JP6190738B2 - Electrophotographic materials - Google Patents

Description

  The present invention relates to an electrophotographic member.

  Conventionally, electrophotographic apparatuses such as electrophotographic copying machines, printers, and facsimiles are known. These electrophotographic apparatuses form an image through processes such as latent image formation by image data exposure on a charged photoreceptor, development, transfer to a transfer medium, and fixing. Therefore, various electrophotographic members are incorporated in the apparatus in order to realize these processes.

  For example, a roll-shaped charging member is incorporated to charge the surface of the photoreceptor. In addition, a roll-shaped developing member is incorporated in order to attach a toner to the electrostatic latent image formed on the surface of the photosensitive member to form a visible image. Also, recently, each toner image formed by a plurality of photoconductors by color is primarily transferred onto the belt surface, and the toner images of each color are superimposed and transferred onto a sheet of paper. It is used.

  Specifically, as the electrophotographic member, for example, Patent Document 1 discloses a developing member having a surface layer in which a polymer-based surface modifier is contained in a matrix polymer. Specifically, this document discloses a surface modifier comprising a copolymer of dimethylaminopropylacrylamide, a (meth) acrylate-modified silicone compound, 2- (perfluorohexyl) ethyl acrylate, and methyl methacrylate. Is described. This document describes that the silicone group in the surface modifier exhibits a slipperiness with a counterpart member that contacts the member surface. In addition, it is described that the toner-releasing property, which is a property that the toner in contact with the member surface is easily separated, is exhibited by the fluorine-containing group in the surface modifier. In addition, it describes that toner chargeability, which is a property of imparting charge to the toner, is exhibited by the amino group in the surface modifier.

JP 2013-205758 A

  However, the conventional technology still has room for improvement in the following points. That is, the amino group for exhibiting toner chargeability has a high affinity for moisture. Therefore, for example, when a conventional electrophotographic member using the above surface modifier is used in a high temperature and high humidity environment of about 32.5 ° C. × 85% RH, between the surrounding moisture and amino groups. Thus, an interaction occurs, and the toner chargeability is lowered. Therefore, it is difficult to obtain an electrophotographic member capable of simultaneously exhibiting the sliding property and / or toner releasability of the member surface and the toner chargeability in a high temperature and high humidity environment.

  The present invention has been made in view of the above background, and can be used for electrophotography capable of simultaneously exhibiting slipperiness and / or toner releasability on a member surface and toner chargeability in a high-temperature and high-humidity environment. The member is to be provided.

One aspect of the present invention is an electrophotographic member used in an electrophotographic apparatus, and includes a polymer layer including a member surface of the electrophotographic member.
The polymer layer has a matrix polymer that forms a skeleton of the polymer layer, and a surface modifier added in the matrix polymer.
The surface modifier includes a first polymer unit based on a first compound having a silicone group in the molecule and / or a second polymer unit based on a second compound having a fluorine-containing group in the molecule, and a quaternary. An electrophotographic member comprising a copolymer containing a third polymer unit based on a third compound comprising a salt of an ammonium cation and a hydrophobic anion.

  In the electrophotographic member, a surface modifier made of a copolymer containing the specific polymerization unit is added to a matrix polymer that forms a skeleton of a polymer layer including the member surface. Therefore, in the electrophotographic member, the first polymer unit and / or the second polymer unit and the third polymer unit in the surface modifier can be forced to exist in the vicinity of the surface of the polymer layer.

  For this reason, the electrophotographic member has a sliding property and / or toner separation on the surface of the member due to the silicone group contained in the first polymer unit and / or the fluorine-containing group contained in the second polymer unit in the surface modifier. A formality is imparted. Here, since the 3rd polymerization unit in the said surface modifier is formed from the 3rd compound which consists of a salt of a quaternary ammonium cation and a hydrophobic anion, it is hard to produce interaction with a water | moisture content. Therefore, even when the electrophotographic member is used in a high temperature and high humidity environment, the toner can be sufficiently charged by the third polymer unit in the surface modifier.

  Therefore, according to the present invention, it is possible to provide an electrophotographic member capable of simultaneously exhibiting the slipperiness and / or toner releasability of the member surface and the toner chargeability in a high temperature and high humidity environment. .

1 is a diagram schematically illustrating an electrophotographic member of Example 1. FIG. It is the figure which showed the II-II cross section in FIG. In the electrophotographic member of Example 1, it is the figure which showed typically the structure of the polymer layer. 6 is a diagram schematically showing an electrophotographic member of Example 2. FIG. It is the figure which showed the VV cross section in FIG.

  The electrophotographic member is a member used in an electrophotographic apparatus. Specific examples of the electrophotographic apparatus include an image forming apparatus such as a copying machine, a printer, a facsimile, a multifunction peripheral, and a POD (Print On Demand) apparatus that employs an electrophotographic system using a charged image.

  Specifically, the electrophotographic member can be a developing member, a charging member, a transfer member, or a cleaning member incorporated in an electrophotographic image forming apparatus. As the transfer member, specifically, an intermediate transfer member can be exemplified. The intermediate transfer member is for primary transfer of the toner image carried on the photosensitive member to the member, and then secondary transfer of the toner image from the member to a transfer material such as paper.

  When the electrophotographic member is used as a developing member, it is easy to suppress fogged images in a high-temperature and high-humidity environment, so that it is easy to improve image quality and reduce toner consumption. When the electrophotographic member is used as a charging member, it becomes easy to negatively charge untransferred toner that causes contamination, and thus it is easy to suppress toner filming in a high temperature and high humidity environment. When the electrophotographic member is used as a transfer member, the negative charge of the toner on the surface of the photoreceptor can be increased even in a high-temperature and high-humidity environment, thereby improving transfer efficiency and improving image quality. It is easy to reduce the toner consumption. When the electrophotographic member is used as a cleaning member, it is easy to negatively charge toner that passes through during cleaning, so that the surface of the charging member is less likely to be stained by the slipping toner even in a high temperature and high humidity environment.

  Specifically, the electrophotographic member includes, for example, (1) a shaft, an elastic layer formed along the outer peripheral surface of the shaft, and a polymer layer formed along the outer peripheral surface of the elastic layer. (2) A structure having a shaft body and a polymer layer formed along the outer periphery of the shaft body, (3) A base layer formed in a cylindrical shape, and formed along the outer peripheral surface of the base layer Configuration having a polymer layer, (4) Configuration having a base layer formed in a cylindrical shape, an elastic layer formed along the outer peripheral surface of the base layer, and a polymer layer formed along the outer peripheral surface of the elastic layer (5) Configuration having a polymer layer formed in a cylindrical shape, (6) Configuration having a blade body, a polymer layer covering a part or all of the blade body surface, and a holding portion for holding the blade body, (7) A polymer layer formed in a blade shape and holding the polymer layer It can be like configuration having a lifting portion. Configurations (1) and (2) are suitable as developing members and charging members, configurations (3) to (5) are suitable as transfer members, and configurations (6) and (7) are suitable as cleaning members.

  Here, the polymer layer in the electrophotographic member has a matrix polymer that forms a skeleton of the polymer layer and a surface modifier added to the matrix polymer.

  The matrix polymer plays an important role as a polymer component that forms the basic skeleton of the polymer layer. As long as the matrix polymer can play the above role, various resins and rubbers (rubbers include elastomers and are omitted below) can be used. These can be used alone or in combination of two or more, and an optimum material can be selected according to the use of the electrophotographic member.

  Examples of the resin include various thermoplastic resins and mixed polymers of thermoplastic resins and thermosetting resins. Specific examples of the resin include urethane resin; urethane silicone resin; urethane fluororesin; polyamide resin; polyimide resin; (meth) acrylic resin; (meth) acrylic silicone resin; (meth) acrylic fluororesin; Resin; Acetal resin; Alkyd resin; Polyester resin; Polyether resin; Carbonate resin; Phenol resin; Epoxy resin; Polyvinyl alcohol; Polyvinylpyrrolidone; Cellulosic resin such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose; Polyethylene glycol; polypropylene glycol; polyvinyl methyl ether; polyamine; polyethylene imine; casein, gelatin, starch and These copolymers; Olefin resins such as copolymers of polyethylene, polypropylene and other olefin monomers; Vinyl chloride resins; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer resins; Vinyl chloride Polyvinyl acetate copolymer resin; polyvinyl acetal resins such as polyvinyl butyral resin and derivatives or modified products thereof; polyisobutylene; polytetrahydrofuran; polyaniline; acrylonitrile-butadiene-styrene copolymer (ABS resin); polyisoprene; Polysiloxanes such as polydimethylsiloxane; polysulfones; polyimines; polyacetic anhydrides; polyureas; polysulfides; polyphosphazenes; polyketones; B olefins and derivatives thereof; and the like can be exemplified UV curable (meth) acrylic resins; melamine resins. Of these, urethane resin, urethane silicone resin, urethane fluororesin, and the like can be preferably used from the viewpoint of improving the flexibility and wear resistance of the polymer layer.

  Specific examples of the rubber include acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), chloroprene rubber (CR), and hydrin rubber (ECO). , CO), isoprene rubber (IR), urethane rubber (U), silicone rubber (Q), ethylene-propylene-diene rubber (EPDM), natural rubber (NR), modified products thereof, and the like. Of these, acrylonitrile-butadiene rubber (NBR), urethane rubber (U), modified products thereof, and the like can be preferably used from the viewpoint of improving the flexibility and wear resistance of the polymer layer.

  On the other hand, the surface modifier contained as an additive in the matrix polymer plays an important role as a component that exists mainly in the vicinity of the surface of the polymer layer and modifies the surface of the polymer layer. The surface modifier includes a first polymer unit based on a first compound having a silicone group in the molecule and / or a second polymer unit based on a second compound having a fluorine-containing group in the molecule, and quaternary ammonium. It is comprised from the copolymer containing the 3rd polymerization unit based on the 3rd compound which consists of a salt of a cation and a hydrophobic anion. The “fluorine-containing group” refers to a group containing a fluorine atom, and includes —F.

  The surface modifier is preferably composed of a copolymer including a first polymer unit, a second polymer unit, and a third polymer unit. In this case, an electrophotographic member capable of simultaneously exhibiting the slipperiness of the member surface, toner releasability, and toner chargeability in a high temperature and high humidity environment can be obtained. Therefore, when this electrophotographic member is used as a developing member or a charging member, in addition to the above-described effects, it is easy to improve durability by suppressing toner filming and toner adhesion. There are advantages.

  The surface modifier may include one or more kinds of first polymerized units and / or one kind or two or more kinds of second polymerized units. Further, the surface modifier may contain one or more third polymer units. Furthermore, the surface modifier can be used alone or in combination of two or more.

  The surface modifier may be a random copolymer or a block copolymer. Preferably, the surface modifier is a random copolymer. In this case, the first polymer unit and / or the second polymer unit and the third polymer unit are likely to be randomly present in the vicinity of the surface of the polymer layer. For this reason, in this case, there is an advantage that unevenness in slipperiness and / or toner releasability and unevenness in toner chargeability are less likely to occur. Further, the surface modifier can have, for example, a linear or branched polymer structure.

  In the first polymer unit, as the first compound, for example, (meth) acrylate having a silicone group in the molecule can be suitably used. In this case, at the time of synthesizing the surface modifier, a copolymerization reaction can be performed using an unsaturated bond of the (meth) acryloyl group. Easy to configure. In the present application, (meth) acrylate is meant to include both acrylate and methacrylate. Similarly, (meth) acryloyl is meant to include both acryloyl and methacryloyl.

  The first compound may have one type or two or more types of silicone groups. Specifically, the silicone group can include, for example, a polydimethylsiloxane skeleton composed of repeating dimethylsiloxane units. In this case, since the molecular weight of the silicone group can be increased by the polydimethylsiloxane skeleton having a relatively simple molecular structure, there is an advantage that the slipperiness of the polymer layer surface can be easily improved.

  The polydimethylsiloxane skeleton may have a weight average molecular weight of preferably 275 or more, more preferably 350 or more, and still more preferably 420 or more, from the viewpoint of improving the slipperiness of the polymer layer surface. The polydimethylsiloxane skeleton has a weight average molecular weight of preferably 20000 or less, more preferably 15000, from the viewpoint of reactivity during the synthesis of the surface modifier, solubility of the polymer layer forming material in a solvent, and the like. Hereinafter, it is even more preferably 12000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  In the second polymerization unit, as the second compound, for example, (meth) acrylate having a fluorine-containing group in the molecule can be suitably used. In this case, at the time of synthesizing the surface modifier, a copolymerization reaction can be carried out utilizing the unsaturated bond of the (meth) acryloyl group. Easy to configure.

  The second compound can have one or more fluorine-containing groups. Specifically, the fluorine-containing group can be composed of, for example, a fluoroalkyl group, a fluoroalkylalkylene oxide group, a fluoroalkenyl group, -F and the like.

  Among these, the fluorine-containing group is a fluoroalkyl group, preferably a fluoroalkyl group having about 4 to 12 carbon atoms, from the viewpoint of toner releasability, availability of a (meth) acrylate having a fluorine-containing group, and the like. A group can be suitably used. In the fluoroalkyl group, all hydrogen atoms of the alkyl group may be fluorinated, or a part of the alkyl group that is not fluorinated may be included. The former is total fluorination and the latter is partial fluorination. Particularly preferably, the fluoroalkyl group may be a perfluoroalkyl group. This is because the perfluoroalkyl group has high structural stability, so it is difficult to keep the toner close to the surface, and the toner releasability on the surface of the polymer layer is easily improved.

  Specific examples of the fluoroalkyl group include trifluoromethyl, trifluoroethyl, trifluorobutyl, pentafluoropropyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, and perfluoro-3. -Methylbutyl, perfluoro-5-methylhexyl, perfluoro-7-methyloctyl, octafluoropentyl, dodecafluoroheptyl, hexadecafluorononyl and the like can be exemplified.

  Specific examples of the hydrophobic anion constituting part of the third compound composed of a salt of a quaternary ammonium cation and a hydrophobic anion in the third polymer unit include, for example, perchlorate anion, bis ( Fluoroalkanesulfonyl) imide anion, trifluoroacetate anion, tetrafluoroborate anion, hexafluorophosphate anion and the like. These can be used alone or in combination of two or more.

  In this case, it is possible to obtain an electrophotographic member that easily charges the toner in a high temperature and high humidity environment. The hydrophobic anion is preferably a bis (fluoroalkanesulfonyl) imide anion, a hexafluorophosphate anion, or the like. This is because the toner chargeability in a high temperature and high humidity environment is excellent.

  The fluoroalkane in the bis (fluoroalkanesulfonyl) imide anion is preferably a fluoroalkane having about 1 to 4 carbon atoms. In the fluoroalkane, all hydrogen atoms of the alkane may be fluorinated, or a part of the alkane that is not fluorinated may be included. Specific examples of the bis (fluoroalkanesulfonyl) imide anion include the bis (trifluoromethanesulfonyl) imide anion.

  In the third polymer unit, the quaternary ammonium cation constituting a part of the third compound consisting of a salt of a quaternary ammonium cation and a hydrophobic anion is specifically a (meth) acryloyl in its structure. Can have groups.

  In this case, at the time of synthesizing the surface modifier, a copolymerization reaction can be carried out utilizing the unsaturated bond of the (meth) acryloyl group. Easy to configure.

  Specific examples of the quaternary ammonium cation include a quaternary ammonium cation having a (meth) acrylate group and a quaternary ammonium cation having a (meth) acrylamide group. These can be used alone or in combination of two or more. More specifically, examples of the quaternary ammonium cation include a cation represented by the following formula 1 and a cation represented by the following formula 2.

In the above formulas 1 and 2, R ₂ is preferably (CH ₂ ) _n (n is 1 to 4), more preferably (CH ₂ ) ₃ from the viewpoint of the hardness of the surface modifier. Good. R ₃ , R ₄ , and R ₅ are all preferably a methyl group, an ethyl group, a propyl group, or a butyl group from the viewpoint of the hardness, hydrophobicity, and compatibility of the surface modifier. .

  More specifically, examples of the quaternary ammonium cation having the (meth) acrylate group include a cation represented by the following formula 3, a cation represented by the following formula 4, and a cation represented by the following formula 5. Etc. can be illustrated. More specific examples of the quaternary ammonium cation having the (meth) acrylamide group include a cation represented by the following formula 6 and a cation represented by the following formula 7. . The quaternary ammonium cation is preferably a cation represented by the following formula 3 from the viewpoint of relatively easy synthesis of the surface modifier.

  In the surface modifying agent, the first compound having a silicone group in the molecule can be more specifically a compound represented by the following formula 8. Moreover, the 2nd compound which has a fluorine-containing group in a molecule | numerator can be made into the compound shown by following formula 9 more specifically. More specifically, the third compound comprising a salt of a quaternary ammonium cation and a hydrophobic anion can be a compound represented by the following formula 10, a compound represented by the following formula 11, or the like. .

In the above formula 8, R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group from the viewpoint of the reactivity of the (meth) acryloyl group. Good. The alkyl group as the skeleton that can constitute R ₃ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or the like from the viewpoint of the reactivity of the (meth) acryloyl group. It is good that it is a butyl group. From the viewpoint of the reactivity of the (meth) acryloyl group, the alkyl group as a skeleton that can constitute R ₄ and R ₅ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, It may be a propyl group or a butyl group. X is preferably a urethane group from the viewpoint of reactivity when adding (synthesizing) dimethylsiloxane having a silanol group or other dimethylsiloxane modification to acrylic acid or acrylic acid modification. . The acrylic acid modified product is, for example, one obtained by adding a highly reactive functional group to acrylic acid. The modified dimethylsiloxane is, for example, one in which dimethylsiloxane having a silanol group is modified so as to be reactive with an acrylic acid terminal. n is preferably an integer of 2 to 270, more preferably an integer of 5 to 160, from the viewpoints of reactivity during synthesis of the surface modifier, slipperiness, and the like.

In the above formulas 10 and 11, R ₂ is preferably (CH ₂ ) _n (n is 1 to 4), more preferably (CH ₂ ) ₃ from the viewpoint of the hardness of the surface modifier. Good. R ₃ , R ₄ , and R ₅ are all preferably a methyl group, an ethyl group, a propyl group, or a butyl group from the viewpoint of the hardness, hydrophobicity, and compatibility of the surface modifier. . In the above formula 10, the quaternary ammonium cation moiety is more preferably a cation represented by the above formula 3. In Formula 11, the quaternary ammonium cation moiety is more preferably a cation represented by Formula 6 described above. A ⁻ is preferably a bis (fluoroalkanesulfonyl) imide anion or a hexafluorophosphate anion from the viewpoint of improving toner chargeability in a high temperature and high humidity environment.

  Since the compounds represented by the formulas 8 to 11 are relatively easy to prepare, the surface modifier can be synthesized relatively easily. Therefore, in these cases, it becomes easy to obtain an electrophotographic member that exhibits the above-described effects.

  The surface modifier may include 0.01 to 60 mol% of the first polymerization unit. The surface modifier may contain 0.01 to 60 mol% of the second polymerization unit. The surface modifier may include 0.01 to 60 mol% of the third polymerization unit. In these cases, it is possible to ensure the slipperiness of the surface of the polymer layer, toner releasability, and toner chargeability in a high temperature and high humidity environment. Moreover, the balance of each characteristic is controllable by adjusting the ratio of each superposition | polymerization unit of a surface modifier within the said range. The ratio of the first polymer unit, the second polymer unit, and the third polymer unit is such that, when other polymer units described later are included, the total ratio of the polymer units including the polymer units is 100 mol%. Can be selected. The ratio of the above polymerized units can be measured by pyrolysis GC / MS analysis, NMR analysis or the like.

  The proportion of the first polymer unit is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.3 mol% or more, from the viewpoint of obtaining sufficient slipperiness. Further, the ratio of the first polymerization unit is preferably 50 mol% or less, more preferably 30 mol% or less, and still more preferably 10 mol% or less, from the viewpoint of solubility in a matrix polymer or a diluent solvent.

  The proportion of the second polymerization unit is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and still more preferably 0.3 mol% or more, from the viewpoint of obtaining sufficient toner releasability. In addition, the proportion of the second polymerization unit is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, from the viewpoint of solubility in a matrix polymer or a diluent solvent.

  The proportion of the third polymer unit is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.3 mol% or more, from the viewpoint of obtaining sufficient toner chargeability in a high temperature and high humidity environment. can do. The proportion of the third polymer unit is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less from the viewpoint of solubility in a matrix polymer or a diluent solvent.

  In addition to the first polymer unit and / or the second polymer unit and the third polymer unit, the surface modifier may contain one or more other polymer units as required.

  For example, the surface modifier may further include a fourth polymer unit based on a fourth compound having a hydroxyl group in the molecule. In addition, the surface modifier can contain 1 type, or 2 or more types of 4th polymerization units.

  In this case, the compatibility between the matrix polymer and the surface modifier can be improved by the hydroxyl group contained in the fourth polymer unit in the surface modifier. Therefore, it becomes possible to improve the durability of the polymer layer. In particular, when the matrix polymer includes a thermosetting polyurethane, the above-described effect is increased because the hydroxyl group reacts with the matrix polymer. In addition, by modifying other functional groups triggered by this hydroxyl group, the above effect can be increased for matrix polymers other than the thermosetting polyurethane.

  In the fourth polymerization unit, as the fourth compound, for example, (meth) acrylate having a hydroxyl group in the molecule, (meth) acrylamide having a hydroxyl group in the molecule can be preferably used. In this case, since the copolymerization reaction can be performed using the unsaturated bond of the (meth) acryloyl group at the time of the synthesis of the surface modifier, the surface modifier having the fourth compound as a polymerization component is used. Easy to configure.

  Specific examples of the fourth compound include 2-hydroxyethyl methacrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethylene oxide-modified (meth) acrylate, and hydroxy. Examples thereof include ethyl (meth) acrylamide. More specifically, the fourth compound is, for example, a compound represented by the following formula 12 or a compound represented by the following formula 13 from the viewpoint of the reactivity of the (meth) acryloyl group, the compatibility with the matrix polymer, and the like. It can be.

In the above formula 12, the alkyl group as a skeleton that can constitute R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group from the viewpoint of the reactivity of the (meth) acryloyl group. Group, propyl group or butyl group. The aryl group as a skeleton that can constitute R ₂ is preferably a phenyl group or a benzyl group from the viewpoints of the reactivity of the (meth) acryloyl group and the compatibility with the matrix polymer. The aralkyl group as a skeleton that can constitute R ₂ is preferably a benzyl group or a phenethyl group from the viewpoint of the reactivity of the (meth) acryloyl group and the compatibility with the matrix polymer.

In the above formula 13, the alkyl group as the skeleton that can constitute R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group from the viewpoint of the reactivity of the (meth) acryloyl group. Group, propyl group or butyl group. The aryl group as a skeleton that can constitute R ₂ is preferably a phenyl group or a benzyl group from the viewpoints of the reactivity of the (meth) acryloyl group and the compatibility with the matrix polymer. The aralkyl group as a skeleton that can constitute R ₂ is preferably a benzyl group or a phenethyl group from the viewpoint of the reactivity of the (meth) acryloyl group and the compatibility with the matrix polymer.

  Further, for example, the surface modifier may further include a fifth polymer unit based on a fifth compound having an alkyl group in the molecule. In addition, the surface modifier can contain 1 type, or 2 or more types of 5th polymerization units.

  In this case, the compatibility between the matrix polymer and the surface modifier can be improved by the alkyl group contained in the fifth polymer unit in the surface modifier. Therefore, it becomes possible to improve the durability of the polymer layer.

  In the fifth polymer unit, as the fifth compound, for example, (meth) acrylate having an alkyl group in the molecule, specifically, alkyl (meth) acrylate can be suitably used. In this case, since the copolymerization reaction can be carried out using the unsaturated bond of the (meth) acryloyl group during the synthesis of the surface modifier, the surface modifier containing the fifth compound as a polymerization component is used. Easy to configure.

  Specific examples of the fifth compound include methyl methacrylate and butyl methacrylate. In this case, at the time of synthesis of the surface modifier, it is easy to copolymerize with the first polymer unit to the fourth polymer unit described above, and it is easy to improve the compatibility between the matrix polymer and the surface modifier, and the above-mentioned effects are obtained. It becomes easy.

  The surface modifier may include 0 to 95 mol% of the fourth polymerization unit. The surface modifier may include 0 to 95 mol% of the fifth polymerization unit. The proportion of the fourth polymer unit is preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more, from the viewpoint of easily ensuring compatibility with the matrix polymer. Further, the ratio of the fourth polymer unit is preferably 94 mol% or less, more preferably 93 mol% or less, from the viewpoint of securing the ratio of the first polymer unit and / or the second polymer unit and the third polymer unit. More preferably, it can be 90 mol% or less. On the other hand, the proportion of the fifth polymer unit is preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more, from the viewpoint of ensuring compatibility with the matrix polymer. . In addition, the proportion of the fifth polymer unit is preferably 94 mol% or less, more preferably 93 mol% or less, from the viewpoint of securing the ratio of the first polymer unit and / or the second polymer unit and the third polymer unit. More preferably, it can be 90 mol% or less.

  The surface modifier may further include a polymer unit based on an organic compound such as (meth) acrylate having a functional group different from the silicone group and / or fluorine-containing group in the molecule.

  In this case, the function resulting from the functional group can be further imparted to the surface of the polymer layer, and the functionality of the surface of the polymer layer can be further improved. Specific examples of the functional group include an ester group and an ether group. Among the functional groups, for example, an ether group, an ester group, and the like have an effect of reducing the electric resistance of the polymer layer.

  More specifically, the surface modifier can be composed of one or more selected from compounds having a molecular structure represented by the following formula 14.

In the above formula 14, R ₆ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group from the viewpoint of the reactivity of the (meth) acryloyl group. Good. R ₇ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group from the viewpoint of the reactivity of the (meth) acryloyl group. For the reasons described above, p in mol% can be 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more, and still more preferably 1.0 or more. In mol%, p can be 50 or less, preferably 40 or less, more preferably 30 or less, and even more preferably 10 or less. Moreover, q in mol% can be 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more, and further preferably 1.0 or more. In mol%, q can be 50 or less, preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. Further, r in mol% can be 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more, and further preferably 1.0 or more. In mol%, r can be 50 or less, preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. Further, s in mol% can be 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more, and further preferably 1.0 or more. In mol%, s can be 94 or less, preferably 93 or less, more preferably 92 or less, and still more preferably 90 or less. Further, t in mol% can be 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more, and further preferably 1.0 or more. In mol%, t can be 94 or less, preferably 93 or less, more preferably 92 or less, and still more preferably 90 or less. As described above, p, q, r, s, and t, which are proportions of the respective polymerized units, are selected so as to be 100 mol% in total. Moreover, both p and q can take 0. However, when p = 0, q> 0, and when q = 0, p> 0, and p and q are not 0 simultaneously. N is preferably an integer of 2 to 270, more preferably an integer of 5 to 160.

  The said polymer layer can contain 0.01-40 mass parts of surface modifiers with respect to 100 mass parts of matrix polymers. In this case, the slipperiness and / or toner releasability of the member surface and the toner chargeability in a high temperature and high humidity environment can be ensured. Moreover, the balance of both characteristics can be controlled by adjusting the content of the surface modifier within the above range.

  The content of the surface modifier is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.5 parts by mass or more, from the viewpoint of obtaining a sufficient effect by addition. can do. The content of the surface modifier is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 9 from the viewpoints of compatibility with the matrix polymer, suppression of bleeding from the matrix polymer, cost, and the like. The amount can be not more than part by mass, more preferably not more than 7 parts by mass, still more preferably not more than 5 parts by mass, most preferably not more than 3 parts by mass. The content of the surface modifier is determined by extracting the extract with a solvent, pyrolyzing GC / MS analysis and NMR analysis of the extract, specifying the structure of the surface modifier, and then pyrolyzing the entire material. It can be measured by analyzing.

The polymer layer can contain, for example, a conductive agent in the matrix polymer. Specific examples of the conductive agent include carbon-based conductive materials such as carbon black, carbon nanotube, and graphite, barium titanate, c-TiO ₂ , c-ZnO, and c-SnO ₂ (where c- indicates conductivity. Ion such as conductive metal oxides or metal nanoparticles, conductive polymers such as polyaniline and polypyrrole, quaternary ammonium salts, borates, perchlorates, ionic liquids, etc. Examples thereof include a conductive agent.

  In addition to the matrix polymer, the above polymer layer may include a reaction catalyst, a filler (inorganic or organic), a coupling agent, a dispersant, a leveling agent, a crosslinking agent, a crosslinking aid, and a plasticizer, as necessary. Various additives such as flame retardants, antifoaming agents, and roughness forming particles can be contained. These can be used alone or in combination of two or more.

  The thickness of the polymer layer is not particularly limited, and can be set to an optimum thickness in consideration of wear resistance, flexibility, and the like. The thickness of the polymer layer can be, for example, about 1 to 100 μm.

  In addition, each structure mentioned above can be arbitrarily combined as needed, in order to acquire each effect etc. which were mentioned above.

  The electrophotographic member of the example will be specifically described with reference to the drawings.

Example 1
A schematic configuration of the electrophotographic member according to the first embodiment will be described with reference to FIGS. As shown in FIGS. 1 and 2, the electrophotographic member R is used in an electrophotographic apparatus. Specifically, the electrophotographic member of this example is a roll-like conductive member incorporated in an electrophotographic image forming apparatus, and can be used as a developing roll as a developing member or a charging roll as a charging member. it can.

  The electrophotographic member R has a polymer layer 1. Specifically, the electrophotographic member R of this example includes a shaft body 2 made of a core metal, and an elastic layer 3 made of a conductive rubber elastic body formed along the outer peripheral surface of the shaft body 2. In addition. However, both end portions of the shaft body 2 are projected from both end surfaces of the elastic layer 3. A polymer layer 1 is formed along the outer peripheral surface of the elastic layer 3.

  When the electrophotographic member R is used as a developing member, for example, a blade member for charging toner by rubbing or forming a toner having a constant thickness is in contact with the surface of the polymer layer 1. Can be used. When the electrophotographic member R is used as a charging member, for example, a blade member for removing the toner remaining on the surface after the fixing step for fixing the toner image on the paper is brought into contact with the surface of the polymer layer 1. It can be used in the state of being let.

  As schematically shown in FIG. 3, the polymer layer 1 includes a matrix polymer 11 that forms the skeleton of the polymer layer 1, and a surface modifier 12 added to the matrix polymer 11.

  Specifically, the matrix polymer 11 is made of a mixed polymer of thermoplastic polyurethane and thermosetting polyurethane. The surface modifier 12 includes a first polymer unit 121 based on a first compound having a silicone group in the molecule and / or a second polymer unit 122 based on a second compound having a fluorine-containing group in the molecule, It consists of a copolymer containing the 3rd polymerization unit 123 based on the 3rd compound which consists of a salt of a quaternary ammonium cation and a hydrophobic anion. In this example, specifically, the copolymer constituting the surface modifier 12 includes a first polymer unit 121, a second polymer unit 122, and a third polymer unit 123.

  In this example, the first compound is a (meth) acrylate having a silicone group in the molecule. The second compound is a (meth) acrylate having a fluorine-containing group in the molecule. The third compound is a salt of a quaternary ammonium cation having a (meth) acryloyl group and a hydrophobic anion.

  The hydrophobic anion is specifically selected from the group consisting of a perchlorate anion, a bis (fluoroalkanesulfonyl) imide anion, a trifluoroacetate anion, a tetrafluoroborate anion, and a hexafluorophosphate anion. Is at least one kind.

  A relatively large amount of the surface modifier 12 is present near the surface of the polymer layer 1. The surface modifier 12 is contained within a range of 0.01 to 40 parts by mass with respect to 100 parts by mass of the matrix polymer 11. In addition, an electronic conductive agent is added to the polymer layer 1 in order to impart conductivity.

(Example 2)
A schematic configuration of the electrophotographic member of Example 2 will be described with reference to FIGS. As shown in FIGS. 4 and 5, the electrophotographic member B is used in an electrophotographic apparatus. Specifically, the electrophotographic member B of this example is an endless belt-like conductive member incorporated in an electrophotographic image forming apparatus, and can be used as an intermediate transfer belt as a transfer member.

  The electrophotographic member B has a polymer layer 4. Specifically, the electrophotographic member B of this example further includes a cylindrical base layer 5 formed of a conductive resin material. A polymer layer 4 is formed along the outer peripheral surface of the base layer 5. As the electrophotographic member B, for example, a blade member for removing toner remaining on the surface after the toner image is secondarily transferred to a sheet can be used in a state where the surface is in contact with the surface of the polymer layer 5.

  Although not shown, the polymer layer 4 has a configuration in which the specific surface modifier is added to the matrix polymer, as in FIG. 3 of Example 1.

  Specifically, the matrix polymer contains rubber as a main component. Therefore, the polymer layer 4 has rubber elasticity. Since the surface modifier has the same configuration as that of Example 1, the description thereof is omitted. An ionic conductive agent is added to the polymer layer 4 in order to impart conductivity.

  Hereinafter, a sample of an electrophotographic member was prepared and evaluated. An experimental example will be described.

<Experimental example>
<Preparation of surface modifier>
First, the following compounds were prepared as raw materials for synthesizing the surface modifier to be added to the matrix polymer of the polymer layer.

Acrylate-modified silicone compound (“X-22-174DX” manufactured by Shin-Etsu Chemical Co., Ltd.)
The acrylate-modified silicone compound is a compound represented by the above formula 8, and in formula 8, R ₁ and R ₂ are both methyl groups. R ₃ is (CH ₂ ) ₃ . The silicone group includes a polydimethylsiloxane skeleton composed of repeating dimethylsiloxane units, and its weight average molecular weight is 4200.
2- (Perfluorohexyl) ethyl acrylate (Daikin Industries, “R-1620”)
・ Dimethylaminopropylacrylamide (DMAPAA) (KOHJIN)
・ Methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Potassium perchlorate (Wako Pure Chemical Industries)
・ Bis (trifluoromethanesulfonyl) imidolithium (Wako Pure Chemical Industries, Ltd.)
・ Sodium trifluoroacetate (Wako Pure Chemical Industries)
・ Sodium tetrafluoroborate (Wako Pure Chemical Industries)
・ Sodium hexafluorophosphate (Wako Pure Chemical Industries)
・ 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Methyl methacrylate (made by Pure Chemical Industries)
Dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) (polymerization initiator) (manufactured by Wako Pure Chemical Industries, “VE-73”)

・ Salt of quaternary ammonium cation having acryloyl group and iodine anion (1)
A 1 L reaction flask was charged with 156 g (1000 mmol) of DMAPAA, 170 g (1200 mmol) of methyl iodide and 1000 g of methanol, and stirred at a temperature of the internal solution of 30 ° C. for 6 hours in a nitrogen atmosphere. Thereafter, the solvent and excess methyl iodide were distilled off under reduced pressure. As a result, a salt (1) of a quaternary ammonium cation having an acryloyl group and iodine anion represented by the following formula 15 was obtained. The iodine anion is one of hydrophilic anions.

.Salt of quaternary ammonium cation having acryloyl group and perchlorate anion (2)
A 200 mL reaction flask was charged with 29.8 g (100 mmol) of the above salt (1), 16.6 g (120 mmol) of potassium perchlorate, and 100 g of methyl isobutyl ketone (MIBK). The mixture was stirred at a temperature of 30 ° C. for 6 hours. Thereafter, 100 mL of pure was added to extract potassium iodide, and the remaining solvent was distilled off under reduced pressure. This obtained the salt (2) of the quaternary ammonium cation which has acryloyl group shown in Formula 16, and a perchlorate anion.

・ Salt of quaternary ammonium cation having acryloyl group and bis (trifluoromethanesulfonyl) imide anion (3)
Into a 200 mL reaction flask, 29.8 g (100 mmol) of the above salt (1), 34.5 g (120 mmol) of bis (trifluoromethanesulfonyl) imide lithium and 100 g of MIBK were charged, and the temperature of the internal solution was 30 under a nitrogen atmosphere. Stir at 6 ° C. for 6 hours. Thereafter, 100 mL of pure was added to extract potassium iodide, and the remaining solvent was distilled off under reduced pressure. As a result, a salt (3) of a quaternary ammonium cation having an acryloyl group and a bis (trifluoromethanesulfonyl) imide anion represented by the formula 17 was obtained.

.Salt of quaternary ammonium cation having acryloyl group and trifluoroacetate anion (4)
In a 200 mL reaction flask, 29.8 g (100 mmol) of the above salt (1), 16.3 g (120 mmol) of sodium trifluoroacetate, and 100 g of MIBK were charged, and the temperature of the internal solution was 30 ° C. in a nitrogen atmosphere. Stir for hours. Thereafter, 100 mL of pure was added to extract potassium iodide, and the remaining solvent was distilled off under reduced pressure. As a result, a salt (4) of a quaternary ammonium cation having an acryloyl group and a trifluoroacetic acid anion represented by Formula 18 was obtained.

.Salt of quaternary ammonium cation having acryloyl group and tetrafluoroborate anion (5)
In a 200 mL reaction flask, 29.8 g (100 mmol) of the above salt (1), 13.2 g (120 mmol) of sodium tetrafluoroborate, and 100 g of MIBK were charged, and the temperature of the internal solution was 30 ° C. in a nitrogen atmosphere. Stir for 6 hours. Thereafter, 100 mL of pure was added to extract potassium iodide, and the remaining solvent was distilled off under reduced pressure. This obtained the salt (5) of the quaternary ammonium cation which has acryloyl group shown by Formula 19, and the tetrafluoroborate anion.

.Salt of quaternary ammonium cation having acryloyl group and hexafluorophosphate anion (6)
In a 200 mL reaction flask, 29.8 g (100 mmol) of the above salt (1), 20.2 g (120 mmol) of sodium hexafluorophosphate, and 100 g of MIBK were charged, and the temperature of the internal solution was 30 ° C. in a nitrogen atmosphere. Stir for 6 hours. Thereafter, 100 mL of pure was added to extract potassium iodide, and the remaining solvent was distilled off under reduced pressure. This obtained the salt (6) of the quaternary ammonium cation which has acryloyl group shown by Formula 20, and the hexafluorophosphate anion.

  Next, each surface modifier was prepared as follows.

・ Surface modifier A
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of an acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, , 7.37 g (73.64 mmol) of methyl methacrylate, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) and 14.38 g of MIBK were charged with nitrogen for 5 minutes while stirring. After bubbling, polymerization was carried out for 7 hours at an internal liquid temperature of 80 ° C. Next, 26.64 g of MIBK was charged to obtain a solution containing the surface modifier A having a solid content of 30%.
The surface modifier A is composed of a linear copolymer containing a first polymer unit, a second polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 1. This surface modifier A is a silicone / fluorine-based surface modifier.

・ Surface modifier B
In a 100 mL reaction flask, 5.51 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (73.64 mmol) of DMAPAA, 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, and methacrylic acid 0.04 g (0.36 mmol) of methyl, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) and 16.4 g of MIBK were charged, and bubbling with nitrogen was performed for 5 minutes while stirring. Thereafter, polymerization was carried out at an internal liquid temperature of 80 ° C. for 7 hours. Next, 30.4 g of MIBK was charged to obtain a solution containing 30% of surface modifier B in terms of solid content.
The surface modifier B is composed of a linear copolymer containing a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 1. This surface modifier B is a fluorine / amine-based surface modifier.

・ Surface modifier C
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of an acrylate-modified silicone compound, 11.50 g (73.64 mmol) of DMAPAA, 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, and 1. 30 g (13 mmol), 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), and 17.8 g of MIBK were charged, and after bubbling with nitrogen for 5 minutes with stirring, the internal solution For 7 hours at a temperature of 80 ° C. Next, 32.9 g of MIBK was charged to obtain a solution containing 30% of surface modifier C in solid content.
The surface modifier C is composed of a linear copolymer containing a first polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 1. The surface modifier C is a silicone / amine-based surface modifier.

・ Surface modifier D
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of an acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (73.64 mmol) of DMAPAA, and methacrylic acid 1.69 g (13 mmol) of 2-hydroxyethyl, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) and 20.6 g of MIBK were charged, and bubbling with nitrogen was performed for 5 minutes while stirring. Then, polymerization was carried out for 7 hours at an internal liquid temperature of 80 ° C. Next, 38.2 g of MIBK was charged to obtain a solution containing the surface modifier D having a solid content of 30%.
The surface modifier D is composed of a linear copolymer containing a first polymer unit, a second polymer unit, a third polymer unit, and a fourth polymer unit based on each compound shown in Table 1. This surface modifier D is a silicone / fluorine / amine-based surface modifier.

・ Surface modifier E
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of an acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (38.57 mmol) of salt (1), 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, 3.51 g (35.07 mmol) of methyl methacrylate, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 20.6 g of MIBK was charged, and bubbling with nitrogen was performed for 5 minutes with stirring, followed by polymerization at an internal liquid temperature of 80 ° C. for 7 hours. Next, 38.2 g of MIBK was charged, and a solution containing 30% surface modifier E in solid content was obtained.
The surface modifier E is a linear co-polymer containing a first polymer unit, a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 2. Composed of coalescence. In addition, the salt (1) used for the structure of the 3rd polymerization unit in this surface modifier E is a salt of the quaternary ammonium cation which has an acryloyl group, and the iodine anion which is a hydrophilic anion.

・ Surface modifier F
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (42.49 mmol) of salt (2), 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, 3.12 g (31.15 mmol) of methyl methacrylate, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 20.3 g of MIBK was charged, and bubbling with nitrogen was carried out for 5 minutes with stirring, followed by polymerization at an internal liquid temperature of 80 ° C. for 7 hours. Next, 37.6 g of MIBK was charged to obtain a solution containing 30% surface modifier F in solid content.
The surface modifier F is a linear co-polymer containing a first polymer unit, a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 2. Composed of coalescence. In addition, the salt (2) used for the structure of the 3rd polymerization unit in this surface modifier F is a salt of the quaternary ammonium cation which has acryloyl group, and the perchlorate anion which is a hydrophobic anion.

・ Surface modifier G
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (25.48 mmol) of salt (3), 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, 4.82 g (48.16 mmol) of methyl methacrylate, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 21.7 g of MIBK was charged, and bubbling with nitrogen was carried out for 5 minutes with stirring, followed by polymerization at an internal liquid temperature of 80 ° C. for 7 hours. Next, 40.2 g of MIBK was charged, and a solution containing 30% surface modifier G in solid content was obtained.
The surface modifier G is a linear co-polymer containing a first polymer unit, a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 2. Composed of coalescence. The salt (3) used in the construction of the third polymer unit in the surface modifier G is a salt of a quaternary ammonium cation having an acryloyl group and a bis (trifluoromethanesulfonyl) imide anion which is a hydrophobic anion. It is.

・ Surface modifier H
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (40.45 mmol) of salt (4), 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, 3.32 g (33.19 mmol) of methyl methacrylate, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 20.5 g of MIBK was charged, and bubbling with nitrogen was performed for 5 minutes while stirring, and then polymerization was performed at an internal liquid temperature of 80 ° C. for 7 hours. Next, 37.9 g of MIBK was charged to obtain a solution containing 30% surface modifier H in solid content.
The surface modifier H is a linear co-polymer containing a first polymer unit, a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 2. Composed of coalescence. In addition, the salt (4) used for the structure of the 3rd polymerization unit in this surface modifier H is a salt of the quaternary ammonium cation which has an acryloyl group, and the trifluoroacetic acid anion which is a hydrophobic anion.

・ Surface modifier I
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of an acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (44.56 mmol) of salt (5), 2-hydroxyethyl methacrylate 1.69 g (13 mmol), methyl methacrylate 2.91 g (29.08 mmol), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) 1.24 g (4 mmol), 20.1 g of MIBK was charged, and bubbling with nitrogen was performed for 5 minutes with stirring, and then polymerization was performed at an internal liquid temperature of 80 ° C. for 7 hours. Next, 37.3 g of MIBK was charged to obtain a solution containing 30% of surface modifier I in solid content.
The surface modifier I is a linear co-polymer containing a first polymer unit, a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 2. Composed of coalescence. In addition, the salt (5) used for the structure of the 3rd polymerization unit in this surface modifier I is a salt of the quaternary ammonium cation which has acryloyl group, and the tetrafluoroborate anion which is a hydrophobic anion.

・ Surface modifier J
In a 100 mL reaction flask, 1.66 g (0.36 mmol) of an acrylate-modified silicone compound, 5.61 g (13 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.50 g (36.37 mmol) of salt (6), 1.69 g (13 mmol) of 2-hydroxyethyl methacrylate, 3.73 g (37.27 mmol) of methyl methacrylate, 1.24 g (4 mmol) of dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 20.8 g of MIBK was charged, and nitrogen bubbling was performed for 5 minutes with stirring, followed by polymerization at an internal liquid temperature of 80 ° C. for 7 hours. Next, 38.5 g of MIBK was charged, and a solution containing 30% surface modifier J in solid content was obtained.
The surface modifier J is a linear co-polymer containing a first polymer unit, a second polymer unit, a third polymer unit, a fourth polymer unit, and a fifth polymer unit based on each compound shown in Table 2. Composed of coalescence. In addition, the salt (6) used for the structure of the 3rd polymerization unit in this surface modifier I is a salt of the quaternary ammonium cation which has an acryloyl group, and the hexafluorophosphate anion which is a hydrophobic anion.

  Tables 1 and 2 collectively show the charged amounts of the respective polymerization components in the synthesis of the surface modifier.

<Preparation of polymer layer forming material>
As shown in Table 3, 10 parts by mass of thermoplastic polyurethane (manufactured by Nippon Polyurethane Industry Co., Ltd., “Nipporan 5199”) and polyether diol (trifunctional polypropylene glycol) (manufactured by ADEKA Co., Ltd., “ADEKA Polyether P”) -1000 ") 60 parts by mass, 30 parts by mass of polyisocyanate (HDI type block isocyanurate) (manufactured by Nippon Polyurethane Industry Co., Ltd.," Coronate L "), and electronic conductive agent (carbon black) (manufactured by Lion Corporation) , "Ketjen EC300J") 3 parts by mass and each surface modifier of a predetermined type and a predetermined blending amount shown in Table 3 are dissolved in MEK to a concentration of 20% by mass, and three rolls are used. And thoroughly mixed and dispersed. Thereby, each polymer layer forming material used for preparation of the conductive roll samples 1-10 was prepared.

<Preparation of conductive roll sample>
By mixing conductive silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., “X-34-264A / B, mixing mass ratio A / B = 1/1”) with a static mixer, an elastic layer forming material is obtained. Prepared.

  A solid cylindrical iron bar with a diameter of 6 mm was prepared as a shaft, and an adhesive was applied to the outer peripheral surface. After this shaft body was set in the hollow space of the roll molding die, the prepared elastic layer forming material was poured into the hollow space, heated and cured at 190 ° C. for 30 minutes, and demolded. Thereby, a roll-shaped elastic layer (thickness 3 mm) made of conductive silicone rubber was formed along the outer peripheral surface of the shaft body.

  Next, each of the prepared polymer layer forming materials was applied to the outer peripheral surface of the elastic layer by a roll coating method, and then heated and cured at 120 ° C. for 45 minutes to form a polymer layer (thickness 15 μm). . Thereby, the conductive roll samples 1-10 of the two-layer structure which have a polymer layer as a polymer layer along the outer peripheral surface of the said elastic layer were produced. The polymer layer contains each surface modifier shown in Table 3 as an additive in a mixed polymer of thermoplastic polyurethane and thermosetting polyurethane that forms the skeleton of the polymer layer.

-Slipperiness-
A contact (made of a steel ball with a diameter of 3 mm) is applied to the surface of a conductive roll sample fixed on the stage of a static / dynamic friction coefficient measuring instrument (“Tribostar 500” manufactured by Kyowa Interface Science Co., Ltd.) A vertical load W50 g was applied. In this state, the stage was moved 1 cm in the horizontal direction at a moving speed of 7.5 mm / sec. Thus, the initial dynamic friction coefficient μk (F / W) on the surface of the polymer layer of the conductive roll sample was calculated from the frictional force F generated between the conductive roll sample and the contact.
The case where the dynamic friction coefficient μk was 1.5 or less was designated as “A” because it was excellent in the slipperiness of the polymer layer surface. A case where the dynamic friction coefficient μk was 1.5 or more and less than 2 was designated as “B” because the slipperiness of the polymer layer surface was good. The case where the dynamic friction coefficient μk was more than 2 was designated as “C” because the friction force on the surface of the polymer layer was large and the slipperiness was poor.

-Toner releasability-
Each of the prepared polymer layer forming materials was heated and cured under the same conditions as in the formation of the polymer layer to prepare sheet-like test pieces (thickness 15 μm). Next, the toner of the cartridge of a digital full-color multifunction peripheral (“Fuji Xerox Co., Ltd.,“ DocuCentre-IV C2260 ”) employing an electrophotographic method was quantitatively dispersed on the surface of each test piece. Next, each test piece sprayed with this toner was set in a centrifuge, and the remaining amount of toner after adding 12000 G was evaluated by image processing. If the remaining area of the toner in the image is less than 30%, the toner release property is “A”. If the remaining area of the toner in the image is 30% or more and less than 50%, the toner release property “B”, and the case where the remaining area of the toner in the image was more than 50% was designated as “C” as having no toner releasability.

-Toner chargeability in high temperature and high humidity environment-
Each conductive roll sample was incorporated in a commercially available color printer (“Color Laser Jet Pro 400 Color M451dn” manufactured by Hewlett-Packard Japan) as a developing roll in a high temperature and high humidity environment of 32.5 ° C. × 85% RH. Output a solid image. At the initial stage of output, the toner (styrene-acrylic toner) on the surface of the polymer layer of the developing roll is sucked and collected using a metal cylindrical tube and a cylindrical filter, and the charge stored in the condenser through the metal cylindrical tube at that time The absolute value Q (μC) of the amount and the total mass M (g) of the collected toner were measured. Then, the toner charge amount Q / M (μC / g) per unit mass was calculated.
From the viewpoint of suppressing fogged images caused by insufficient charging of toner in a high temperature and high humidity environment, the toner chargeability in a high temperature and high humidity environment is determined when the toner charge amount Q / M is 18 (μC / g) or more. It was set as "A" as it was excellent in. Further, from the viewpoint that fog images are likely to occur due to insufficient charge of toner in a high temperature and high humidity environment, the toner charge amount Q / M is 12 (μC / g) or more and less than 18 (μC / g). The toner chargeability was inferior, and “B” was assigned. From the viewpoint that fog images are easily generated due to insufficient charging of toner in a high temperature and high humidity environment, the toner charge amount Q / M is less than 12 (μC / g). The toner chargeability under the environment was further inferior, and “C” was assigned.
The suctioned area A (cm ² ) was also measured and the toner transport amount M / A (mg / cm ² ) per unit area was calculated. Was about 0.5 (mg / cm ² ). Accordingly, it can be said that both have toner transportability that does not cause a problem to function as a developing roll.

  The detailed configuration and evaluation results of each conductive roll sample are shown in Table 3 below.

According to Table 3, the following can be understood.
In the conductive roll of Sample 1, silicone / fluorine-based surface modifier A is added to the polymer layer. The surface modifier A does not have a third polymer unit based on a third compound composed of a salt of a quaternary ammonium cation and a hydrophobic anion. Therefore, the conductive roll of Sample 1 could not exhibit toner chargeability in a high temperature and high humidity environment.

  In the conductive roll of sample 2, a fluorine / amine-based surface modifier B is added to the polymer layer. That is, the surface modifier B does not have a third polymer unit based on a third compound composed of a salt of a quaternary ammonium cation and a hydrophobic anion, and tries to obtain toner chargeability by an amino group. Is. Therefore, in the conductive roll of Sample 2, the interaction between the surrounding moisture and the amino group occurred in a high temperature and high humidity environment, and the toner chargeability was lowered. Moreover, since the surface modifier B does not have the 1st polymerization unit containing a silicone group, it was not able to exhibit slipperiness.

  In the conductive roll of Sample 3, a silicone / amine-based surface modifier C is added to the polymer layer. That is, the surface modifier C does not have a third polymer unit based on a third compound composed of a salt of a quaternary ammonium cation and a hydrophobic anion, and tries to obtain toner chargeability by an amino group. Is. Therefore, in the conductive roll of Sample 3, the interaction between the surrounding moisture and the amino group occurred in a high temperature and high humidity environment, and the toner chargeability was lowered. Further, since the surface modifier B does not have the second polymerization unit containing a fluorine-containing group, the toner releasability cannot be exhibited.

  In the conductive roll of Sample 4, the surface modifier D, which is a silicone / fluorine / amine-based surface modifier, is added to the polymer layer. That is, the surface modifier D does not have a third polymer unit based on a third compound composed of a salt of a quaternary ammonium cation and a hydrophobic anion, and tries to obtain toner chargeability by an amino group. Is. For this reason, the conductive roll of Sample 4 had an interaction between the surrounding water and the amino group in a high temperature and high humidity environment, and the toner chargeability was lowered.

  In the conductive roll of sample 5, the surface modifier E is added to the polymer layer. However, in the surface modifier E, the third polymer unit is configured based on a third compound composed of a salt of a quaternary ammonium cation and an iodine anion which is a hydrophilic anion. Therefore, in the conductive roll of Sample 5, the interaction between the surrounding moisture and the amino group occurred in a high temperature and high humidity environment, and the toner chargeability was lowered.

  On the other hand, the conductive rolls of Sample 6 to Sample 10 are all the first polymer unit based on the first compound having a silicone group in the molecule and the fluorine-containing group in the molecule in the matrix polymer of the polymer layer. A surface modifier F comprising a copolymer comprising a second polymerized unit based on a second compound having a third polymer unit based on a third compound comprising a salt of a quaternary ammonium cation and a hydrophobic anion, One of G, H, I, and J is contained.

  Therefore, it was confirmed that the conductive rolls of Sample 6 to Sample 10 can simultaneously exhibit the slipperiness of the surface of the polymer layer, which is the member surface, the toner releasability, and the toner chargeability in a high temperature and high humidity environment.

  As mentioned above, although the Example of this invention was described in detail, this invention is not limited to the said Example, A various change is possible within the range which does not impair the meaning of this invention.

R, B Electrophotographic member 1 Polymer layer 11 Matrix polymer 12 Surface modifier 121 First polymer unit 122 Second polymer unit 123 Third polymer unit

Claims (5)

An electrophotographic member used in an electrophotographic apparatus, having a polymer layer including a member surface of the electrophotographic member,
The polymer layer has a matrix polymer that forms a skeleton of the polymer layer, and a surface modifier added in the matrix polymer.
The surface modifier includes a first polymer unit based on a first compound having a silicone group in the molecule and / or a second polymer unit based on a second compound having a fluorine-containing group in the molecule, and a quaternary. An electrophotographic member comprising a copolymer containing a third polymer unit based on a third compound comprising a salt of an ammonium cation and a hydrophobic anion.   The hydrophobic anion is at least one selected from the group consisting of a perchlorate anion, a bis (fluoroalkanesulfonyl) imide anion, a trifluoroacetate anion, a tetrafluoroborate anion, and a hexafluorophosphate anion. The electrophotographic member according to claim 1.   The electrophotographic member according to claim 1, wherein the copolymer further includes a fourth polymer unit based on a fourth compound having a hydroxyl group in the molecule. The first compound is a (meth) acrylate having the silicone group in the molecule,
The second compound is a (meth) acrylate having the fluorine-containing group in the molecule,
The electrophotographic member according to any one of claims 1 to 3, wherein the quaternary ammonium cation has a (meth) acryloyl group.   The electrophotographic member according to claim 1, wherein the electrophotographic member is a developing member, a charging member, a transfer member, or a cleaning member incorporated in an electrophotographic image forming apparatus.

Images