A1 and A2 satisfy the relationship shown in the following formula (1) when an interpenetrating polymer network structure is formed. A1>A2 (1)

[0071] One method for decomposing the first resin is the pyridine decomposition method, which will be described later. In the conductive layer, when the peak top temperature of the thermal chromatogram corresponding to the first resin in the first region is T1 (°C), and the peak top temperature of the thermal chromatogram corresponding to the first resin in a second region with a thickness of 0.1 μm extending 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 shown in the following formula (3). T1>T2 (3)

[0072] The fact that the above equation (3) is satisfied can be confirmed by the micro-sampling mass spectrometry method described above. Furthermore, it is preferable that T1 and T2 satisfy the following formula (5). (T1-T2)>1.0(℃) (5)

[0073] The fact that the above equation (5) is satisfied can be confirmed by the micro-sampling mass spectrometry method described above. One of the functions of the conductive layer is to alleviate the mechanical stress that the developer carrier imparts to the toner. To fully perform this function, it is preferable that the conductive layer be flexible.

[0074] To achieve this, it is preferable that the IPN structure does not exist in a second region with a thickness of 0.1 μm extending from the surface facing the substrate of the conductive layer toward the outer surface. Alternatively, even if an IPN structure is present, it is preferable that it is an IPN structure in which the degree of penetration of the second resin is weaker compared to, for example, the IPN structure in the first region.

[0075] Therefore, it is preferable that the first and second regions of the conductive layer satisfy the relationship shown in formula (3) above, and more preferably that they satisfy the relationship shown in formula (5) above. Here, T1 (°C) is the peak top temperature of the thermal chromatogram corresponding to the first resin, measured from a sample sampled from the first region. T2 (°C) is the peak top temperature of the thermal chromatogram corresponding to the first resin, measured from a sample sampled from the second region.

[0076] The values ​​of T1 and T2 can be adjusted by the concentration of the treatment solution, UV irradiation intensity, etc. Furthermore, the peak top temperature of the thermal chromatogram corresponding to the first resin in a third region extending from the outer surface of the conductive layer to a depth of 1.0 μm or more and 1.1 μm or less is defined as T3 (°C). In this case, it is preferable that T1, T2, and T3 satisfy the relationship shown in formula (6) and formula (7) below. T1>T3 (6) |T1-T3|>|T3-T2| (7)

[0077] The fact that equations (6) and (7) above are satisfied can be confirmed by the micro-sampling mass spectrometry method described above. In order to better perform the functions of the conductive layer described above, when a third region is defined as a region with a depth of 1.0 μm or more and a depth of 1.1 μm or less and a thickness of 0.1 μm from the outer surface of the conductive layer, it is preferable that no IPN structure exists in the third region adjacent to the first region. Alternatively, even if an IPN structure exists, it is preferable that it is an IPN structure in which the degree of penetration of the second resin is weaker compared to the IPN structure in the first region.

[0078] Therefore, when T3 (°C) is the peak top temperature of the thermal chromatogram corresponding to the first resin, measured from the sample sampled from the third region, it is preferable that T1, T2, and T3 satisfy the relationship shown in equation (6) and the relationship shown in equation (7) above. The value of T3 can be adjusted by the crosslinking density of the first resin, etc.

[0079] <Cross-linked acrylic resin> The crosslinked acrylic resin according to this disclosure is a crosslinked acrylic resin having at least one substructure selected from the group consisting of formulas (C-3) to (C-5) within its molecule.

[0080] The first region of the elastic layer according to this disclosure, extending from the outer surface to a depth of 0.1 μm, comprises the first resin and the second resin. Preferably, when the peak area of ​​carbon(1s) atoms, whose bond energy peak position is 286.0 eV to 287.0 eV as measured by electron spectrochemical analysis (ESCA) of the second sample obtained by decomposing the first resin contained in the first sample, is α, and the peak area of ​​sulfur(2p3 / 2) atoms, whose bond energy peak position is 166.0 eV to 170.0 eV, is β, then α and β satisfy the following formula (2). 300 > α / β (2)

[0081] In ESCA, when the oxygen in a single bond is adjacent to a carbon (-OC, also called ether carbon), the bond energy of the carbon 1s orbital is 286.0 eV to 287.0 eV. α above indicates the amount of carbon adjacent to the oxygen. In the case of sulfonyl sulfur (O=S=O), the bond energy of the sulfur 2s orbital is 166.0 eV to 170.0 eV. β above indicates the amount of sulfur corresponding to the sulfonyl group.

[0082] In formula (2) above, α / β represents the amount of ether carbon per amount of sulfonyl sulfur. When the above α / β is less than 300, it indicates that the amount of ether carbon per sulfonyl sulfur is relatively small in the first region. In this disclosure, the amount of electron-rich ether components that can cause electrostatic repulsion with FSI anions is reduced. Therefore, it is expected that the opportunity for FSI anions to localize on the outermost surface of the conductive layer will increase. As a result, conductivity on the outermost surface will be ensured, and it is expected that charge-up of the electrophotographic material will be suppressed even in harsh low-temperature environments, leading to the suppression of ghosting.

[0083] On the other hand, when the α / β ratio is greater than 300, the amount of electron-rich ether components increases relative to the FSI anions. This may limit the opportunities for FSI anions to localize on the outermost surface of the conductive layer. As a result, the conductivity of the outermost surface decreases, which may lead to charge buildup in electrophotographic components, especially in harsh low-temperature environments, and potentially result in the manifestation of ghosting.

[0084] Furthermore, in this disclosure, when γ is the peak area of ​​a carbon(1s) atom whose bond energy peak position is in the range of 288 eV to 290 eV (288.0 eV to 290.0 eV), as measured by electron spectrochemical analysis (ESCA) of the second sample, it is preferable that α and γ satisfy the following formula (4). 1.5 > α / γ (4)

[0085] In ESCA, for carbonyl carbons (O=C), the bond energy of the carbon 1s orbital is 288.0 eV to 290.0 eV. The above γ represents the amount of carbon corresponding to the carbonyl group. Therefore, α / γ in formula (4) represents the amount of ether carbon (carbon atoms in the CO bond) per carbonyl carbon. When α / γ is less than 1.5, it indicates that the amount of ether carbon per carbonyl carbon is relatively small in the first region.

[0086] In this disclosure, the amount of electron-rich ether components that can repel FSI anions is reduced, while the amount of electron-poor carbonyl components that can electrostatically attract FSI anions to each other is increased.

[0087] At this time, it is expected that the opportunities for FSI anions to localize on the outermost surface of the conductive layer will increase. As a result, conductivity on the outermost surface will be ensured, and it is expected that charge-up of electrophotographic components will be suppressed even in harsh low-temperature environments, leading to a reduction in the harmful effects of ghosting.

[0088] On the other hand, if the α / γ ratio is greater than 1.5, the proportion of electron-rich ether components relative to electron-poor carbonyl components increases, which may limit the opportunities for FSI anions to localize on the outermost surface of the conductive layer. This can lead to a decrease in the conductivity of the outermost surface, which is particularly likely to cause charge buildup in electrophotographic components under harsh low-temperature environments, potentially leading to the manifestation of ghosting. The α / γ ratio can be adjusted by changing the structure or content of the second resin.

[0089] <Other ingredients> In addition to the above, the conductive layer may contain conductive substances, crosslinking agents, plasticizers, fillers, bulking agents, vulcanizing agents, vulcanizing aids, crosslinking aids, antioxidants, anti-aging agents, processing aids, leveling agents, etc., to the extent that they do not impair the function of the conductive layer.

[0090] Furthermore, if surface roughness is required for the conductive layer, fine particles can be included to impart roughness to the conductive layer. Specifically, fine particles of polyurethane resin, polyester resin, polyether resin, polyamide resin, (meth)acrylic resin, polycarbonate resin, etc., can be used.

[0091] 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. Rzjis is a value measured according to JIS B0601 (1994).

[0092] <<Electrophotographic components>> The embodiments for carrying out the present invention will be described in more detail below. Figure 1 shows a cross-sectional view of a roller-shaped electrophotographic member according to one aspect of the present invention, in a direction perpendicular to the axial direction. In the developing roller 1 shown in Figure 1(a), a surface layer 3 is directly formed on the outer circumferential surface of a cylindrical or hollow cylindrical base body 2.

[0093] Furthermore, as shown in Figure 1(b), the developing roller 1 may have one or more elastic layers 4 formed between the substrate 2 and the surface layer 3. In addition, as shown in Figure 1(c), the developer carrier 1 may have a three-layer structure with an intermediate layer 5 placed between the surface layer 3 and the elastic layer 4, or a multi-layer structure with multiple intermediate layers 5. Known intermediate layers of developing rollers can be used as the intermediate layers.

[0094] <Base> The conductive substrate 2 functions as an electrode and support member for the electrophotographic component 1. The substrate is made of a conductive material such as, for example, a metal or alloy such as aluminum, copper alloy, or stainless steel; iron plated with chromium or nickel; or a conductive synthetic resin.

[0095] Furthermore, a primer may be applied to the surface of the substrate to improve the adhesion between the substrate and the elastic layer described later. Examples of primers include silane coupling agent primers, urethane-based, acrylic-based, polyester-based, polyether-based, or epoxy-based thermosetting resins or thermoplastic resins.

[0096] Examples of commercially available primers include the following: "DY39-051", "DY39-012", "DY39-115" (all are product names, manufactured by Toray Dow Corning Co., Ltd.); "X-33-173", "PRIMER-NO.4", "PRIMER-NO.32", "PRIMER-NO.35" (all are product names, manufactured by Shin-Etsu Chemical Co., Ltd.); "XP81-405", "XP81-A6361", "XP81-B7015", "ME21", "ME151", "ME153", "XC9214" (all are product names, manufactured by Momentive Performance Materials Japan LLC).

[0097] To improve its adhesion, the primer may be supplemented with known alkoxysilanes, titanates, or the like. Specific examples of alkoxysilanes and titanates include tetramethoxysilane, tetraethoxysilane, tetran-butoxysilane, tetraethoxytitanium, tetraisopropoxytitanium, and tetran-butoxytitanium. It is preferable to add 0.1 to 20 parts by mass of these substances per 100 parts by mass of the primer.

[0098] <Elastic layer> The elastic layer 4 has the function of providing the electrophotographic member 1 with the elasticity necessary to form a nip of a predetermined width at the contact portion between the electrophotographic member 1 and the photoreceptor, when the electrophotographic member is in the shape of a roller, i.e., an electrophotographic roller. The elastic layer 4 is preferably a molded body of rubber material.

[0099] Various rubber materials conventionally used in conductive rubber rollers can be used as the rubber material. Specifically, examples of rubbers that can be used as 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, NBR hydride, polysulfide rubber, and urethane rubber. These may be used individually or in mixtures of two or more. Among these, silicone rubber is particularly preferred from the viewpoint of stability against deformation, such as set performance.

[0100] Examples of silicone rubber include polydimethylsiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polyphenylvinylsiloxane, and copolymers of these polysiloxanes.

[0101] The elastic layer 4 may contain various additives as appropriate, such as conductivity imparters, non-conductive fillers, crosslinking agents, and catalysts. As conductivity imparters, 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 amount of additive.

[0102] Specifically, the carbon black that can be used includes conductive carbon blacks such as Ketjenblack (trade name, manufactured by Lion Corporation) and acetylene black; rubber carbon blacks such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, and MT; and other carbon blacks for color inks that have undergone oxidation treatment, as well as pyrolysis carbon black.

[0103] These may be used individually or in combination of two or more. When carbon black is used as a conductivity imparting agent, it is more preferable to blend 10 to 80 parts by mass of carbon black with 100 parts by mass of rubber in the rubber material.

[0104] Examples of non-conductive fillers include silica, quartz powder, titanium dioxide, zinc oxide, or calcium carbonate. Examples of crosslinking agents include di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, or dicumyl peroxide. Examples of catalysts include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, with platinum-based catalysts being particularly preferred.

[0105] The elastic layer 4 may be formed from multiple layers. An intermediate layer 5 may also be provided between the substrate 2 and the elastic layer 4, and between the elastic layer 4 and the conductive 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.

[0106] <<Electrophotographic device>> The electrophotographic component according to this disclosure can be suitably used as a developer carrier or developer regulating component in an electrophotographic apparatus. The electrophotographic component can be applied to any type of developing apparatus, including non-contact developing apparatuses and contact developing apparatuses using magnetic one-component toner or non-magnetic one-component toner, as well as developing apparatuses using two-component toner. In other words, it is preferable that the electrophotographic image forming apparatus according to this disclosure is equipped with the electrophotographic component according to this disclosure as a developing component.

[0107] The developing apparatus disclosed herein is A developing apparatus comprising toner and a developing roller that supports the toner on its surface, The developing roller includes the electrophotographic component of this disclosure, The toner comprises toner matrix particles containing a binder resin, and toner particles containing an organosilicon polymer on the surface of the toner matrix particles. The surface of the toner matrix particles has protrusions composed of the organosilicon polymer.

[0108] Figure 2 is a schematic cross-sectional view showing an example of an electrophotographic apparatus in which the electrophotographic component according to this disclosure is mounted as a developing roller in a contact-type developing apparatus using a single-component toner. As shown in Figure 2, a developing apparatus 22 is detachably attached to the electrophotographic apparatus.

[0109] The developing device 22 consists of a toner container 20 containing toner 15 as a single-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.

[0110] The developing roller 16 is located in a longitudinally extending opening within the toner container 20 and is positioned opposite the photoreceptor 18. Furthermore, a process cartridge 17, consisting of the photoreceptor 18, cleaning blade 26, waste toner container 25, and charging roller 24, is detachably mounted in the electrophotographic apparatus. The photoreceptor 18, cleaning blade 26, waste toner container 25, and charging roller 24 may also be located within the main body of the electrophotographic apparatus.

[0111] The printing operation of the electrophotographic apparatus will be described below. Figure 3 is a schematic cross-sectional view of an example of an electrophotographic apparatus according to one 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 a laser beam 23, which is an exposure means.

[0112] The electrostatic latent image is made visible as a toner image (developed) by a developing device 22 that is in contact with the photoreceptor 18 and toner 15 is applied to it. The development is a so-called inversion development that forms a toner image in the exposed area.

[0113] The toner image formed on the photoreceptor 18 is transferred to the recording medium, paper 34, by a transfer roller 29, which is a transfer member. The paper 34 is fed into the device via a paper feed roller 35 and a suction roller 36, and is transported between the photoreceptor 18 and the transfer roller 29 by an endless belt-shaped transfer transport belt 32.

[0114] The transfer conveyor belt 32 is operated by driven rollers 33, drive rollers 28, and tension rollers 31. Voltage is applied to the transfer rollers 29 and suction rollers 36 from the bias power supply 30.

[0115] The paper 34 onto which the toner image has been transferred is fixed by the fuser unit 27 and then discharged from the unit, ending the printing operation. Meanwhile, any remaining toner that was not transferred and remains on the photoreceptor 18 is scraped off by the cleaning blade 26, a cleaning component for cleaning the surface of the photoreceptor, and stored in the waste toner container 25. The cleaned photoreceptor 18 then repeats the above printing operation.

[0116] <<Electrophotographic Processing Cartridge>> The electrophotographic process cartridge of this disclosure is configured to be detachably attached to the main body of an electrophotographic image forming apparatus and comprises the developing apparatus of this disclosure. The electrophotographic image forming apparatus of this disclosure comprises the electrophotographic process cartridge of this disclosure.

[0117] The electrophotographic components described herein can be suitably used as developing components such as a developer carrier, a developer supply / stripping component, and a developer regulating component in a process cartridge. That is, the electrophotographic process cartridge described herein is an electrophotographic process cartridge configured to be detachably attached to the main body of an electrophotographic apparatus and may include the electrophotographic components described herein. Furthermore, it is preferable to include the electrophotographic components described herein as developing components. [Examples]

[0118] The present disclosure will be described in detail below with reference to specific examples, but the technical scope of the present disclosure is not limited to these.

[0119] (Creation of elastic roller K-1) A SUS304 mandrel with a diameter of 6 mm and a total length of 278.9 mm was coated with a primer (product name, DY35-051; manufactured by Toray Dow Corning Co., Ltd.) and baked in an oven heated to 180°C for 20 minutes to form the substrate.

[0120] The substrate prepared above was placed in the mold, and an addition-type silicone rubber composition, which was a mixture of the following materials, was injected into the cavity formed inside the mold. <Addition-type silicone rubber composition> • Liquid silicone rubber material (Product name, SE6724A / B; manufactured by Toray Dow Corning) 100 parts by mass • Carbon Black (Product name: Toka Black #4300; manufactured by Tokai Carbon Co., Ltd.) 15 parts by mass • Silica powder as a heat-resistant agent: 0.2 parts by mass ·Platinum catalyst 0.1 part by mass

[0121] Next, the mold was heated to 150°C for 15 minutes to vulcanize and cure the silicone rubber. After demolding the substrate, which had a cured silicone rubber layer formed on its circumferential surface, from the mold, the substrate was further heated to 180°C for 1 hour to complete the curing reaction of the silicone rubber layer. In this way, an elastic roller K-1 was fabricated, in which a 12 mm diameter silicone rubber elastic layer was formed on the outer circumference of the substrate.

[0122] (Preparation of conductive layer) The following shows a synthesis example for obtaining the conductive layer according to the present invention. <Synthesis of ionic conductive agents> (Synthesis of ionic conductive agent A-1) Place a stirring bar and 50 ml of tetrahydrofuran (THF, manufactured by Kanto Chemical Co., Ltd.) into a round-bottom flask fitted with a condenser tube, disperse 12.5 g (0.52 mol) of sodium hydride (manufactured by Kanto Chemical Co., Ltd.), and cool the round-bottom flask in an ice bath.

[0123] After slowly adding a solution of 8.8 g (0.13 mol) of the nucleophile G-1 (imidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 ml of THF, remove the ice bath and stir at room temperature for 2 hours.

[0124] 41.3 g (0.33 mol) of the electrophile H-1 (2-bromoethanol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature, and the mixture was heated under reflux at 70°C for 7 hours. The reaction mixture was filtered, insoluble matter was washed away with THF, and the solvent from the resulting filtrate was removed under reduced pressure. The mixture was then dissolved again in dichloromethane, filtered, and the filtrate was collected. The solvent was then removed under reduced pressure to obtain a concentrate.

[0125] The obtained concentrate was washed with diethyl ether and dried under reduced pressure to obtain 28 g of ionic conductive agent precursor. Subsequently, in order to replace the anions of the obtained ionic conductive agent with the target anions, the entire amount of the obtained ionic conductive agent precursor was dissolved in 100 ml of methanol at room temperature.

[0126] While stirring the solution, 27.6 g of ion exchange salt I-1 (potassium N,N-bis(fluorosulfonyl)imide, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), dissolved in 50 ml of pure water, was added and the mixture was stirred at room temperature for 24 hours. After the reaction, methanol was removed by vacuum distillation, and after liquid-liquid extraction with dichloromethane / water, the organic layer was recovered. The layer was then washed twice with water, the solvent was removed by vacuum distillation, and after drying, ionic conductive agent A-1 was obtained as a white powder.

[0127] (Synthesis of ionic conductive agents A-4 to A-7 and AH-1) Ionic conductive agents A-4 to A-7 and AH-1 were obtained in the same manner as the synthesis of ionic conductive agent A-1, except that the types and amounts of nucleophiles, electrophiles, and ion exchange salts used as raw materials were changed as shown in Table 1. Details of the nucleophile No., electrophile No., and ion exchange salt No. in Table 1 are described in Tables 2 to 4.

[0128] [Table 1]

[0129] [Table 2]

[0130] [Table 3]

[0131] [Table 4]

[0132] (Synthesis of ionic conductive agent A-2) In a flask fitted with a Liebig cone, 6.1 g (0.09 mol) of the nucleophile G-1 (imidazole, manufactured by Tokyo Chemical Industry Co., Ltd.), 23.7 g (0.14 mol) of the electrophile H-2 (6-bromo-1-hexanol, manufactured by Tokyo Chemical Industry Co., Ltd.), 25 g (0.18 mol) of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), and 200 ml of acetone were added, and the mixture was heated under reflux overnight. After the reaction, the reaction mixture was filtered, and the solvent in the filtrate was removed by reduced pressure. The mixture was then purified by silica gel column chromatography (ethyl acetate) to obtain a compound in which the nucleophile had been tertiarily converted.

[0133] The resulting compound was then dissolved in 50 ml of dichloromethane, and 17.5 g (0.14 mol) of the electrophile H-1 (2-bromo-ethanol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was heated under reflux at 40°C for 18 hours. After the reaction, the solvent was removed by distillation under reduced pressure, washed with diethyl ether, and dried to obtain a quaternized ion conductive agent precursor as a white powder.

[0134] Next, to convert the anion to the target anion, the entire amount of the obtained ion conductive agent precursor was dissolved in 100 ml of methanol at room temperature. While stirring the solution, 19.3 g of ion exchange salt I-1 (potassium N,N-bis(fluorosulfonyl)imide, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), dissolved in 50 ml of pure water, was added, and the mixture was stirred at room temperature for 24 hours. After the reaction, methanol was removed by vacuum distillation, liquid-liquid extraction was performed with dichloromethane / water, the organic layer was recovered, washed twice with water, the solvent was removed by vacuum distillation, and after drying, a white powder ion conductive agent A-2 was obtained.

[0135] (Synthesis of ionic conductive agent A-3) Ion conductive agent precursor A-3 was obtained in the same manner as the synthesis of ion conductive agent precursor A-2, except that the types and amounts of nucleophiles and electrophiles used as raw materials were changed as shown in Table 5.

[0136] [Table 5]

[0137] Table 6 shows the basic structure of the obtained ionic conductive agent. Table 7 shows the anionic species, the number of hydroxyl groups, and the structure of the substituents.

[0138] [Table 6]

[0139] [Table 7]

[0140] <Synthesis of hydroxyl-terminated urethane prepolymers> (Synthesis of hydroxyl-terminated urethane prepolymer B-1) Under a nitrogen atmosphere, 100 parts by mass of polypropylene glycol (product name: Sannix GP-600, manufactured by Sanyo Chemical Industries, Ltd.) and 6.3 parts by mass of monomeric MDI (product name: Millionate MT, manufactured by Tosoh Corporation) were heated and stirred at 90°C for 3 hours to react. Subsequently, methyl ethyl ketone (MEK) was added to the resulting reaction product to prepare hydroxyl-terminated urethane prepolymer B-1 with a solid content of 50.5% and a hydroxyl value of 20.2 mgKOH / g.

[0141] <Synthesis of isocyanate-terminated prepolymers> (Synthesis of isocyanate-terminated prepolymer C-1) Under a nitrogen atmosphere, 38 parts by mass of polymeric MDI (product name: Millionate MR200, manufactured by Tosoh Corporation) were gradually added dropwise to 100 parts by mass of polypropylene glycol (product name: Sannix GP-600, manufactured by Sanyo Chemical Industries, Ltd.) in a reaction vessel while maintaining the temperature in the reaction vessel at 65°C. After the addition was complete, the reaction was allowed to proceed at 65°C for 2 hours to obtain the reaction mixture.

[0142] The resulting reaction mixture was cooled to room temperature and diluted with methyl ethyl ketone (MEK) to obtain a solution of isocyanate-terminated prepolymer C-1 with a solid content of 64.6% and an isocyanate group content of 5.4%.

[0143] <Preparation of impregnation treatment solution> The materials shown in Table 8 below were dissolved and mixed as the impregnation solution for the impregnation treatment. The structural formulas of acrylic monomers J-1 to J-5 and JH-1 to JH-5 in Table 8 are listed below.

[0144] [Table 8]

[0145] [ka] In each formula, n, m, x, y, and z each independently represent the degree of polymerization.

[0146] <Preparation of paint for forming a conductive layer> (Preparation of conductive layer-forming coating E-1) The following materials were mixed together by stirring to form the conductive layer. • Hydroxyl-terminated urethane prepolymer B-1: 130 parts by mass • Ethylene oxide / propylene oxide monool (product name: Newpol HB-660, manufactured by Sanyo Chemical Industries): 5 parts by mass • Isocyanate-terminated urethane prepolymer C-1: 55 parts by mass Ionic conductive agent A-1: ​​0.1 parts by mass • Carbon Black (1) (Product Name: SUNBLACK X15, manufactured by Asahi Carbon Co., Ltd.): 18 parts by mass • Carbon Black (2) (Product Name: SUNBLACK X55, manufactured by Asahi Carbon Co., Ltd.): 5 parts by mass • Silicone oil (product name: TSF4445, manufactured by Momentive): 1 part by mass • Urethane resin particles (product name: Dymic Beads UCN-5190D, manufactured by Dainichi Seika Kogyo Co., Ltd.): 82.5 parts by mass

[0147] Next, methyl ethyl ketone is added so that the total solids content ratio is 30% by mass, and then Sandmi The mixture was then prepared using a methyl ethyl ketone to adjust the viscosity to 10-13 cps, thereby preparing conductive layer-forming coating E-1.

[0148] <Toner> (Manufacturing example of toner L-1) <Preparation of Resin Particle Dispersion 1> 78.0 parts of styrene, 20.7 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-granting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. To this solution, the entirety of an aqueous solution prepared by dissolving 2.0 parts of linear alkylbenzene sulfonate sodium (product name: Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) in 150 parts of deionized water was added and dispersed.

[0149] While stirring slowly for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10 parts deionized water was added. After nitrogen purging, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was complete, the reaction solution was cooled to room temperature, and deionized water was added to obtain resin particle dispersion 1 with a solid content concentration of 12.5% ​​by mass and a volume-based median diameter of 0.2 μm.

[0150] <Preparation of mold release agent dispersion 1> 100 parts of a release agent (behenyl behenate, melting point: 72.1°C) and 15 parts of an aliphatic alcohol alkylene oxide adduct were mixed with 385 parts of deionized water and dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Jokoh Co., Ltd.) to obtain release agent dispersion 1. The concentration of release agent dispersion 1 was 20% by mass.

[0151] <Preparation of colorant dispersion 1> As a coloring agent, 100 parts of carbon black "Nipex35 (manufactured by Orion Engineered Carbons)" and 15 parts of an aliphatic alcohol alkylene oxide adduct were mixed with 885 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 to obtain coloring agent dispersion 1.

[0152] <Example of preparation of toner core particle dispersion 1> (Dispersion process) A mixture of 1:265 parts resin particle dispersion, 1:10 parts mold release agent dispersion, 1:10 parts colorant dispersion, 2.9 parts aliphatic alcohol alkylene oxide adduct, and 0.6 parts linear alkylbenzene sulfonate sodium (Neogen RK) was dispersed using a homogenizer (IKA: Ultra-Turrax T50). The temperature inside the container was adjusted to 30°C while stirring, and a 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 8.0.

[0153] (Agglutination process) As a flocculant, an aqueous solution of 0.08 parts aluminum chloride dissolved in 10 parts deionized water was added over 10 minutes while stirring at 30°C. After standing for 3 minutes, the temperature was raised to 50°C to generate associated particles. In this state, the particle size of the associated particles was measured using a "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). When the number-average particle size reached 6.1 μm, 0.9 parts sodium chloride and 5.0 parts aliphatic alcohol were added to stop particle growth.

[0154] A 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 9.0, and then the temperature was raised to 95°C to sphereize the aggregated particles. When the average circularity reached 0.980, the temperature was lowered and cooled to room temperature to obtain toner core particle dispersion 1.

[0155] <Example of preparation of monomer dispersion 1 containing silica and a binding component> 100 parts of styrene, 20 parts of methacryloxypropyltrimethoxysilane, and 100 parts of colloidal silica were dispersed using a homogenizer (IKA: Ultra-Turrax T50), and the temperature inside the container was adjusted to 25°C. The mixture was stirred for 1 hour to obtain monomer dispersion 1 containing silica and a binding component.

[0156] Next, we will explain an example of toner manufacturing. (Manufacturing example of toner L-1) Toner core particle dispersion 1 was obtained by adding 1:100 parts of monomer dispersion obtained by the above method in a ratio of 1:2.75 parts and potassium persulfate 0.005 parts, adjusting the temperature inside the container to 90°C, and stirring for 2 hours using a full-zone stirring blade.

[0157] Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was stirred and left for 1 hour. Then, solid-liquid separation was performed using a pressure filter to obtain a toner cake. This was re-slurred with deionized water to obtain another dispersion, and then solid-liquid separation was performed using the aforementioned filter. The re-slurrying and solid-liquid separation process was repeated until the electrical conductivity of the filtrate was 5.0 μS / cm or less, and finally, solid-liquid separation was performed to obtain the toner cake. The obtained toner cake was dried and further classified using a classifier to obtain toner particles 1. The number-average particle size of the primary particles of toner particles 1 was 6.0 μm. The obtained toner particles 1 were sieved through a mesh with a mesh opening of 75 μm to obtain toner L-1.

[0158] (Example of Toner L-2 manufacturing) [Manufacturing of magnetic material 1] An aqueous solution containing ferrous hydroxide was prepared by mixing 1.00 to 1.10 equivalents of caustic soda solution relative to iron, an amount of P2O5 equivalent to 0.15% by mass relative to iron in terms of phosphorus, and an amount of SiO2 equivalent to 0.50% by mass relative to iron in terms of silicon. The pH of the aqueous solution was adjusted to 8.0, and the oxidation reaction was carried out at 85°C while blowing in air to prepare a slurry liquid containing seed crystals.

[0159] Next, 0.90 to 1.20 equivalents of ferrous sulfate aqueous solution relative to the initial alkali content (sodium component of caustic soda) were added to the slurry. The slurry was then maintained at a pH of 7.6, and the oxidation reaction proceeded while blowing air into it to obtain a hydrated slurry containing magnetic iron oxide. After filtration and washing, this hydrated slurry was temporarily removed. At this time, a small amount of the hydrated sample was taken and its water content was measured.

[0160] Next, this hydrated sample was placed in another aqueous medium without drying, and while stirring and circulating the slurry, the magnetic iron oxide was redispersed using a pin mill, and the pH of the redispersed solution was adjusted to approximately 4.8. Then, while stirring, 1.6 parts by mass of n-hexyltrimethoxysilane coupling agent was added to 100 parts by mass of magnetic iron oxide, and hydrolysis was carried out.

[0161] The amount of magnetic iron oxide was calculated by subtracting the water content from the water-containing sample. After that, the mixture was thoroughly stirred, the pH of the dispersion was adjusted to 8.6, and the surface was treated with a silane coupling agent. The resulting hydrophobic magnetic material was filtered using a filter press, washed with a large amount of water, and then dried at 100°C for 15 minutes and 90°C for 30 minutes. The resulting particles were crushed to obtain magnetic material 1 with a volume-average particle size of 0.21 μm.

[0162] [Manufacturing of Polyester Resin 1] The materials shown in Table 9 below were placed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, and reacted for 10 hours at 230°C under a nitrogen stream while distilling off the water produced. The reaction was then carried out under reduced pressure of 5-20 mmHg, and when the acid value became 2 mg KOH / g or less, it was cooled to 180°C, 10 parts by mass of trimellitic anhydride were added, and the reaction was carried out for 2 hours under atmospheric pressure and in a sealed state. The reaction product was then removed, cooled to room temperature, and pulverized to obtain polyester resin 1. Polyester resin 1 had a main peak molecular weight (Mp) of 10500, as measured by gel permeation chromatography (GPC).

[0163] [Table 9]

[0164] [Manufacturing of developer particles 1] In a container, 450 parts by mass of a 0.1 M Na3PO4 aqueous solution was added to 720 parts by mass of ion-exchanged water and heated to 60°C. Then, 67.7 parts by mass of a 1.0 M CaCl2 aqueous solution was added to obtain an aqueous medium containing a dispersion stabilizer. Meanwhile, the materials shown in column 1 of Table 10 below were uniformly dispersed and mixed using an attritor (trade name, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) to obtain a polymerizable monomer composition.

[0165] This polymerizable monomer composition was heated to 60°C, and the materials shown in column 2 of Table 10 below were added, mixed, and dissolved. Then, the materials shown in column 3 of Table 10 were added, mixed, and dissolved as polymerization initiators to obtain a developer composition.

[0166] [Table 10]

[0167] The above developer composition was added to the above aqueous medium and granulated by stirring at 12,000 rpm for 10 minutes at 60°C under an N2 atmosphere using a TK type homomixer (product name, manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was then reacted at 74°C for 6 hours while stirring with a paddle agitator. After the reaction was complete, the suspension was cooled, washed with hydrochloric acid, filtered, and dried to obtain developer particles 1. The obtained magnetic developer particles 1 had a weight-average particle size of 8.0 μm and an average circularity of 0.938.

[0168] [Manufacturing of Developer L-2] The materials shown in Table 11 below were placed in a Henschel mixer FM10C (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.), and mixed for 5 minutes at a constant rotation speed of 4000 rpm. After mixing, coarse particles were removed using a circular vibrating screen with a diameter of 500 mm and a mesh size of 75 μm to obtain toner L-2.

[0169] [Table 11]

[0170] <<Developing Roller>> <Developing Roller GZ-1> First, the previously prepared elastic roller K-1 was immersed in the conductive layer-forming paint E-1 to form a coating of the paint on the surface of the elastic layer, and then air-dried. Furthermore, by heating it at a temperature of 150°C for 1 hour, a conductive layer with a thickness of approximately 15 μm was formed on the outer periphery of the elastic layer, thereby producing a developing roller precursor.

[0171] Next, the precursor was immersed in impregnation solution G-1 for 2 seconds. After that, it was air-dried at room temperature for 30 minutes, and then dried at 90°C for 1 hour to evaporate the solvent. The dried elastic roller was rotated while the integrated light intensity was 15,000 mJ / cm². 2 The (meth)acrylic component was cured by irradiating it with ultraviolet light in such a manner. A high-pressure mercury lamp (product name: Handy Type UV Curing Device, manufactured by Mario Network Co., Ltd.) was used as the ultraviolet irradiation device. This resulted in obtaining the developing roller GZ-1 used in the example.

[0172] <Examples and Comparative Examples> Except for using the conductive layer-forming coating shown in Table 12, developing rollers according to the following examples and comparative examples were obtained in the same manner as the developing roller described above.

[0173] [Table 12]

[0174] The conductive roller and developer obtained in the examples were evaluated for the following items. The results are shown in Table 13.

[0175] <Finished product roller analysis> [Measurement of T1, T2, T3, A1, A2] Using the microsampling mass spectrometry method described above, thermal chromatograms were obtained for a first region from the outer surface of the developing roller to a depth of 0.1 μm, a second region with a thickness of 0.1 μm from the back surface of the conductive layer toward the surface, and a third region from the surface to a depth of 1.0 μm or more and 1.1 μm or less.

[0176] From the obtained thermal chromatograms, the peak top temperatures T1, T2, and T3 of the thermal chromatograms originating from the cross-linked urethane resin in the first, second, and third regions were determined.

[0177] Furthermore, the peak top temperature A1 of the thermal chromatogram derived from the cross-linked acrylic resin in the first region was obtained. In addition, the peak top temperature A2 of the thermal chromatogram derived from the cross-linked acrylic resin, measured from a second sample obtained by decomposing the cross-linked urethane resin contained in the sample sampled from the first region, was obtained. Samples from each region were collected using a microsampling method with a FIB-SEM (product name: NVision40, manufactured by SII Nanotechnology).

[0178] Specifically, first, a razor blade was used to make an incision from the surface of the developing roller toward the substrate, and a piece of rubber was cut out with the cross-sections of the conductive layer and intermediate layer exposed. This piece of rubber was placed on the sample stage of the SEM with the roller cross-section facing upwards, and a sampling probe was fixed to the position of the rubber piece corresponding to the roller surface. Furthermore, a FIB cutting process was performed at a position 0.1 μm inward from the surface corresponding to the roller surface, thereby collecting a sample of the first region.

[0179] For the second region, a FIB (Filtration-Induced Brain) cutting process was performed 1.0 μm from the interface between the back surface of the conductive layer and the intermediate layer toward the front surface. A sampling probe was fixed to the resulting cut surface, and a FIB cutting process was performed at a position corresponding to 0.1 μm inward from the cut surface to collect a sample of the second region.

[0180] Furthermore, for the third region, the same rubber piece as described above was cut using FIB at a position 1.0 μm inward from the surface corresponding to the roller surface, thereby exposing the third region. A sampling probe was fixed to the exposed surface, and a sample of the third region was collected by cutting using FIB at a position 0.1 μm inward from the exposed surface. In all cutting processes, the FIB acceleration voltage was set to 30kV and the beam current to 27mA.

[0181] [Pyridine decomposition method] The pyridine decomposition method is a method for selectively decomposing urethane bonds. In a sample having an IPN structure of a crosslinked acrylic resin and a crosslinked urethane resin, performing the pyridine decomposition method makes it possible to obtain the crosslinked acrylic resin after removing structures derived from the crosslinked urethane. From the obtained crosslinked acrylic resin, changes in the peak temperature of thermal chromatograms depending on the presence or absence of an IPN structure can be grasped. Specifically, the pyridine decomposition method was performed by the following procedure.

[0182] Using a microtome, samples each having a thickness of 0.1 µm were cut out from the surface of the developing roller, and 500 mg of the cut samples were collected. To the obtained sample, 0.5 mL of a mixed solution obtained by mixing pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and water at a ratio of 3:1 was added, and decomposition was performed by heating at 130°C for 15 hours in a closed container made of fluororesin (Teflon (registered trademark)) with a stainless steel jacket. Pyridine was removed by subjecting the obtained decomposition product to a reduced pressure treatment. Using the sample thus obtained, the above-mentioned microsampling mass spectrometry was performed to obtain a value of A2.

[0183] [Measurement of α, β, γ] The aforementioned α, β, and γ are calculated as described below using ESCA. Elemental analysis of the second sample is performed using the following apparatus under the following conditions. - Measuring apparatus: Quantum2000 (trade name, manufactured by ULVAC-PHI, Inc.) - X-ray source: monochromatic Al Kα - X-ray Setting: 100µmφ (25W (15KV)) - Photoelectron take-off angle: 45 degrees - Neutralization conditions: combined use of a neutralization gun and an ion gun - Analysis area: 300×200µm - Pass Energy: 58.70eV - Step size: 1.25eV - Analysis software: Maltipak (PHI Inc.).

[0184] Here, the peak C(1s) (BE (bond energy) 286.0~287.0 eV) was used to calculate the quantitative value of carbon atoms adjacent to oxygen atoms (carbon atoms in CO bonds), the peak C(1s) (BE 288.0~290.0 eV) was used to calculate the quantitative value of carbonyl carbon atoms (carbon atoms in C=O bonds), and the peak S(2p3 / 2) (BE 166.0~170.0 eV) was used to calculate the quantitative value of sulfur atoms.

[0185] <Evaluation of roller resistance fluctuations> The roller resistance values ​​were measured using conductive rollers that had been left in a 0°C environment for more than 6 hours. [Measurement of initial roller resistance] Figure 4 shows a schematic configuration diagram of the roller resistance value fluctuation evaluation jig according to this disclosure. In Figure 4(a), in a 0°C environment, a cylindrical metal 37 with a diameter of 24 mm is rotated at a surface speed of 50 mm / sec while pressing both ends of a conductive shaft body 42 with a load of 4.9 N each via a conductive bearing 38, thereby driving the conductive roller 41.

[0186] Next, in Figure 4(b), a voltage of 50V was applied by the high-voltage power supply 39, and the potential difference across a resistor with a known electrical resistance (one with an electrical resistance at least two orders of magnitude lower than the electrical resistance of the conductive roller) placed between the cylindrical metal 37 and ground was measured. A voltmeter 40 (FLUKE 189 TRUE RMS MULTIMETER) was used to measure this potential difference.

[0187] The current flowing through the cylindrical metal via the conductive roller 41 is calculated from the measured potential difference and the electrical resistance of the resistor. The electrical resistance of the conductive roller 41 is determined by dividing the applied voltage of 50V by the obtained current. Here, the potential difference was measured by sampling for 3 seconds starting 2 seconds after the voltage was applied, and the value calculated from the average value was taken as the initial roller resistance value.

[0188] [Measurement of roller resistance after evaluation] After performing the ghost evaluation described later, the roller was immediately removed and its resistance was measured in a 0°C environment after power was applied.

[0189] [Electrical degradation] The value obtained by dividing the roller resistance value after evaluation by the initial roller resistance value (evaluated roller resistance value / initial roller resistance value) was used as an indicator of electrical conductivity degradation.

[0190] <<Developing Roller>> [Ghost Rating] Next, the conductive rollers, whose initial roller resistance had been measured as described above, were left in a 0°C environment for more than 6 hours, and then the following evaluations were performed.

[0191] A laser printer (product name, LBP7700C; manufactured by Canon Corporation) having the configuration shown in Figure 3 was placed in a 0°C environment, and the conductive roller used as an electrophotographic component in this embodiment was loaded as a developing roller, and ghosting was evaluated.

[0192] First, a normal halftone image (Image H) was printed using toner L-1 or L-2. Next, as an image pattern, a 15mm square solid black image was printed at the leading edge of the sheet, followed by a full-page halftone image (Image G).

[0193] The density ratio H / N of the density H in the obtained image H and the density G of the halftone area after the first pass of the developing roller following the solid black pattern in the above image G, and the density unevenness of the period of the developing roller as a toner carrier appearing in the halftone area were visually evaluated, and the ghost performance was determined as follows. A: 0.95 ≤ H / N ≤ 1.00 (No ghosts are detected) B: 0.90 ≤ H / N ≤ 0.95 (Very slight ghosting is observed) C:(H / N)<0.90 (Significant ghosting observed)

[0194] [Table 13]

[0195] In the table, "E + number" is the exponential notation of the number. For example, "5.4E+05" is "5.4 × 105 , the same applies hereinafter. For the developing rollers according to the examples and comparative examples in Table 13, it was confirmed by the analysis operation using the above-mentioned pyridine decomposition method that formula (1) is satisfied, and it was confirmed that an IPN structure is present in any of the developing rollers.

[0196] <Consideration of Evaluation Results> The electrophotographic members and electrophotographic image forming apparatuses according to Examples 1 to 26 contain a compound having a structure represented by formula (C-1) or formula (C-2) according to the present disclosure in the conductive layer according to the present disclosure, and at least one of the structures represented by formulas (C-3) to (C-5) according to the present disclosure is included on the outermost surface. They exhibit little resistance increase after image output in an environment of 0°C and maintain good image quality.

[0197] In particular, in Examples 1 to 23, when a toner containing a specific structure is used, ghost performance is further improved. This is presumed to be because the combination of the electrophotographic member and the toner allows good triboelectric charging to occur, and the toner coat layer on the member is uniformly charged. In contrast, Comparative Examples 1 to 6, which do not contain the structure according to the present disclosure, exhibit a large resistance increase before and after image output in the above environment, and significant adverse effects also occur in image evaluation.

[0198] <<Charging Roller>> <Preparation of NBR Rubber Elastic Roller> Each material in the type and amount shown in Table 14 below was mixed with a pressure kneader to obtain an A-stage kneaded rubber composition.

[0199]

Table 14

[0200] Further, 166.0 parts by mass of the A-stage kneaded rubber composition and each material in the type and amount shown in Table 15 below were mixed with an open roll to prepare an unvulcanized rubber composition.

[0201]

Table 15

[0202] Next, a crosshead extruder was prepared, which had a conductive shaft core supply mechanism and an unvulcanized rubber roller discharge mechanism. A die with an inner diameter of 16.5 mm was attached to the crosshead, and the crosshead extruder was set to 80°C, with the conveying speed of the conductive shaft core set to 60 mm / sec.

[0203] Under these conditions, the unvulcanized rubber composition was supplied from the extruder, and the unvulcanized rubber composition was used to coat the circumferential surface of the conductive shaft core prepared above as an unvulcanized rubber layer within the crosshead, thereby obtaining an unvulcanized rubber roller.

[0204] Next, the unvulcanized rubber roller was placed in a 170°C hot air vulcanization furnace and heated for 60 minutes to obtain an unpolished conductive roller. After that, the edges of the vulcanized NBR rubber elastic layer were cut and removed, and the surface of the NBR rubber elastic layer was polished with a rotary grinding wheel. This produced elastic roller K-2 with diameters of 8.4 mm at 90 mm from the center to both ends, and a central diameter of 8.5 mm.

[0205] <Charging rollers TD-1 and TDH-1> Charging rollers TD-1 and TDH-1 were obtained in the same manner as developing roller 1, except that the elastic layer used was K-2. Details are shown in Table 16.

[0206] [Table 16]

[0207] <Evaluation of the electrostatic roller> [Image evaluation of horizontal stripes] Next, the obtained electrostatic rollers were evaluated using the aforementioned roller resistance value fluctuation evaluation method, and the following items were evaluated using these as electrostatic rollers.

[0208] Changes in conductivity (increase in electrical resistance) due to the energization of the charging roller can cause fine, streaky density variations (horizontal streaks) to appear in halftone images. These are called horizontal streaky images. These horizontal streaks tend to occur more as the conductivity of the charging roller changes and become more noticeable with long-term use of the electrophotographic device. The electrophotographic component of this disclosure was incorporated as a charging roller into an electrophotographic device, and the following evaluation was performed.

[0209] The conductive rollers obtained in Example 28 and Comparative Example 7 were attached as charging rollers to an electrophotographic laser printer (product name: HPColor Laserjet Enterprise CP4515dn, manufactured by HP Corporation) used as an electrophotographic device. A durability test was then conducted by continuously outputting images with a print density of 4% (an image in which horizontal lines with a width of 2 dots and spacing of 50 dots are drawn perpendicular to the rotation direction of the photoreceptor).

[0210] Furthermore, after outputting 24,000 consecutive images, a halftone image (an image with horizontal lines of 1 dot width and 2 dot spacing drawn perpendicular to the rotation direction of the photoreceptor) was output for image checking. The obtained images were visually observed, and fine streaky density variations (horizontal streaks) were evaluated. The evaluation results are shown in Table 17. A: No horizontal streaks appear at all. B: Horizontal streaks are only present to a slight degree at the edges of the image. C: Horizontal streaks appear in almost half of the image area, making them quite noticeable.

[0211] [Table 17]

[0212] In the charging rollers of the examples and comparative examples in Table 17, the analytical procedure using the pyridine decomposition method described above confirmed that the formula (1) was satisfied, and that the IPN structure was present in all of the developing rollers.

[0213] <Discussion of Evaluation Results> The electrophotographic component fabricated in Example 27 contains a compound having the structure according to the disclosure in the conductive layer, which serves as the conductive layer according to the disclosure. As a result, there is little increase in resistance after image output in a 0°C environment, and the image quality remains good. In contrast, Comparative Example 7, which does not include the structure described herein, shows a significant increase in resistance before and after image output under the above environment, resulting in significant problems in image evaluation.

[0214] <<Developing blades GB-1 and GBH-1>> Figure 5 shows a cross-sectional view of the electrophotographic component fabricated in this embodiment. As the base 51, a 0.08 mm thick SUS sheet (manufactured by Nisshin Steel Co., Ltd.) was press-cut to dimensions of 200 mm in length and 23 mm in width.

[0215] Next, the cut SUS sheet was immersed in conductive layer-forming paint E-1 so that the length 53 from the longitudinal end of the cut SUS sheet was 1.5 mm, forming a coating film of the paint, which was then dried. Furthermore, it was heat-treated at a temperature of 140°C for 1 hour to produce a precursor for the developing blade DB-1 (electrophotographic component precursor).

[0216] Next, the precursor was immersed in impregnation solution G-1 for 2 seconds to impregnate it with a (meth)acrylic component such as an ion-conductive monomer. After that, it was air-dried at room temperature for 30 minutes and then dried at 90°C for 1 hour to evaporate the solvent.

[0217] After drying, the developing blade is rotated, and the integrated light intensity reaches 15,000 mJ / cm². 2 By irradiating with ultraviolet light in such a manner, the (meth)acrylic monomer was cured to form a resin layer 52 as a conductive layer.

[0218] A high-pressure mercury lamp (product name: Handy Type UV Curing Device, manufactured by Mario Network Co., Ltd.) was used as the ultraviolet irradiation device. This resulted in obtaining the GB-1 developing blade used in the example. A comparative example developing blade GBH-1 was prepared using the same procedure as in the above example, except that the impregnation solution was changed to GH-1. Details are shown in Table 18.

[0219] [Table 18]

[0220] <Evaluation of developing blades> [Evaluation of electrical resistance] The electrical resistance of the developing blade was measured in the same manner as the resistance measurement of the conductive roller described above. However, the roller-shaped electrophotographic component 1 in Figure 4(a) is replaced here by the developing blade shown in Figure 5. Specifically, the bearings 38 were brought into contact with both longitudinal ends of the base 51 of the blade component shown in Figure 5, and a load of 1.0 N was applied to each end so that the resin layer at the tip of the blade component was in contact with the cylindrical metal 37 perpendicular to its circumferential surface.

[0221] Next, without rotating the cylindrical metal 37, a voltage of 50V was applied by a high-voltage power supply 39, and the potential difference across a resistor with a known electrical resistance (more than two orders of magnitude lower than the electrical resistance of the electrophotographic component 1) placed between the cylindrical metal 37 and ground was measured. A voltmeter 40 (product name: 189 TRUE RMS MULTIMETER, manufactured by Fluke) was used to measure the potential difference. From the measured potential difference and the electrical resistance of the resistor, the current flowing through the cylindrical metal 37 via the developing blade was calculated.

[0222] The electrical resistance of the electrophotographic component 1 was determined by dividing the applied voltage of 50V by the obtained current. Here, the potential difference was measured by sampling for 3 seconds starting 2 seconds after the voltage was applied, and the resistance value was calculated from the average value.

[0223] [Regulatory misapproval] The electrophotographic component to be evaluated was loaded as a developing blade into a laser printer (product name: LBP7700C; manufactured by Canon) having the configuration shown in Figure 3. After leaving the laser printer in a 0°C environment for more than 2 hours, 100 images with 1% print density in black were printed continuously. Subsequently, a solid white image was printed on new copy paper.

[0224] After outputting these images, the condition of the toner coating on the surface of the developing material was observed, and the presence or absence of electrostatic toner aggregation (poor regulation) caused by abnormal charging of the toner was visually checked. The results of this observation were evaluated according to the following criteria. The evaluation results are shown in Table 19. A: No regulatory defects are present on the toner coating. B: There is a regulatory defect on the toner coating, but it is not visible in the image. C: Regulatory errors appear in the image.

[0225] [Table 19]

[0226] In the developing blades of the examples and comparative examples in Table 19, the analytical procedure using the pyridine decomposition method described above confirmed that the formula (1) was satisfied, and that the IPN structure was present in all of the developing blades.

[0227] <Discussion of Evaluation Results> Because Example 28 has the structure according to the present disclosure, no increase in resistance was observed in a 0°C environment, and no regulation failure occurred. On the other hand, in Comparative Example 8, an increase in resistance was observed, and regulation failure occurred. The regulation failure in a 0°C environment is thought to have occurred as a result of the resistance of the developing blade becoming high, preventing the blade bias from being applied to the specified value, and causing uneven charging of the toner.

[0228] This embodiment includes the following configuration. (Composition 1) An electrophotographic component comprising a substrate and a conductive layer on the substrate, The thickness of the conductive layer is 0.1 μm or more. The conductive layer contains a first resin, a second resin, and a bis(fluorosulfonyl)imide anion. The first resin is a crosslinked urethane resin having at least one selected from the group consisting of a cationic structure represented by the following formula (C-1) and a cationic structure represented by the following formula (C-2), as well as a polymer chain within its molecule. The second resin is a crosslinked acrylic resin having at least one selected from the group consisting of a substructure represented by the following formula (C-3), a substructure represented by the following formula (C-4), and a substructure represented by the following formula (C-5), as well as a polymer chain within its molecule. When the region from the outer surface of the conductive layer to a depth of 0.1 μm is defined as the first region, the first resin and the second resin in the first region constitute an interpenetrating polymer network structure. An electrophotographic component characterized by the above. [ka] (In formula (C-1), R 11 ~R 15 Each is independently selected from the group consisting of (a) to (c) below, and R 11 ~R 15 Any two of these are (c). (a) Hydrogen atom (b) saturated hydrocarbon groups having 1 to 6 carbon atoms (c) A structure including a portion that is bonded to the polymer chain of the crosslinked urethane resin. [ka] (In formula (C-2), R 21 ~R 26 Each of these is independently selected from the group consisting of (a) to (c), and R 21 ~R 26 Two of these are (c) above. [ka] (In formula (C-3), R 1 (* represents a structure consisting of carbon atoms with 2 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) [ka] (In formula (C-4), R 2 (* represents a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) [ka] (In formula (C-5), R 3 (* represents a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * represents a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) (Configuration 2) The first region comprises the first resin and the second resin, Let A1 (°C) be the peak top temperature of the thermal chromatogram derived from the second resin, measured from the first sample sampled from the first region, and let A2 (°C) be the peak top temperature of the thermal chromatogram derived from the second resin, measured from the second sample obtained by decomposing the first resin contained in the first sample. Then, A1 and A2 satisfy the relationship shown in the following formula (1). A1>A2 (1) The electrophotographic component according to configuration 1, wherein when the peak area of ​​a carbon (1s) atom whose bond energy peak position is 286.0 eV to 287.0 eV, as measured by electron spectrochemical analysis (ESCA) of the second sample, is α, and the peak area of ​​a sulfur (2p3 / 2) atom whose bond energy peak position is 166.0 eV to 170.0 eV is β, α and β satisfy the following formula (2). 300 > α / β (2) (Composition 3) Let T1 (°C) be the peak top temperature of the thermal chromatogram corresponding to the first resin in the first region. When a region with a thickness of 0.1 μm extending from the inner surface of the conductive layer toward the outer surface is defined as a second region, and the peak top temperature of the thermal chromatogram corresponding to the first resin included in the second region is defined as T2 (°C), The electrophotographic component according to configuration 1 or 2, wherein T1 and T2 satisfy the relationship shown in the following formula (3). T1>T2 (3) (Composition 4) The electrophotographic component according to configuration 2, wherein, when γ is the peak area of ​​a carbon(1s) atom whose bond energy peak position is 288 eV to 290 eV, as measured by electron spectrochemical analysis (ESCA) of the second sample, α and γ satisfy the following formula (4). 1.5 > α / γ (4) (Composition 5) The electrophotographic component according to any one of configurations 1 to 4, wherein the monomer forming the second resin is a monomer with three or more functionalities. (Composition 6) The electrophotographic component according to any one of configurations 1 to 5, wherein the amount of anion component contained in the conductive layer is 0.01 parts by mass or more and 0.2 parts by mass or less, relative to a total of 100 parts by mass of the first resin and the second resin contained in the conductive layer. (Composition 7) The electrophotographic component according to any one of configurations 1 to 6, wherein 80% by mass or more of the resin contained in the first region of the conductive layer consists of the first resin and the second resin. (Composition 8) The electrophotographic component according to any one of configurations 1 to 7, wherein 80% by mass or more of the anionic components contained in the conductive layer are bis(fluorosulfonyl)imide anions. (Composition 9) A developing apparatus comprising toner and a developing roller that supports the toner on its surface, The developing roller includes an electrophotographic component described in any one of configurations 1 to 8. The toner comprises toner matrix particles containing a binder resin, and toner particles containing an organosilicon polymer on the surface of the toner matrix particles. A developing apparatus in which protrusions composed of the organosilicon polymer are present on the surface of the toner matrix particles. (Composition 10) An electrophotographic process cartridge that is detachably attached to the main body of an electrophotographic image forming apparatus, An electrophotographic process cartridge comprising the developing apparatus described in configuration 9. (Composition 11) An electrophotographic image forming apparatus comprising the electrophotographic process cartridge described in configuration 10. [Explanation of Symbols]

[0229] 1: Developing material 2: Base 3: Elastic layer 4: Conductive layer 5: Middle class

Claims

1. An electrophotographic component comprising a substrate and a conductive layer on the substrate, The thickness of the conductive layer is 0.1 μm or more. The conductive layer contains a first resin, a second resin, and a bis(fluorosulfonyl)imide anion. The first resin is a crosslinked urethane resin having at least one selected from the group consisting of a cationic structure represented by the following formula (C-1) and a cationic structure represented by the following formula (C-2), as well as a polymer chain within its molecule. The second resin is a crosslinked acrylic resin having at least one selected from the group consisting of a substructure represented by the following formula (C-3), a substructure represented by the following formula (C-4), and a substructure represented by the following formula (C-5), as well as a polymer chain within its molecule. When the region from the outer surface of the conductive layer to a depth of 0.1 μm is defined as the first region, the first resin and the second resin in the first region constitute an interpenetrating polymer network structure. An electrophotographic component characterized by the above. 【Chemistry 1】 (In formula (C-1), R １１ ~R １５ Each is independently selected from the group consisting of (a) to (c) below, and R １１ ~R １５ Any two of these are (c). (a) Hydrogen atom (b) Saturated hydrocarbon groups having 1 to 6 carbon atoms (c) A structure including a portion that is bonded to the polymer chain of the crosslinked urethane resin. 【Chemistry 2】 (In formula (C-2), R ２１ ~R ２６ Each of these is independently selected from the group consisting of (a) to (c), and R ２１ ~R ２６ Two of these are (c) above. 【Transformation 3】 (In formula (C-3), R １ represents a structure consisting of carbon, hydrogen and oxygen having 2 to 8 carbon atoms, and * represents a structure including a portion bonded to the polymer chain of the crosslinked acrylic resin.) 【Chemistry 4】 (In formula (C-4), R ２ (* indicates a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * indicates a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.) 【Transformation 5】 (In formula (C-5), R ３ (* indicates a structure consisting of carbon atoms with 3 to 8 carbon atoms, hydrogen atoms, and oxygen atoms, and * indicates a structure including the portion bonded to the polymer chain of the crosslinked acrylic resin.)

2. The first region includes the first resin and the second resin, When the peak top temperature of the thermal chromatogram derived from the second resin, measured from the first sample sampled from the first region, is denoted as A1 (°C), and the peak top temperature of the thermal chromatogram derived from the second resin, measured from the second sample obtained by decomposing the first resin contained in the first sample, is denoted as A2 (°C), then A1 and A2 satisfy the relationship shown in the following formula (1): A1 > A2 (1) The electrophotographic component according to claim 1, wherein when the peak area of ​​a carbon (1s) atom whose bond energy peak position is 286.0 eV to 287.0 eV, as measured by electron spectrochemical analysis (ESCA) of the second sample, is α, and the peak area of ​​a sulfur (2p³ / 2) atom whose bond energy peak position is 166.0 eV to 170.0 eV, is β, then α and β satisfy the following formula (2). ３００＞α／β （２）

3. Let T1 (°C) be the peak top temperature of the thermal chromatogram corresponding to the first resin in the first region. When a region with a thickness of 0.1 μm extending from the inner surface of the conductive layer toward the outer surface is defined as a second region, and the peak top temperature of the thermal chromatogram corresponding to the first resin included in the second region is T2 (°C), The electrophotographic member according to claim 1, wherein T1 and T2 satisfy the relationship shown in the following formula (3). T1 > T2 (3)

4. The electrophotographic member according to claim 2, wherein when γ is the peak area of ​​a carbon (1s) atom whose bond energy peak position is between 288 eV and 290 eV, as measured by electron spectrochemical analysis (ESCA) of the second sample, α and γ satisfy the following formula (4). 1.5 > α / γ (4)

5. The electrophotographic member according to claim 1, wherein the monomer forming the second resin is a monomer with three or more functionalities.

6. The electrophotographic member according to claim 1, wherein the amount of anion component contained in the conductive layer is 0.01 parts by mass or more and 0.2 parts by mass or less with respect to a total of 100 parts by mass of the first resin and the second resin contained in the conductive layer.

7. The electrophotographic member according to claim 1, wherein 80% by mass or more of the resin contained in the first region of the conductive layer is the first resin and the second resin.

8. The electrophotographic member according to claim 1, wherein 80% by mass or more of the anionic components contained in the conductive layer are bis(fluorosulfonyl)imide anions.

9. A developing apparatus comprising toner and a developing roller that supports the toner on its surface, The developing roller includes an electrophotographic component as described in any one of claims 1 to 8. The toner comprises toner matrix particles containing a binder resin, and toner particles containing an organosilicon polymer on the surface of the toner matrix particles. A developing apparatus in which protrusions composed of the organosilicon polymer are present on the surface of the toner matrix particles.

10. An electrophotographic process cartridge that is detachably attached to the main body of an electrophotographic image forming apparatus, An electrophotographic process cartridge comprising the developing apparatus described in claim 9.

11. An electrophotographic image forming apparatus comprising the electrophotographic process cartridge described in claim 10.

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