JP6789771B2 - Electrophotographic components, process cartridges and electrophotographic equipment - Google Patents

Description

The present invention relates to an electrophotographic member used in an electrophotographic apparatus, a process cartridge having the electrophotographic member, and an electrophotographic apparatus.

In an electrophotographic apparatus, as an electrophotographic member such as a developing roller, a charging member, a toner supply roller, a cleaning blade, and a developing blade, an electric resistance value such as 1 × 10 ⁵ to 1 × 10 ⁹ Ω (hereinafter, “resistance”). An electrophotographic member having a conductive layer (referred to as "value") is used. Patent Document 1 describes a conductive roll in which a conductive rubber member made of a rubber-like elastic body containing an ionic liquid having a specific cation structure as a conductive agent is provided around the core member. Further, Patent Document 2 has an elastic layer formed on the outer peripheral surface of the shaft body and a urethane coat layer formed on the outer peripheral surface of the elastic layer, and the urethane coat layer is a urethane resin and a pyridinium type. Conductive rollers containing at least one ionic liquid selected from ionic liquids and amine-based ionic liquids are described.

Japanese Unexamined Patent Publication No. 2003-202722 Japanese Unexamined Patent Publication No. 2011-53658

In recent years, electrophotographic devices are required to be able to maintain high image quality and high durability even in a harsher environment. According to the study by the present inventors, the resistance value of the conductive roll according to Patent Document 1 and the conductive roller according to Patent Document 2 may increase particularly in a low temperature environment such as a temperature of 0 ° C.

The present invention is aimed at providing an electrophotographic member having a small increase in resistance value even in a low temperature environment such as a temperature of 0 ° C. The present invention also aims to provide an electrophotographic apparatus capable of stably outputting a high-quality electrophotographic image and a process cartridge used therein.

According to one aspect of the present invention, it is an electrophotographic member having a conductive substrate and a resin layer, and the resin layer is at least selected from the group consisting of the following structural formulas (1) and (2). Provided is an electrophotographic member comprising a resin having one structure and at least one cation structure selected from the group consisting of the following structural formulas (3) to (6), and an anion:

(In structural formula (1), R1 represents a hydrogen atom, a fluorine atom or a methyl group. X1 represents any structure or fluorine atom selected from the formula (X101) or (X102):

In formulas (X101) and (X102), Y1 represents a fluoroalkyl group having 1 to 6 carbon atoms. );

(In the structural formula (2), R2 represents a hydrogen atom or a methyl group. X2 represents any structure selected from the formula (X201) or (X202).

In formulas (X201) and (X202), R3 to R5 each independently represent a hydrocarbon chain having 1 or more and 4 or less carbon atoms. Y2 represents a straight or branched silicone group. );

(In the structural formula (3), R6 represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. At least one of Z1 to Z3 is a group consisting of structural formulas (Z101) to (Z103). Represents one of the structures selected from the above, and represents a hydrocarbon group having 1 or more and 4 or less carbon atoms.

(In the structural formula (4), R7 and R8 are independently each of the hydrocarbon chains required for the nitrogen-containing heterocycle in the structural formula (4) to form a 5-membered ring, a 6-membered ring or a 7-membered ring. Represents at least one of Z4 to Z7 represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the others represent hydrogen atoms or carbon atoms 1 or more and 4 or less. One of the two Ns contained in the nitrogen-containing heterocycle in the structural formula (4) is N ⁺ .)

(In the structural formula (5), R9 represents a hydrocarbon chain required for the nitrogen-containing heterocycle in the structural formula (5) to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. Z8 to Z10. At least one of them represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the other represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. .)

(In the structural formula (6), R10 represents a hydrocarbon chain required for the nitrogen-containing heterocycle in the structural formula (6) to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. Z11 to Z13. At least one of them represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the other represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. .)

(In the structural formulas (Z101) to (Z103), R11, R12 and R13 each independently represent a hydrocarbon chain having a straight chain or a branch. The symbol "*" represents a nitrogen atom in the structural formula (3). Represents the bond site with the nitrogen atom or carbon atom constituting the nitrogen-containing heterocycle in the structural formulas (4) to (6), and the symbol "**" represents the bond site with the nitrogen atom or carbon atom constituting the resin. Represents the bond site with the carbon atom of.).

Further, according to another aspect of the present invention, the process cartridge is a process cartridge that is detachably attached to the main body of the electrophotographic apparatus, and at least one of the electrophotographic members is the above-mentioned electrophotographic member. Is provided.
Further, according to another aspect of the present invention, there is provided an electrophotographic apparatus including an electrophotographic photosensitive member, wherein at least one of the electrophotographic members is the above-mentioned electrophotographic member. To.

According to one aspect of the present invention, an electrophotographic member having a small increase in resistance value can be obtained even in a low temperature environment such as a temperature of 0 ° C. Further, according to another aspect of the present invention, an electrophotographic apparatus capable of stably outputting a high-quality electrophotographic image and a process cartridge used therein can be obtained.

It is the schematic sectional drawing of the roller for electrophotographic which concerns on one Embodiment of this invention. It is schematic cross-sectional view of the electrophotographic blade which concerns on one Embodiment of this invention. It is the schematic sectional drawing of the electrophotographic apparatus which concerns on one Embodiment of this invention. It is a schematic block diagram of the process cartridge which concerns on one Embodiment of this invention. It is a schematic block diagram of the jig for evaluating the resistance value of a developing roller.

The present inventors have made extensive studies to achieve the above object. As a result, they have found that by using an electrophotographic member containing a resin having a specific chemical structure and an anion in the resin layer, an increase in resistance value is suppressed even in a low temperature environment such as a temperature of 0 ° C. I came to make an invention.

(1) Electrophotographic member The electrophotographic member according to an embodiment of the present invention has a conductive substrate and at least one conductive resin layer on the substrate.

As an example of the electrophotographic member, roller-shaped electrophotographic members (electrophotograph rollers) are shown in FIGS. 1 (a) to 1 (c). The electrophotographic roller 1A shown in FIG. 1A is composed of a conductive substrate 2 and a conductive resin layer 3 provided on the outer periphery thereof. As shown in FIG. 1B, an elastic layer 4 may be further provided between the substrate 2 and the resin layer 3. Further, as shown in FIG. 1C, the electrophotographic roller 1A may have a three-layer structure in which an intermediate layer 5 is arranged between the elastic layer 4 and the resin layer 3, and a plurality of intermediate layers 5 are arranged. It may have a multi-layered structure. In order to more effectively exert the effect according to the embodiment of the present invention in the electrophotographic roller 1A, as shown in FIGS. 1A to 1C, the resin layer 3 is the electrophotographic roller 1A. It preferably exists as the outermost layer. Further, the electrophotographic roller 1A preferably has an elastic layer 4.
The layer structure of the electrophotographic roller 1A is not limited to the resin layer 3 existing on the outermost surface layer of the electrophotographic roller 1A. Specific examples of the electrophotographic roller 1A include those having a surface layer on the substrate 2 and the conductive resin layer 3 provided on the outer periphery thereof, and those having the resin layer 3 as an intermediate layer 5. ..

Further, as another example of the electrophotographic member, a blade-shaped electrophotographic member (electrophotograph blade) can be mentioned. 2 (a) and 2 (b) are schematic cross-sectional views of the electrophotographic blade 1B. The electrophotographic blade 1B shown in FIG. 2A is composed of a conductive substrate 2 and a conductive resin layer 3 provided on the outer periphery thereof. In the electrophotographic blade 1B shown in FIG. 2B, an elastic layer 4 is further provided between the substrate 2 and the resin layer 3.

The electrophotographic member can be used for a developing roller, a charging member, a toner supply roller, a developing blade, and a cleaning blade. In particular, it can be suitably used as a developing roller, a developing blade, and a toner supply roller. Hereinafter, the configuration of the electrophotographic member according to the embodiment of the present invention will be described in detail.

<Hpokeimenon>
The substrate 2 functions as a support member for the electrophotographic member and, in some cases, as an electrode. The substrate 2 is made of a metal or alloy such as aluminum, copper alloy, stainless steel; iron plated with chromium or nickel; a conductive material such as a conductive synthetic resin. When the electrophotographic member has a roller shape, the base 2 has a solid cylindrical shape or a hollow cylindrical shape, and when the electrophotographic member has a blade shape, the base 2 has a thin plate shape.

<Elastic layer>
The elastic layer 4 forms a nip having a predetermined width at the contact portion between the electrophotographic roller 1A and the photoconductor, particularly when the electrophotographic member has a roller shape (electrophotograph roller 1A). The elastic required for the electrophotographic roller 1A is provided. The elastic layer 4 is preferably a molded product made of a rubber material. Examples of the rubber material include the following. Ethylene-propylene-diene copolymer rubber, acrylic nitrile-butadiene rubber, chloroprene rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, fluororubber, silicone rubber, epichlorohydrin rubber, urethane rubber. These can be used alone or in admixture of two or more. Among these, silicone rubber is preferable from the viewpoint of compression set and flexibility. Examples of the silicone rubber include a cured product of an addition-curable silicone rubber.

Examples of the molding method of the elastic layer 4 include a method of molding a liquid rubber material and a method of extruding a kneaded rubber material. The thickness of the elastic layer is preferably 0.3 mm or more and 4.0 mm or less.

A conductivity-imparting agent is appropriately added to the elastic layer 4 in order to impart conductivity. As the conductivity-imparting agent, fine particles of conductive metal oxide such as carbon black; aluminum and copper; and conductive metal oxide such as tin oxide and titanium oxide can be used. Among these, carbon black is preferable because it can be obtained relatively easily and good conductivity can be obtained. When carbon black is used as the conductivity-imparting agent, it is preferable to add 2 to 50 parts by mass of carbon black to 100 parts by mass of rubber.

Various additives such as a non-conductive filler, a cross-linking agent, and a catalyst may be appropriately blended in the elastic layer 4. Non-conductive fillers include silica, quartz powder, titanium oxide, or calcium carbonate. Examples of the cross-linking agent include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane or dicumyl peroxide. Examples of the catalyst include a platinum catalyst.

<Resin layer>
Hereinafter, the configuration of the resin layer 3 according to the embodiment of the present invention will be described in detail. The resin layer according to one embodiment of the present invention is selected from at least one structure selected from the group consisting of the structural formulas (1) and (2) and the group consisting of the structural formulas (3) to (6). Includes a resin having at least one structure and an anion.

Among the resins according to the present invention, the structure represented by the structural formula (1) represents, for example, a structure derived from fluoroethylene, a vinyl compound having a fluoroalkyl group, or a (meth) acrylate having a fluoroalkyl group. The structure represented by the structural formula (2) represents, for example, a structure derived from a (meth) acrylate having a silicone group. In addition, "(meth) acrylate" means methacrylate or acrylate (hereinafter, the same applies).

Similarly, at least one structure selected from the group consisting of structural formulas (3) to (6) includes, for example, an ionic compound having at least one hydroxyl group, amino group, and glycidyl group in the cation structure, polyisocyanate, and the like. It is obtained by reacting with melamine or the like. In the structural formulas (3) to (6), the structural formula (Z101) is a residue formed by reacting, for example, a hydroxyl group introduced into a cation with an isocyanate group contained in a matrix resin. The structural formula (Z102) is, for example, a residue formed by reacting an amino group introduced into a cation with an isocyanate group contained in a matrix resin. The structural formula (Z103) is, for example, a residue formed by reacting a glycidyl group introduced into a cation with a hydroxyl group of a matrix resin.

The present inventors discuss the reason why having the resin layer containing the resin and the anion according to the present invention has an unexpected effect of suppressing an increase in the resistance value in a low temperature range near 0 ° C. I guess as follows.
In general, in a resin to which an ionic conductive agent is added, the ratio of ionic compounds dissociating into cations and anions (ionization rate) decreases in a low temperature range. That is, in the low temperature region, the cation and the anion tend to form an ionic bond "salt", so that the conductivity tends to decrease. Therefore, in order to suppress the decrease in conductivity in the low temperature range, it is necessary to stabilize the state in which the ionic compound is dissociated into cations and anions.
In the present invention, the resin is represented by structural formulas (Z101) to (Z103) derived from residues (reaction residues) in which a hydroxyl group, an amino group or a glycidyl group reacts with an isocyanate group in the vicinity of a cation site. It is characterized by having at least one structure. When this reaction residue is present in the vicinity of the cation site, the positive charge of the cation is stabilized by the interaction between the cation and the reaction residue by hydrogen bonding, which contributes to the improvement of the ionization rate in the low temperature range. Conceivable.

Further, the structures represented by the structural formulas (1) and (2) existing in the resin are relatively hydrophobic sites because they contain a fluorine atom and a silicone component, respectively. On the other hand, the cation structures represented by the structural formulas (3) to (6) are hydrophilic sites. Therefore, it is considered that the hydrophilic parts and the hydrophobic parts are likely to be densely packed in the resin. As a result, the cation structures in the structural formulas (3) to (6) are densely packed, and the reaction residue of another cation structure existing around the cation structure in the same dense region also has a cation stabilizing action. It is considered to receive. It is considered that the two cation stabilizing actions described above maintain a high ionization rate even in a low temperature range and suppress an increase in resistance value.

The structures represented by the structural formulas (1) and (2) and the cation structures represented by the structural formulas (3) to (6) will be described in detail below.

In the structural formula (1), R1 represents a hydrogen atom, a fluorine atom or a methyl group. X1 represents any structure or fluorine atom selected from (X101) or (X102).
In formulas (X101) and (X102), Y1 represents a fluoroalkyl group having 1 to 6 carbon atoms.

Examples of the structure represented by the structural formula (1) include structures derived from polyfluoroethylene, fluoroalkyl (meth) acrylate, and fluoroalkyl vinyl compounds.
Specific examples of the polyfluoroethylene include 1-fluoroethylene and 1,1-difluoroethylene. Along with the structure represented by the structural formula (1), 1,1,2-trifluoroethylene, 1,1,2,2-tetrafluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, α, β, β-trifluoro It can also have a structure in which styrene is copolymerized.

Specific examples of the fluoroalkyl (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoroethyl (meth) acrylate, 2-. (Perfluoroethyl) Ethyl (Meta) Acrylate, 2- (Perfluorobutyl) Ethyl (Meta) Acrylate, 2- (Perfluorohexyl) Ethyl (Meta) Acrylate, 1H, 1H, 3H-Tetrafluoropropyl (Meta) Acrylate , 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoro (meth) acrylate, 1H-1- (trifluoromethyl) ) Trifluoroethyl (meth) acrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl (meth) acrylate can be mentioned.

Specific examples of the fluoroalkyl vinyl compound include trifluoromethylethylene, perfluoroethylethylene, 4,4,4-trifluoro-1-butene, perfluorobutylethylene, perfluorohexylethylene, 3-(. Perfluorobutyl) -1-propene and 3- (perfluorohexyl) -1-propene can be mentioned.

It is also possible to use a commercially available polyol material having the structure represented by the structural formula (1). Commercially available products (all trade names) include, for example, Cefral Coat (registered trademark) PX-40, A202B, A606X, CF803 (all manufactured by Central Glass Co., Ltd.); Lumiflon (registered trademark) LF-100, LF-200, LF. -302, LF-400, LF-554, LF-600, LF-986N (manufactured by Asahi Glass Co., Ltd.); Zaflon FC-110, FC-220, FC-250, FC-275, FC-310, FC-575, XFC -973 (all manufactured by Toagosei Co., Ltd.); Zeffle (registered trademark) GK-510 (manufactured by Daikin Industries, Ltd.); Fluonate series (manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like.

In the structural formula (2), R2 represents a hydrogen atom or a methyl group. X2 represents either structure selected from formula (X201) or (X202).
In formulas (X201) and (X202), R3 to R5 each independently represent a hydrocarbon chain having 1 or more and 4 or less carbon atoms. Y2 represents a straight or branched silicone group.

Examples of the structure represented by the structural formula (2) include a structure derived from (meth) acrylate having a silicone group. Examples of the (meth) acrylate having a silicone group include polymerizable compounds having a siloxane bond in the side chain, and various commercially available products can be used. Specifically, as the one-terminal modified dimethylpolysiloxane, the following commercially available products (both are trade names) can be used. Silaplane (registered trademark) FM-0711, Silaplane FM-0725 (above, manufactured by JNC Corporation), and X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.). Further, X-22-2426 and X-22-174ASX (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used. The polymerizable compound having these siloxane bonds in the side chain can be used alone or in combination of two or more.

It is more preferable that the resin layer according to the present invention contains both the structure represented by the structural formula (1) and the structure represented by the structural formula (2). The structure represented by the structural formula (1) having a relatively high hydrophobicity has a higher effect of condensing the above-mentioned cation structure. Further, it is considered that the inclusion of the structure represented by the structural formula (2), which tends to reduce the crystallinity of the resin in the low temperature range, suppresses the decrease in the mobility of the anion, and a higher effect can be obtained.

The number average molecular weight of the portion having the structural unit represented by the structural formula (1) or (2) shall be 2000 or more and 70,000 or less from the viewpoint of both the effect of suppressing the increase in the resistance value at the time of energization and the compatibility. Is preferable. When having both the structures represented by the structural formulas (1) and (2), it is preferable that the total number average molecular weight of the portions having the respective structural units is 2000 or more and 70,000 or less. When the number average molecular weight is 2000 or more, the resistance fluctuation during energization is suppressed, and when it is 70,000 or less, the compatibility with the binder resin is excellent.

(Cation structure)
The resin according to this embodiment has at least one cation structure selected from the group consisting of structural formulas (3) to (6) in the molecule. These structures can be obtained, for example, by reacting a polyisocyanate with an ionic compound having at least one hydroxyl group, amino group, or glycidyl group in the cation structure.

In structural formulas (3) to (6), at least one of Z1 to Z3, at least one of Z4 to Z7, at least one of Z8 to Z10, and at least one of Z11 to Z13. Each independently represents any structure selected from the group consisting of the following structural formulas (Z101) to (Z103).

In the structural formulas (Z101) to (Z103), R11, R12 and R13 each independently represent a hydrocarbon chain having a straight chain or a branch. As the hydrocarbon chain, an alkylene group having 1 to 8 carbon atoms is preferable. The symbol "*" indicates a bond site with a nitrogen atom in the structural formula (3) or a bond site with a nitrogen atom or a carbon atom constituting the nitrogen-containing heterocycle in the structural formulas (4) to (6). Representing, the symbol "**" represents a bonding site with a carbon atom in a polymer chain constituting the resin.

The structural formula (Z101) is, for example, a residue formed by reacting a hydroxyl group introduced into a cation with an isocyanate group contained in a matrix resin.
The structural formula (Z102) is, for example, a residue formed by reacting an amino group introduced into a cation with an isocyanate group contained in a matrix resin.
The structural formula (Z103) is, for example, a residue formed by reacting a glycidyl group introduced into a cation with a hydroxyl group of a matrix resin.

In the structural formula (3), R6 represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. As the hydrocarbon group, an alkyl group is preferable. At least one of Z1 to Z3 represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the other represents a hydrocarbon group having 1 or more and 4 or less carbon atoms. .. As the hydrocarbon group, an alkyl group is preferable. The structural formula (3) specifically represents an ammonium cation having a bonding portion with a resin.

The structure represented by the structural formula (3) can be obtained, for example, by reacting an ionic compound having at least one hydroxyl group, amino group or glycidyl group with isocyanate.

Specific examples of the cation having a hydroxyl group that gives the structure represented by the structural formula (3) include, for example.
2-Hydroxyethyltrimethylammonium cation, 2-hydroxyethyltriethylammonium cation, 4-hydroxybutyltrimethylammonium cation, 4-hydroxybutyl-tri-n-butylammonium cation, 8-hydroxyoctyltrimethylammonium cation, 8-hydroxyoctyl- Tri-n-butylammonium cation;
Bis (hydroxymethyl) dimethylammonary cation, bis (2-hydroxyethyl) dimethylammonium cation, bis (3-hydroxypropyl) dimethylammonary cation, bis (4-hydroxybutyl) dimethylammonary cation, bis (8-hydrochioctyl) dimethyl Ammonium cations, bis (8-hydrochioctyl) -di-n-butylammonium cations;
Tris (hydroxymethyl) methylammonium cation, tris (2-hydroxyethyl) methylammonium cation, tris (3-hydroxypropyl) methylammonium cation, tris (4-hydroxybutyl) methylammonium cation, tris (8-hydroxyoctyl) methyl Ammonium cations; and derivatives thereof.

Examples of the ammonium cation having an amino group and a glycidyl group include cations having a structure in which the hydroxyl group in the cation is replaced with an amino group and a glycidyl group.

In the structural formula (4), R7 and R8 independently form the hydrocarbon chains required for the nitrogen-containing heterocycle in the structural formula (4) to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. Represent. At least one of Z4 to Z7 represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the other is a hydrogen atom or a hydrocarbon having 1 or more and 4 or less carbon atoms. Represents a group. As the hydrocarbon group, an alkyl group is preferable. At least one of Z4 and Z5 is preferably any structure selected from the group consisting of structural formulas (Z101) to (Z103). One of the two Ns contained in the nitrogen-containing heterocycle in the structural formula (4) is N ⁺ . The structural formula (4) specifically represents a heterocyclic cation having a bond with a resin and containing two nitrogen atoms in the ring structure.

Examples of the nitrogen-containing heterocycle in the structural formula (4) include imidazolium, imidazolidinium, imidazolinium; pyrazinium, pyrimidinium, piperazinium; [1,3] -diazepanium, and [1,4] -diazepanium. The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring, more preferably imidazolium.

As an example, a cation having an imidazolium ring structure and a hydroxyl group, which gives the structure represented by the structural formula (4), is listed below.
1-Methyl-3-hydroxymethylimidazolium cation, 1-methyl-3- (2-hydroxyethyl) imidazolium cation, 1-methyl-3- (3-hydroxypropyl) imidazolium cation, 1-methyl-3-3 (4-Hydroxybutyl) imidazolium cation, 1-methyl-3- (6-hydroxyhexyl) imidazolium cation, 1-methyl-3- (8-hydroxyoctyl) imidazolium cation, 1-ethyl-3- (2) -Hydroxyethyl) imidazolium cation, 1-n-butyl-3- (2-hydroxyethyl) imidazolium cation, 1,3-dimethyl-2- (2-hydroxyethyl) imidazolium cation, 1,3-dimethyl- 2- (4-Hydroxybutyl) imidazolium cation, 1,3-dimethyl-4- (2-hydroxyethyl) imidazolium cation;
1,3-Bishydroxymethylimidazolium cation, 1,3-bis (2-hydroxyethyl) imidazolium cation, 2-methyl-1,3-bishydroxymethylimidazolium cation, 2-methyl-1,3-bis (2-Hydroxyethyl) imidazolium cation, 4-methyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 2-ethyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 4- Ethyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 2-n-butyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 4-n-butyl-1,3-bis ( 2-Hydroxyethyl) imidazolium cation, 1,3-bis (3-hydroxypropyl) imidazolium cation, 1,3-bis (4-hydroxybutyl) imidazolium cation, 1,3-bis (6-hydroxyhexyl) Imidazolium cation, 1,3-bis (8-hydroxyoctyl) imidazolium cation, 1-methyl-2,3-bis (2-hydroxyethyl) imidazolium cation, 1-methyl-3,4-bis (2-) Hydroxyethyl) imidazolium cation, 1-methyl-3,5-bis (2-hydroxyethyl) imidazolium cation;
1,2,3-Trishydroxymethylimidazolium cation, 1,2,3-tris (2-hydroxyethyl) imidazolium cation, 1,2,3-tris (3-hydroxypropyl) imidazolium cation, 1,2 , 3-Tris (4-Hydroxybutyl) imidazolium cation, 1,2,3-Tris (6-hydroxyhexyl) imidazolium cation, 1,2,3-Tris (8-hydroxyoctyl) imidazolium cation, 1, 3,4-Tris (2-hydroxyethyl) imidazolium cation, 1,3,4-tris (3-hydroxypropyl) imidazolium cation, 1,3,4-tris (4-hydroxybutyl) imidazolium cation, 1, , 3,4-Tris (6-hydroxyhexyl) imidazolium cation, 1,3,4-tris (8-hydroxyoctyl) imidazolium cation; and derivatives thereof.

Examples of the cation having an amino group and a glycidyl group include cations having a structure in which the hydroxyl group in the above cation is replaced with an amino group and a glycidyl group.

Among the cation structures represented by the structural formulas (3) to (6), when the resin having the cation structure represented by the structural formula (4) is contained, the ionization rate is high even in a low temperature range due to the chemical structure of the cation. Therefore, the resistance value does not easily increase even in a low temperature environment such as 0 ° C., which is preferable.

In the structural formulas (5) and (6), R9 and R10 independently form a 5-membered ring, a 6-membered ring or a 7-membered ring by the nitrogen-containing heterocycle in the structural formula (5) or (6), respectively. Represents the hydrocarbon chain required for this. At least one of Z8 to Z10 and at least one of Z11 to Z13 represent any structure selected from the group consisting of structural formulas (Z101) to (Z103), otherwise hydrogen. Represents an atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. As the hydrocarbon group, an alkyl group is preferable. In the structural formula (5), at least one of Z8 and Z9 is preferably any structure selected from the group consisting of the structural formulas (Z101) to (Z103). Further, in the structural formula (6), Z11 is preferably any structure selected from the group consisting of the structural formulas (Z101) to (Z103). The structural formulas (5) and (6) specifically represent a heterocyclic cation having a bond with a resin and containing one nitrogen atom in the ring structure.

Examples of the nitrogen-containing heterocycle in the structural formula (5) include pyrrolidinium, pyrrolium, pyrrolinium; piperidinium; and azepanium. The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring, and more preferably pyrrolidinium.
The nitrogen-containing heterocycle in the structural formula (6) is preferably a 5-membered ring or a 6-membered ring, and more preferably pyridinium.

As an example, cations having a pyrrolidinium ring structure and having a hydroxyl group, which give the structure represented by the structural formula (5), are listed below.
1-Methyl-1,2-bis (2-hydroxyethyl) pyrrolidinium cation, 1-ethyl-1,2-bis (2-hydroxyethyl) pyrrolidinium cation, 1-butyl-1,2-bis ( 2-Hydroxyethyl) pyrrolidinium cation, 1-methyl-1,2-bis (4-hydroxybutyl) pyrrolidinium cation; and derivatives thereof.

As an example, cations having a pyridinium ring structure and having a hydroxyl group, which give the structure represented by the structural formula (6), are listed below.
1-Hydroxymethylpyridinium cation, 1- (2-hydroxyethyl) pyridinium cation, 1- (3-hydroxypropyl) pyridinium cation, 1- (4-hydroxybutyl) pyridinium cation, 1- (6-hydroxyhexyl) pyridinium cation , 1- (8-Hydroxyoctyl) pyridinium cation, 2-methyl-1- (2-hydroxyethyl) pyridinium cation, 3-methyl-1- (2-hydroxyethyl) pyridinium cation, 4-methyl-1- (2) -Hydroxyethyl) pyridinium cation, 3-ethyl-1- (2-hydroxyethyl) pyridinium cation, 3-n-butyl-1- (2-hydroxyethyl) pyridinium cation, 1-methyl-2-hydroxymethylpyridinium cation, 1-Methyl-3-hydroxymethylpyridinium cation, 1-methyl-4-hydroxymethylpyridinium cation, 1-methyl-2- (2-hydroxyethyl) pyridinium cation, 1-methyl-3- (2-hydroxyethyl) pyridinium Cation, 1-methyl-4- (2-hydroxyethyl) pyridinium cation, 1-ethyl-3- (2-hydroxyethyl) pyridinium cation, 1-n-butyl-3- (2-hydroxyethyl) pyridinium cation, 2 -Methyl-4-n-Butyl-1- (2-hydroxyethyl) pyridinium cation;
1,2-Bishydroxymethylpyridinium cation, 1,3-bishydroxymethylpyridinium cation, 1,4-bishydroxymethylpyridinium cation, 1,2-bis (2-hydroxyethyl) pyridinium cation, 1,3-bis ( 2-Hydroxyethyl) pyridinium cation, 1,4-bis (2-hydroxyethyl) pyridinium cation, 1,2-bis (3-hydroxypropyl) pyridinium cation, 1,3-bis (3-hydroxypropyl) pyridinium cation, 1,4-bis (3-hydroxypropyl) pyridinium cation, 1,2-bis (4-hydroxybutyl) pyridinium cation, 1,3-bis (4-hydroxybutyl) pyridinium cation, 1,4-bis (4-hydroxybutyl) pyridinium cation Hydroxybutyl) pyridinium cation, 1,2-bis (6-hydroxyhexyl) pyridinium cation, 1,3-bis (6-hydroxyhexyl) pyridinium cation, 1,4-bis (6-hydroxyhexyl) pyridinium cation, 1, 2-Bis (8-Hydroxyoctyl) pyridinium cation, 1,3-bis (8-hydroxyoctyl) pyridinium cation, 1,4-bis (8-hydroxyoctyl) pyridinium cation, 2-methyl-1,3-bis (2-methyl-1,3-bis) 2-Hydroxyethyl) pyridinium cation, 2-ethyl-1,3-bis (2-hydroxyethyl) pyridinium cation, 5-methyl-1,3-bis (2-hydroxyethyl) pyridinium cation, 5-ethyl-1,5, 3-Bis (2-hydroxyethyl) pyridinium cation;
1,2,4-Tris hydroxymethylpyridinium cation, 1,2,4-tris (2-hydroxyethyl) pyridinium cation, 1,2,4-tris (3-hydroxypropyl) pyridinium cation, 1,2,4- Tris (4-hydroxybutyl) pyridinium cation, 1,2,4-tris (6-hydroxyhexyl) pyridinium cation, 1,2,4-tris (8-hydroxyoctyl) pyridinium cation, 1,3,5-trishydroxy Methylpyridinium cation, 1,3,5-tris (2-hydroxyethyl) pyridinium cation, 1,3,5-tris (3-hydroxypropyl) pyridinium cation, 1,3,5-tris (4-hydroxybutyl) pyridinium Cations, 1,3,5-tris (6-hydroxyhexyl) pyridinium cations, 1,3,5-tris (8-hydroxyoctyl) pyridinium cations; and derivatives thereof.

Examples of the cation having an amino group and a glycidyl group include cations having a structure in which the hydroxyl group in the above cation is replaced with an amino group and a glycidyl group.

(Anion)
The resin layer according to the present invention has at least one structure selected from the group consisting of structural formulas (1) and (2) and at least one cation selected from the group consisting of structural formulas (3) to (6). It is characterized by containing an anion as well as a structure.
Examples of anions include fluoroalkylsulfonylimide anion, fluorosulfonylimide anion, fluoroalkylsulfonate anion, fluorosulfonate anion, fluoroalkylcarboxylic acid anion, fluoroalkylmethide anion, fluoroborate anion, fluorophosphate anion, disianamide anion, and thiocyanate. Included are anions, bisoxalatoborate anions, perchlorate anions, and derivatives thereof.

Specific examples of the fluoroalkylsulfonylimide anion include bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonylimide anion, bis (heptafluoropropanesulfonyl) imide anion, and bis (nonafluorobutanesulfonyl) imide anion. , Bis (dodecafluoropentane sulfonyl) imide anion, bis (perfluorohexanesulfonyl) imide anion, fluoroalkylsulfonylimide anion having 1 or more and 6 or less carbon atoms, and N, N-hexafluoropropane. Cyclic fluoroalkylsulfonylimide anions such as -1,3-disulfonylimide can be mentioned.
Specific examples of the fluorosulfonylimide anion include a bis (fluorosulfonyl) imide anion.

Specific examples of the fluoroalkyl sulfonate anion include trifluoromethanesulfonic acid anion, fluoromethanesulfonic acid anion, perfluoroethanesulfonic acid anion, perfluoropropanesulfonic acid anion, perfluorobutanesulfonic acid anion, and perfluoropentanesulfonic acid. Examples thereof include anions, perfluorohexane sulfonic acid anions, and perfluorooctane sulfonic acid anions.
Specific examples of the fluoroalkylcarboxylic acid anion include trifluoroacetic acid anion, perfluoropropionic acid anion, perfluorobutyrate anion, perfluorovalerate anion, and perfluorocaproate anion.

Specific examples of the fluoroalkylmethide anion include tris (trifluoromethanesulfonyl) methide anion, tris (perfluoroethanesulfonyl) methide anion, tris (perfluoropropanesulfonyl) methide anion, tris (perfluorobutanesulfonyl) methide anion, and tris (perfluorobutanesulfonyl) methide anion. Examples thereof include fluoroalkylsulfonylmethideanions such as perfluoropentanesulfonyl) methideanion, tris (perfluorohexanesulfonyl) methideanion, and tris (perfluorooctanesulfonyl) methideanion.

Specific examples of the fluoroborate anion include tetrafluoroborate anion.
Specific examples of the fluorophosphate anion include hexafluorophosphate anion.

Among these anions, fluoroalkylsulfonylimide anions, fluorosulfonylimide anions, fluoroboric acid anions, disyanamide anions, and isothiocyanate anions are particularly preferable because they have less decrease in conductivity in a low temperature environment.

(Matrix resin)
In the present invention, the resin layer preferably contains a resin having a structure represented by the structural formulas (1) and (2) and a structure other than the structures represented by the structural formulas (3) to (6) as the matrix resin.

Examples of the resin contained as the matrix resin include polyurethane resin, polyester resin, polyether resin, acrylic resin, epoxy resin, and amino resin such as melamine. From the viewpoint of film strength and toner chargeability, polyurethane resin and melamine crosslinked resin are preferable. Among them, a thermosetting polyether polyurethane resin and a thermosetting polyester polyurethane resin are preferably used because they have flexibility. These thermosetting polyurethane resins are obtained by reacting a known polyol component such as a polyether polyol or a polyester polyol with an isocyanate compound.

Examples of the polyol component include polyether polyols, polyester polyols or polycarbonate polyols, polyolefin polyols, and acrylic polyols. Among these, a polyether polyol, a polyester polyol or a polycarbonate polyol, and a urethane prepolymer polyol obtained by reacting these with an isocyanate are preferable from the viewpoint of self-membrane reinforcing property and compatibility with an ionic compound.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Further, examples of the polyester polyol include the following. Diol components such as 1,4-butanediol, 3-methyl-1,4-pentanediol, neopentyl glycol, or triol components such as trimethylolpropane, and adipic acid, phthalic anhydride, terephthalic acid, hexahydroxyphthalic acid. A polyester polyol obtained by a condensation reaction with a dicarboxylic acid such as.

Further, examples of the polycarbonate polyol include the following. With diol components such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, A polycarbonate polyol obtained by a condensation reaction with a dialkyl carbonate such as phosgen or dimethyl carbonate, or a cyclic calcarbonate such as ethylene carbonate.

When a polyurethane resin is used, a matrix resin is used when a polyol having a branched ether structure represented by the following structural formulas (7) to (10) and a branched ester structure represented by the structural formula (11) is used. It is particularly preferable because the crystallinity of the resin is lowered and the resistance value in a low temperature environment such as 0 ° C. is further lowered. That is, the matrix resin preferably contains a reaction product of a polyol having any structure selected from the group consisting of the following structural formulas (7) to (11) and an isocyanate compound.

The structures represented by the structural formulas (7) and (8) can be obtained, for example, by using a polyether polyol obtained by ring-opening polymerization of 3-methyltetrahydrofuran.
The structures represented by the structural formulas (9) and (10) can be obtained, for example, by using a polyether polyol obtained by ring-opening polymerization of propylene oxide.
The structure represented by the structural formula (11) can be obtained, for example, by using a polyester polyol obtained by a condensation reaction of 3-methyl-1,5-pentanediol with a dicarboxylic acid such as adipic acid. Alternatively, it can also be obtained by using 3-methyl-1,5-pentanediol and a dialkyl carbonate such as phosgene or dimethyl carbonate.

If necessary, these polyol components can also be used as a prepolymer in which the chain is extended with an isocyanate compound such as 2,4-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), or isophorone diisocyanate (IPDI). Good.

The isocyanate compound is not particularly limited, but is an aliphatic polyisocyanate such as ethylene diisocyanate and 1,6-hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI), cyclohexane 1,3-diisocyanate, cyclohexane 1, Alicyclic polyisocyanates such as 4-diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polyether diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene Aromatic isocyanates such as diisocyanates; and copolymers thereof, isocyanurates, TMP adducts, biurets, and blocks thereof can be used. Among these, aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polyether diphenylmethane diisocyanate are preferable.

The polyol component and the isocyanate compound are mixed so that the ratio (molar ratio) of the isocyanate groups in the isocyanate compound to 1.0 hydroxyl group in the polyol component is in the range of 1.0 or more and 2.0 or less. Is preferable. When the mixing ratio is within the above range, it is possible to suppress the residual unreacted components.

(Preparation of paint for forming resin layer)
When a urethane resin is used as the matrix resin, for example, the following materials are mixed and reacted to obtain the resin layer forming coating material of the present invention.
1. 1. As a material for forming matrix resin
・ Polyether polyol, polyester polyol, etc. ・ Polyisocyanate 2. 2. A polyol having a structure represented by the structural formula (1) and / or the structural formula (2). An ionic compound containing at least one selected from a hydroxyl group, an amino group, and a glycidyl group in the cation structure. The state after these reactions is known by, for example, thermal decomposition GC / MS, FT-IR, NMR, etc. It can be confirmed by analysis by means.

The content of the polyol having the structure represented by the structural formula (1) and / or the structural formula (2) in the resin layer shall be 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the matrix resin. Is preferable.
The content of the structure represented by at least one selected from the group consisting of the formulas (3) to (6) in the resin layer is 100 parts by mass of the matrix resin from the viewpoint of conductivity and suppression of resistance fluctuation due to energization. On the other hand, it is preferably 1 part by mass or more and 10 parts by mass or less.

(Method of forming resin layer)
The method for forming the resin layer is not particularly limited, and examples thereof include spray coating, immersion coating, and roll coating. Among these, the dipping coating method in which the paint overflows from the upper end of the dipping tank as described in Japanese Patent Application Laid-Open No. 57-5047 is simple and excellent in production stability as a method for forming a resin layer. Therefore, it is preferably used.
The thickness of the resin layer is preferably 1.0 μm or more and 20.0 μm or less.

(Other components in the resin layer)
The resin layer may contain a non-conductive filler such as silica, quartz powder, titanium oxide, zinc oxide and calcium carbonate, if desired. By adding these non-conductive fillers to the resin layer forming paint, they exhibit a function as a film forming aid when the paint is coated in the resin layer forming step. The content of the non-conductive filler is preferably 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin forming the resin layer.
Further, if necessary, the resin layer may contain a conductive filler as long as it does not interfere with the effects of the present invention. As the conductive filler, fine particles of carbon black; conductive metal such as aluminum and copper; and fine particles of conductive metal oxide such as zinc oxide, tin oxide and titanium oxide can be used. Among these, carbon black is particularly preferably used because it is relatively easily available and has high conductivity-imparting property and reinforcing property.
When the resin layer is the outermost layer and a certain surface roughness is required as the electrophotographic member, fine particles for roughness control (roughness control fine particles) may be added to the resin layer. As the roughness control fine particles, fine particles of polyurethane resin, polyester resin, polyether resin, polyamide resin, acrylic resin, or phenol resin can be used. The volume average particle diameter of the roughness control fine particles is preferably 1 μm or more and 15 μm or less. The content of the roughness control particles in the resin layer is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin forming the resin layer.

(2) Electrophotographic apparatus The electrophotographic member according to the present invention can be suitably used as a developing roller, a charging roller, a toner supply roller, a developing blade, and a cleaning blade in an electrophotographic apparatus. The electrophotographic member can be applied to any of a non-contact developing device and a contact developing device using a magnetic one-component toner and a non-magnetic one-component toner, and a developing device using a two-component toner. it can.

FIG. 3 is a schematic cross-sectional view showing an example of an electrophotographic apparatus in which the electrophotographic member according to the present invention is mounted as a developing roller of a contact-type developing apparatus using a one-component toner. The developing apparatus 22 regulates the thickness of the toner container 20 containing the toner 15 as one component toner, the developing roller 16, the toner supply roller 19 for supplying the toner to the developing roller 16, and the toner layer on the developing roller 16. Includes a developing blade 21 to be processed. The developing roller 16 is located in an opening extending in the longitudinal direction in the toner container 20 and is placed in contact with the photoconductor 18. The photoconductor 18, the cleaning blade 26, the waste toner container 25, and the charging roller 24 may be arranged in the main body of the electrophotographic apparatus. The developing device 22 is prepared for each color toner of black (Bk), cyan (C), magenta (M), and yellow (Y), and enables color printing.

The printing operation of the electrophotographic apparatus will be described below. The photoconductor 18 rotates in the direction of the arrow and is uniformly charged by the charging roller 24 for charging the photoconductor 18. Next, an electrostatic latent image is formed on the surface of the photoconductor 18 by the laser light 23 which is an exposure means. The electrostatic latent image is visualized as a toner image (development) by applying the toner 15 from the developing rollers 16 which are arranged in contact with the photoconductor 18 by the developing device 22. Development is so-called reverse development in which a toner image is formed on an exposed portion. The toner image formed on the photoconductor 18 is transferred to the paper 34, which is a recording medium, by the transfer roller 29, which is a transfer member. The paper 34 is fed into the apparatus via the paper feed roller 35 and the suction roller 36, and is conveyed between the photoconductor 18 and the transfer roller 29 by the endless belt-shaped transfer transfer belt 32. The transfer transfer belt 32 is operated by a driven roller 33, a drive roller 28, and a tension roller 31. A voltage is applied to the developing roller 16, the developing blade 21, and the suction roller 36 from the bias power supply 30. The paper 34 on which the toner image is transferred is fixed by the fixing device 27, discharged to the outside of the device, and the printing operation is completed. On the other hand, the transfer residual toner that remains on the photoconductor 18 without being transferred is scraped off by the cleaning blade 26, which is a cleaning member for cleaning the surface of the photoconductor, and is stored in the waste toner storage container 25. The cleaned photoconductor 18 repeats the above printing operation.

(3) Process Cartridge The electrophotographic member according to the present invention can be suitably used as a developing roller, a charging roller, a toner supply roller, a developing blade, and a cleaning blade in a process cartridge. FIG. 4 is a schematic cross-sectional view of an example of a process cartridge according to an aspect of the present invention. In FIG. 4, the electrophotographic member is mounted as a developing roller 16. The process cartridge 17 is configured to be removable from the main body of the electrophotographic apparatus. The process cartridge 17 is a combination of a developing device 22 including a developing roller 16 and a developing blade 21, an electrophotographic photosensitive member 18, a cleaning blade 26, a waste toner storage container 25, and a charging roller 24. The developing device 22 further includes a toner container 20, and the toner container 20 is filled with the toner 15. The toner 15 in the toner container 20 is supplied to the surface of the developing roller 16 by the toner supply roller 19, and a layer of toner 15 having a predetermined thickness is formed on the surface of the developing roller 16 by the developing blade 21.

Specific examples and comparative examples according to the present invention are shown below. First, raw materials for resins having the structures represented by the structural formulas (1) and (2) were synthesized.

<Synthesis of resins having the structures represented by structural formulas (1) and (2)>
(Synthesis of resin L-1)
A reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device and a nitrogen gas introduction tube was charged with 42.9 parts by mass of dried methyl ethyl ketone, heated to a temperature of 87 ° C. under a nitrogen gas stream, and heated to reflux. Next, 2- (perfluorohexyl) ethyl methacrylate (trade name: CHEMINOX FAMAC-6, manufactured by Unimatec) 45.9 parts by mass, methacryl-modified silicone (trade name: X-22-174ASX, manufactured by Shinetsu Silicone) 47 .8 parts by mass, styrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 2.8 parts by mass, 2-hydroxyethyl methacrylate (trade name: Light Ester HO-250 (N), manufactured by Kyoeisha Chemical Co., Ltd.) 3.5 parts by mass, initiator (Product name: Kayaester O, manufactured by Kayaku Akzo Corporation) 0.2 parts by mass of the mixture was gradually added dropwise over 1 hour, the temperature was maintained at 87 ° C., and the mixture was heated and refluxed for another 3 hours. The mixture was allowed to cool to room temperature to obtain a fluorine / silicone-containing resin L-1.

(Synthesis of resins L-2 to L-5)
The same operations as in the synthesis of the resin L-1 were carried out except that the monomer species and the mixing ratio were changed as shown in Table 1, to obtain fluorine and / or silicone-containing resins L-2 to L-5. In the table, "part" represents "part by mass".

(Synthesis of resin L-6)
Methyl ethyl ketone 100 in a glass reactor equipped with a stirrer, thermometer, cooling tube and dry nitrogen gas inlet, with 100.0 g of soluble fluororesin (trade name: Lumiflon LF-200, manufactured by Asahi Glass Co., Ltd.) in a dry nitrogen atmosphere. It was dissolved in 0.0 g. Then, a solution prepared by dissolving 1.7 g of allyl isocyanate (manufactured by Sigma-AldRich) in 5 g of methyl ethyl ketone was gradually added dropwise while maintaining the temperature inside the reactor at 80 ° C. After completion of the dropping, the mixture was stirred at a temperature of 80 ° C. for 2 hours to react the hydroxyl group of "Lumiflon LF-200" in the side chain with the isocyanate group of allyl isocyanate. The resulting reaction mixture was cooled to room temperature. In this way, a radically polymerizable group-containing fluororesin K-1 was obtained.

Next, 0.5 g of trimethylsilanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a glass reactor equipped with a mechanical stirrer and a dropping funnel, and the mixture was stirred in an ice bath. Subsequently, 3.6 ml of a hexane solution of n-butyllithium (1.6 mol / L) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was stirred in an ice bath for 1 hour, and then a solution prepared by dissolving 24.66 g of hexamethylcyclotrisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 g of tetrahydrofuran was gradually added dropwise. After completion of the dropping, the ice bath was removed and the mixture was stirred for 6 hours, 1.0 g of chlorodimethylvinylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, and the mixture was further stirred for 12 hours. Then, a 10 mass% sodium hydrogen carbonate aqueous solution was added to the obtained reaction solution, and the aqueous layer was removed to obtain an organic layer. The organic layer was washed with pure water and then dehydrated with magnesium sulfate (manufactured by Umai Chemical Co., Ltd.) to remove volatile components under the conditions of 50 ° C./10 mmHg. In this way, a terminal vinyl-modified dimethylpolysiloxane resin K-2 having a vinyl group at one end of dimethylsiloxane was obtained.

Next, in a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, a radically polymerizable group-containing fluororesin K-1: 24.4 g, xylene 14.1 g, n-acetate Butyl 15.8 g, methyl methacrylate (manufactured by Mitsubishi Gas Chemicals) 2.4 g, n-butyl methacrylate (trade name: Light Ester NB, manufactured by Kyoei Kagaku Co., Ltd.) 2.8 g, 2-hydroxyethyl methacrylate (trade name: Light) Ester HO-250 (N), manufactured by Kyoeisha Chemical Co., Ltd.) 1.4 g, terminal vinyl-modified dimethylpolysiloxane resin K-2: 5.1 g, and radical polymerization initiator (trade name: Perbutyl O, manufactured by Nippon Oil & Fats Co., Ltd.) 0 .1 g was added and reacted at 90 ° C. for 5 hours under a nitrogen atmosphere. The obtained reaction mixture was cooled to room temperature to obtain 28.1 g of a siloxane-containing fluororesin L-6 having a structure in which dimethylsiloxane was grafted onto the fluororesin.

(Resin L-7)
Lumiflon LF-200 (trade name, manufactured by Asahi Glass Co., Ltd.) was used as the resin L-7.
Next, an ionic compound used as an ionic conductive agent was synthesized.

<Synthesis of ionic compounds>
(Synthesis of ionic compound IP-1)
Under a nitrogen atmosphere, 15.0 g of imidazole (manufactured by Nippon Synthetic Chemical Co., Ltd.) and 9.2 g of sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 60.0 g of tetrahydrofuran. 60.7 g of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise thereto over 30 minutes at room temperature, and the mixture was heated under reflux at 85 ° C. for 12 hours. Then, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure.
The obtained product was dissolved in 200 ml of pure water, and 69.6 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) was added as an anion raw material. The mixture was stirred at room temperature for 1 hour. 200 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 120 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound IP-1. The ionic compound IP-1 is a compound represented by the following formula.

(Synthesis of ionic compounds IP-2 to IP-5)
Ionic compounds IP-2 to IP-5 were obtained in the same manner as in the synthesis of ionic compound IP-1, except that the anionic raw material and the blending amount thereof were changed as shown in Table 2.

(Synthesis of ionic compound IP-6)
2- (2-Methyl-1H-imidazol-1-yl) ethanol (manufactured by Sigma-Aldrich) 15.0 g, sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry) 9.2 g, tetrahydrofuran 80.0 g Was dissolved in. 14.5 g of ethyl bromide (manufactured by Showa Kagaku Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise thereto over 30 minutes at room temperature, and the mixture was heated under reflux at 85 ° C. for 12 hours. Next, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure.
The obtained product was dissolved in 100 ml of pure water, 16.0 g of lithium trifluoroacetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as an anionic raw material, and the mixture was stirred at room temperature for 1 hour. 100 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 80 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound IP-6. The ionic compound IP-6 is a compound represented by the following formula.

(Synthesis of ionic compounds IP-7 and IP-8)
Ionic compounds IP-7 and IP-8 were obtained in the same manner as in the synthesis of ionic compound IP-6, except that the anionic raw material and the blending amount thereof were changed as shown in Table 3.

(Synthesis of ionic compound IP-9)
15.0 g of bis (2-hydroxyethyl) dimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 40.0 g of ion-exchanged water. Next, 27.9 g of anionic raw material: lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.) dissolved in 60 g of ion-exchanged water was added dropwise over 30 minutes. Then, the mixture was stirred at 30 ° C. for 2 hours. The reaction solution was then extracted twice with 100.0 g of ethyl acetate. Next, the ethyl acetate layer obtained by separating the liquids was washed three times with 60 g of ion-exchanged water. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain an ionic compound IP-9. The ionic compound IP-9 is a compound represented by the following formula.

(Synthesis of ionic compounds IP-10 and IP-11)
Ionic compounds IP-10 and IP-11 were obtained in the same manner as in the synthesis of the ionic compound IP-9, except that the anionic raw material and the blending amount thereof were changed as shown in Table 4.

(Synthesis of ionic compound IP-12)
30.0 g of a 50% aqueous solution of tris (2-hydroxyethyl) methylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50.0 g of ion-exchanged water. Next, 26.1 g of anionic raw material: lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.) dissolved in 30 g of ion-exchanged water was added dropwise over 30 minutes. Then, the mixture was stirred at 30 ° C. for 6 hours. The reaction solution was then extracted twice with 100.0 g of ethyl acetate. Next, the separated ethyl acetate layer was washed 3 times with 80 g of ion-exchanged water. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain ionic compound IP-12. The ionic compound IP-12 is a compound represented by the following formula.

(Synthesis of ionic compounds IP-13 and IP-14)
Ionic compounds IP-13 and IP-14 were obtained in the same manner as in the synthesis of the ionic compound IP-12, except that the anionic raw material and the blending amount thereof were changed as shown in Table 5.

(Synthesis of ionic compound IP-15)
4. Dissolve 15.0 g of 4-Pyridine-4-yl-butan-1-ol (manufactured by Sigma-Aldrich) in 45.0 g of acetonitrile and 4-bromo-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature. After dropping 7 g over 30 minutes, the mixture was heated under reflux at 90 ° C. for 12 hours. Next, the reaction solution was cooled to room temperature, and acetonitrile was distilled off under reduced pressure. The obtained concentrate was washed with 30.0 g of diethyl ether, and the supernatant was removed by separation. The washing and liquid separation operation were repeated 3 times to obtain a residue.
Further, the obtained residue was dissolved in 110.0 g of dichloromethane and then dissolved in 40.0 g of ion-exchanged water. Anion raw material: Lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115) , Mitsubishi Materials Denshi Kasei Co., Ltd.) 31.4 g was added dropwise over 30 minutes, and the mixture was stirred at 30 ° C. for 12 hours. The obtained solution was separated, and the organic layer was washed 3 times with 80.0 g of ion-exchanged water. Subsequently, dichloromethane was distilled off under reduced pressure to obtain ionic compound IP-15. The ionic compound IP-15 is a compound represented by the following formula.

(Synthesis of ionic compounds IP-16 and IP-17)
Ionic compounds IP-16 and IP-17 were obtained in the same manner as in the synthesis of the ionic compound IP-15, except that the anionic raw material and the blending amount thereof were changed as shown in Table 6.

(Synthesis of ionic compound IP-18)
15.0 g of 2- (2-hydroxyethyl) -1-methylpyrrolidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 13.5 g of sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 65.0 g of tetrahydrofuran. I let you. Next, the reaction system was placed in a nitrogen atmosphere and ice-cooled. Subsequently, 16.0 g of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40.0 g of tetrahydrofuran was added dropwise over 30 minutes. After heating and refluxing the reaction solution for 12 hours, 100 ml of water was added, and the solvent was distilled off under reduced pressure. 80 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure.
The obtained product was dissolved in 160 ml of pure water, and 36.7 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) was added as an anion raw material. The mixture was stirred at room temperature for 1 hour. 70 ml of chloroform was added to the reaction solution, 40 ml of a 5% by mass aqueous sodium carbonate solution was added, the mixture was stirred for 30 minutes and then separated, and the chloroform layer was washed 3 times with 50 g of ion-exchanged water. Next, chloroform was distilled off under reduced pressure to obtain ionic compound IP-18. The ionic compound IP-18 is a compound represented by the following formula.

(Synthesis of ionic compounds IP-19 and IP-20)
Ionic compounds IP-19 and IP-20 were obtained in the same manner as in the synthesis of the ionic compound IP-18, except that the anionic raw material and the blending amount thereof were changed as shown in Table 7.

(Synthesis of ionic compound IP-21)
15.0 g of diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 35.0 g of tetrahydrofuran. Next, the reaction system was placed in a nitrogen atmosphere and ice-cooled. Subsequently, 45.5 g of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise over 30 minutes. After heating and refluxing the reaction solution for 12 hours, 100 ml of water was added, and the solvent was distilled off under reduced pressure. 100 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure.
The obtained product is dissolved in 160 ml of pure water, and 46.0 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) is added as an anion raw material. , Stirred for 1 hour at room temperature. The reaction solution was then extracted twice with 100.0 g of ethyl acetate. Next, the separated ethyl acetate layer was washed 3 times with 60 g of ion-exchanged water. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain ionic compound IP-21. The ionic compound IP-21 is a compound represented by the following formula.

(Synthesis of ionic compound IP-22)
Ionic compound IP-22 was obtained in the same manner as in the synthesis of ionic compound IP-21, except that the anionic raw material and the blending amount thereof were changed as shown in Table 8.

(Synthesis of ionic compound IP-23)
As a cation raw material, 15.0 g of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50.0 g of dichloromethane, and 44.9 g of epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50.0 g of dichloromethane was 30 at room temperature. The mixture was added dropwise over a minute and heated under reflux for 6 hours. Next, the reaction solution was cooled to room temperature, 200 ml of a 5 mass% sodium carbonate aqueous solution was added, the mixture was stirred for 30 minutes and then separated, and the dichloromethane layer was washed twice with 120 g of ion-exchanged water. Next, dichloromethane was distilled off under reduced pressure to obtain a residue.
Further, the obtained residue was dissolved in 50.0 g of acetone and then dissolved in 150.0 g of ion-exchanged water. Anion raw material: Lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115) , Mitsubishi Materials Denshi Kasei Co., Ltd.) 69.6 g was added dropwise over 30 minutes, and the mixture was stirred at 30 ° C. for 2 hours. The obtained solution was separated, and the organic layer was washed 3 times with 50.0 g of ion-exchanged water. Subsequently, acetone was distilled off under reduced pressure to obtain an ionic compound IP-23. The ionic compound IP-23 is a compound represented by the following formula.

(Synthesis of ionic compound IP-24)
Ionic compound IP-24 was obtained in the same manner as in the synthesis of ionic compound IP-23, except that the anionic raw material and the blending amount thereof were changed as shown in Table 9.

Table 10 shows the cations and anions contained in the ionic compounds obtained above.

<Synthesis of isocyanate group-terminated prepolymer>
(Synthesis of isocyanate group-terminated prepolymer B-1)
PTG-L1000 (trade name, manufactured by Hodogaya Chemical Co., Ltd.) 100.0 to 84.1 parts by mass of polypeptide MDI (trade name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) in a reaction vessel under a nitrogen atmosphere. The parts by mass were gradually added dropwise while maintaining the temperature inside the reaction vessel at 65 ° C. After completion of the dropping, the reaction was carried out at a temperature of 65 ° C. for 2.5 hours, and 80.0 parts by mass of methyl ethyl ketone was added. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated urethane prepolymer B-1 having an isocyanate group content of 5.4% by mass.

<Making a developing roller>
[Example 1]
(Preparation of substrate)
A primer (trade name: DY39-012, manufactured by Toray Dow Corning Co., Ltd.) was applied to a core metal made of stainless steel (SUS304) having a diameter of 6 mm, and the core metal was baked and prepared as a substrate.

(Formation of elastic layer)
The substrate prepared above was placed in a mold, and an addition type silicone rubber composition mixed with the following materials was injected into a cavity formed in the mold.
-Liquid silicone rubber material (trade name: SE6905A / B, manufactured by Toray Dow Corning): 100.0 parts by mass-Carbon black (trade name: Talker Black # 4300, manufactured by Tokai Carbon Co., Ltd.): 15.0 parts by mass- Platinum catalyst: 0.1 parts by mass Subsequently, the mold was heated, and the silicone rubber was vulcanized and cured at a temperature of 150 ° C. for 15 minutes. After the substrate on which the cured silicone rubber layer was formed on the peripheral surface was removed from the mold, the core metal was further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. In this way, an elastic roller D-1 having a silicone rubber elastic layer having a diameter of 12 mm was produced on the outer periphery of the substrate 2.

(Formation of resin layer)
The following materials were mixed and stirred as the material of the resin layer.
-Polyether polyol (trade name: PTG-L1000, manufactured by Hodoya Chemical Industry Co., Ltd.): 100.0 parts by mass-Isocyanate (trade name: Millionate MR-400, manufactured by Toso Co., Ltd.): 45.7 parts by mass-Resin L- 1: 7.65 parts by mass ・ Ion compound IP-1: 7.28 parts by mass ・ Silica (trade name: AEROSIL (registered trademark) 200, manufactured by Nippon Aerosil Co., Ltd.): 30.6 parts by mass ・ Urethane resin fine particles (trade name) : Art Pearl C-400, manufactured by Negami Kogyo Co., Ltd.): 15.3 parts by mass Next, methyl ethyl ketone was added so that the total solid content ratio was 30% by mass, and then mixed by a sand mill. Then, the viscosity was further adjusted to 10 to 12 cps with methyl ethyl ketone to prepare a coating material for forming a resin layer.

The elastic roller D-1 produced earlier was immersed in the resin layer forming paint to form a coating film of the paint on the surface of the elastic layer of the elastic roller D-1 and dried. Further, by heat-treating at a temperature of 150 ° C. for 1 hour, a developing roller according to Example 1 having a resin layer having a film thickness of about 15 μm on the outer periphery of the elastic layer was produced.

[Examples 2 to 8]
The developing rollers according to Examples 2 to 8 were produced in the same manner as in Example 1 except that the types and blending amounts of the fluorine / silicone-containing resin and the ionic compound were changed as shown in Table 11.

[Example 9]
The following materials were mixed and stirred as the material of the resin layer.
-Polyester polyol (trade name: Claret polyol P-2010, manufactured by Claret): 70.0 parts by mass-Isocyanate group-terminated prepolymer B-1: 113.3 parts by mass-Resin L-3: 7.82 parts by mass- Ion compound IP-9: 7.07 parts by mass ・ Silica (trade name: AEROSIL200, manufactured by Nippon Aerozil): 31.3 parts by mass ・ Urethane resin fine particles (trade name: Artpearl C-400, manufactured by Negami Kogyo Co., Ltd.): After 20.6 parts by mass, the developing roller according to Example 9 was produced in the same manner as in Example 1.

[Examples 10 to 20]
The developing rollers according to Examples 10 to 20 were produced in the same manner as in Example 9 except that the types and blending amounts of the fluorine / silicone-containing resin and the ionic compound were changed as shown in Table 11.

[Example 21]
The following materials were mixed and stirred as the material of the resin layer.
-Polybutadiene polyol (trade name: Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd.): 110.0 parts by mass-Isocyanate (trade name: Millionate MR-400, manufactured by Toso Co., Ltd.): 23.9 parts by mass-Resin L-5 : 7.01 parts by mass ・ Ion compound IP-21: 6.31 parts by mass ・ Silica (trade name: AEROSIL200, manufactured by Nippon Aerosil Co., Ltd.): 28.1 parts by mass ・ Urethane resin fine particles (trade name: Artpearl C-400) (Manufactured by Negami Kogyo Co., Ltd.): From 15.9 parts by mass onward, the developing roller according to Example 21 was produced in the same manner as in Example 1.

[Examples 22 to 24]
The developing rollers according to Examples 22 to 24 were produced in the same manner as in Example 21 except that the types and blending amounts of the fluorine / silicone-containing resin and the ionic compound were changed as shown in Table 11.

[Comparative Examples 1 to 4]
The developing rollers according to Comparative Examples 1 to 4 were produced in the same manner as in Example 21 except that the types and blending amounts of the fluorine / silicone-containing resin and the ionic compound were changed as shown in Table 12. In Comparative Examples 3 and 4, the fluorine / silicone-containing resin was not added.

<Evaluation of developing roller>
The following evaluations were performed on the obtained developing rollers according to Examples 1 to 24 and Comparative Examples 1 to 4. The evaluation results are summarized in Table 13.

[Measurement of roller resistance]
After leaving the developing roller for 6 hours in an environment of 23 ° C. and 50% RH (hereinafter referred to as “N / N”) and in an environment of 0 ° C., measurement was performed in each environment.

(Measurement of resistance value)
FIG. 5 shows a schematic configuration diagram of a jig used in this measurement for evaluating the resistance value of the developing roller. As shown in FIG. 5 (a), a cylindrical metal 37 having a diameter of 30 mm is rotated while pushing both ends of the conductive substrate 2 via a conductive bearing 38 with a load of 4.9 N, respectively, and the developing roller 16 Was driven to rotate at a speed of 60 rpm. Next, as shown in FIG. 5 (b), a voltage of 50 V is applied by the high-voltage power supply 39, and a known resistance value (relative to the resistance value of the developing roller 16) is arranged between the cylindrical metal 37 and the ground. The potential difference between both ends of a resistor having a resistance value of two digits or more) was measured. A voltmeter 40 (trade name: 189 TRUE RMS MULTIMETER, manufactured by FLUKE) was used for measuring the potential difference. From the measured potential difference and the resistance value of the resistor, the current flowing through the cylindrical metal 37 via the developing roller 16 was calculated. Then, the resistance value of the developing roller 16 was obtained by dividing the applied voltage of 50 V by the obtained current. Here, in the measurement of the potential difference, sampling was performed for 3 seconds from 2 seconds after the voltage was applied, and a value calculated from the average value was used as the roller resistance value.

[Performance evaluation as a developing roller]
(Evaluation of ghosts in an environment with a temperature of 0 ° C)
The following evaluation was carried out using a developing roller whose resistance value was measured in an environment of 0 ° C.
The developing rollers obtained in each Example and Comparative Example were loaded as the developing rollers 16 into a process cartridge for a laser printer (trade name: LBP7700C, manufactured by Canon Inc.) having the configuration shown in FIG. Then, the process cartridge was incorporated into the laser printer, installed in an environment of 0 ° C., and then left for 2 hours.
Next, the ghost image was evaluated. That is, using black toner, a 15 mm square solid black image was printed at the tip of one image pattern, and then a halftone image was printed on the entire surface. Next, the density unevenness (ghost) of the toner carrier cycle appearing in the halftone portion was visually confirmed. The evaluation criteria for ghost evaluation are as follows.
A: No ghosts are found.
B: Very slight ghost is recognized.
C: Significant ghost is observed.

In the table, * 1 and * 2 represent the following compounds, respectively.
* 1: N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.)
* 2: 1-Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.)

Since the developing rollers according to Examples 1 to 24 contain a resin having a specific structure in the resin layer, the resistance value does not increase much in a low temperature environment such as 0 ° C., and the image quality is maintained good. Was there. In particular, in Examples 1 to 14 including both the structures represented by the structural formulas (1) and (2), the increase in the resistance value was suppressed at a higher level.
On the other hand, in the developing rollers according to Comparative Examples 1 to 4 containing no such structure, an increase in resistance value and generation of a ghost image were observed in a low temperature environment.

<Manufacturing of developing blade>
[Example 25]
As a substrate, a stainless steel sheet having a thickness of 0.08 mm (SUS304, manufactured by Nisshin Steel Co., Ltd.) is press-cut to a size of 200 mm in length and 23 mm in width, and a stainless steel sheet (hereinafter referred to as "SUS sheet"). I prepared. Next, as shown in FIG. 2, the cut SUS sheet was immersed in the resin layer forming paint prepared in Example 1 so that the length L from the longitudinal end was 1.5 mm. A coating film of the paint was formed and dried. Further, by heat-treating at a temperature of 140 ° C. for 1 hour, a developing blade according to Example 25 having a resin layer having a film thickness T of 10 μm was produced on the surface of the longitudinal end portion of the SUS sheet.

[Example 26]
The developing blade according to Example 26 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Example 6.

[Example 27]
The developing blade according to Example 27 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Example 13.

[Example 28]
The developing blade according to Example 28 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Example 15.

[Example 29]
The developing blade according to Example 29 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Example 20.

[Example 30]
The developing blade according to Example 30 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Example 21.

[Example 31]
The developing blade according to Example 31 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Example 24.

[Comparative Example 5]
The developing blade according to Comparative Example 5 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Comparative Example 1.

[Comparative Example 6]
The developing blade according to Comparative Example 6 was produced in the same manner as in Example 25 except that the resin layer forming paint was changed to the resin layer forming paint prepared in Comparative Example 3.

<Evaluation of developing blade>
The following evaluations were performed on the developing blades according to Examples 25 to 31 and Comparative Examples 5 and 6. The evaluation results are shown in Table 14.

[Measurement of blade resistance]
After leaving the developing blade in an environment of 23 ° C. and 50% RH (hereinafter referred to as “N / N”) and in an environment of 0 ° C. for 6 hours, the resistance value was measured in each environment.

(Measurement of resistance value)
The resistance value of the blade was measured as follows using the resistance value fluctuation evaluation jig shown in FIG. A developing blade was used instead of the developing roller 16 in the jig shown in FIG. As shown in FIG. 5 (a), a cylindrical metal 37 having a diameter of 30 mm is pushed by a load of 4.9 N at both ends of the developing blade via a conductive bearing 38, which does not form a resin layer. The developing blade was fixed without rotating. Next, as shown in FIG. 5 (b), a voltage of 50 V is applied by the high-voltage power supply 39, and a known resistance value (2 with respect to the resistance value of the developing blade) is arranged between the cylindrical metal 37 and the ground. The potential difference between both ends of a resistor having a resistance value lower than an order of magnitude) was measured. A voltmeter 40 (trade name: 189 TRUE RMS MULTIMETER, manufactured by FLUKE) was used for measuring the potential difference. From the measured potential difference and the resistance value of the resistor, the current flowing through the cylindrical metal 37 through the developing blade was calculated. Then, the resistance value of the developing blade was obtained by dividing the applied voltage of 50 V by the obtained current. Here, in the measurement of the potential difference, sampling was performed for 3 seconds from 2 seconds after the voltage was applied, and a value calculated from the average value was used as the blade resistance value.

[Performance evaluation as a developing blade]
(Evaluation of poor regulation)
The developing blades of each Example and Comparative Example were loaded into a process cartridge for a laser printer (trade name: LBP7700C, manufactured by Canon Inc.) having the configuration shown in FIG. Then, the process cartridge was incorporated into the laser printer, installed in an environment of 0 ° C., and then left for 2 hours. Next, 100 black images with a printing rate of 1% were continuously output. After that, a solid white image was output on a new copy paper. After outputting these images, the state of the toner coat on the surface of the developing blade was observed, and the presence or absence of electrostatic toner aggregation (improper regulation) due to abnormal charging of the toner was visually observed. This observation result was evaluated according to the following criteria. If improper regulation occurs, for example, spot-like unevenness may occur in the non-printed portion, or toner lumps may occur on the image, which may cause an image adverse effect.
A: There is no regulation defect on the toner coat.
B: There is a regulation defect on the toner coat, but it does not appear in the image.
C: Poor regulation appears in the image.

In the table, * 1 represents N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.).

Since the developing blades according to Examples 25 to 31 contain a resin having a specific structure in the resin layer, the resistance value does not increase much in a low temperature environment such as 0 ° C., and the image quality is maintained good. Was there. In particular, in Examples 25 to 27 including both the structures represented by the structural formulas (1) and (2), the increase in resistance was suppressed at a higher level.
On the other hand, in the developing blades according to Comparative Examples 5 and 6 which do not contain such a structure, an increase in resistance value and occurrence of poor regulation were observed in a low temperature environment.

<Manufacturing toner supply rollers>
[Example 32]
As a substrate, a core metal having a diameter of 5 mm made of stainless steel (SUS304) was placed in a mold, and a urethane rubber composition mixed with the following materials was injected into a cavity formed in the mold.
-Polyether polyol (trade name: EP550N, manufactured by Mitsui Chemicals, Inc.): 85.0 parts by mass-Isocyanate (trade name: Cosmonate TM20, manufactured by Mitsui Chemicals, Ltd.): 25.0 parts by mass-Fluorine / silicone-containing resin L-1: 5.0 parts by mass ・ Ion compound IP-1: 10.0 parts by mass ・ Silicone foam stabilizer (trade name: SRX274C, manufactured by Toray Dow Corning Silicone): 1.0 part by mass ・ Amin catalyst (Product name: TOYOCAT-ET, manufactured by Toso Co., Ltd.): 0.3 parts by mass ・ Amine catalyst (Product name: TOYOCAT-L33, manufactured by Toso Co., Ltd.): 0.2 parts by mass ・ Water: 2.0 parts by mass

Subsequently, the mold was heated, the urethane rubber composition was vulcanized at a temperature of 50 ° C. for 20 minutes to be foam-cured, and the substrate having the polyurethane foam layer formed on the peripheral surface was removed from the mold. In this way, the toner supply roller according to Example 32 having a polyurethane foam layer having a diameter of 16.1 mm on the outer periphery of the substrate was produced.

[Examples 33 to 38]
The toner supply rollers according to Examples 33 to 38 were produced in the same manner as in Example 32 except that the types and blending amounts of the ionic compound and the fluorine / silicone-containing resin were changed as shown in Table 15.

[Comparative Examples 7 and 8]
The toner supply rollers according to Comparative Example 7 and Comparative Example 8 were produced in the same manner as in Example 32 except that the types and blending amounts of the ionic compound and the fluorine / silicone-containing resin were changed as shown in Table 15. In the table, * 1 represents N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.).

<Evaluation of toner supply roller>
The toner supply rollers according to Examples 32 to 38 and Comparative Examples 7 and 8 obtained were evaluated as follows. The evaluation results are summarized in Table 16.

[Measurement of roller resistance]
In the same manner as the evaluation of the developing roller, the toner supply roller was left in an N / N environment and an environment of 0 ° C. for 6 hours, and then the resistance value was measured in each environment.

(Measurement of resistance value)
The resistance value of the toner supply roller was measured using the same device as the measurement of the resistance value of the developing roller described above. However, the load applied to both ends of the substrate 2 was 2.5 N, and the rotation speed of the roller at the time of measurement was 32 rpm. Other than that, the measurement was performed in the same manner as the developing roller, and the resistance value of the toner supply roller was used.

[Performance evaluation as a toner supply roller]
(Evaluation of poor regulation)
The toner supply rollers of the respective examples and comparative examples were loaded into a process cartridge for a laser printer (trade name: LBP7700C, manufactured by Canon Inc.) having the configuration shown in FIG. Then, the process cartridge was incorporated into the laser printer, installed in an environment of 0 ° C., and then left for 2 hours. Next, 100 black images with a printing rate of 1% were continuously output. After that, a solid white image was output on a new copy paper. After outputting these images, the state of the toner coat on the surface of the developing blade was observed, and the presence or absence of electrostatic toner aggregation (improper regulation) due to abnormal charging of the toner was visually observed. The evaluation criteria for poor regulation evaluation are as follows.
A: There is no regulation defect on the toner coat.
B: There is a regulation defect on the toner coat, but it does not appear in the image.
C: Poor regulation appears in the image.

In the table, * 1 represents N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.).

Since the toner supply rollers according to Examples 32 to 38 contain a resin having a specific structure in the resin layer, the resistance value does not increase much in a low temperature environment such as 0 ° C., and the image quality is also good. I kept it. In particular, in Examples 32 to 34 including both the structures represented by the structural formulas (1) and (2), the increase in the resistance value was suppressed at a higher level.
On the other hand, in the toner supply rollers according to Comparative Examples 7 and 8 which do not contain such a structure, an increase in resistance value and occurrence of poor regulation were observed in a low temperature environment.

1A Xerographic roller 1B Xerographic blade 2 Base 3 Resin layer 16 Development roller 19 Toner supply roller 21 Development blade

Claims (6)

An electrophotographic member having a conductive substrate and a resin layer.
The resin layer is
A resin having at least one structure selected from the group consisting of the following structural formulas (1) and (2) and at least one cation structure selected from the group consisting of the following structural formulas (3) to (6). When,
Electrophotographic members characterized by containing anions:

(In structural formula (1), R1 represents a hydrogen atom, a fluorine atom or a methyl group. X1 represents any structure or fluorine atom selected from the formula (X101) or (X102):

In formulas (X101) and (X102), Y1 represents a fluoroalkyl group having 1 to 6 carbon atoms. );

(In the structural formula (2), R2 represents a hydrogen atom or a methyl group. X2 represents any structure selected from the formula (X201) or (X202).

In formulas (X201) and (X202), R3 to R5 each independently represent a hydrocarbon chain having 1 or more and 4 or less carbon atoms. Y2 represents a straight or branched silicone group. );

(In the structural formula (3), R6 represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. At least one of Z1 to Z3 is a group consisting of structural formulas (Z101) to (Z103). Represents one of the structures selected from the above, and represents a hydrocarbon group having 1 to 4 carbon atoms in the other.

(In the structural formula (4), R7 and R8 are independently each of the hydrocarbon chains required for the nitrogen-containing heterocycle in the structural formula (4) to form a 5-membered ring, a 6-membered ring or a 7-membered ring. Represents at least one of Z4 to Z7 represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the others represent hydrogen atoms or carbon atoms 1 or more and 4 or less. One of the two Ns contained in the nitrogen-containing heterocycle in the structural formula (4) is N ⁺ .)

(In the structural formula (5), R9 represents a hydrocarbon chain required for the nitrogen-containing heterocycle in the structural formula (5) to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. Z8 to Z10. At least one of them represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the other represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. .)

(In the structural formula (6), R10 represents a hydrocarbon chain required for the nitrogen-containing heterocycle in the structural formula (6) to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. Z11 to Z13. At least one of them represents any structure selected from the group consisting of structural formulas (Z101) to (Z103), and the other represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. .)

(In the structural formulas (Z101) to (Z103), R11, R12 and R13 each independently represent a hydrocarbon chain having a straight chain or a branch. The symbol "*" represents a nitrogen atom in the structural formula (3). Represents the bond site with the nitrogen atom or carbon atom constituting the nitrogen-containing heterocycle in the structural formulas (4) to (6), and the symbol "**" represents the bond site with the nitrogen atom or carbon atom constituting the resin. Represents the bond site with the carbon atom of.). The electrophotographic member according to claim 1, wherein the resin has a structure represented by the structural formulas (1) and (2). The electrophotographic member according to claim 1 or 2, wherein the resin has a cation structure represented by the structural formula (4). The resin further contains a matrix resin, and the matrix resin contains a reaction product of a polyol having any structure selected from the group consisting of the following structural formulas (7) to (11) and an isocyanate compound. The electrophotographic member according to any one of claims 1 to 3.

A process cartridge that is detachably attached to the main body of the electrophotographic apparatus, wherein at least one of the electrophotographic members is the electrophotographic member according to any one of claims 1 to 4. Process cartridge. An electrophotographic apparatus including an electrophotographic photosensitive member, wherein at least one of the electrophotographic members is the electrophotographic member according to any one of claims 1 to 4. apparatus.

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