JP2019049625A - Developing member, process cartridge and electrophotographic device - Google Patents

Abstract

To provide a developing member which causes little leaching out of an ionic conductive agent, has high electrical conductivity and little durability variation of chargeability of the developing member, and to provide a process cartridge and an electrophotographic device each using the developing members.SOLUTION: The developing member is provided which includes an electrically conductive base and a surface layer. The surface layer is a resin layer including a resin, the resin layer includes a specific anion, and the resin has at least one partial structure selected from a group consisting of structural formulae (1) and (2) and a partial structure shown by a structural formula (3).SELECTED DRAWING: None

Description

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

An electrophotographic member provided with a conductive layer, such as a developing member and a charging member used in an electrophotographic image forming apparatus, has an electric resistance value of, for example, 1.0 × 10 ^{5 to} 1.0. It is necessary to control to × 10 ⁹ Ω. In order to control the electrical resistance value of a conductive layer in the above-mentioned range, it is known to contain an ion conductive agent. However, in the conductive layer whose conductivity is controlled by the ion conductive agent, ions derived from the ion conductive agent may be unevenly distributed in the conductive layer and the conductivity may be changed due to long-term use.

  For such problems, Patent Document 1 discloses a conductive roller provided with an elastic layer and a urethane coat layer provided on the outer peripheral portion of the elastic layer. In the conductive roller, the urethane coating layer is composed of a reaction product of an ionic liquid having two hydroxyl groups, a polyol other than the ionic liquid, and a polyisocyanate.

JP, 2011-118113, A

  According to the study of the present inventors, the conductive roller according to Patent Document 1 is that the conductivity is unlikely to change even after long-term use because one of the ions is fixed in the molecule of the urethane resin. I have confirmed that I will be effective. However, when the conductive roller according to Patent Document 1 is used as a developing roller for forming an electrophotographic image for a long time, fog may occur in the obtained electrophotographic image.

One aspect of the present invention is directed to the provision of a developing member capable of forming a high quality electrophotographic image even with long-term use.
Another aspect of the present invention is directed to the provision of an electrophotographic apparatus capable of stably outputting a high quality electrophotographic image and a process cartridge used therefor.

According to one aspect of the present invention, there is provided a developing member having a conductive substrate and a surface layer,
The surface layer contains a resin and an anion,
The anion may be a fluorinated sulfonate anion, a fluorinated carboxylate anion, a fluorinated sulfonylimide anion, a fluorinated sulfonyl methide anion, a fluorinated alkyl fluoroborate anion, a hexafluorophosphate anion, a hexafluoroarsenate anion, hexa At least one member selected from the group consisting of fluoroantimonate anion and dicyanamide anion,
The resin is
A developing member having at least one partial structure selected from the group consisting of Structural Formula (1) and Structural Formula (2) and a partial structure represented by Structural Formula (3):

[In structural formula (1),
X represents a nitrogen atom, an oxygen atom or a sulfur atom,
When X is a nitrogen atom, p is 1, and when X is an oxygen atom or a sulfur atom, p is 0,
R11 to R15 are each independently selected from the group consisting of the following (a) to (c), and any two of R11 to R15 are (c):
(A) hydrogen atom,
(B) a saturated hydrocarbon group having 1 to 6 carbon atoms,
(C) A structure including a portion bonded to the polymer chain of the resin via a urethane bond. ],

[In the structural formula (2), R 21 to R 26 are each independently selected from the group consisting of (a) to (c) above, and any two of R 21 to R 26 are (C). ],

[In structural formula (3),
n is an integer of 2 or more and 4 or less,
R 35 represents an alkylene group having 2 to 4 carbon atoms, and a plurality of R 35 s may be the same or different,
R31 to R34 are each independently selected from the group consisting of (d) to (f) below, and a plurality of R34 may be the same or different and at least one of R31 to R34 Four are (f):
(D) hydrogen atom,
(E) alkyl group having 1 to 4 carbon atoms,
(F) A structure including a portion bonded to the polymer chain of the resin via a urethane bond or a urea bond. ].

  Further, according to another aspect of the present invention, there is provided a process cartridge configured to be detachable from a main body of an electrophotographic apparatus and having at least a developing unit, wherein the developing unit is the developing member as described above. A process cartridge is provided, characterized in that

  Furthermore, according to another aspect of the present invention, there is provided an electrophotographic apparatus comprising at least a developing unit, wherein the developing unit comprises the developing member described above.

According to one aspect of the present invention, it is possible to obtain a developing member that contributes to stable formation of a high quality electrophotographic image.
Further, according to the present invention, it is possible to obtain a process cartridge and an electrophotographic apparatus capable of stably forming a high quality electrophotographic image.

It is a conceptual diagram which shows an example of the image development roller of this invention. It is a conceptual diagram which shows an example of the image development blade of this invention. It is a schematic block diagram which shows an example of the process cartridge of this invention. FIG. 1 is a schematic configuration view showing an example of an electrophotographic apparatus of the present invention. It is a schematic block diagram of the measuring apparatus which measures the electric current value of the image development member of this invention. It is a schematic block diagram of the measuring apparatus which measures the electrification amount of the image development member of this invention. It is a schematic block diagram of the measuring apparatus which measures the electric current value of the image development blade of this invention.

When using the conductive roller according to Patent Document 1 as a developing roller, the present inventors consider the generation mechanism of the problem that fogging occurs in the electrophotographic image as a large number of electrophotographic images are formed. did. In the process, it was found that the charge amount of the toner carried on the surface of the conductive roller in the process of forming an electrophotographic image was lower than in the initial stage.
Then, the present inventors speculated that the decrease in the charge amount of the toner is due to the anion in the surface layer of the conductive roller being unevenly distributed to the side closer to the substrate of the surface layer.
That is, the charge amount of the toner on the developing member is influenced by the electronic state of atoms on and near the surface of the developing member in contact with the toner.

  In the surface layer of the conductive roller according to Patent Document 1, a urethane resin having a cationic structure in the molecule and a free anion are present. In the new state, the anions are uniformly distributed without being unevenly distributed in the thickness direction of the surface layer. Therefore, positive and negative charges are balanced across the surface layer, and the surface of the conductive roller is kept electrically neutral. However, when used as a developing roller for forming an electrophotographic image for a long time, the anion moves in the surface layer toward the substrate by application of a bias between the conductive roller and the electrophotographic photosensitive member. Do. As a result, the anions are localized near the substrate in the surface layer, and the concentration of the anions near the surface of the developing member is reduced. On the other hand, since the cation forming a pair with the anion is fixed in the molecule of the urethane resin, it is difficult to move in the surface layer even by the application of the bias. Therefore, on the surface of the conductive roller and in the vicinity thereof, the concentration of the cation becomes higher than the concentration of the anion, and the surface of the conductive roller becomes positively charged as compared with the case of a new state. . As a result, even though the toner is negatively charged due to the friction with the developing member, it bonds to the positive charge on the surface of the surface layer of the conductive roller while being supported on the surface of the conductive roller. It is considered that the charge amount of the toner decreases.

  That is, the problem in the conductive roller according to Patent Document 1 is that the surface layer contains a resin having a cationic structure in the molecule and an anion that is relatively easy to move in the surface layer than the resin. It is considered to be On the other hand, the surface layer containing a resin having a cationic structure in the molecule and an anion that is more likely to move in the surface layer relatively than the resin has an advantage that the conductivity is unlikely to change even after long-term use. The thing is as having mentioned above.

The problem of the conductive roller according to Patent Document 1, that is, the fluctuation of the toner tribo when the bias is continuously applied, is formed by using a cation in which the resin in the surface layer has two hydroxyl groups as a raw material In particular, it is particularly prominent when the anion is a specific anion with high conductivity.
In the surface layer, the cation and the anion in the resin molecule electrostatically interact, and the anion is considered to move by hopping conduction between the plurality of immobilized cations. Therefore, the mobility of the anion is also influenced by the freedom of the cation.
In addition, the degree of freedom of the cation shows a remarkable difference between the case where the number of hydroxyl groups of the ion conductive agent which is a raw material of the resin is two, and the case where the number is three or more.
That is, in the resin obtained by using the ion conductive agent having two hydroxyl groups according to the present invention, the cation structure is bonded to the polymer chain at two places. In this case, the cationic structure is prone to micro-brown movement. On the other hand, in the resin obtained by using an ion conductive agent having three hydroxyl groups, the cation is bonded to the polymer chain at three points. Since the cation structure is located at a branch portion of the resin, ie, a crosslinking point, it is considered that the degree of freedom of the cation structure is reduced.
Therefore, in a developing member having a surface layer containing a resin obtained by using an ion conductive agent having two hydroxyl groups together with an anion, it is considered that the uneven distribution of the anion is more likely to occur by the application of a bias.

The present inventors repeated studies for the purpose of obtaining a developing member capable of solving the problem caused by the configuration of the surface layer without impairing the merit of the surface layer of the conductive roller according to Patent Document 1. .
As a result, a surface layer including a resin having an anion and at least one partial structure selected from the group consisting of Structural Formula (1) and Structural Formula (2) and the partial structure represented by Structural Formula (3) Has been found to be effective in achieving the above object.

[In structural formula (1),
X represents a nitrogen atom, an oxygen atom or a sulfur atom,
When X is a nitrogen atom, p is 1, and when X is an oxygen atom or a sulfur atom, p is 0,
R11 to R15 are each independently selected from the group consisting of the following (a) to (c), and any two of R11 to R15 are (c):
(A) hydrogen atom,
(B) a saturated hydrocarbon group having 1 to 6 carbon atoms,
(C) A structure including a portion bonded to the polymer chain of the resin via a urethane bond. ],

[In Structural Formula (2), R 21 to R 26 are each independently selected from the group consisting of (a) to (c), and any two of R 21 to R 26 are c). ],

[In structural formula (3),
n is an integer of 2 or more and 4 or less,
R 35 represents an alkylene group having 2 to 4 carbon atoms, and R 35 may be the same or different,
R31 to R34 are each independently selected from the group consisting of (d) to (f) below, and R34 may be the same or different and at least four of R31 to R34 Is (f):
(D) hydrogen atom,
(E) alkyl group having 1 to 4 carbon atoms,
(F) A structure including a portion bonded to the polymer chain of the resin via a urethane bond or a urea bond. ].

  When a voltage is continuously applied to the developing member, the anions are localized on the substrate side in the surface layer, and the surface of the developing member may be positively charged. However, the nitrogen atom in the amino structure represented by the structural formula (3) incorporated in the molecule of the resin has a noncovalent electron pair. Therefore, even if the negative charge of the toner carried on the surface of the developing member is taken away by the surface of the developing member, it is considered that the negative charge is again imparted by the non-shared electron pair possessed by the nitrogen atom in the amino structure. Be Therefore, the developing member according to this aspect can effectively suppress the fluctuation of the charge amount of the toner carried on the surface even if the surface is positively charged by the application of the bias.

Hereinafter, the developing member according to an aspect of the present invention will be described with reference to the drawings.
Examples of the developing member according to one aspect of the present invention include a roller-shaped developing member (hereinafter also referred to as “developing roller”) and a developing member having a blade shape (hereinafter also referred to as “developing blade”). Be
The developing roller shown in FIG. 1A has a conductive substrate 2 and an elastic layer 3 as a surface layer on the outer periphery thereof. The developing roller shown in FIG. 1B has a conductive base 2, an elastic layer 3 covering the outer periphery of the base 2, and a surface layer 4 covering the outer periphery of the elastic layer 3. As shown in FIG. 1C, the developing roller may have a three-layer structure in which the intermediate layer 5 is disposed between the elastic layer 3 and the surface layer 4 or a multilayer structure in which a plurality of intermediate layers 5 are disposed. . In the case of FIG. 1 (b) and (c), the surface layer of the present invention is applicable to the surface layer 4. FIG. 2 shows an embodiment in which the developing member according to the present invention is applied as a developing blade. As shown in FIG. 2, the developing member according to the present invention can be composed of a supporting base K-2 and a resin layer 50 covering the outside thereof. In this case, the resin layer 50 is a surface layer made of the resin according to the present invention. In this case, as the resin layer 50, a resin similar to the resin used as the developing roller can be used.

<Substrate>
The substrate 2 functions as an electrode and a supporting member of the developing member 1 and, for example, a metal or alloy such as aluminum, copper alloy, stainless steel; iron plated with chromium or nickel; It is made of a conductive material such as synthetic resin. The form may be solid or hollow.

<Elastic layer>
The elastic layer 3 provides the developing member with elasticity necessary to form a nip of a predetermined width at the contact portion between the developing member and the photosensitive member.
The elastic layer 3 is preferably formed of a molded body of a rubber material. Examples of rubber materials include the following. Ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), fluororubber, Silicone rubber, epichlorohydrin rubber, NBR hydride, urethane rubber. These can be used alone or in combination of two or more.
Among these, silicone rubber is preferable because it is difficult to cause compression set in the elastic layer even when another member (such as a developer regulating blade) abuts for a long period of time. The silicone rubber may, for example, be a cured product of an addition-curable silicone rubber. Furthermore, it is particularly preferable to use a cured product of an addition curing type dimethyl silicone rubber.

  In the elastic layer 3, various additives such as a conductivity imparting agent, a nonconductive filler, a crosslinking agent, and a catalyst are appropriately blended. As the conductivity imparting agent, carbon black; conductive metal such as aluminum and copper; fine particles of conductive metal oxide such as zinc oxide, tin oxide and titanium oxide can be used. Among these, carbon black is particularly preferable because it is relatively easily available and good conductivity can be obtained. When using carbon black as a conductivity imparting agent, it is mix | blended 2-50 mass parts with respect to 100 mass parts of rubber | gum in rubber material. Non-conductive fillers include silica, quartz powder, titanium oxide, zinc oxide or calcium carbonate. Crosslinking agents include di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane or dicumyl peroxide.

<Surface layer>
The surface layer 4 contains a resin and an anion. The anion may be a fluorinated sulfonate anion, a fluorinated carboxylate anion, a fluorinated sulfonylimide anion, a fluorinated sulfonyl methide anion, a fluorinated alkyl fluoroborate anion, a hexafluorophosphate anion, a hexafluoroarsenate anion, hexa It is at least one selected from the group consisting of fluoroantimonate anion and dicyanamide anion.

<Anion>
As a fluorinated sulfonate anion, a trifluoromethane sulfonate anion, a fluoromethane sulfonate anion, a perfluoroethyl sulfonate anion, a perfluoropropyl sulfonate anion, a perfluorobutyl sulfonate anion, a perfluoropentyl sulfonate anion, a perfluoropentyl sulfonate anion Examples include hexyl sulfonate anion and perfluorooctyl sulfonate anion.

  Examples of the fluorinated carboxylate anion include trifluoroacetate anion, perfluoropropionate anion, perfluorobutyrate anion, perfluorovalerate anion, and perfluorocaproate anion.

  As the fluorosulfonylimide anion, trifluoromethanesulfonylimide anion, perfluoroethylsulfonylimide anion, perfluoropropylsulfonylimide anion, perfluorobutylsulfonylimide anion, perfluoropentylsulfonylimide anion, perfluorohexylsulfonylimide anion, And a cyclic anion such as perfluorooctylsulfonylimide anion, fluorosulfonylimide anion, or cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide.

  As the sulfonyl fluoride methionide anion, trifluoromethanesulfonyl methide anion, perfluoroethyl sulfonyl methide anion, perfluoropropyl sulfonyl methide anion, perfluorobutyl sulfonyl methide anion, perfluoropentyl sulfonyl methide anion, perfluoro sulfonyl methide anion Examples include hexylsulfonyl methide anion and perfluorooctyl sulfonyl methide anion.

  As the fluorinated alkyl fluoroborate anion, trifluoromethyl trifluoroborate anion and pentafluoroethyl trifluoroborate anion can be mentioned.

  Among the anions listed above, as the anion of the ion conductive agent, a fluorinated sulfonylimide anion is preferable in that the conductivity of the surface layer to be obtained becomes high.

  The resin has at least one partial structure selected from the group consisting of Structural Formula (1) and Structural Formula (2), and a partial structure represented by Structural Formula (3).

[In structural formula (1),
X represents a nitrogen atom, an oxygen atom or a sulfur atom,
When X is a nitrogen atom, p is 1, and when X is an oxygen atom or a sulfur atom, p is 0,
R11 to R15 are each independently selected from the group consisting of the following (a) to (c), and any two of R11 to R15 are (c):
(A) hydrogen atom,
(B) a saturated hydrocarbon group having 1 to 6 carbon atoms,
(C) A structure including a portion bonded to the polymer chain of the resin via a urethane bond. ],

[In Structural Formula (2), R 21 to R 26 are each independently selected from the group consisting of (a) to (c), and any two of R 21 to R 26 are c). ],

[In structural formula (3),
n is an integer of 2 or more and 4 or less,
R 35 represents an alkylene group having 2 to 4 carbon atoms, and a plurality of R 35 s may be the same or different,
R31 to R34 are each independently selected from the group consisting of (d) to (f) below, and a plurality of R34 may be the same or different and at least one of R31 to R34 Four are (f):
(D) hydrogen atom,
(E) alkyl group having 1 to 4 carbon atoms,
(F) A structure including a portion bonded to the polymer chain of the resin via a urethane bond or a urea bond. ].

<Structural formula (1) and (2)>
In Structural Formula (1), R 11 to R 15 are each independently selected from the group consisting of the following (a) to (c), and any two of R 11 to R 15 are c).
(A) a hydrogen atom (b) a saturated hydrocarbon group having 1 to 6 carbon atoms (c) a structure including a portion bonded to the polymer chain of the resin via a urethane bond, and in structural formula (2), R21 to R26 is each independently selected from the group consisting of (a) to (c), and any two of R21 to R26 are (c).

Examples of the (b) saturated hydrocarbon group having 1 to 6 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl groups; Isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2 And-alkyl groups having a branched chain such as -dimethylpropyl group, and cycloalkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl.
The structure (c) containing a portion bonded to the polymer chain of the resin via a urethane bond is a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, The structure etc. after the structure which has hydroxyl groups, such as a hydroxy octyl group and a triethylene glycol ether group, and an isocyanate group are mentioned.
Among the partial structures represented by the structural formula (1), those in which X is a nitrogen atom are preferable in that a development member having relatively high conductivity can be obtained even if the addition amount of the ion conductive agent is small.

<Structural formula (3)>
In Structural formula (3), an ethylene group, a propylene group, and an isopropylene group are mentioned as a C2-C4 alkylene group represented by R35. R 35 may be the same or different.
R31 to R34 are each independently selected from the group consisting of (d) to (f) below, and R34 may be the same or different and at least four of R31 to R34 Is (f).
(D) a hydrogen atom (e) an alkyl group having 1 to 4 carbon atoms (f) a structure including a portion bonded to a polymer chain of the resin via a urethane bond

Examples of the (e) alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group.
As the structure of (f), in addition to the structures exemplified as the structure of (c), aminoethyl group, aminopropyl group, aminobutyl group, aminopentyl group, aminohexyl group, aminoheptyl group, aminooctyl group and the like And structures after reaction with an isocyanate group.

  Among the partial structures represented by the structural formula (3), it is a partial structure derived from the reaction of a compound represented by the structural formula (4) with a polyisocyanate, from the viewpoint of easy handling of the raw material before the reaction Is preferred.

[In structural formula (4),
m represents an integer of 2 or more and 4 or less,
R 45 is an alkylene group having 2 to 4 carbon atoms, and R 45 may be the same or different,
R41 to R44 are each independently the following RA or RB, and R44 may be the same or different, and at least four of R41 to R44 are RA,
RB represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
RA is any one selected from the group consisting of the following (g) to (i),
(G) a hydroxyalkyl group having 1 to 8 carbon atoms,
(H) an aminoalkyl group having 2 to 8 carbon atoms,
(I) A group represented by the following structural formula (5). ],

[In structural formula (5), R51 is a C2-C5 alkylene group, R51 may be same or different, j is 2 or 3.]. ]

<Structural formula (4) and (5)>
Examples of the alkylene group having 2 to 4 carbon atoms represented by R 45 in the structural formula (4) include the same groups as those exemplified as the alkylene group having 2 to 4 carbon atoms represented by R 35.
As a C1-C4 alkyl group represented by RB, the group similar to the group illustrated as said (e) C1-C4 alkyl group is mentioned.

(G) Examples of the hydroxyalkyl group having 1 to 8 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl and the like. Examples of the alkyl constituting the hydroxyalkyl group include linear, branched and cyclic alkyl. Among them, linear alkyl is preferable. Moreover, although the substitution position of hydroxy in alkyl may be any position, it is preferable that hydroxy is substituted at the terminal of alkyl. As such a hydroxyalkyl group, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyheptyl etc. can be mentioned, for example.

(H) Examples of the aminoalkyl group having 2 to 8 carbon atoms include an aminoethyl group, an aminopropyl group, an aminobutyl group, an aminopentyl group, aminohexyl, aminoheptyl, aminooctyl and the like. Examples of the alkyl constituting the aminoalkyl group include linear, branched and cyclic alkyl. Among them, linear alkyl is preferable. Moreover, although the substitution position of amino in alkyl may be any position, it is preferable that amino be substituted at the end of alkyl. As such an aminoalkyl group, 2-aminoethyl, 3-aminopropyl, 4-aminobutyl, 5-aminopentyl, 6-aminoheptyl etc. can be mentioned, for example.
Examples of the alkylene group having 2 to 5 carbon atoms represented by R 51 in the structural formula (5) include the same groups as those exemplified as the alkylene group having 2 to 4 carbon atoms represented by R 35.

  Among the compounds represented by the structural formula (4), the compound represented by the structural formula (6) is preferable from the viewpoint of the stability of the charge imparting ability by continuous use of the developing member. The reason for this is presumed to be that localization of the anion described later is difficult to occur due to the difference in the structure after the compound represented by the structural formula (4) is reacted with the polyisocyanate. That is, among the compounds represented by the structural formula (4), when the compound represented by the structural formula (6) is used, a urethane bond is formed around the amino compound. As a result, it is thought that a hard segment is formed between urethane bonds to prevent localization of anions.

[In the structural formula (6), R 61 to R 64 each independently represent an alkylene group having 2 or 3 carbon atoms, plural R 64 s may be the same or different, and k represents an integer of 2 or more and 4 or less . ].

As mentioned above, although the structure of the resin which comprises the said surface layer (resin layer) was demonstrated, since the handling of the raw material used for reaction among this resin is easy,
A polyisocyanate, and a compound represented by the structural formula (4);
It is preferable that it is a reactant with at least one compound selected from the group consisting of Structural Formula (7) and Structural Formula (8).

[In the structural formula (7), Y is a nitrogen atom, an oxygen atom or a sulfur atom,
When Y is a nitrogen atom, q is 1, and when Y is an oxygen atom or a sulfur atom, q is 0,
R71 to R75 are each independently selected from the group consisting of the following (g) to (i), and any two of R71 to R75 are (i).
(G) hydrogen atom,
(H) a saturated hydrocarbon group having 1 to 6 carbon atoms,
(I) A group having a hydroxyl group at the end. ],

[Wherein, R 81 to R 86 in the structural formula (8) are each independently selected from the group consisting of (g) to (i), and any two of R 81 to R 86 are (I). ].
Among the compounds represented by Structural Formula (7), those in which Y is a nitrogen atom are preferable in that a relatively high developing member can be obtained even with a small addition amount.

<Method of manufacturing surface layer (resin layer)>
The surface layer is formed, for example, by forming a coating film of a paint for forming the surface layer including the raw material of the resin contained in the surface layer on the elastic layer and reacting the raw materials of the resin in the coating film with each other. can do.

The paint contains the following (i) to (iii) as a resin raw material.
(I) An ion conductive agent for introducing a cationic partial structure represented by at least one of structural formula (1) and structural formula (2) into a resin;
(Ii) an amino compound for introducing an amino structure represented by the structural formula (3) into a resin;
(Iii) A polyisocyanate which forms a urethane resin by reacting with the ion conductive agent and the amino compound.

<(I) Ion conductive agent>
The ion conductive agent is a compound having two hydroxyl groups, and has a cation and an anion. The structure of the cation corresponds to the compound represented by the structural formula (7) or (8).

Among these, imidazolium cations and pyridinium cations are preferable in that the conductivity of the obtained surface layer is relatively high.
Among these, imidazolium cation is particularly preferable. The reason for this is that the positive charge of the imidazolium cation is delocalized on the imidazolium ring, and the effect that the charge of the toner is deprived by the cationic organic group can be relatively suppressed.
The anion of the ion conductive agent is as described above.

  It is preferable that the compounding quantity of an ion conductive agent is 0.01 mass part or more and 20 mass parts or less with respect to a surface layer. A highly conductive surface layer is obtained as it is 0.01 mass part or more. If the amount is 20 parts by mass or less, a surface layer with less leaching of the ion conductive agent is obtained.

The ion conductive agent according to the present invention can be obtained by performing a known ion exchange reaction after synthesizing a precursor using a known nucleophilic substitution reaction such as, for example, a Menschkin reaction or the like in one or more steps. .
Therefore, as the nucleophile, for example, a compound having a nucleophilic nitrogen atom such as an imidazole compound, a pyridine compound, a pyrazole compound, an oxazole compound, a thiazole compound can be used.
Further, as the electrophile, for example, a halogenated alkyl compound in which a hydroxyl group is substituted can be used.
Furthermore, as the alkali metal salt used for the ion exchange reaction, for example, an alkali metal salt containing an anion according to the present invention, such as lithium fluoride alkyl sulfonate or potassium fluoride alkylsulfonylimide, can be used.
The target ion conductive agent can be synthesized by a combination of known methods by changing the nucleophile used for the nucleophilic substitution reaction, the electrophile and the alkali metal salt used for the ion exchange reaction into a desired combination.

<(Ii) amino compound>
The amino compound corresponds to the compound represented by the structural formula (4), preferably the compound represented by the structural formula (6).

The functional group of the amino compound is preferably a hydroxyl group rather than an amino group. This is because the bond obtained after the reaction with the polyisocyanate is different in the case of a hydroxyl group (urethane bond) and in the case of an amino group (urea bond). If the urethane bond is present around the amino structure, which is the structure after reaction of the amino compound, the interaction by the hydrogen bond with other urethane bonds in the urethane resin becomes stronger, and the amino structure moves more in the resin It is because it becomes difficult.
The amino compound according to the present invention has at least four or more functional groups (hydroxyl group or primary amine group) in one molecule. Therefore, it bonds with the polyisocyanate at multiple points. The larger the number of functional groups (hereinafter referred to as "group number"), the more preferable. This is because the amino compound reacts with the resin at multiple points, so the amino structure of the obtained resin is difficult to move before and after durability, and the change in chargeability is small.
In addition, the larger the n of the amino compound, the higher the ability to replenish the toner with a negative charge, and the smaller the fluctuation of the charge imparting property.
It is preferable that the compounding quantity of an amino compound is 1 mass part or more and 30 mass parts or less with respect to a surface layer. When the amount is 1 part by mass or more, a developing member with less variation in chargeability before and after continuous use can be obtained. If it is 30 parts by mass or less, a developing member excellent in flexibility can be obtained.

<(Iii) Polyisocyanate>
Examples of isocyanate compounds include aliphatic diisocyanates such as ethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), alicyclic ones such as cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate Polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate, xylylene diisocyanate, aromatic polyisocyanates such as naphthalene diisocyanate And isocyanate compounds such as copolymers, isocyanurates, TMP adducts, biurets, and blocks thereof. Be
Among these, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and polymeric diphenylmethane diisocyanate are preferable. These compounds are highly reactive with the hydroxyl group of the cation, and the proportion of the cation not bound to the resin is reduced. Therefore, a surface layer with less permeation of the ion conductive agent can be obtained.
In addition, as the polyisocyanate, polyether polyol or polyester polyol described later was reacted in advance with isocyanate such as 2,4-tolylene diisocyanate (TDI), 1,4-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) It is preferred to use as an isocyanate terminated prepolymer. The reason for this is that the polyether polyol or polyester polyol and the ion conductive agent or the amino compound can be dispersed and disposed in the resin. Therefore, a surface layer excellent in flexibility can be obtained.
The blending amount of polyisocyanate is such that the ratio of isocyanate group is 1.0 to 2.0 with respect to the total number 1.0 of the hydroxyl group possessed by the ion conductive agent and the hydroxyl group and / or amino group possessed by the amino compound. It is preferable that it is a range. The surface layer which is excellent in charging property as it is 1.0 or more is obtained. If it is 2.0 or less, a surface layer excellent in flexibility is obtained. In addition, the number of the above-mentioned sum includes the number of hydroxyl groups which a polyol has, when using a polyol.

<Polyol>
The paint for forming the surface layer may further contain a polyol other than the above-mentioned ion conductive agent and amino compound (hereinafter also referred to as "other polyol"). Other polyols have a plurality of hydroxyl groups in the molecule, and the hydroxyl groups react with the polyisocyanate. The other polyols are not particularly limited, and include, for example, polyether polyols and polyester polyols. Examples of polyether polyols include polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Further, as polyester polyols, diol components such as 1,4-butanediol, 3-methyl-1,4-pentanediol, neopentyl glycol, triol components such as trimethylolpropane, adipic acid, phthalic anhydride, terephthalic acid The polyester polyol obtained by the condensation reaction with dicarboxylic acid with an acid, hexahydroxy phthalic acid etc. is mentioned.

  The surface layer may be, if necessary, a general resin other than the resin according to the present invention, a rubber material, a compounding agent, a conductivity imparting agent, a nonconductive filler, a crosslinking agent, to the extent that the effect of the present invention is not impaired. A catalyst may be added. The styrene-propylene-diene copolymer rubber which may be added, acrylonitrile-butadiene rubber, chloroprene rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, silicone rubber, epichlorohydrin rubber, urethane rubber and the like can be mentioned. Examples of the compounding agent include fillers generally used for resins, softeners, processing aids, tackifiers, antiblocking agents, foaming agents and the like. Examples of the conductivity imparting agent include carbon black; conductive metals such as aluminum and copper; conductive zinc oxide, conductive tin oxide, and fine particles of conductive metal oxide such as conductive titanium oxide. Non-conductive fillers include, for example, silica, quartz powder, titanium oxide, or calcium carbonate. The crosslinking agent is not particularly limited, and, for example, tetraethoxysilane, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane or dicumyl Peroxide is mentioned.

  When surface roughness is required as a surface layer of the developing member, fine particles for roughness control may be added to the surface layer. In particular, when the developing member of the present invention is applied to a developing roller, as fine particles for controlling roughness used in the surface layer, a developing roller having an excellent ability to convey toner that the volume average particle diameter is 3 to 20 μm. It is preferable because The amount of fine particles added to the surface layer is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin solid content of the surface layer, in order not to impair the effects of the present invention. As fine particles for controlling roughness, fine particles of polyurethane resin, polyester resin, polyether resin, polyamide resin, acrylic resin, and phenol resin can be used.

  Although it does not specifically limit as a formation method of a surface layer, The spray by paint, immersion, or roll coating is mentioned. The dip coating method in which the paint overflows from the upper end of the dip tank as described in JP-A-57-5047 is simple and excellent in production stability as a method of forming a surface layer. Further, as a method of forming the surface layer when applying the surface layer according to the present invention to the elastic layer 3 shown in FIG. 1A, a known method can be used in the developing member. For example, a method of extruding the substrate and the material for the surface layer together and molding, or if the material for forming the surface layer is liquid, holds the cylindrical pipe and the substrate disposed at both ends of the pipe For example, a method of injecting the material into a mold provided with a frame and a base and heating and curing the material may be mentioned. Moreover, it does not specifically limit as a formation method at the time of applying the surface layer which concerns on this invention to the resin layer 50 shown in FIG. For example, in addition to the above forming method (spray, immersion, roll coating), a method of extruding and molding the surface layer together with the supporting substrate K-2 and then heat curing can be applied.

The developing member of the present invention can be applied to a member for electrophotography such as a developing roller and a developing blade.
When the developing member of the present invention is applied to a developing roller in a developing device, the developer may be magnetic or nonmagnetic, and may be one-component or two-component. The developing device may be noncontact or contact type.

<Process cartridge, electrophotographic apparatus>
FIG. 3 is a cross-sectional view of a process cartridge according to the present invention. In the process cartridge 17 shown in FIG. 3, the developing roller 16, the developing blade 21, the electrophotographic photosensitive member 18, the cleaning blade 26, the waste toner container 25, and the charging roller 24 are integrated. Further, the process cartridge is configured to be removable from the main body of the electrophotographic image forming apparatus. The developing device 22 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 onto the surface of the developing roller 16 by the toner supply roller 19, and a layer of toner of a predetermined thickness is formed on the surface of the developing roller 16 by the developing blade 21.

  FIG. 4 is a cross-sectional view of an electrophotographic apparatus according to the present invention. A developing device 22 including a developing roller 16, a toner supply roller 19, a toner container 20 and a developing blade 21 is detachably mounted on the electrophotographic apparatus of FIG. In the electrophotographic apparatus according to the present invention, the developing member is used as the developing roller 16 and / or the developing blade 21. A process cartridge 17 comprising a photosensitive member 18, a cleaning blade 26, a waste toner container 25 and a charging roller 24 is detachably mounted. The photosensitive member 18, the cleaning blade 26, the waste toner container 25 and the charging roller 24 may be disposed in the main body of the electrophotographic apparatus. The photosensitive member 18 rotates in the direction of the arrow, is uniformly charged by the charging roller 24 for charging the photosensitive member 18, and the laser beam 23 serving as an exposure unit that writes an electrostatic latent image on the photosensitive member 18 Form an electrostatic latent image. The electrostatic latent image is developed by applying toner by the developing device 22 disposed in contact with the photosensitive member 18, and is visualized as a toner image.

The development is performed so-called reversal development in which a toner image is formed on the exposed portion. The visualized toner image on the photosensitive member 18 is transferred to the paper 34 as a recording medium by the transfer roller 29 as a transfer member. The paper 34 is fed into the apparatus through a paper feed roller 35 and a suction roller 36, and is conveyed between the photosensitive member 18 and the transfer roller 29 by an endless belt-like transfer conveyance belt 32. The transfer conveyance belt 32 is operated by the driven roller 33, the drive roller 28, and the tension roller 31. A voltage is applied to the transfer roller 29 and the attraction roller 36 from the bias power supply 30. The paper 34 to which the toner image has been transferred is subjected to a fixing process by the fixing device 27 and discharged out of the apparatus, and the printing operation is completed.
On the other hand, the toner remaining on the photosensitive member 18 without being transferred to the paper 34 is scraped off by the cleaning blade 26 and stored in the waste toner container 25.

  The developing device 22 includes a toner container 20 containing toner as a one-component developer, and a developing device as a developer carrying member positioned at an opening extending in the longitudinal direction in the toner container 20 and opposed to the photosensitive member 18. And a roller 16. The developing device 22 develops and visualizes the electrostatic latent image on the photosensitive member 18.

  In the following, when the surface layer according to the present invention is applied to the surface layer 4 of the developing member 1 as shown in FIG. 1 (b), and as shown in FIG. An Example and a comparative example at the time of applying the surface layer which concerns are shown. The present invention is not limited to these examples and the like.

(Creating elastic roller K-1)
A primer (trade name, DY 35-051; manufactured by Toray Dow Corning) was applied to a core metal of 6 mm in diameter and 278.9 mm in total length made of SUS304, and baked for 20 minutes in an oven heated to a temperature of 180 ° C. to form a substrate.
The substrate prepared above was placed in a mold, and an addition type silicone rubber composition in which the following materials were mixed was injected into a cavity formed in the mold.
<Addition-type silicone rubber composition>
Liquid silicone rubber material (trade name, SE 6724 A / B; manufactured by Toray Dow Corning) 100 parts by mass Carbon black (trade name: Toka Black # 4300; manufactured by Tokai Carbon) 15 parts by mass Heat resistance imparting agent 0.2 parts by mass of silica powder and 0.1 parts by mass of platinum catalyst Subsequently, the mold was heated to 150 ° C. for 15 minutes to cure and cure the silicone rubber. After the substrate having the silicone rubber layer cured on the circumferential surface was removed from the mold, the substrate was further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. Thus, an elastic roller K-1 having a silicone rubber elastic layer with a diameter of 12 mm formed on the outer periphery of the base was produced.

(Preparation of Supporting Base Material K-2)
A SUS sheet (manufactured by Nisshin Steel Co., Ltd.) having a thickness of 0.08 mm was press-cut to a size of 200 mm in length and 23 mm in width to produce a supporting base K-2.

(Preparation of surface layer)
Hereinafter, synthetic examples for obtaining the surface layer according to the present invention will be shown.
<Synthesis of Ion Conducting Agent>
(Synthesis of Ion Conducting Agent A-1)
Place a stir bar and 50 ml of tetrahydrofuran (hereinafter THF, manufactured by Kanto Chemical Co., Ltd.) in an eggplant flask equipped with Jimroth, and disperse 12.5 g (0.52 mol) of sodium hydride (manufactured by Kanto Chemical Co., Ltd.). Cool with. A solution of 8.8 g (0.13 mol) of a nucleophile G-1 (imidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 ml of THF was slowly dropped, the ice bath was removed, and the mixture was stirred at room temperature for 2 hours. After adding 41.3 g (0.33 mol) of H-1 (2-bromoethanol) (made by Tokyo Chemical Industry Co., Ltd.) which is an electrophilic agent at room temperature, it heated and refluxed at 70 ° C. for 7 hours. The reaction solution after reaction was filtered, the insoluble matter was washed away with THF, and the solvent of the obtained filtrate was evaporated under reduced pressure. The residue was again dissolved in dichloromethane, filtered, and the filtrate was recovered and the solvent was evaporated under reduced pressure. The obtained concentrate was washed with diethyl ether and dried under reduced pressure to obtain 28 g of an ion conductive agent precursor. Subsequently, in order to exchange the anion of the obtained ion conductive agent with the target anion, the entire amount of the obtained ion conductive agent precursor was dissolved in 100 ml of methanol at room temperature. While the solution was stirred, 57.4 g of ion exchange salt I-1 (lithium bis (trifluoromethanesulfonyl) imide, manufactured by Kanto Chemical Co., Ltd.) dissolved in 50 ml of pure water was added, and stirred at room temperature for 24 hours. After the reaction, methanol is distilled off under reduced pressure, and after liquid separation with dichloromethane / water, the organic layer is recovered, washed twice more with water, the solvent is distilled off under reduced pressure, and after drying, the ion conductive agent A-1 as a white powder I got

(Synthesis of Ion Conducting Agents A-5 to A-16, A-20, A-21, A-23, and A-26)
An ion conductive agent A- was prepared in the same manner as in the synthesis of the ion conductive agent A-1, except that the types and blending amounts of the nucleophile, electrophile and ion exchange salt as raw materials were changed as described in Table 1. 5-A-16, A-20, A-21, A-23 and A-26 were obtained. In addition, nucleophile No. 1 in Table 1 , Electrophilic agent No. And ion exchange salt Nos. The details of are listed in Tables 2 to 4.

(Synthesis of Ion Conducting Agent A-2)
G-1 (imidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) 6.1 g (0.09 mol) as a nucleophile, H-3 (2- [2- (2- Chloroethoxy) ethoxy] ethanol, manufactured by Tokyo Chemical Industry Co., Ltd., 23.7 g (0.14 mol), potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) 25 g (0.18 mol), and 200 ml of acetone were added, and the mixture was heated to reflux overnight. After the reaction, the reaction mixture was filtered, and the solvent of the filtrate was evaporated under reduced pressure, and then purified by silica gel column chromatography (ethyl acetate) to obtain a compound in which the nucleophile was quaternized.
Subsequently, the obtained compound is dissolved in 50 ml of dichloromethane, and 17.5 g (0.14 mol) of H-1 (2-bromo-ethanol, manufactured by Tokyo Chemical Industry Co., Ltd.), which is an electrophilic agent, is added thereto, Heated to reflux. After the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with diethyl ether, and after drying, a quaternized ion conductive agent precursor was obtained as a white powder.
Subsequently, in order to make the anion the target anion, the entire amount of the obtained ion conductive agent precursor was dissolved in 100 ml of methanol at room temperature. While stirring the solution, 40.2 g of ion exchange salt I-1 (lithium bis (trifluoromethanesulfonyl) imide, manufactured by Kanto Chemical Co., Ltd.) dissolved in 50 ml of pure water was added, and the mixture was stirred at room temperature for 24 hours. After the reaction, methanol is distilled off under reduced pressure, liquid separation with dichloromethane / water is carried out, the organic layer is recovered, and the organic layer is further washed twice with water, the solvent is distilled off under reduced pressure, and after drying, the ion conductive agent A- is a white powder. I got two.

(Synthesis of Ion Conducting Agents A-3 and A-4)
An ion conductive agent precursor A- was prepared in the same manner as in the synthesis of the ion conductive agent precursor A-2, except that the types and blending amounts of the nucleophiles and electrophiles as the raw materials were changed as described in Table 5. 3 and A-4 were obtained.

(Synthesis of Ion Conducting Agent A-17)
10 g (0.08 mol) of the electrophile H-1 (2-bromoethanol) is reacted with tert-butyldimethylsilyl chloride for 3 hours at room temperature in the presence of imidazole in N, N-dimethylformamide, in ethyl acetate / water After liquid separation and drying, a compound in which a hydroxyl group is silylated is obtained. 12.8 g (0.054 mol) of a nucleophile G-6 (5-bromo-4-methyl-2-phenyl-1,3-oxazole) is dissolved in 400 ml of distilled THF under an inert atmosphere to obtain dry ice / It cooled to -78 degreeC by the methanol bath. Subsequently, 23 ml (60 mmol) of n-butyllithium / hexane 2.6 mol / l solution (manufactured by Kanto Chemical Co., Ltd.) was slowly added dropwise and stirred for 30 minutes.
Subsequently, a THF solution (50 ml) of silylated H-1 was added dropwise. After reacting at -78.degree. C. for 3 hours and at room temperature overnight, hydrochloric acid was added to the reaction solution and stirred at room temperature for 1 hour for desilylation.
The solvent was distilled off under reduced pressure, and the residue was partitioned between dichloromethane / water and dried to give 5-hydroxyethyl-4-methyl-2-phenyl-1,3-oxazole as a white powder. This is dissolved in 50 ml of dichloromethane, and 7.5 g (0.06 mol) of H-1 (2-bromoethanol, manufactured by Tokyo Chemical Industry Co., Ltd.), which is an electrophilic agent for quaternization, is added, and it is kept at 40 ° C. for 18 hours. Heated to reflux. After the reaction, the solvent was distilled off under reduced pressure, washed with diethyl ether and dried to obtain a quaternized ion conductive agent precursor which is a white powder.
The anion of this ion conductive agent precursor is a bromide ion. Subsequently, in order to exchange the anion to the target anion, the entire amount of the obtained ion conductive agent precursor was dissolved in 100 ml of methanol at room temperature. While stirring the solution, add 54.2 g (0.14 mol) of ion exchange salt I-3 (bis (pentafluoroethanesulfonyl) imide lithium, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 ml of pure water while stirring the solution, Stir for 24 hours. After the reaction, methanol is distilled off under reduced pressure, liquid separation with dichloromethane / water is carried out, the organic layer is recovered, and the organic layer is further washed twice with water, the solvent is distilled off under reduced pressure, and after drying, the ion conductive agent A- is a white powder. I got 17

(Synthesis of Ion Conducting Agent A-18)
An ion conductive agent A-18 was synthesized in the same manner as the ion conductive agent A-17 except that the types and amounts of the nucleophile and ion exchange salt used for the reaction were changed as described in Table 6.

(Synthesis of Ion Conducting Agent A-19)
20 g (0.12 mol) of bis (2-hydroxyethyl) dimethylammonium chloride were dissolved in 100 ml of methanol. While stirring this solution at room temperature, 51.7 g (0.18 mol) of ion exchange salt I-1 (lithium bis (trifluoromethanesulfonyl) imide, manufactured by Kanto Chemical Co., Ltd.) dissolved in 100 ml of methanol was added dropwise. After stirring for 24 hours at room temperature, the methanol was distilled off under reduced pressure. After liquid separation with dichloromethane / water, the organic layer is recovered, and the organic layer is further washed twice with water, the solvent is distilled off under reduced pressure, and after drying, the ion conductive agent A-19 (bis (hydroxyethyl) dimethylammonium as white powder 33 g of bis (trifluoromethanesulfonyl) imide) was obtained.

(Synthesis of Ion Conducting Agent A-22)
As the ion conductive agent A-22, commercially available 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as it was.

(Synthesis of Ion Conducting Agent A-24)
Place a stir bar and 50 ml of tetrahydrofuran (hereinafter THF, manufactured by Kanto Chemical Co., Ltd.) in an eggplant flask equipped with Jimroth, and disperse 12.5 g (0.52 mol) of sodium hydride (manufactured by Kanto Chemical Co., Ltd.). It cooled with. A solution of 8.8 g (0.13 mol) of a nucleophile G-1 (imidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 ml of THF was slowly dropped, the ice bath was removed, and the mixture was stirred at room temperature for 2 hours. After adding 41.3 g (0.33 mol) of H-1 (2-bromoethanol) (made by Tokyo Chemical Industry Co., Ltd.) which is an electrophilic agent at room temperature, it heated and refluxed at 70 ° C. for 7 hours. The reaction solution after reaction was filtered, the insoluble matter was washed away with THF, and the solvent of the obtained filtrate was evaporated under reduced pressure. The residue was again dissolved in dichloromethane, filtered, and the filtrate was collected, and the solvent was evaporated under reduced pressure. The obtained concentrate was washed with diethyl ether and dried under reduced pressure to obtain 28 g of an ion conductive agent A-24 (1,3-bis (2-hydroxyethyl) imidazolium bromide).

(Synthesis of Ion Conducting Agent A-25)
In a three-necked flask, 200 ml of pure water and 18.1 ml (0.045 mol) of tris (2-hydroxyethyl) methylammonium hydroxide (45 to 50% aqueous solution) were placed. In addition, an aqueous solution in which 11.4 g (0.040 mol) of 1,1,1-trifluoro-N-trifluoromethylsulfonyl methanesulfonylamide (manufactured by Kanto Chemical Co., Ltd.) is dissolved in 15.7 ml of pure water is added to the dropping funnel. The
The aqueous solution was dropped from the dropping funnel over 30 minutes into the three-necked flask while flowing nitrogen into the three-necked flask and under an ice bath. After dropping, the mixture was stirred at room temperature (23 ° C.) for 24 hours. Then, after 3 liquid separation with ethyl acetate / pure water, the organic layer is recovered and dried, and then the solvent is distilled off under reduced pressure to obtain ion conductive agent A-25 (tris (2-hydroxyethyl) methylammonium bis as a yellow liquid. 11 g of (trifluoromethanesulfonyl) imide was obtained.
The basic skeleton of the obtained ion conductive agent is shown in Table 7. In addition, Table 8 shows the anion species, the number of hydroxyl groups, and the structures of substituents.

<Synthesis of Amino Compound>
(Synthesis of Amino Compound B-1)
100 g (0.85 mol) of 2,2'-diamino-N-methyldiethylamine and 200 parts by mass of pure water as a reaction solvent are charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping device and a temperature controller. Warm to 40 ° C. while stirring. Next, 297 parts by mass (5.13 mol) of propylene oxide was gradually added dropwise over 30 minutes while maintaining the reaction temperature at 40 ° C. or less. The reaction was further stirred for 2 hours to obtain a reaction mixture. The resulting reaction mixture was heated under reduced pressure to distill water away to obtain amino compound B-1 (N, N, N ′ ′, N ′ ′-tetrakis (2-hydroxypropyl) -N′-methyldiethylene triamine) .

(Synthesis of Amino Compounds B-2 to B-17)
An amino compound B- was prepared in the same manner as the amino compound B-1, except that the species of amino compound used in the reaction, the type and amount of addition raw material, the type of solvent, the reaction time and the reaction temperature were changed as described in Table 9. 2 to B-17 were synthesized.

The basic skeleton of the obtained amino compound is shown in Table 10. Further, the number of “n” in the basic skeleton, the type of functional group, the number of functional groups (number of groups) contained per molecule of amino compound, and the structure of substituents are shown in Table 11.

<Synthesis of Polyisocyanate>
(Synthesis of isocyanate group-terminated prepolymer C-1)
Polyol F-1 (poly (tetramethylene glycol) / (trade name) with respect to 38 parts by mass of isocyanate D-1 (Polymeric MDI / (trade name: Millionate MR200 manufactured by Nippon Polyurethane Industry Co., Ltd.)) in a reaction vessel under a nitrogen atmosphere. : PTMG 2000; manufactured by Mitsubishi Chemical Corporation)) 100 parts by mass was gradually dropped while keeping the temperature in the reaction vessel at 65 ° C. After completion of the dropwise addition, reaction was carried out at a temperature of 65 ° C. for 2 hours. The resulting reaction mixture was cooled to room temperature and diluted with 50 parts by mass of methyl ethyl ketone (MEK) to obtain a solution of isocyanate group-terminated prepolymer C-1 having an isocyanate group content of 3.4%.

(Synthesis of isocyanate group terminal prepolymer C-2 to C-4)
The isocyanate group-terminated prepolymer C- is the same as in the case of the isocyanate group-terminated prepolymer C-1, except that the types and blending amounts of the isocyanate and polyol used in the reaction are changed as described in Tables 12 to 14. 2 to C-4 were synthesized.

Example 1
Hereinafter, the method for producing the developing member of the present invention will be described.
The following materials were stirred and mixed as materials for the surface layer.
<Material of surface layer>
Reactive compound Isocyanate group terminal prepolymer C-1 286.7 parts by mass Amino compound B-1 13.3 parts by mass Ion conductive agent A-1 3.0 parts by mass Urethane resin fine particles (trade name, art pearl C-400; Negami Industrial Co., Ltd. 90.0 parts by mass

Next, after adding methyl ethyl ketone (following MEK) so that a total solid content ratio might be 30 mass%, it mixed by the sand mill. Subsequently, the viscosity was further adjusted to 10 to 13 cps with MEK to prepare a paint for forming a surface layer.
The elastic roller K-1 produced previously was immersed in the paint for surface layer formation, the coating film of the said coating material was formed in the surface of the elastic layer of elastic roller K-1, and it was made to dry. Furthermore, a heat treatment was performed at a temperature of 160 ° C. for 1 hour to provide a surface layer having a film thickness of about 15 μm around the elastic layer, and a developing member according to Example 1 was produced.

(Examples 2 to 28)
The coating material for surface layer formation was prepared like Example 1 except having used the material of following Table 15 as a material of surface layer. Then, each paint was applied, dried and heated to the elastic roller K-1 in the same manner as in Example 1 to prepare developing members according to Examples 2 to 28.

(Comparative example 1)
As a material of the surface layer, 3.0 parts by mass of ion conductive agent A-1, 288.8 parts by mass of isocyanate group-terminated prepolymer C-1, and urethane resin fine particles (for 11.2 parts by mass of amino compound B-16) A trade name, Art Pearl C-400; manufactured by Negami Co., Ltd. 90.0 parts by mass was mixed with stirring.
Thereafter, the paint for forming a surface layer according to Comparative Example 1 was prepared in the same manner as the method for preparing a paint for forming a surface layer according to Example 1. This surface layer forming paint was applied onto the surface of the silicone rubber elastic layer of the elastic roller K-1 in the same manner as in Example 1 and dried to form a surface layer, whereby a developing member of Comparative Example 1 was produced.

(Comparative examples 2 to 12)
The coating material for surface layer formation was prepared like comparative example 1 except having used the material of following tables 16 and 17 as material of surface layer. Then, each paint was applied, dried, and heated to the elastic roller K-1 in the same manner as in Comparative Example 1 to produce a developing member according to Comparative Examples 2 to 12. In Comparative Examples 3 to 6, the polyols for Comparative Examples shown in Table 16 were used instead of the amino compounds.

<Polyol for Comparative Example>

(Reference Examples 1 and 2)
As materials for the surface layer, 2.9 parts by mass of ion conductive agent A-25, 287.3 parts by mass of isocyanate group-terminated prepolymer C-1, and urethane resin fine particles (based on 12.7 parts by mass of amino compound B-1) A trade name, Art Pearl C-400; manufactured by Negami Co., Ltd. 90.0 parts by mass was mixed with stirring. Thereafter, the paint for forming the surface layer according to the reference example 1 was prepared in the same manner as the method for preparing the paint for forming the surface layer according to the example 1. This surface layer forming paint was applied onto the surface of the silicone rubber elastic layer of the elastic roller K-1 in the same manner as in Example 1 and dried to form a surface layer, whereby a developing member of Reference Example 1 was produced. A developing member of Reference Example 2 was produced in the same manner as Reference Example 1 except that the type and amount of the ion conductive agent were changed as shown in Table 18 below.

(Example 29)
FIG. 2 shows a cross-sectional view when the resin of the present invention is formed on the blade surface. The support substrate K-2 prepared above is immersed in the surface layer-forming paint of Example 1 so that the length 51 from the longitudinal end is 1.5 mm, and the coated film of the paint is Formed and dried. Further, heat treatment was performed at a temperature of 160 ° C. for 1 hour to provide a resin layer 50 having a film thickness 52 of about 15 μm on the surface of the longitudinal side end of the SUS sheet, and a developing blade according to Example 29 was produced.

(Example 30, Example 31 and Comparative Example 13)
The developing blades according to Example 30, Example 31, and Comparative Example 13 were produced in the same manner as in Example 29 except that the type of the material used for the paint for forming the surface layer was changed as described in Table 19. .

The fact that the resin in the surface layer includes the structures represented by the structural formulas (1) to (3) can be obtained, for example, by pyrolysis GC / MS, analysis of evolved gas (EGA-MS), analysis by FT-IR or NMR, etc. It is possible to confirm.
About the surface layer obtained in the present example, a thermal decomposition apparatus (trade name: Pyro foil sampler JPS-700, manufactured by Japan Analysis Industry Co., Ltd.) and a GC / MS apparatus (trade name: Focus GC / ISQ, Thermo Fisher Scientific) The analysis was carried out using a thermal decomposition temperature of 590 ° C. and helium as a carrier gas. As a result, it was confirmed from the obtained fragment peaks that the resin in the surface layer has a structure represented by structural formulas (1) to (3).
The following items were evaluated using the developing members according to Examples 1 to 28 and Comparative Examples 1 to 12 thus obtained as the developing roller 16.

<Evaluation as a developing roller>
[Measurement of developing roller current value]
The developing roller current value was measured in an N / N environment by leaving the developing roller in an environment of 23 ° C. and 45% RH (hereinafter referred to as N / N) for 6 hours or more.
The schematic block diagram of the roller electric current value evaluation jig based on this invention is shown in FIG. When the conductivity of the surface layer is high (the resistance is low), the current value flowing to the roller is large. Therefore, the conductivity of the surface layer can be evaluated by measuring the value of the current flowing to the developing roller when a constant voltage is applied. First, in FIG. 5A, the cylindrical metal 37 having a diameter of 40 mm is rotated while pushing both ends of the conductive substrate 2 with a load of 4.9 N via the conductive bearing 38, and the developing roller 16 is rotated. Driven at a speed of 60 rpm. Next, a high voltage power supply 39 applies a voltage of 50 V, and it has a known electrical resistance (having a resistance lower than that of the developing roller 16 by at least two digits) disposed between the cylindrical metal 37 and the ground. The potential difference across the resistor was measured. A voltmeter 40 (189 TRUE RMS MULTIMETER manufactured by Fluke) was used to measure the potential difference. From the measured potential difference and the electrical resistance of the resistor, the current flowing to the cylindrical metal 37 through the developing roller 16 is calculated by calculation. Here, for measurement of the potential difference, sampling was performed for 3 seconds from 2 seconds after voltage application, and a value calculated from the average value was used as a roller current value.

[The amount of frictional charge on the developing roller]
The triboelectric charge of the developing roller is measured according to the following procedure in the H / H environment after leaving the developing roller in an environment of temperature 35 ° C. and relative humidity 85% (hereinafter H / H) for 6 hours or more. The
For measurement, the measurement unit shown in FIG. 6 was used by connecting to a cascade-type surface charge amount measuring apparatus TS-100AT (trade name, manufactured by Kyocera Chemical Corporation). As shown in FIG. 6, the developing roller 16 was placed on the insulating support rod 48, and the carrier 43 was inserted into the powder inlet 41 and dropped for 10 seconds to cause contact charging on the carrier 43. The carrier used the standard carrier N-01 (Japanese Imaging Society). The total electrification amount of the carrier 43 dropped into the receiving tray 44 installed on the insulating plate 45 was measured by an potentiometer 47 connected in parallel with the capacitor 46, and was defined as the electrification amount Q [μC]. Furthermore, the mass (g) of the carrier dropped into the receiving tray 44 was measured, and the charge amount Q / M (μC / g) per unit mass was determined as the charge amount from these values. The amount of frictional charge obtained by the developing roller 16 in this measurement was taken as the initial amount of roller charge. Furthermore, at the time of the following [fog image evaluation], the developing roller 16 after outputting 10000 images is taken out from the laser printer, installed in the measuring device shown in FIG. 6, and the roller charging amount is measured again. Amount.

[Cover image evaluation]
The conductive roller as the evaluation target was loaded as a developing roller 16 into a laser printer (trade name, LBP 7700C; manufactured by Canon Inc.) having the configuration shown in FIG. 4 to evaluate the fog. First, the laser printer loaded with the developing roller 16 to be evaluated was allowed to stand in the H / H environment for 6 hours or more after installation. Then, after intermittently outputting a black, 1% printing ratio image to a predetermined number of copy sheets while providing a pause time of 10 minutes for every 100 sheets, output a white solid image on a new copy sheet, The printer was stopped while outputting a white solid image. At this time, the developer deposited on the photosensitive member is peeled off with a tape (trade name, CT18; manufactured by Nichiban Co., Ltd.), and a reflection densitometer (trade name, TC-6DS / A; manufactured by Tokyo Denshoku Co., Ltd.) The reflectance was measured at. The amount (%) of decrease in reflectance based on the reflectance of the tape was measured and used as the fog value.
The fog value measured after outputting 100 sheets of an image having a printing rate of 1% was taken as an initial fogging value, and the image measured after outputting 10000 sheets of an image having a printing rate of 1% was taken as a fog value after endurance.

[The amount of triboelectricity of toner]
In order to evaluate the charge imparting property of the developing roller to the toner, the triboelectric charge amount was measured. At the time of the above-mentioned fog image evaluation, the toner carried on the narrow portion of the portion between the developer regulation blade of the developing roller and the photosensitive member contact position is attracted and held by the metal cylindrical tube and the cylindrical filter. Gathered. At that time, the amount of charge stored in the condenser through a metal cylindrical tube (measuring instrument trade name: 8252; manufactured by ADSC) and the mass of the developer attracted were measured. From these values, the amount of charge per unit mass (μC / g) was calculated. When a negatively chargeable toner is used, the sign of the charge amount per unit mass is negative, and the larger the absolute value is, the higher the charge imparting property of the developing roller is. As in the case of the above-mentioned fog evaluation, the charge amount measured after outputting 100 sheets of an image with a printing rate of 1% was measured after the image with an initial charge amount of 1% and an printing rate of 1% was output. Amount.
The types of ion conductive agent and amino compound used in each example, the current value of the obtained developing roller, the charge amount of the developing roller at the initial stage and after the endurance, and the charge amount and the fog value of the initial stage and after the endurance 20 and Table 21.

Since the developing roller according to Examples 1 to 28 contains the resin according to the present invention in the surface layer, the fluctuation of the charge amount at the initial stage and after the endurance is small, and a high quality image is obtained.
In particular, since the resin according to Examples 1 to 7 and 12 to 18 uses a compound having a hydroxyl group in the amino compound as compared with Examples 8 to 11, the amount of change in the charge amount before and after durability is smaller , Stable image is obtained.
Further, the resins according to Examples 1 to 7 are the resins according to Examples 19 to 21 and 24 to 26 in that the anion in the resin uses an ion conductive agent having a fluorinated sulfonylimide anion. It is different. Due to the difference in the resin involved, the developing members according to Examples 1 to 7 have a smaller amount of change in charge amount and a more stable image than the developing members according to Examples 19 to 21 and 24 to 26. It is obtained.
The resin which concerns on Comparative Example 1-6 with respect to the said Example does not use the amino compound which concerns on this invention. Therefore, in the developing members according to Comparative Examples 1 to 6, the change of the charge amount before and after the endurance is large and the fog is deteriorated as compared with the developing members according to the Examples.
Moreover, the resin which concerns on the comparative examples 7-12 does not use the ion conductive agent which concerns on this invention with respect to the said Example. Therefore, in the developing members according to Comparative Examples 7 to 12, the change in the charge amount before and after the endurance is large, and the fog is deteriorated, as compared with the developing members according to the Examples.
In the resins according to Reference Examples 1 and 2, the number of hydroxyl groups in the ion conductive agent is 3 or more. Therefore, in the developing members of Reference Examples 1 and 2, fluctuation of the charge amount before and after the endurance does not occur.

<Evaluation as a development blade>
The following items were evaluated using the developing blades according to Examples 29 to 31 and Comparative Example 13.
[Evaluation of current value of developing blade]
The measurement of the current value of the developing blade was performed by leaving the developing blade in an environment of N / N for 6 hours or more, and performing the measurement in an N / N environment. FIG. 7 shows a schematic configuration diagram of a jig for evaluating the current value of the developing blade, which is used in the main measurement. As shown in FIG. 7A, the resin layer 50 of the developing blade is set in contact with the cylindrical metal 53 fixed in the jig. At this time, since the adjustment valve in the height direction is installed in a jig (not shown) for fixing the developing blade, adjustment is performed so that a constant load of 0.3 N / cm is applied to the cylindrical metal 53 Do. Next, as shown in FIG. 7B, one end of the supporting base K-2 was held by the conductive clip 54, and a voltage (100 V) was applied by the high voltage power supply 55. Then, the potential difference between both ends of a resistor having a known electric resistance (one having a lower electric resistance by two digits or more with respect to the electric resistance value of the developing blade) disposed between the cylindrical metal 53 and the ground was measured. A voltmeter 56 (trade name: 189TRUE RMS MULTIMETER, manufactured by FRUKE) was used to measure the potential difference. From the measured potential difference and the electrical resistance of the resistor, the current flowing to the cylindrical metal 53 through the developing blade is calculated and used as the blade current value. Here, for measurement of the potential difference, sampling was performed for 3 seconds from 2 seconds after voltage application, and a value calculated from the average value was used as a blade current value.

[The amount of frictional charge on the developing blade]
In the apparatus of FIG. 6, a developing blade was used instead of the developing roller, and the carrier 43 was placed in contact with the resin layer 50 of the developing blade so as to be contact charged. Further, the angle between the falling direction of the carrier 43 and the plane of the resin layer 50 of the developing blade was adjusted to be 45 °. The amount of frictional charge of the developing blade was measured in the same manner as [the amount of frictional charge of the developing roller] except the above. The amount of frictional charge obtained by the developing blade in this measurement was taken as the amount of blade charge.

[Image evaluation of fog / amount of frictional charge of developer]
In the laser printer (trade name: LBP 7700C; manufactured by Canon Inc.) having the configuration shown in FIG. 4, the developing roller was not changed, and the developing blade according to this example or the comparative example was loaded as the developing blade 21. [Image evaluation of fogging] and [frictional charge of toner] were carried out in the same manner as [Fogging image evaluation of developing roller] and [frictional charging amount of developer] except the above.
<Evaluation as a developing blade>, types of ion conductive agent and amino compound used in each example, blade current value of the obtained developing blade, blade charge amount, charge amount after initial and endurance The fogging values are shown in Table 22 below.

  In Examples 29, 30, and 31, since the developing blade having the resin of the structure according to the present invention is used, the fluctuation of the charge amount before and after the endurance is small, and a stable image is obtained. On the other hand, in Comparative Example 13, since n of the amino compound used was small, the fluctuation of the charge amount before and after the endurance was large, and the fog after the endurance was deteriorated.

1: Developing member 2: Substrate 3: Elastic layer 4: Surface layer 5: Intermediate layer

Claims (8)

A developing member having a conductive substrate and a surface layer,
The surface layer contains a resin and an anion,
The anion is
Fluorinated sulfonic acid anion, fluorinated carboxylic acid anion, fluorinated sulfonyl imide anion, fluorinated sulfonyl methide anion, fluorinated alkyl fluoroborate anion, hexafluorophosphate anion, hexafluoroarsenate anion, hexafluoroantimonate anion And at least one selected from the group consisting of dicyanamide anions,
The resin is
At least one partial structure selected from the group consisting of structural formula (1) and structural formula (2)
And a partial structure represented by a structural formula (3):
[In structural formula (1),
X represents a nitrogen atom, an oxygen atom or a sulfur atom,
When X is a nitrogen atom, p is 1, and when X is an oxygen atom or a sulfur atom, p is 0,
R11 to R15 are each independently selected from the group consisting of the following (a) to (c), and any two of R11 to R15 are (c):
(A) hydrogen atom,
(B) a saturated hydrocarbon group having 1 to 6 carbon atoms,
(C) A structure including a portion bonded to the polymer chain of the resin via a urethane bond. ],
[In Structural Formula (2), R 21 to R 26 are each independently selected from the group consisting of (a) to (c), and any two of R 21 to R 26 are c). ],
[In structural formula (3),
n is an integer of 2 or more and 4 or less,
R 35 represents an alkylene group having 2 to 4 carbon atoms, and R 35 may be the same or different,
R31 to R34 are each independently selected from the group consisting of (d) to (f) below, and R34 may be the same or different and at least four of R31 to R34 Is (f):
(D) hydrogen atom,
(E) alkyl group having 1 to 4 carbon atoms,
(F) A structure including a portion bonded to the polymer chain of the resin via a urethane bond or a urea bond. ]. The partial structure represented by the structural formula (3) is a partial structure including a compound represented by the structural formula (4) and a urethane bond or a urea bond derived from a reaction with a polyisocyanate. Developing member:
[In structural formula (4),
m represents an integer of 2 or more and 4 or less,
R 45 is an alkylene group having 2 to 4 carbon atoms, and R 45 may be the same or different,
R41 to R44 are each independently the following RA or RB, and R44 may be the same or different, and at least four of R41 to R44 are RA,
RB represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
RA is any one selected from the group consisting of the following (g) to (i),
(G) a hydroxyalkyl group having 1 to 8 carbon atoms,
(H) an aminoalkyl group having 2 to 8 carbon atoms,
(I) A group represented by the following structural formula (5). ],
[In structural formula (5), R51 is a C2-C5 alkylene group, R51 may be same or different, j is 2 or 3.]. ]. The developing member according to claim 2, wherein the compound represented by the structural formula (4) is a compound represented by the structural formula (6):
[In structural formula (6), R61 to R64 each independently represent an alkylene group having 2 or 3 carbon atoms, R64 may be the same or different, and k represents an integer of 2 or more and 4 or less. ]. The resin is
Polyisocyanate and
A compound represented by the structural formula (4):
The developing member according to claim 2 or 3, which is a reactant with at least one compound selected from the group consisting of Structural Formula (7) and Structural Formula (8):
[In the structural formula (7), Y is a nitrogen atom, an oxygen atom or a sulfur atom,
When Y is a nitrogen atom, q is 1, and when Y is an oxygen atom or a sulfur atom, q is 0,
R71 to R75 are each independently selected from the group consisting of the following (g) to (i), and any two of R71 to R75 are (i).
(G) hydrogen atom,
(H) a saturated hydrocarbon group having 1 to 6 carbon atoms,
(I) A group having a hydroxyl group at the end. ],
[Wherein, R 81 to R 86 in the structural formula (8) are each independently selected from the group consisting of (g) to (i), and any two of R 81 to R 86 are (I). ].   The developing member according to any one of claims 1 to 4, wherein in the structural formula (1), X is a nitrogen atom.   The developing member according to any one of claims 1 to 5, wherein the anion is a fluorinated sulfonylimide anion.   A process cartridge configured to be removable from a main body of an electrophotographic apparatus and having at least a developing unit, the developing unit having a developing member according to any one of claims 1 to 6. Process cartridge characterized in that.   An electrophotographic apparatus comprising at least a developing unit, wherein the developing unit comprises the developing member according to any one of claims 1 to 6.